IN F O R M A T IO N TO USERS This dissertation was produced fro m a m icro film copy o f the original docum ent. W hile the most advanced technological means to photograph and reproduce this docum ent have been used, the q u a lity is heavily dependent upon the q u a lity of the original subm itted. The follow ing explanation o f techniques is provided to help you understand m arkings or patterns w hich may appear on this reproduction. 1. T h e sign or “ target" fo r pages apparently lacking fro m the docum ent photographed is "Missing Page(s)". If it was possible to o b tain the missing pagels) or section, they are spliced in to the film along w ith adjacent pages. This may have necessitated cutting th ru an image and duplicating adjacent pages to insure you com plete c o n tin u ity . 2. 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T h e m a jo rity o f users indicate that the te x tu a l con ten t is of greatest value, however, a som ew hat higher q u a lity reproduction could be made from dissertation. “ photographs" Silver prints if essential to th e understanding o f the of “ photographs" m ay be ordered at additional charge by w ritin g the O rder D e p a rtm en t, giving the catalog num ber, title , au th o r and specific pages you wish reproduced. University Microfilms 300 N orth Z eeb fload A n n A rb o r. M ic h ig a n 4 3 1 0 6 A Xerox Education Company I 73-5450 MOREAU, Richard Barnaba, 1935THE INTERACTION OE LINEAR PHOSPHATES WITH SOLUBLE AND PARTICULATE CALCIUM AND NATURAL COLORED ORGANIC ACIDS IN THE THUNDER BAY, ALPENA, MICHIGAN. Michigan State University, Ph.D., 1972 Limnology U niversity M icrofilm s, A XEROX Com pany , A n n A rb o r, M ich ig an THE INTERACTION OF LINEAR PHOSPHATES WITH SOLUBLE AND PARTICULATE CALCIUM AND NATURAL COLORED ORGANIC ACIDS IN THE THUNDER BAY, ALPENA, MICHIGAN BY Richard Barnaba Moreau A THESIS Submitted to Michigan State University in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY Department of Fisheries and Wildlife 1972 P L E A SE NOTE: S ome p a g es may have i n d i s t in c t F il m e d as University Microfilms, print. received. A Xerox E d u c at i on Company ABSTRACT THE INTERACTION OF LINEAR PHOSPHATES WITH SOLUBLE AND PARTICULATE CALCIUM AND NATURAL COLORED ORGANIC ACIDS IN THE THUNDER BAY, ALPENA, MICHIGAN BY Richard Barnaba Moreau The Thunder Bay Watershed has been found to have a relatively high water quality, with much of the 1250-square-wile drainage basin still in its natural state. The regional inventory of the watershed showed domestic, agricultural, and industrial influences on the quality of the water, character of the watershed resources, and aquatic species composition. The local sewage plant effluent contained a high level of the simple linear phosphates: ortho, pyro, and tripoly. These forms would be involved In phosphorus availability and contribute to eutrophicatlon of Thunder Bay, Calcareous particles from natural limestone sources and calcinated cement dust can serve as adsorption sites for the soluble linear phosphate forms. The removal of ortho, pyro, and tripolyphosphates from standard solutions and phosphorus from composite sewage samples by the cement dust indicated a probable uptake of phosphates in the bay by dust particles. Oxidation of natural water samples showed that there exists an interaction between calcium and natural organic matter. colored materials had an acidic nature and were recovered in The Richard Barnaba Moreau sufficient concentration to determine metal-organic acid-phosphat Interactions. The Interaction of phosphate linear forms with thl natural complex was determined In standard calcium-phosphate solu tlons using calcium and hydrogen electrodes. The mllllequlvalence response of the calc1um-phosphate mixtures was reduced In the presence of concentrated colored organic acids from the watershed. The values of association constants for the mixtures were increased by involvement of theae natural organic acids. The phosphates in the calcium complexes may occur as PxOy.n“ bonded through soluble calcium to the acidic groups of the organic matter in natural waters. In the Thunder Bay Watershed, the adsorption of phosphates on calcareous sediments and the formation of a soluble complex between the caleiurn-phosphate system and natural organic acids, will certainly Influence the movement and availability of phos­ phorus In the Thunder Bay ecosystem. ACKNOWLEDGMENTS To God: It Is our duty to glory tn the cross of our Lord. He saves us and sets us free; through Him we find salvation, life, and resurrection. I wish to thank my major professor, Dr, Frank M. D'ltrl, for his guidance and encouragement throughout this research, I would also like to acknowledge the support of the National Science Foundation through a Science Faculty Fellowship for an academic year. As well, the assistance and suggestions of Dr, Niles R. Kevern, Dr Clifford R. Humphrys* Dr. Andrew Tlmnlck, Jack E. Petoskey, Charles S, Annett, Thomas E. Hears, numerous technical students and local Industrial personnel have been essential to the completion of this project. To my family and parents, may I say, that without your support and prayers, this task would never have been accomplished. To Joyce, my wife, for her typing skill and whose devotion and encouragement sustained me In my many moments of frustration. Be praised, 0 Lord, through our sister Mother Earth, For she sustains and guides our life, And yields us divers fruits, with tinted flowers and grass, Praise and bless my Lord, and thank him too, And serve him all,, in great humility, St . Francis of Assisi 11 TABLE OF CONTENTS Page LIST O F T A B L E S ............................ . ..................... v LIST O F F I G U R E S .................................................. 1* I N T R O D U C T I O N .................... „ ............................... 1 O B J E C T I V E S .................................. ..................... 5 METHODS O F S T U D Y .................................................. 7 METHODS O F A N A L Y S I S .............................................. 10 S e a l i n g S t a t i o n * .................... - .................... Equipment and R e a g e n t s .................................... 10 12 ANALYTICAL P R O C E D U R E S ........................................... 15 R E S U L T S ........................................................... 33 Phosphorus Sources and Levels In Thunder B a y ........... Phosphate Adsorption on Cement D u s t ....................... Use of Calcium Select-Ion E l e c t r o d e ................ 52 Meas uresent of Organic Acids In H a t e r . . . . . . . . . . Organic Acid Separation .................................... Potential Coe^arlson M e t h o d ................................ Potential-Tit rat Ion M e t h o d ............. Potentlometric (pH) Titration of Natural Organic Acids. . Fotentlometrlc (pH) Titration of Phosphates .............. Potentlometric (pH) Titration of Organic Acid-Phosphate . M i x t u r e s .................................................. 33 43 55 59 64 66 74 80 87 D I S C U S S I O N ......................................................... 99 Water Quality of the B a s i n ................................ Hydrolysis of Complex P h o s p h a t e s ......................... Cultural A d d i t i v e s ......................................... Ca i d i m M e a s u r e m e n t ......................................... Potential Comparison M e t h o d ................................ Potentlal-TltratIon M e t h o d ................ Natural Colored Organic Acids .............................. Identification of Natural Organic Acids .................. Potentlometric (pH) Titration Method .................... 99 102 102 104 105 106 108 109 112 S U W 1 A K T ...................................................... 117 Hi Page RECOMMENDATIONS FORCEMENT DUST . .............................. 119 C O N C L U S I O N S .................................................... 121 B I B L O G R A P H Y .................................................... 123 Appendix I. Historical R e v i e w .......... ..................... 133 ....................... 161 Appendix II. Thunder Bay Drainage Basin G e o l o g y .................................... 164 T o p o g r a p h y ................................. 168 170 Land R e s o u r c e s ............................. S o i l s ...................................... 171 Waterholding Capacity ........................ 177 177 Water A v a i l a b i l i t y ......................... Present Forest Resources ...................... 182 Climatic Conditions .......................... 187 Current Patterns in Bay ............. 190 The Watershed Cultural Dischargee ........... 195 Thunder Bay Water Quality and Resources ... 199 Summary of Thunder Bay Watershed Resources . . 207 Appendix III. Thunder Bay Watershed Resources, Geographic Sites and Sampling L o a a t i o n s .......... Appendix IV. . . Michigan Water Quality Standards ............... iv 235 241 LIST OF TABLES Table Page 1. Description of the Tributaries of the Thunder Bay River 11 2. Composition of Natural Constituents Used in Cem ent Production . . . . . . . ....................... . . . 34 3. Characteristics of Cement Dust - Phosphate Available from D u s t .................................................. 35 4. Mass-Balance Relationships 5. Characteristics of Sewage Plant Effluent 6. Anion-Exchange Chromatographic Analysis of Phosphate Mixtures and Sewage S a m p l e s .............................. 40 7. Characteristics of Cement Dust - Cement Dust as Suspended Solids In Natural S y s t e m s ................................ 44 3. Characteristics of Cement Dust - pH of Aqueous Solutions with Cement D u s t ......................... 9. .............................. . . . . . . . 36 39 45 Phosphate and Calcium Inherent In Cement D u s t ............ 47 Table 10, 11, and 12 H e a d i n g s ........................... 48 10. Phosphate Adsorption (mg/1) on Cement Dust In Aqueous S y s t e m s ..................................................... 49 11. Phosphate Adsorption on Cement Dust in Natural and Domestic Sewage S a m p l e s .................................. 50 12. High Phosphate Adsorption on Cement Dust In De-Ionized W a t e r ............................................... 51 13. Calcium Ion Electrode Standard V a l u e s .................. 53 14. Effect of pH on Calcium Ion Electrode Potential (mv). . 56 15. Temperature and Calcium Ion Electrode Potential (mv). . 58 16. Organic Color Measurement In Thunder B a y Watershed . . 60 List of Tables (Cont'd.) Table 17. Page The Infrared Assignment of Bands for Organic Func­ - . tional G r o u p s .......... 62 18. Association Constant by Potential Comparison 65 19. Association Constant by Potential Comparison in the Presence of Natural Organic Acids ................. 67 Association Constant by Potential-Titration Using Calcium . . . . . ................................... 69 Association Constant by Potential-Titration Using Phosphate ................. 73 Association Constant by Potential-Titration in the Presence of Natural Organic Acids ................. 75 23. pH Measurement of Natural Organic Acids with Base . . 77 24. pH Measurements of Phosphates with N a O H ............. 84 25. pH Measurements of Phosphates with Ca( 0 H ) 2 ......... 85 26. Mean Equivalent Measurements of Phosphate Mixtures with NaOH ................................ 88 Mean Equivalent Measurements of Phosphate Mixtures with Ca(0H ) 2 ....................................... 95 The Phosphate-Ca-Organic Acid Interactions by pH M e a s u r e m e n t ....................................... 96 Association-Constant Means for Potential Comparison and Potential-Titration Methods . . . . 107 30. Stratigraphic Units of Michigan Bedrock .............. 167 31. Description of Alpena County Land Resource Area Map . 173 32. Description of Montmorency County Land Resource Area Map ............................... 174 33. Major Soil Types on Principal Thunder Bay Tributaries 34. Thunder Bay Watershed Soil T y p e s ....................... 179 35. Waterholding Capacity „ 36. Water Availability 20. 21. 22. 27. 28. 29. . . . , . vi . . . . 178 .............................181 184 List of Tables (Cont'd ) Table Page 37. Forest Types along Major Thunder Bay Streams . . . . 185 38. Forest Cover Types of Thunder Bay Watershed ......... 39. Climatological Data for Thunder Bay A r e a ..........188 40. Prevailing Weather Conditions of Thunder Bay . . . . 189 41. The Mean Composition of Emitted Cement Dust Material 196 42. Prevailing Mean Wind Conditions of Thunder Bay 198 43. Thunder Bay Water Quality . . . . . . 44. Lake Huron Water Q u a l i t y ........................... 203 45. The Color of Thunder Bay Yellow Organic Natural Acids 46. Total and Mean Discharge of Thunder Bay River at . . Ninth Street D a m ................................. 210 47. Alpena Sewage Plant - Physical Analysis of Composite 211 48. Alpena Sewage Plant - Chemical Analysis of Composite 212 49. Coliform (MFN/100 ml) in Thunder B a y .............. 213 50. Thunder Bay Watershed Discharge D a t a .............. 215 51. Summary of Watershed Discharge D a t a ................ 216 52. Water Resources C o m i s s l o n Water Quality Data for . . Thunder Bay River Watershed ........................ 186 . . . ................ 202 208 217 53. Water Resources Commission Physical and Chemical . . Water Quality Data - Main Branch Thunder Bay River at Breakwall ................................. 218 54. Thunder Bay and River Sampling Data by City Health Department and Local Analysis ...................... 220 55. Local Analysis of Thunder Bay Watershed - 1967-1968 221 56. 1970-1971 Local Physical Data at Thunder Bay Water­ shed S t a t i o n s ..................................... 222 57. 19 70-1971 Local Chemical Data at Thunder Bay Water­ shed Stations .......................... 58. . Distribution of Selected Parameters at Specific Sites in Thunder Bay River and Thunder B a y ........... 225 vii 223 List of Tables (Cont'd,) Table *9. 60. Page 1970 Mean Monthly Phosphate (wg/1) for Thunder Bay and River Survey .......... 226 1971 Mean Monthly Phosphate (mg/1) for Thunder Bay and River Survey . ................. 227 61. Calcium in Thunder Bay Watershed......................... 228 62. Acid-Extractable Phosphate of Thunder Bay Suspended S o l i d s ................................................ 230 63. Dissolved Oxygen (mg/1) and Temperature (C) Profile in Thunder B a y ....................................... 231 64. Phosphate Measurement (mg/1) at Various Depths in Thunder B a y ........... , .............................. 232 65. Monthly Means («g/l) by Day for Alpena Sewage Effluent ............... 233 Alpena Sewage Effluent CosEposite Means for Specific D a y s ........... 234 67. Description of Thunder Bay Basin Geographic Sites . . 236 68. Description of Liwnological Sampling Stations in Thunder Bay B a s i n ..................................... 238 66. viii LIST OF FIGURES Figure Page 1. Fluorescence vs. Organic Acids Concentration . . . . 19 2. Sampling Sites - Thunder Bay, Lake Huron, Alpena, ................. Michigan 29 Monthly Dilution Relationship for Sewage Phosphate Discharge and River Flow . . . . . ............... 37 4. Separation of Sewage Effluent by Anion Chromatography 41 5. Standard Calcium Curve . . . . . 54 6. Effect of pH on Calcium Ion Electrode Potential . . 57 7. Infrared Spectrum of Thunder Bay Organic Acid In Ethly A l c o h o l ..................................... 61 Titration of Na 3 PO^ (1.10x10" 3 M) with Calcium at Variable p H ....................................... 70 3. 8. .................... 9. Titration of CaClj (1.0x 10"3M) with Na^PO^ ......... 71 10. Titration of Linear Phosphate Forms with C a C ^ ... 72 11. Titration of N a 3 PO^ (I.17xl0“ 3 . pH-7.2) with CaCl 2 in the Presence of Thunder Bay Organic Acids . . . 76 12. Titration of Organic Acids with N a O H .............. 13. Titration of Organic Acids with CaCOH)^ 14. Titration of Linear Phosphate Forms with NaOH . . , 81 15. Titration of Na^PO^ with Ca( 0 H )2 et Variable Rates . 82 16. Titration of Pyrophosphate and Tripolyphosphate 83 17. Titration of Na^PO^, CaCl 2 and Main Branch Organic Acids with N a O H ............................ 86 Titration of Na^p 2 0 -?, CaClj and Main Branch Organic Acids with NaOH ............... 89 18. ix ........... . . 78 79 List of F i g u r e s (Cont'd,'! Page Figure 19. 20. 21. 22. Titration of Wa^P^PjQ, CaCl 2 and Main Branch Organic Acids with N a O H " ................................... 90 Titration of Na^PO^, CaCl 2 and No. Branch Organic Acida with N a O H ................................... 91 Titration of N a ^ ^ O ^ and ^ 5 8 3 0 3 0 with CaCl 2 and No. Branch Organic Acids using NaOH . . . . . . . 92 Titration of Na^PO, and No. Branch Organic Acida with Ca(OH)......................................... 93 d- 23. 24. Titration of Na^PO^ and Main Branch Organic Acida with Ca(OH ) 2 ....................................... 94 Northern Lake Michigan and Lake Huron Drainage Area, Lower P e n i n s u l a ................... i2 25. Thunder Bay River Basin . ........................... 163 26. Bedrock of Michigan . . . . . . . . 166 27. Areal Geology of Alpena County, Michigan ........... 169 28. General Soil Map, Alpena C o u n t y ............. 175 29. General Soil Map, Montmorency C o u n t y .................. 176 30. Waterholdlng Capacity in Thunder Bay Watershed . . . 180 31. Water Availability of Thunder Bay Watershed 183 32. Monthly Precipitation for Alpena, Michigan ......... 191 33. Monthly Total Discharge of the Thunder Bay River 192 34. Surface Water Currents in Lake Huron ................ 35. Areal Photograph of Thunder B a y ....................... 204 36. Thunder Bay Watershed Sampling Locations . . . . . . ............... T . . . . , . 194 235 INTRODUCTION This project has been developed within the frame of reference of the far-aweeplng reco n endatIona of the American Chemical Society (ACS) Conalttee on Chemistry and Public Affaire (1969). This thesis concerns natural water, particularly from a chemical point of view, in order to upgrade man's knowledge of his environment and the means whereby it may be controlled. The ACS Comalttee emphasized that extensive fundamental research is required to elevate nun's understanding of the environmental system around him. It was evident that there was a need for an Initiation of such research on the resources of the Thunder Bay Watershed in Northeastern Michigan's Lower Peninsula. The survey-analysis program was developed for the purpose of obtaining physical and chemical data on the quality of the waters flowing Into the Thunder Bay River and Thunder Bay, The physical and chemical characteristics of the natural water of the Thunder Bay Watershed were determined under different seasonal conditions and over a four year period. From results of these Investigations» the degree of eutrophlcation and the amounts of nutrients contributed from watershed drainage as well as domestic or industrial sources can be evaluated. 1 2 The ACS C o m l t t e e tecom e n d e d chat beelc data should be gathered systematically to delineate the presence and relative importance of agricultural and domestic sources of compounds of nitrogen tnd phosphorus In surface waters The study of the interaction of soluble calcium from natural limestone sources with phosphorus nutrients * in the form of ortho-, pyro-, and tripolyphosphates discharged from domestic sewage effluents, would reflect phosphorus availability. The water quality of our aquatic environment is related to the water sources feeding the system^ and the resultant effect which the composition of these sources has on the components of the aquatic system. The constant Increasing water requirements of our society has resulted in a growing concern about the presence of nutrients In surface waters The productivity of a given body of water has been found to depend on solar radiation, temperature, and the concentration of plant nutrients which are available to these organisms in the water (Lee, 1970). Nitrogen and phosphorus nutrients and some trace metals are often considered to be significant in limiting the growth of aquatic plants in surface water Mackenthun (1968) reviewing the phosphorus problem in natural water concluded that when phosphorus Is present in excess of a critical concentration, and when other environmental conditions are favorable, It can stimulate aquatic plant growths which will produce scums and odors, remove oxygen and destroy water uses The lower limit of optimum growth has been reported to occur when available phosphorus concentrations reaches a level of 0 02 mg/1 in the water (Fitzgerald, 1970). 3 Another concern of the ACS Committee was the investigation of naturally occurring and pollutant particles in water as to their size, charge, composition and adeorptlve properties. A prevalent source of pollutant particles in Thunder Bay is an industrial cement dust discharge into the atmosphere over the bay. The second phase of this study was to establish the possible Involve­ ment of the dust In phosphate adsorption relative to its composition and assimilation in water. The presence of large amounts of suspended solids can Influence aquatic plant production by limiting light penetration and providing adsorption sites for phosphorus forms. Lake nutrlent-budget studies have shown that the sediments cf an eutrophic lake are greatly enriched in phosphorus (Frink, 1967). Keup (1968) has indicated that suspended particles m a y have a key role In phosphorus movement in natural water. He concluded that significant quantities of phosphorus may pass downstream unmeasured as bed-loads or with floating materials. Uptake or release of dissolved Inorganic phosphate by sediments has been considered to be pH and redox dependent. The phosphate released to a soluble form from an adsorption complex in the sediments results from an equilibrium exchange. Much soluble phosphorus m a y be available for algal growth when the sediment is somehow physically mixed with the overlying water. Natural flow of water over sediments, stirring action of currents and o r g a n i s m s , movement of sediments by wind action, diffusion processes, and gas formation and release from mud can all re-suspend the upper layer of sediment into overlying water. 4 The ACS Cossalttee considered research on specific chemical c o ^ > o u n d s t particularly organic compounds, which are present In both waste and natural waters, of a regional inventory. as being essential to the knowledge The m a j o r phase cf this research project was concerned w i t h the organic soluble materials of the area waters and the cultural effluents and their interaction with domestic phosphate discharge In Thunder Bay at Alpena, Michigan. Vlt h respect to the phosphorus balance In a given water system, the Interactions of co^ilex physical and chemical factors Involving the equilibria present In natural systems Influences the seasonal utilization of phosphorus. Chemical coaqilexatlon by metal Ions and soluble organic matter can play an Important role In affecting the phosphorus concentration In a water environment. The availability of phosphate forms, from natural, agricultural, and sewage sources In Thunder Bay waters has been determined in view of their involvement In a possible chemical cosq>lexatlon with soluble cal c l i m and natural yellow organic acids, »wd physical adsorption o n calcareous particles. A co^irehenslve review of the literature has been accoaq>l 1 shed and Is presented In Appendix 1. OBJECTIVES The areas of this study were selected to determine the forms of phosphorus prevalent and available for ecological utilization in Thunder Bay natural waters. Their Involvement In three means of phosphorus fixation above the bottom sediments (mud-water interface) was measured. (1) The Interaction of calcium Ions with the phosphorus forms ( o r t h o - , pyro-, potentlometric the phosphates. and tripolyphosphate) was followed by (mv) titration of the calcium In the presence of The p H titration of the phosphates In the presence of calcium was also carried out. The field studies on calcium complexatlon were done In the Thunder Bay Watershed where limestone deposits are prevalent. Calcium was considered as an Important part of the phosphorus cycle In the river and bay. (2) The second area of study was concerned with the suspended solids wh i c h may provide adsorption sites for the phosphorus forms. The solids could be Important In the consideration of the movement of phosphorus in the Thunder Bay natural systems. The possible adsorption of ortho-, pyro-, and tripolyphosphates and any variation in the fixation was measured by sediment extraction methods. Substantial amounts of phosphorus m a y be temporarily stored In stream-bottom deposits that can be subsequently scoured from the channel and rapidly discharged Into the aquatic ecosystem. 5 6 Bed-load transport of aollda m a y be a algnlfleant mode of transporting of nutrient* Incorporated with the solids. The Thunder Bay field studies concerned the calcareous particles from natural sources and from the Industrial cement operation In Alpena, Michigan. (3) The laboratory and field testing of the Interaction of soluble organic matt e r with the phosphorus forms (ortho, pyro, and trlpoly) In the presence of calcium, were followed by the some procedures used In the calcium-phosphate co^>lexatlon determination. The organic material was primarily the yellow organic acids of natural colored water extracted from the Thunder Bay River and Its tributaries. The foregoing three studies were all conducted In the laboratory by two method*. The first part of each one was the determination of the direct Interaction of species dissolved In double-deionized water of appropriate Ionic strength. The second part was performed with Thunder B a y natural waters. The parameter composition of the artificial waters used In these experiments to maintain co^>arable ionic strengths was based upon results which Kramer (1964) obtained from Great Lakes water. Kramer's model was a good approximation for fresh water because It allows the calculation of: (a) upper limits for fresh water composition due entirely to natural processes; (b) degree of pollution from comparison of the actual composition with the natural process calculation; (c) absolute concentration limits because of natural sources and pollution additives. METHODS OF STUC3Y This study Involved the complexatlon reactions of the three phosphate forms with the soluble constituents (calcium and natural organic acids) and adsorption on cement dust particles. These reactions were studied relative to the composition of the natural water, sewage discharge, and suspended materials. With respect to a phosphorus balance in a given water system, complex physical and chemical Interactions Involving equilibria present in natural systems produce seasonal fluctuations of aquatic phosphorus. There are two basic physical conditions and two chemical reaction systems that influence phosphorus concentration In a water envlronent. The physical adsorption of phosphorus compounds on bottom sediments and suspended solids would affect the amount of available phosphorus. Chemical complexatlon by metal Ions and soluble organic matter have an Important Involvement in phosphate availability. The purpose of „ne adsorption Investigation was to measure the availability of the phosphate forms fixed on suspended calcareous sediments. The calcareous suspended particles entering the bay come from two sources: natural particles from limestone deposits In the area and from the emission, over the bay,, of calcinated dust from the local cement plant. The stability of the bound phosphorus on the sediments vei determined by soil extraction methods. 7 8 A major source of phosphorus In Thunder Bay Is a domestic sewage discharge. The sewage was analyzed for the three phosphate forms by chromatographic anion-exchange separation. The phosphate content was determined by colorimetric methods. The phosphate fixation with soluble components was measured In two ways. The effect of calcium Ion on the prevalent phosphorus forms such as ortho-, pyro-, tripolyphosphates, wss determined by use of a Corning Calcium Select-Ion electrode. The association constants of calcium Ions and phosphate forms Involved In complexatlon can be calculated by the measurement of the free calcium* Ion activity In the presence of the phosphate Ions using the electrode. When the constants have been determined, the Influence on these constants of the organic acids from three selected tributaries were measured. The Interaction of soluble organic matter with phosphates and calcium ions was also studied using pH titration, In order to determine the change in the weak acid function of the phosphates identified by Odajlrl and Nickerson (1964). This phosphate function, which occurs before precipitation, was followed by measurement for the phosphate forms using sodium hydroxide and calcium hydroxide. Sodium hydroxide was also used in the presence of calcium chloride to titrate the function. Finally, sodium hydroxide and calcium hydroxide were used in the presence of the organic acids, with, and without, soluble calcium. The results were compared with Vlsser (1962) who followed a similar procedure with casein. The organic material was primarily the fulvlc acid portions of natural colored water recovered from the Thunder Bay Watershed. 9 The current Interaction of the organic matter with ealcltm and phosphorus was determined by oxidation of river and bay samples. The potentlometric titration of natural aaqilcs and measurement of calcium-ion activity determined the extent of the metal ion - organic acid and phosphate Interactions, Hutchinson and Bowen (1947) described the phosphorus cycle in natural water as Involving several areas In stratified lakes. These I n c l u d e : (1) liberation of the phosphorus into the eplllmnion from the decoy of littoral vegetation; (2) uptake of liberated phosphorus by bacteria, phytoplankton and vegetation; (3) loss of phosphorus as a soluble compound from the phytoplahkton with possible slow regeneration of ionic phosphate; (4) sedimentation of phytoplankton and other phosphorus containing seston; (5) liberation of phosphorus from sediments and at the mud-water Interface in the hypollmnlon; (6) diffusion of phosphorus from the sediments into the water at those depths at which the superficial layer o f the mud lacks an oxidized microzone. This research project was cejcerned primarily with phosphorus as a nutrient in the Thunder Bay Watershed - soluble p h o s p h a t e , the phosphate adsorbed on suspended solids, and phosphorus cowplexed by natural soluble calcium and organic matter. The results of the study will give additional information about the water quality in Thunder Bay and movement of phosphorus through­ out the watershed. A thorough survey of the resources and regional Inventory of the water quality of the Thunder Bay Watershed have been conducted and are presented in Appendix II. METHODS 07 ANALYSIS SAMPLING STATIONS S a p l i n g station* are particular a it** vhera water s o p lea are collected systematically over a period of tlaa for uae In a a t i t i r a n t of w a t e r quality. There were eighteen s a p l i n g station* established In the Thunder B a y Watershed. Stations w e r e located as close as possible to the souths of all major tributaries of the Thunder Bay River and below all possible sources of cultural discharges on the m a i n branch of tha river. Soples for physical and chcalcal analysis were collected d u r i n g each season. The a a s u r a m e n t of discharge was dona at least once at each station (Appendix III). the a s s u r e d flow w a s also obtained Data representing froa the nearest U. S. Geological gaging station and froa Alpena Power Coapany records at the hydroelectric d a s . The description of tributaries in the Thunder Bay Basin are given In Table I. The location and descriptions of s a p l i n g stations and geographic sites are given In Appendix III. These description* concern width and depth of water c o u r s e t bottoa materials and v e g e t a t i o n , and other pertinent reeources unique for the season. The lake shore classification of Thunder Bay w a s considered prim a r i l y low-wet swamp with sari and boulders, 10 Table I Description of the Tributaries of the Thunder Bay River Water Courae Hunt Creek Montmorency Length (ml.) 8.5 Miller Creek Montmorency Alpena 10.0 1.5 920-1000 780-860 Brushwood and cleared areas Crooked Creek Crooked Lake Montmorency i) M 5.5 860-1000 680 Brushwood and cleared areas Headwaters at Avery Lake Sheridan Creek Montmorency 5.0 1000-1250 Gilchriat Creek Montmorency Oscoda 8.0 4.0 780-900 1000 Woods and brushland Brush Creek Montmorency Alpena 6.5 5.5 900-1000 760-840 Woods and brushwood Porestland Beaver Creek Alpena 6.4 750-875 Brushwood and marshes emitting from Beaver Lake Wolf Creek Alpena Alcona 13.5 6.5 725-750 750-900 Brushwood and forest land along with marsl and swampland into cleared, farmed areas above Lower S o . Branch Bean Creek Alpena 9.0 750 North Branch Montmorency Presque Isle Alpena 8.5 7.0 22.0 875 750-850 725-820 Woodlands and swamp areas from Kush Lake Marshland and clear areas Variety of land areas Lower So. Branch Alpena 17.5 680-780 Alcona 8.5 750-1000 Forestland and marshland with farmed land below Hubbard Lake Swamp lands and brushwood Oscoda Montmorency Alpena 8.5 6.5 4.0 900-1000 750-900 750 Woods and brushland from Shamrock Lake Brushwood and marshland up to Fletcher Pond and woodland below the pond Upper So. Branch County Elevation (feet) 800-1100 Description Plows through woods and brushwood Plows through woods and brushwood into McCormick Lake Marsh and swamp land 12 marsh and low-sand plain with vat a«nd, and small amounts of baach rldga with sand. All samples wara collactad according to praacrlbad methods takan froa Standard Method* (1965) procedures. The a m p l a a wara collactad In brown acld-waahad polypropylene bottles, preserved (chlorofons or mercuric chloride) and stored In an Insulated b o x until refrigerated. Subsequent analyses ware made as soon as feasible. At the stations: temperature, dissolved oxygen, discharge, alkalinity, hardness, and chloride measure­ ments were conducted prior to preservation. Samples were subjected to further analysis for hydrogen Ion concentration (pH), suspended and total solids, i^monla, nitrate, phosphates, Iron, calcium, magnesium, detergents. sulfate, chlorine, color, and These chemical and physical determinations were m a d e at the Alpena Comeunlty College quantitative laboratory. EQUIPMENT AND REAGENTS Equipment Included a Mllllpore Filtering apparatus, Bausch & Lomb Spectronlc 20 colorimeter, Sargent-Welch NX digital meter, Corning Calcium Select-lon electrode, Turner Fluorometer, Heath pH Recording Electrometer, Frlden 1162 Electronic Calculator, H & L Infrared Spe c t r o s w t e r , and portable meters (Dissolved Oxygen, pH, and Temperature). The chromatographic set-up includes a small plastic coltmn (2.5 x 25 cm) packed with strong-base anion-exchange resin In chloride form, Dowex 1-X8. 13 HaCar a a p l a a from tha rlvar and bay aa wall aa Cha watar- ahad samplas wara collactad and atorad In tha polypropylana bottlas, prasarvad and rafrlgaratad. Tha duat samplas wara obtalnad from atack amlaalon praclpltatora of tha camant plant. Aftar collection, tha aampta waa wall-mixed and atorad In a molatura-proof plaatlc contalnar. Compoalta aamplaa from tha sewaga plant wara obtalnad for 24-hour parloda and kapt rafrlg­ aratad until analyala. Tha flald kit for organic acid aaparatlon conalatad of a support contalnar, five-gallon plaatlc bottles, raaln columns, battary-oparatad watar pump, anion resin, and a 12-volt atoraga battary. Standard aolutlona wara praparad from Amarlcan Chamlcal Soclaty raaganta with doubla da-lonlcad watar. Phoaphata eoncantratlon In natural Thundar Bay watar waa found to ba 0.10 to 0.30 mg/1 ao complaxatIon concantratlona wara from 0.001)1 to 0.01M. Tha alkali matal aalta of orthophoaphata, pyrophoaphata and trlpolyphoaphata wara uaad to prapara aolutlona. Tha aolutlona wara rafrlgaratad until uaa and chackad ragularly for hydrolyala. Tha phoaphata aolutlona wara standardized by praparlng tha acid form of tha phoaphata by paaalng tha aolutlona through a column of Dowex 50W-X2 cation-axchanga raaln (100-200 maah). Aa tha acid form waa alutad from tha coltmu with watar. It waa tltratad Imaed lately undar nltrogan gaa with standard solution of (CH 3 )4 lK>H. Tha titration waa carrlad out at 25C ualng a combination pH alactroda at a spaclflc dapth and constant stirring. Tha ( C ^ ^ H O H aolutlon contalnad tha i m a eoncantratlon 14 of phoaphata aalt aa tha phoaphata aolutlona to eliminate dilution affact. Tha calcium aolutlona wara prepared in concentrations of 1 x 10 " 2 to 1 x 10~® M, depending on artificial and natural environmental conditions. Reagent grade calcium chloride waa used to ma k e up tha standard solutions and diluted with double 4a-ionized water to any desired concentration. The calcium solutions were standardized by passing tha solution through a 20 cm coltmui of Dowex 50H-X2 (100-200 mesh) form. in hydrogen The eluate was titrated with standard N a O H and (CH^^NDH, The calcium electrode was calibrated with tha standard CaCl 2 solutions, assuming CaClj was cosq>letely dissociated at a constant Ionic strength. ANALYTICAL PROCEDURES Temperature The temperature was measured, either using the temperature probe of the oxygen analyzer or a centigrade (Celclus) at various depths and sites In the streams or bay. thermometer, The temperature values are reported as a profile at selected depths or as the mean value for the water course. Dissolved Oxygen (P. 0.) The dissolved oxygen was measured In the field w i t h a Precision Galvanic Cell Oxygen Analyzer (No. 68850) manufactured by Precision Scientific Company. The dissolved oxygen values were determined from appropriate calibration tables. The probe was standardized by Winkler method using azlde-modiflcatlon. When the meter was not used, the modified azlde technique was followed (Standard Methods, 1965). Hydrogen-Ion Concentratlor (pH) The p H of the solutions was measured lnstrumentally with a Beckman Zeromatic pH meter or a Heath Recording pH meter as soon as possible after collection. A Sargent-Welch portable pH meter was used at selected stations In the watershed. Suspended (Filterable) Solids The watershed, river and bay sasiples were m e a sured suspended solids following FWQA (1970) procedures. for A glass fiber filter disc (Reeve Angel Type 934AH, 2.1 cm) was prepared 15 16 by Insertion Into the bottom of a suitable Gooch crucible. While vacu u m Is applied, the disc Is washed with three successive 20 ml volumes of de-Ionized water. were rcmcved by suction, After last traces of water the crucible and rliter were dried in an oven at 105C for one hour, removed, cooled in a desiccator and weighed. The filtering apparatus and crucible w e r e assembled and suction begun. The sample was * le aelected to find actual concentration In voline. factor of 27 unita/mg/100 m l w a a determined. The converalon A log plot of F unlta va. m g of organic aclda gave a linear curve (Figure 1). The fluoreacence reading w a a fairly conatant In a temperature range of 0C to 40C. Thla allowed for adaptation of the fluoreacence method In the field. The apectrophonmtrie method for determination of humlc aclda (Semenov, mt a l . . 1963) waa evaluated with a B t c V m n DK-2 Spectrophotometer. There were abaorbence peaka at 325 m u and in the 400 to 450 m u range, aa well aa In the Infrared range of 1010 to 1880 mu. The excitation abaorbence at 340 m u and tranamlttance at 440 mu ualng a Bauech & Lomb Spectronlc 20 colorimeter gave reaulta, aa Organic Carbon (Humlc Acid) In mg/1, comparable with the fluorometer reaulta. Thla apectro- photometric method waa uaed for field teatlng of color concentration In the Thunder Bay Waterehed. Hltrogen-Aamonla The mnaonla-nitrogen in the emaplea waa meaaured by direct Meaalerlsatlon method from Standard Method* (1965). Selected 2.0 5 0 Log F 0 e a Figure 1 -C Fluorescence vs V% ' ^rgartic Acid# + 1.0 C o n c entration 20 •■ p l M vtr * M u u r t d for MHonli-nltrogtii using Standard Hathoda (1965) distillation procedure. Tha raaulta wara comparable w i t h tha dlract Hasslariiatlon m e thod used. mtrogen-Mltrcte Tha m a t h o d waa basad upon the reaction of tha nitrate Ion with brucine sulfate with sulfanillc acid in strong sulfuric acid aolution at a temperature of 1000. Tha yellow color of tha resulting complex was measured at 410 mu. Tha nitrate concentration (mg/ 1 ) was determined from a standard curve. The curve was prepared with samples and standards analysed simultaneously. Phosphate (Soluble and Total) The soluble (ortho) and total phosphate in sewage s m p l o s and watershed or bay samples were measured by Standard Methods (1965) procedures. A Bausch & Lomb Spectronlc 20 colorimeter was used for measurement of abaorbence of the stannous chlorideblue c o ^ lax at 690 mu. Dilution with de-ionised water was neceesary for the composite sewage samples. Phosphate F o u Separation and Concentration The composition and concentration of phosphate forms present in the composite sewage samples were determined by lon-exchange chromatography. Anion-exchange resins have been used by Peters and Rleman (1956) and Grande and Beufcenkm^ (1956) for analysis o f mixtures of condensed phosphates. They used buffered potaeelum chloride solutions as eluants. In this study, a strong base anion-exchanger In chloride form. Dowex 1-X8, 50-100 mesh, was used following procedures modified 21 from Puchkova and Mironova (1967) and Harold <1967), to separate standard mixtures and domestic sewage samples. The rate of elution was four to six ml/mln on a resin column 2 x 15 cm. The eluate fractions separated were recovered according to the following sequence: 1. 2. 3. 4. Ortho Pyro Tripoly Remain - 50 ml 75 ml -75 150 ml 0.5N KC1 0.5N KC1 ml 1.ON 1.0N KC1 + + 50 ml 0.001N 75 ml 0.001N KC1 + 75ml 0.010N + 150 ml 0.100N HC1 HC1 HC1 HC1 (pH (pH (ph (ph - 3.60) 3.40) 3.00) 2.00) The total phosphorus In each eluted fraction was determined according to standard Methods (1965) digestion procedures for total phosphate. Detergents The methyl green method was used to measure the detergent In the water sample by extraction with toluene. Ten milliliters of Hach sulfate buffer was added to 300 ml sasq>le and de-ionized water blank along with methyl green powder. detergent complex was extracted with toluene. The methyl greenToluene Is added to the blank and separated for use In standardizing the co l o r ­ imeter at 100X. The blue color of the detergent complex In toluene Is measured at 615 mu. Sulfate The sample was measured by the turbidity developed with soluble barium chloride and suspended with conditioning agent (Standard Methods, 1965). The sulfate ion concentration was determined by comparison of the percent transmittance with a standard curve. 22 Total Hardness Dlsodlum m a g n e s i u m EDTA exchanges aagnealum on an equivalent basis for any calcium and other cations in the sample to form a more stable EDTA chelate than magnesium. The free magnesium reacts with Eriochrome Black at a buffered pH of 10 to give a red-violet complex. The EDTA waa standardized with calcium carbonate at 1.0 mg/1.0 ml {1000 mg/1). The selected volume (25 ml) of sample was titrated w i t h EDTA and mg/1 of hardness expressed as CaCO^ waa determined. Total Alkalinity Methyl orange was used as the indicator in this method because its pH range is in the same range as the equivalence point for total alkalinity. The Indicator was added to a specific volume of sample (25 ml) and the solution titrated with standard HC1 solution (0.2N). The volume of acid used was converted to total alkalinity (methyl orange) as mg/1 CaC03 . Iron Total iron in the samples was determined with 1,10-phenanthroline. Twenty-five milliliters of sample were mixed with Hach 1,10-phenanthroline powder or solution. was allowed to develop for several minutes. The orange color The iron-phenan- throllne complex color was measured at 500 mu. Chloride The chloride ion in solution was measured with standard mercuric chloride using an acidified (HNO 3 ) indicator of 23 S-diphenyl c«rbazon« and xylene cyanol. The a o u n t of chloride In the a a p l e vat found for a 100 ml sample as: 5 (volume of t l t rant). The argentometrlc method (Standard Methods, 1965) was used from 1967 to 1969. Chlorine The Hach method measured the total available chlorine In water. The reaction procedure uses ELtrh orthotolldlne in solution or powder form combined wit h 25 ml of sample. The y e l l o w color which develops was m e a sured colorlmetrlcally at 440 m u after 3 to 5 minutes. colorimeter at The original sample was used to set the 1 0 0 X. Collform Multiple-tube fermentation test gives an actual collform count per 100 ml. The membrane filter technique for collform determination (multiple-tube densities) gives 'most probable number* (KPN) per 100 ml of sample. Collform count per 100 ml has been measured In the Thunder B ay area by the membrane filter technique to give a result of MFN/100 ml for multiple-tube collform densities. The analyses have been conducted by Michigan Department of Public Health. Calcium (Soluble) The Corning Calcium Select-Ion electrode was used with a Sargent-Welch NX Digital meter for the measurement of the free calclim In solution. The calclim electrode of the liquid-Ion exchange type Is subject to pH Influence. The t m p l e ' i pH should be adjusted to 24 at laaat 2 p H unite higher than tha e w p l e ' e equivalent pCe++ aad not hlghar than p H 10. Roaa (1967) found tha potential raepouaa of tha aleetroda to ha llnaar for p H S to 10, which la within tha nonaal range of natural watar apetana. ( C H j ^ H O H and HC1 wara uaad w h a n naadad to edjuat tha p H of ataadard aolutlona to tha daelrad p H range. Tha alactroda functione bp tha a o v w n t of the exchanger, ao the reaponaa la Influenced bp tenparature. The range of temperature for a reproducible reaponaa waa meaaured. The e m ^ l e a wore allowed to cone to room tenparature before neaaurenant ao aa to be within tha ranga found. Tha lower limit of detection of tha electrode la uauallp determined bp tha eolubllltp of tha liquid Ion-exchanger. Tha uppe r limit of detection for liquid membrane alactrodea la determined bp the level at which there la an appreciable eolubllltp of tha Iona from tha aanple into the Ion exchange phaaa. Tha natural range aelactad for the etandard aolutlona of CaCl 2 waa 1 x 10 " 2 to 1 x 10* 5 M. Calclmt CompTaxation with Natural Organic Matter (Oxldlzable Calcium) Tha determination of exlatlng calc line-organic-phoaphata Interactlona in the Thunder Bap watera waa done bp oxidation of the water aanplea from the bap and river with concentrated nitric acid. Tha c a l d w concentration In aaa^le before oxidation waa determined w i t h the calcium electrode. The oxidized realdua waa dlaeolved and Increaae In free calcium meaaured with the electrode. Aup change In phoaphata leval (fixed) waa meaaured la tha pre- and poet-oxidized aolutlona. 25 Organic Acid 8«yir«tlon Tha extraction of the organic aclda fraa aoloctod Thnndar Bay natural watar sourcea In the field waa beat accomplished b y use of anion-exchange chromatography. o f Dewex 1 -X 8 anion raaln In the chloride form (50-100 mesh) waa pro-soaked In coltmn. Ten to fifteen grams 0 .0 0 1 M HC 1 before being placed on the plaatlc The realn la rinsed with de-ionised water until acid la washed off column (neutral). The water enable (5 gallons) was passed through the coltaen until the exchange capacity of the realn waa attained. This capacity was indicated by a deep brown color on the y e llow realn solid. The resin waa removed from the coltam and combined with a solution composed ?f 50 ml of 2M HaCl and 50 ml o f 1M NaOH. The ad.xture was allosed to stand for two hours. The colored solution was deranted and solid treated w i t h additional of the extractent and left overnight. 100 ml The decantatea were combined and treated with HC1 until the orange solution turned y e l l o w (pH - 5). The solution was evaporated to dryness. ninety-five percent alcohol was added to the solid residue to extract soluble polar-acids. The solution was decanted and alcohol added to remaining residue and subsequent recoveries done until brown color was r m m d , combined. Alcohol extracts were A measured portion was dried at 105C to obtain the concentration (mg/ml) of acids In tha extracted solution. H a turally Available Adsorbed Phosphate and Calcine la Cement Dust Tha available phosphate and calclme extractable from the cement dust ware measured from collected s a p l * . For the Measurement of phosphate «d»otif of duet was used. o-c tlc» 1 b* river end bey ««r* analysed for phosphate and other savage effluent constituents at aelectad sites in the bay area (Figure 2). The pltne of the river waa followed by Measurement of phosphate concentrations at the selected sites. The p h o s p h o r u s , chloride, and nitrogen coaqtounds were being contributed m a i n l y from the sewage plant, industrial wood-products discharge, and natural river discharge. The discharge of the river and tributaries were found by direct measurement on stromas. The on-stream measurements are included in the seasonal siamarlea. Power Company (1971) records and V. Discharge data from Alpe n a 8 . Geological Survey (1966+ 1967) gaging stations are given in Appendix II. Organic Acid Identification The Identification of the Important functional groups present in the colored organic acids isolated from natural water sources baa been done by infrared spectrometry. Midwood and Felbeat (1968), Black and Oirietnan (1963), and Steallnk (1963) have used different Infrared Instruments and natural water from different sources to establish the organic nature of these groups. A Hllger-Vatts Infragraph H1200 (Wilks Scientific) was used to identify the similarity between tha organic acids from Thunder Bay watars and that characterized above. The acids are In ethyl alcohol solution, so tha C-H, 0-H, and C-C bands of an aliphatic alcohol will be present in spectra. HURON CEMENT 9 TH ST PO RTLA ND CO DAM * ABITIBI COR SEWAGE PLANT “ n i< ? BOAT W ATER TREATMENT PLANT jQ s>* HARBOR O ' - ' ' Q O 1000 SCALE (F E E T ) Figure 2. SAMPLING SITES THUNDER BAY, LAKE HURON, M IC H IG A N 30 Co^>lexatlon H t a t u r w e n t The determination of the extent of complexatlon between soluble calclim with phosphates end oiganlc acids, using potential measurements with the calcium electrode, was done b y two methods. In the potential comparison method (Rechnltz and Zamochnlck, 1964), the potential of a standard calcium ion solution Is measured. The electrode is transferred to another solution which contains a known analytical concentration of the test phosphate. Increments of a k n o w n calcium solution are added to the sample solution until the potential of the sample solution equals that of the initial standard (reference) solution. At this point, the activity of calcium In the two solutions must be the same. In the standard solution, Since the concentrations of calcium total metal Ion In the sample solution, and phosphate in the sample solution are all known, association constant can be readily calculated. the complex The point of Identity was approached from both the direction of excess phosphate and of excess calcium. Constants were determined with and without natural organic acid present. largely eliminates electrode drift. This method Variation In solution composition w o u l d be negligible. In the titration method (Rechnltz and Bauner, 1964), a plot of electr ode potential vs , - Log(calcturn ion) is prepared as a calibration curve In the absence of complexlng phosphate forms. A known Initial concentration of calcium chloride Is titrated with a standard solution of phosphate. From the 31 calibration curve, apparent concentrat lor jt free calcium la determined at aflected volume increments,, With appropriate correction for dilution effe.ts, the comple < association constant ran be calculated from the original Ion concentration, the amount of completing phosphate added, ard the measured decrease In metal ion concentration at the specific volumes used. Constants were measured with end without the organic acids added to the calcium solution. The other method for evaluation of Interactions was based on the pH measurement of the change In the weak acid function of the phosphate forms In the presence of calcium and natural organic acids (Odagiri and Nickerson, 1964). The standard solutions of ortho, p y r o , and tripoly-phosphate are adjusted to a pH of 2,5 with HC1 and titrated with stanoi'-d solutions of NaOH and Ca(OH>2 . The plot of pH vs* volume gives an S curve which can be evaluated as a weak acid equivalence of the phosphate forms. The weak-acid hydrogen has been found to come from the terminal P0 4 groups of polyphosphate molecules fVanWazer and Campanella, 1950). The only type of complex formation that can affect the strength of the weak-acid function must involve the terminal groups. The milliqulvalence of the organic acids and CaCl 2 solutions used were determined from the pH titration with s standard base. The titrations with Ca(OH ) 2 were conducted at fast and slow rates to note precipitation present at the concentrations used in this study. As well, known increments of C«C1 2 were added to phoaphata aolutlona and titrated w i t h NaOH. The organic aclda were extracted froa three tributaries: North Branch Thunder Bay River, Bean Creek, and W o l f Creek, aa well as the m a i n branch at tha bay. These concentratad extracts were added to phoaphata aolutlona before titration with CaCOH)^ end along with CaCl^ before titration with NaOH. The decreaae in the weak-acid equivalence of the phosphate forma theoretically would Indicate a change In the availability of the phosphate Ionic sites for reaction because of cooqtlexatlon with calcium, with or without the lnvolvesmnt of organic aclda. RESULTS Both the river end the sewage pianc eifluent are contributing phosphorus and nitrogen containing nutrlenta to the natural waters o f Thunder Bap. The aaount of total phosphates frow the sewage plant discharged Into the river had a dally wean of 25 to 30 mg/1. The average total phosphate level of the river was 0.15 to 0.20 mg/1. In addition, the wood-products discharge gave an apparent high total phosphate result. The raw materials used In c o u n t production are composed of minerals (Table 2) which when emitted as dust can either physically or chemically affect the availability of phosphate forms in the natural waters of Thunder Bay. The duat used tiom the cement plant In this study had 5.75 m g of acid-extractable phosphate per gram of dust and an aqueous solubility of 0.06 mg of phosphate In de-ionised wa t e r (Table 3). These levels of phosphate were considered as back­ ground In studies Involving the cement dust. A monthly mass-balance between the river flow and phosphate discharge from sewage plant effluent showed a direct, between added phosphates and river flow. between river and sewage stable relation The yearly mass-balance flow showed a gradual Increased relationship between the flows (Table 4). The comparison of phosphate concen­ tration In the sewage effluent and the river discharge showed the dilution effect of the river water (Figure 3). 33 34 Table 2 Composition of Natural Constituents Used In Ccaent Prodnctlon (Me an Weight P e r c e n t a g e t , Dowj 1971 ) Ll»estone Analysis C«003 - 90.32 Mg CO 3 - 2.64 CaO - 50.56 MgO - 1. 33 S10 2 - 4.84 ■VI2O 3 - 1 .28 Fe2°3 - 0.14 k 2o - 0.24 SC 3 - 0.46 Shale Analysis CaO - 2.02 Si0 2 - 57.76 A1 2O 3 - 15.22 Fe2°3 - 6.18 MgO - 2.75 KjO - 3.52 SO3 - 7.24 35 Table 3 Characteristics of Cenent Dust Phosphate Available Wt. !>uft frow Duat Water-Soluble POi Acid-Extractable PO^ (rn&) r^TT) - 24.0 55.0 62.5 106.5 147.5 0.03 0.07 0.15 0.18 0.24 0.13 0.36 0.40 0.62 0.83 Mean 1.53 + 0.26 n g / g 5.66 + 0.62 ng/g Coetparlsor by Acid-Extraction Wt. Dust (»g) Phosphate Extracted (™g/l) Phosphate Available ("mg PO^/g dust) 10.2 50.3 0.56 0.80 6.00 14.5 63.0 0.36 0.69 6.80 31.6 53.3 0.500 0.625 5.10 51.6 101.4 0.55 0.80 5 05 100.4 152.2 0.80 1.10 5.80 Mean - 5.75 + 0.81 mg/g 36 Table 4 MASS- BALANCE RELATIONSHIPS 1967 1968 1969 1970 1971 Mean Average CPS 1222 995 1180 886 1215 1071 Total Flow CF x 109 Gallon x 109 39.5 296 31.4 236 37.2 278 27.8 208 38.4 287 34.0 261 River Flow Sewage Flow Average MGD 2.56 2.23 2.69 2.52 3.01 2.50 Total-Gallon x 109 0.936 0.818 0.983 0.922 1.102 0,952 3.16 3.46 3,54 4.43 3.82 3.65 Dilution Factor Total Sew. Gal ., Q _ 3 Total Riv. Gal. 1/71 2/71 3/71 4/71 5/71 6/71 881 571 987 637 1563 1008 3709 2393 1282 827 1083 700 Mean MGD 1.98 2.36 3.98 Total P0 4 (mg/1) Kg/day 24 182 24 215 19 288 0.100 0.090 0.077 River Flow Average CFS Mean MGD Sewage Flow Dally Sewage PO/. Mean River Flow (mg P04 /llter) River Flow Average CFS Mean MGD 4.54 3.69 3.47 207 17 243 14 185 0.024 0.077 0.067 12 7/71 8/71 9/71 10/71 11/71 12/71 1004 648 663 427 583 388 575 373 701 452 1536 991 3.07 2.67 2,01 1.87 3.07 Sewage Flow Mean MGD 3.39 Total P04 (mg/1) Kg/day 20 10 22 21 259 117 223 160 29 138 13 152 0.106 0.072 0.150 0.114 0.082 0.040 Daily Sewage P0& Mean River Flow (mg PO^/liter) 37 0.130 0.100 Liter 0.050 Jan Figure 3. Feb Mar Apr May Jun Jul Aug Sep Oct Nov Monthly Dilution Relationship for 1971 Sewage Phosphate Discharge and River Flow Dec 38 The sewage plant's primary treatment operation achieves removal of organic nutrient matetlals (Table 5). 20 (BOD) and suspended solids The sewage plant has been estimated to achieve up to percent removal of phosphates primary treatment from the effluent during the (LaMarre, 1970) This will be Increased to 90 percent removal on completion of a proposed secondary treatment facility with chemical phosphate r e m o v a l . The chroautographlc separation of the sewage samples by anlonexchange chromatography Indicated that forma are present In the effluent. sewage effluent (Table 6 three basic linear phosphate Approximately 80 percent of the ) being added to the Thunder Bay system consists of the simpler phosphate forms (ortho, pyro, and trlpoly) as measured by the anion-exchange separation (Figure 4), were selected These forms for this study concerning phosphate availability in the bay. The percentages for phosphate recovered In chromatographic analysis of aewage effluent indicated a continual variation in the phosphate composition of the effluent. The extent of hydrolysis of polyphosphates would be related to the physical conditions existing during treatment of the sewage. The presence of organic phosphorus could Influence the separation and removal of phosphates column through from the fouling. Condensed phosphates as pyrophosphate and tripolyphosphate make up over 90 percent of detergent phosphorus. In sewage, Flnsteln and Hunter (196 7) found condensed phosphates generally have a halflive in excess of one day, while In surface waters they m a y persist for weeks or months, Pomeroy (1960) found that residence time of 39 Table 5 Characteristics of Sewage Plant Effluent (LaMarre, 1 9 7 l " 5 Year River Flow at 9th St. Pan Total Gallons Raw Sewage Flow Total Gallons Mean MGD 00 9.36 1968 2.36 x 10 11 8.17 x 108 2.23 1969 2.78 x 10 11 9.83 x 108 2.69 1970 2.08 x 10 11 9. 22 x 1 0 8 2.52 1971 2.87 x 10 11 1 1 . 0 2 x 108 3.01 Mean 2.61 x 10 11 9.52 x 108 2.60 Year Mean BOO (lbs/month) Suspended Solids (lb s/month) Remvd. O 2.96 x 10 11 M 1967 2.56 Phosph ates (mg PO 4 ) Monthly Soluble Monthly Total Est. Remvd In Out Remvd. In Out 196 7 1546 1090 287L 2383 1313 50% 6.5 26.5 20 % 1968 1518 1090 28% 1926 1032 47% 9.0 26.0 20 % 1969 1914 1250 34% 2680 1343 46% 14.0 29.0 15% 1970 1881 1352 28% 2066 1006 52% 12.0 24.0 15% 1971 1650 1170 29% 1810 950 48% 12. 5 25.0 20% Mean 1704 1170 30% 2173 1130 48% 11.0 26. 1 18% T a b le 6 Anion-Exchange Chromatographic Analysis of Phosphate Mixtures and Sewage Samples 1. n 100• I'S- Analysis of Prepared Phosphate (mg/1) Mixtures Found 4 Taken 1 2 Phosphate Form 4.4 4.4 4.6 Ortho - Na-jPO^ 4.5 Pyro - Na^P20 7 Tripoly - NB 5P 3010 2. Mean 4.6 + 0.2 Taken 22.4 Found 22.6 + 0.2 6.4 6.4 6.8 6.8 6.6 6.6 + 0.2 32.7 32.8 + 0.2 8 8 9.2 8.8 9.2 8.2 8.9 + 0 . 5 44.9 44.3 + 0.5 99.7 + 0.3*o Analysis of Sewage Effluent ( n A ) Total Recovery Total P Ortho Pyro Tripoly Remainder Amt. Percent 4.43 1.77 (48.17.) 0.56 (15.2%) 0.59 (16.0%) 0.76 (20.7%) 3,68 - 85.0% 3.67 1.75 (47.0%) 0.75 (20.0%) 0.73 (19.6%) 0,50 (13.4%) 3.72 - 102% 3.00 1.15 (34.4%) 0.56 (16.8%) 0.88 (26.3%) 0.75 (22.5%) 3.34 - 111% 7.50 2.50 (35.7%) 1.50 (21.4%) 1.40 (20.0%) 1.60 (22.9%) 7.00 - 93,0% 7.33 2.60 (33.3%) 1,70 (21.8%) 2.20 (28.2%) 1.30 (16.7%) 7.80 - 106% 6.00 2.20 (39.3%) 1.00 (17.9%) 1.10 (19.6%) 1,30 (23.3%) 5.6C - 93.0% 39.6+6.5% 18.9+2.2% 216+4.6% 19.9+4.1% 98.5+11.1% 50 30 20 10 Per cent of Fnoflpnot^a Form in Sewage 40 100 200 300 500 Volume (ml) of Eluant Figure 4- S e p a r a t i o n of Sewage Effluent by Anion Chromatography 600 700 42 dissolved phosphates in natural water varies from approximately 0.5 to 200 hours. The turn-over rate of phosphate was between 0.01 and 1.0 milligram of phosphorus per cubic teter per hour A rapid flux of phosphate would be typical of a highly productive system. The phosphate forms from sewage plant are available In Thunder Bay to produce biologically active systems. This has only recently become apparent in the form of floating plankton blooms off bay beaches. The sewage discharge for 1970 was 922 million gallons and for 1971 was 1172 million gallon*. The total river flow during 1970 was 27.84 billion cubic feet (208 billion gallons) and for 1971 was 38.36 billion cubic feet (287 billion gallons). The contribution of total phosphate from the sewage discharge for 1970-1971 at 30 mg/1 for 2,50 million gallons pet day is 500 lb/day. The average 1970-1971 daily river contribution of phosphate at 0.20 mg/1 for 575 million gallons daily discharge at Ninth Street Dsn Is approximately 960 lb/day. The sampling of the area near the river mouth and inner bay Indicated that the sewage effluent moved from the south (right) side of the river to the center of the river being diluted by the river flow. As the river reaches the bay with the natural, wood-products, and sewage discharges, the plume moves out into the shipping channel and swings to the right. The extent of drift is dependent on the wind and influencing currents in the bay. The wind direction is predominantly west-northwest months of the year. for eight For approximately 250 days, the dust from A3 the cement plant Is moving primarily out over the bay. This would give an estimated suspended material of 25,000 to 50,000 tons annually. PHOSPHATE ADSORPTION ON CEMENT DUST The dust in the bay waters would be available as suspended parti­ cles for comp legation to a limited extent (Table 7). The cement dust sample produced an average suspended solids of l.A m g /1 In test solu­ tions. the bay. Most of these solids would eventually settle to the bottom of The dust particles would contain an Inherent phosphate concen­ tration of approximately 5.75 mg/g (55.7 lb/ton) and adsorbed phos­ phates from natural and domestic sources. The suspended solids in the bay ranged from A to 10 mg/1 with a mean of ? mg/1. The acid-extractable phosphate of these suspended solids had a mean of 0 .2 A mg/1. This would Indicate that some phos­ phorus Is being tied up by the suspended particles prevalent in the river and bay. In sewage treatment, phosphate precipitation with sodium alumlnite (alum) and similar chemicals has been found to be pH dependent. The cement dust when placed In de-Ionized water showed a definite change In the pH of the water up to a maximum level (Table 8 ). As well, these substances have been used In eutrophlc lakes to remove phosphates. When alum has been applied to the top two feet of water in a Wisconsin lake (Anon, 1971), particles of it settled, apparently taking phosphates along. Water clarity Improved, winter fish kills were eliminated, and there were no blue-green algae blooms during the summer. Calculations Indicated that about 110 pounds of phosphorus were removed by 11 tons of alum. The cement dust contains water-soluble and acld-extractable calcium along with the other com- 44 Table 7 Characteristic* of Cement Dust Cement Duat aa Suspended Solids In Natural Systerna W t . Dust Added to Water Suspended (Filterable) Solids 1.5 »g 1.2 m g /1 3.5 1.4 6.0 1.2 13.0 1.7 16.0 1.5 25.0 1.2 50.0 1.6 100.0 1.6 Mean - 1 . 4 + 0 . 45 Table 8 Characteriatlea of Cement Duet of Aqueoua Solutions with Ceiaent Puat Wt, Duat - pH pH Dlfference/g-Puat 6.54 - 53.5 7. 70 21.7 99.0 9. 30 16.8 164.0 10.40 23.5 211.0 10. 70 19.7 20.9 + 1000 11.40 4.87 3.0 46 ponents. These may be a factor involved in the absorption process occurring in the bay (Table 9). When a standard orthophosphate solutico wa* used, the amount of removal (adsorption) of phosphate from solution for a specific weight of duat showed a mean of 23.2 mg/g (46.2 lb PO^/ton of dust). For standard pyrophosphate solution, the mean removal was 28.4 mg/g (56.5 lb PO^/ton of dust). For standard tripolyphosphate, a mean 58.4 mg/g (116.8 lb PO^/ton of dust) were removed from solution (Table 10). The phosphates of the composite sewage samples were removed by cement dust (Table 11). The adsorption of phosphates was lover in river water, indicating a possible Involvement of other factors pre­ sent in natural river water. One of these factors could be soluble organic substances such as natural yellow acids since twenty-five per cent of the natural waters of the Thur^er Bay River system is discharged from tributaries that have high organic colored materials (Anon, 1963). The potentiometric titration (pH) of the phosphate-duat inter­ actions Indicated that there is a saturation limit for the dust. A definite amount of phosphorus can be accomodated by a specific quan­ tity of solid. The titration method of Dolltnan (1968) seemed ade­ quate to measure higher amounts of phosphate adsorbed together with the reactive sites on the dust (Table 12). The phosphate adsorption by cement dust in both de-ionised water and natural river water varied with the water source, amount of dust used, the type of phosphate form, and its respective concentration. Up to the saturation point of the dust, there would be a definite influence of the calcinated material on the availability of phosphorus 47 Table 9 Phoephate and Calcium Inherent In Cement Duat Water-Soluble Wt. Duat 24.0 mg 53.5 58.6 99.0 107.6 160.2 164.0 211.0 280.7 Phoephate 0.06 0.14 0.16 0.46 0.56 1.04 0.99 1.12 1.19 P0&/Duat 2.5 2.7 2.7 4.6 5.2 6.5 6.0 5.3 ^ 2 Calcium Ca/Duet 10.8 20.8 29.7 30.5 71.1 86.4 42.9 62.9 102.9 450 388 507 308 661 539 262 298 367 4.4 + 1.4 mg/g 420 + 131 mg/g Acid-Extractable Wt. Duat 2 0 . 0 mg 56.0 82.3 97.5 106.5 164.0 Phoephate 0.10 0.25 0.40 0.62 0.62 1.44 POi/Dust 5.0 4.5 4.8 6 .4 5.8 8.8 Calcium 17 55 80 78 118 134 5.9 + 1.6 mg/g Ca/Duat 850 982 850 800 751 817 842 + 78 mg/g 48 Table 10, 11 and 12 Headings o f dust used Vt. Duet - Amount Total PO^ - Amount of phosphate In original solution PO^ Filtrate - Total phosphate in filtrate after aeparatlon of solids from mixture PO^ Residue - Total phosphate In residue by acid extraction with hydrochloric acid Total Recv„ - Sum of filtered and residue phosphate Dust PO 4 - Amount of phosphate extractable from duat with acid Total P0 4 Add - Milligrams of total phosphate In standard solution used, dust phosphate (5.75 mg/g), and phosphate measured In Milllpore filter paper (0.13 mg/1) and reagents used (0.26 mg/l) PO 4 Removed - Amount of phosphate removed from the phosphate added by duat used measured in milligrams per gram PO^ Adsorbed - Amount of phosphate recovered from the dust as milligram of phosphate per gram of dust used T a b le 10 The P h o ep h ate A d s o r p tio n Sample Na3P04 1.10 mg/1 Vt. Dust (mg) 15.6 23.2 23.3 32.7 38.4 50.0 60.4 63.0 81.8 89.0 POa Filtrate (mg/l) (c m /1 ) on Cement D uet In Aqueoua Systems PO/j Residue Totil Recv. (mg/l) (mg/l) 0.61 0.80 0.70 0,22 0.33 0.01 0.08 0.18 0.01 0.14 0.75 0.65 0.36 0.85 1.20 1.30 1.55 1.30 1.65 2.50 1.36 1.45 1.06 1,07 1.53 1.31 1.63 1.48 1.66 2.64 31.4 31.0 17.2 26.9 20.0 22.0 17.0 15.0 13.4 23.2 21.7+6.4 25.6 11.2 15.5 12.2 18.8 17.0 15.5 13.5 11.2 19.3 16.0+4.2 P0/. Removed (mg/g) P0/f Adsorbed (mg/g) Na3P0, 2.20 mg/l 31.0 63.0 89.0 1,21 0.65 0.14 0.65 1.19 1.72 1.86 1.84 1.86 32.1 24.6 23.2 21.1 19.0 19,3 Na 3P04 3.4 mg/l 78.6 102.2 151.2 0.62 0.38 0.13 2.86 3.12 3.40 3.48 3.50 3.53 32.8 29.5 21.6 36.4 30.7 22.5 Na4P207 22.0 30.0 62.0 63.5 81.5 93.0 102.0 1,30 2.30 0.95 1.55 1.15 0.74 0.13 1.15 1.05 1.30 2.40 2.10 2.90 4.40 2.45 3.35 2,25 3.95 3.25 3.64 4.53 22.7 30.0 23.4 26.0 26.5 26.4 31.8 26.9+3.3 25.8 34.0 29.2 27.8 30.8 22.6 39.0 29.9+5.4 13.5 26.7 50.0 54,3 100.0 109.6 2.96 1.95 0.83 1.14 0.37 0.62 0,94 1.96 3.50 3.05 3.83 3.53 3.90 3.91 4.33 4.19 4.20 415 76.5 76.8 76.7 52.7 46.3 30.8 60.0+19.6 70.0 73.4 66.3 56.2 42.3 32.2 56.7+16.' 3.20 mg/l Na5p30io 4.0 mg/l T a b le 11 P hosphate A d s o r p tio n on Cement D uat In N a t u r a l i Wt, Duat («g) Sample 47.0 54.7 70.0 112.0 9th St. 18.0 40.0 64.5 81.7 9th St. Dam + Na3P0A 41.0 44.0 62.0 Total P0& (mg/l) ReaidiePO/, (mg/l) nt PO. (mg) POi Removed («g/g) PO/. Adsorb. W 8) 0 075 0.280 0.330 0.020 0.70 0.75 0.80 0.90 0 30 0.35 0.43 0.68 1.50 0.91 1.57 1.28 1.32+0.31 1 59 1.37 1.14 1.30 1 35+0 18 1.250 1.05 0.40 0.03 0.10 0.70 1.35 2.55 3.40 0.10 0.23 0.37 0.47 11.1 21.2 19.0 13.0 16.1+4.8 18.8 21.1 30.0 34.6 26.3+7.4 9th St. Dam + Na4P207 22.4 12.0 13.0 9.5 12.2 11.5 13.0 0.24 0.28 0.46 25.4 21.4 20.8 22.5+2.5 24.5 24.0 20.0 24.2+2.4 66.4 146.0 210.0 Composite Savage (Dll.) 2.42 0.82 0.29 0.12 - 0.38 0.94 1.21 24.2 14,6 11,0 16.7+6.9 33.9 22.7 17.9 24.7+7,9 53.7 100.0 144.1 200.0 Composite Savage (Dll.) 2.86 1.92 0.52 0.46 0.42 * 0.31 0.58 0.93 1.16 17.5 23.4 16.7 12.2 17.5+5.6 27.9 29.2 26.2 18.0 25.4+5.8 68.0 140.0 Savage In 2.51 1.17 0.69 - 0.43 0.81 20.0 13.1 30.0 20.7 55.0 150.0 Savage Out 2.20 1.21 0.37 - 0,32 0.87 2.05 18,0 13.1 5.5 28.4 19.7 11.9 Dam 0.145 0.330 0.440 0,145 Filtr. PO^ (mg/l) D om estic Sewage Samples _ T a b le 12 H ig h P ho sp h ate A d s o r p tio n on Cement D ust In D e -Io n is e d W a te r Wt, Duat (mg) Sample (mg/l) 50.0 106.0 205.0 Na3P04 12.3 34.8 54.0 109.6 Na3P04 26.8 41.0 50.0 86.2 Na3P04 78.6 102.2 151.2 Na3P04 31.0 63.0 61.7 89.0 Na3P°4 Mean Na3P04 23.0 9.8 7,2 3 J i4 f 2.2 POa Ptltr. (mg/l) 8.50 2.35 1.75 PO/, Residue (mg/l) Duat POy. (mg) Total Recv. (mg/l) PO/f Removed (mg/l) POy Adsorb (mg/l) 18.75 22.00 19.00 0.29 0.61 1.09 27.25 24.35 20.75 290 195 104 196+92 364 199 86 216+108 7.3 4.0 3.2 2.1 2.65 4.3 4.4 6.5 0.07 0.20 0.31 0.64 9.95 8.30 7.60 8.60 203 167 193 61 156+65 187 no 71 51 105+40 4.10 3.40 2.60 0.22 2.60 4.80 5.70 7.20 0.16 0.24 0.29 0.50 6.70 8.20 8.30 7.42 106 93 92 81 93+10 81 106 103 78 92+15 0.62 0.38 0.13 2.86 3.12 3.40 0.48 0.59 0.82 3.48 3.50 3.53 33 30 22 28.3+5,1 36 31 23 30,0+6,6 0.65 0,18 0.10 0.14 1.70 2.30 2.35 2.50 0.18 0.37 0,36 0.51 2.35 2 48 2.45 2.64 50 32 34 23 34.8+11.2 40.7 26.5 26.0 19,4 28.7+8.9 21.7+6,4 16.0+4.2 1.10 mg/l 52 In the waters of the bay. The extent of this involvement was Indic­ ated by the adsorptive removal of phosphate for a definite amount of dust present. Based on the amount of duat added, the difference in amounts of phosphate left in the filtrate compared to the amount of phosphate originally taken, substantiated the extent of adsorption. USE OP CALCIUM SELECT- ION ELECTRODE In most cases where phosphorus compounds are added to natural systems, the presence of calcium ions results in greater fixation of phosphorus in soils or complexatlon in water. Calcium Iona In solution are Involved in the phosphate uptake or release In natural water. The calcium select-Ion electrode can be used in the pH range of natural water for the study of the formation of soluble calclumphosphorus complexes by potentiometrlc titration (mv). The standard solutions for the electrode were prepared from CaCl 2 and the potentiometrlc response (millivolts) of the solutions was measured on a digital pH meter for concentrations from 1 x 10“ ^ to 1 x 10" 5 M. The potentiometrlc (mv) response for these standard solutions are given In Table 13. The plot of concentration vs. millivolts resulted in a linear curve (Figure 5). Ionic Strength and Millivolts The ionic strengths of the solutions were maintained between 0.01 and 0 . 0 0 1 molar and the millivolt variation did not exceed four milli­ volts for the ten-fold change In the Ionic strength. The measurement of millivolt response for diluted standard solutions and solutions with constant ionic strength gave a uniform change for the electrode (Table 13). The ionic strengths and pH values were maintained by using (CH^J^NOH, H C 1 , and ( CH ^ ^ N C l were required. 53 Table 13 Calcium Ion Electrode Standard Values New Electrod e Original Electrode C «C1;> MV CaCl? 9.12 x 10"hi - 42 1.0 x 1 0 " 2M +14 ».i; * io' 4 - 66 t.O x 1 0 " 3 - 6 9.12 x IO' 5 - 90 1.0 x IO* 4 -24 9.12 x 10"6 - 105 1.0 x IO" 5 -42 Ionic Strength and MV C«C1? mv (Scan. S o l n .) rav ( P - 0.01) 0.01 M - 62 - 61 0.005 - 68 - 67 0.001 - 85 - 83 0.0005 - 93 - 91 0.0001 - Ill - 110 0.00005 -1 18 - 1 17 0.00001 - 133 - 130 MV 54 -50 -40 _ 30 — -20 _ MV -10 — 0 — +10 - +20 3,0 4.0 - Log(f. s++) Figure 5. Standard C a l c i u m Curve 55 pH vs. millivolts The Influence of hydrogen ion on the millivolt response of the stsndsrd CaClj solutions was measured for the three solutions most _2 representative of calcium levels of natural water systems (1 x 10 to 1 x 10"^ M) . in Figure 6 . The results are given in Table 14 and represented This plot of mv vs, pH indicated the extent of usabil- ity of the electrode as the linear portion of the curve for each concentration. Temperature and millivolts The temperature of the CaClj solutions was varied in the range of the normal natural water temperatures. The results for the three standard solutions showed a definite temperature relationship with the potential of the solutions, especially the more concentrated, as indicated in Table 15. Measurement of Organic Acids In Water Initially, the fluorescent response of the natural colored mater­ ial was used to determine the concentration of organic acids in the Thunder Bay Watershed samples. At an excitation wavelength of 365 mu, the fluorescence was measured at 470 mu in fluorescent units taken from the Turner Fluorometer, The fluorescent reading was related to organic mas a by evaporation of a known volume of the concentrated extracts in alcohol, determined, A conversion factor of 27 units/mg/100 ml was A log plot of F vs. log mg of organic matter gave a linear curve. The following specific results were found by fluorescent measure­ ment using the fluorometer: Sep/69 - Thunder Bay River at the Breakwall ■ 42 mg/l Sep/69 - Wolf Creek (Hubbard Lake Road) « 54 mg/l 56 Table 14 Effect of pH on Calciuw Ion Electrode Potential (av) Solucton CaCl 2 1 .0 2 x 1 0 " 2 -43 »v (pH-6 . 78) pH mv 3.2 3.5 3.9 4.2 4.8 5.8 6.4 6.9 7.7 - 8 25 41 43 43 43 43 43 43 43 43 43 43 44 45 48 8.2 9.1 10.0 10.2 10.5 11.0 12.0 Solution CaCl 2 9.12xl0*A -61 mv (pH. 6 .35) pH 3.0 3.4 3.8 4,6 5.4 6 .2 6.6 7.0 7. 3 8.0 8.5 8.9 9.5 10.8 1 1 .0 11.5 12.0 wv -43 51 57 59 61 61 61 62 62 63 64 65 66 68 70 71 75 Solution CaCl 2 1 .0 x 1 0 " 4 -81 wv (pH-6,82) pH wv 3.1 3.3 3.5 3.7 3.8 4.0 4.2 4.6 4.8 5.2 -14 26 30 36 45 48 65 75 78 80 80 81 81 81 81 81 82 6.0 6.2 6.6 7.3 7.8 8.6 9.2 9.6 10.0 10.4 1 1.0 86 89 93 96 57 90 -80 - 70 -60 9 . 1 2 x 10"4 m CaCl -50 MV -40 1 . 0 2 x 1 0 ' CaCl -30 -20 -10 3,0 Figure 6. 5.0 7.0 9. 0 11.0 Effect o f p H on C a l c i u m Ion Electrode Potential 58 Tabic 15 Temperature (C) and Calclua Ion Electi^de Potential (mv) SolutIon Temg 11 CaCl 2 1 x 10 " 2 - 26 mv 13 15 17 18 19 20 22 24 25 26 28 30 32 33 35 36 38 40 42 45 mv SolutIon 12 -10 12 CaCl-4- 14 16 18 1 x 10"3 20 22 - 50 mv 23 24 25 26 27 28 28 28 28 28 29 30 30 32 Tg»P 13 14 16 17 19 20 21 22 23 24 25 27 28 30 31 32 35 37 38 40 mv -42 45 47 48 49 50 50 51 51 52 52 53 53 53 54 55 56 58 60 61 65 SolutIon CaCl 2 1 x 10-4 -69 mv TeptP mv 12 -64 13 14 15 16 18 66 68 20 22 24 25 26 27 28 29 30 32 33 34 35 38 42 69 70 69 69 69 69 70 70 71 72 73 74 75 76 78 80 83 86 59 The fluorescence readings were fairly constant In a temperature range of OC to 40C which would be adaptable to field measurements. The spectrophotometr 1c method for determination of huatlc acids (Semenov, _al., 1963) was checked using a Beckman DK-2 Spectro­ photometer. There were absorbance peaks at 325 mu and In 400 to 450 mu range and In the Infrared area of the spectrum. The excitation absorbance at 340 mu and transmittance at 440 mu gave comparlble results as Organic Carbon (Humic acid) in mg/l with that of the fluorescent method. This spectrophotometrie procedure was used for subsequent field measurement of color concentration In the Thunder Bay Watershed. The results of watershed sampling where significant amounts of organic color were found are given In Table 16, The Infrared spectrums for three sources were run on the HllgerWatts Infrared spectrophotometer. The spectral curve for organic extract from the Main Branch of Thunder Bay River (in ethyl alcohol) Is given in Figure 7. The assignment of functional groups to the observed peaks were taken from VanderMaas (1969) and are given In Table 17, Organic Acid Separation The water samples when passed through the anion-exchange resin, turned the resin from yellow to brown as the exchange proceeded down the column until its capacity (saturation) was attained. The material was removed from the column and fresh resin put on until the five gallon sample was used. On mixing with NaCl and NaOH, the resin and attached anionic organic material lightened in color and the solution became orange-brown. The filtrate from solids on treatment with HC1 also lightens and effervescence occurred. gave a brown solution In ethyl alcohol- The residue on evaporation These alcohol solutions had 60 Table 16 Organic Color Measurement In Thunder Bay Watershed Season Date Sample Location mg/l |i 8/19/70 8/22/70 8/26/70 8/26/70 8/30/70 Bean Creek Wolf Creek Upper So, Bran. Thunder Bay Main Branch at Breakvall No. Bran. Thunder Bay 58.0 15.5 11.3 7.2 10.5 Winter fl II VI If II If 11/8/70 11/8/70 11/23/70 11/23/70 12/3/70 12/3/70 12/3/70 Bean Creek Upper So. Bran. Thunder Bay Wolf Creek No. Bran. Thunder Bay Main Branch - Atlanta Main Branch - 9th St. Dan Main Branch at Breakvall 56.0 2 2 .0 25 ,3 53.8 26.3 50.0 21.9 Spring M II II H II 5/13/71 5/15/71 5/23/71 5/23/71 5/23/71 5/31/71 No, Bran. Thunder Bay Wolf Creek Main Branch - 4~mlle Dam Main Branch - 9th St. Daa Main Branch at Breakvall Bean Creek 55.0 18.8 36.0 29.0 35.6 59,0 Suiier II II 11 6/27/71 6/26/71 6/27/71 7/22/71 32.6 31 „4 39.0 94.0 M 8/2/71 Brush Creek Main Branch - Hillman Main Branch at M-32 Main Branch at Breakvall (Bridge Construction) Main Branch at Breakvall Fall ir 11 81.0 INFRARED SPECTRUM OF THUNDER BAY NATURAL ORGANIC ACIDS WAVELENGTH (MICRONS) I00 00 90 90 80 00 +- -4 + TRANSMfTT ANCE f%) 70 60 60 40 40 4-- 30 20 20 ■-P—* 4000 H I 3000 2000 1000 1600 1400 FREQUENCY ( C M ') 1200 1000 800 650 62 Table 17 The Infra-Red Assignment of Bands for Organic Functional Groups (Vender Haas, 1969) Source Strong car Thunder Ba y River Main Branch + North Branch Wolf Creek Bean Creek 1 Moderate Group cm* * Group 32003600 29503020 1650- 70 13901420 1090 1050 880 -0B - COOH C-H 32003600 29003000 1460 13901410 1040- 90 890 -OH -COOH C-H 0-X 0 -X2 805 32003550 29003000 13901410 1090 1050 880 -OH -COOH 1650 - OOOH 1580 1460 1330 1280 805 000 R-00-OH 0 -CH-OH3 -C-OH 0-X 0-X2 R- 0-OH C-H -OH - C-OH 0-X 0-X2 1460 R-0- 1330 0-OH 1280 0-0- R 805 **X n (Pheny 1 1710-20 0 1640- 50 1280 0-0-R 1200 0-OH *~X n * 0-0-R 0 * - 63 organic acid eoacantratlona In a range of 1 to 3 ag/>l. For a Thunder Bay River a ample with 80 a g of Organic Carbon (Humic acid) per liter, the amount of organic aclda recovered waa 2,5 mg/ml. For a W o l f Creek saaqple with 50 v g of carbon per liter, the extraction procedure gave 1.5 mg/ml of organic aclda. The detenainatlon of available and fixed calcltm waa done at the aampling altea In the river and bay. The change In concentration of aoluble calcluat haa been attributed to the complexatlon with oxldis­ able , anionic organic-aubatancea ( H o f f u v and Ehrllch, 1970). The poaalblc Involvement of phoaphatea in thle complexatlon waa a major portion of thla atudy. The meaaurement of theae InteractIona waa eatabllahed from changea In the weak-acid function (milllequlvalence) of the phosphate forma and lncreaaea in aeaociatlon conatanta of calclum-phoaphate complexea In the preaence of organic aclda. The potential comparleon method uaed the potential reeponee (arv) of a known concentration of calcium to coapare the original free cal­ cium with that of complexed calcium. lar exchange at a pH of Ca+ + + H 2 P04" The reactiona aaaumlng unimolecu- 4.5 to 7.0 would be: - C a H 2 P04+ while at a pH of 7.5 to 9.0: Ca4* and + HP04“ - CaHP0 4 at a pH of 9,0 to10.5: 3Ca+ + + 2P 0 4 " 3 - CaP04" + CajF04+ Wh«.**i the pH la maintained below 9.0, precipitation la avoided. In theae equilibria, the concentration of the aoluble lone would be found according to: 64 ii (Ca)c - Complexed calcium Ion (Ca+ + )t - Original calcium solution (Ca+ + )e - Free calcium at equilibrium (P)t - Original phoephate solution (P)_ - Free phoephate at equilibrium eo that after correction for dilution: (Ca-P)c - Concentration of calclum-phoephate complex c e (P>t - (Ca+ + )c and the aaaoclatlon constant Kf - (Kf) would be found from: (Ca-P)c (Ca^). - (P)e Sample calculation for Kf: Phosphate solution - K a 3 P 0 ^ - 1.02 x 10" Calcium tltrant - C eCl 2 • 1.00 x 10" CM d © + 1 cn cn cn cn »n O o- o © o MH . .. mH cn m cm \o cn © cn M <5 CM m « cn "4 -«o in 0 0 u i in 0 m 0 8 0 0 co © r- cm • • ■ t O' cm un 8 g “? 8 1 H rl 0 H Ml ■tfcn -4 in in n bb b b 0 SI u 1 «g«g^ r w « xCl 0 £ o 0 h « in in >\X .■ cn cn © o %pH%pH X N CO Os • ft nO CM o cn cn P m J? Be 100 100 + 1 •>} "O «0 W © o o o © b © pH pH N N g $ H H » 1 % Cm m 0 Be cn cn b b pH pH K N cn cn pH pH pH pH fv.\Q pH pH • 1 r- cn cn in m 1 • i i © o O o PH pH pH pH H H N K © © cn cn » » > « pH pH O' O' m m ob pH pH H N cn cn « i O' © mm bb pH pH K H cn cn . . O O' in n n n 1 • L_ © O O d ^ i B 0 pH ^ t - - (C**+)c - 9.27 x 10-5(100/150) - 6,18 x 1.02 x 10’4 (50/150) « 3.40 (Ca^lg (P04 )e Kf - 10*5 M x 10' 5 M 5.25 x 10 ’ 5 M (6,18-5.25) x lO- 5 - 0.93 x 10"5 m - (Ca-P)c (3,40-0 93) x lO" 5 - 2.47 x 10' 5 H _________ C 2 ^ 3 _ x _ 1 0 - ^ _______ (5.25 x 10’ 5 ) (2. 47 x 10-5 . 720Q ) Precipitation was noted when the concentration of the phosphate solution approached a 2 to 1 ratio of calcium to phosphate. When the pH of the solution was above 9,0, the reaction mixture was cloudy. However, when pH was above standing. 10,0, a white precipitate settled out on The association constants determined by Potential-Titration method were done at different pH values comparlble to those used In 67 Table 19 Association Constant by Potential Cosqiarlson In the Presence of Natural Organic Acids Ca Titrant Phosphate Sswpla £ 2 *± 2 . 1 Soln Cone Cone Vol Vol 2 are given in Figures 12 and 13. The titration curve, between 2,5 and 11.0, represents the alkali con­ sumption of the organic material by neutrallzatlon of the carboxylic and phenolic groups. 75 Table 22 Aaaoclatlon Constant by Potentisl-Titration In the Ptesence of ral Organic Acids 6 5- 7.5) Phosphate Sample Soln Cone N a 3 POA + Org acid 1.17x10" N a 3 POA + Org acid 1.17x10' Calcium Tltrant Vol Cone Vol Kf (Ca-P) 4 418 23 3. 29x10"4 448 .0 x 1 0 " 2 20 4.67x10"4 765 1 .0 x 1 0 " 2 30 4.67x10"4 964 100 1 .0 x 1 0 " 2 16 3.80x10"4 710 1.06x10"3 100 1 .0 x 1 0 ' 2 17 4.53x10 " 4 1000 1.13xl0‘ 3 100 1 .0 x 1 0 " 2 15.5 3.40x10'4 874 1.13x10"3 100 1 .0 x 1 0 " 2 18.0 5.30x10"4 1240 1 0 0 ml 1 .0 x 1 0 " 2 150 1 .0 x 1 0 " 2 3 100 1 1.17x10'3 150 NaAP 2 0 7 + Org acid 1.06x10" 3 N a 5p 3°10 + Org acid 3 1,17x10 15. 0ml 3.00x10" 76 -30 -25 -20 MV - 15 - 10 © 5 -Wi th out Organic Acid X - W i t h Organic Acid 5 Figure 11, 15 10 Volume (ml) - CaClj (0.01N) 20 25 Titration of K a 3 PO^ (1.17*lO~3f p H - 7,2) with CaC l 2 In the Presence of Thunder Bay Organic Acids 77 Table 23 p H Measurements of Natural Organic Acids with Base Sample Source Organic Cone , Main Branch Organic Salta - Main Branch Org Salta - North Branch Org Salts Tltrant Base Cone NeOH NaOH NaOH 0„0912 0,0886 0.0886 Ca(OH > 2 Ca(OH > 2 0.0263 0.0100 Base Vol fB - me 2,45 ml 3.10 2.50 0. 223 0.275 8.00 0.210 28.0 0.222 0.280 - NaOH NaOH NaOH 0.0886 0.0886 0.0886 3 10 2.40 1.95 0.275 0.213 0.173 1.80 0.314 North Branch Org Acids 1 - g /1 NaOH 0.0911 Wolf Creek Org Acids 3 rag/I NaOH 0.0911 34.0 3.040 Ca(OH ) 2 0.0060 14, 0 0.084 Bean Creek 0 .5 rag /1 78 14 10 pH Main Branch North Branch Wolf Creek 5 Figure 12. 10 15 Volume (ml) - Na O H (0.091IN) Titration of Organic Aclda vith NaOH 20 25 79 10 -Main Branch -Worth Branch -Bean Creek. 10 Volume Figure 13 30 20 (ml) - Ca( 0H ) 2 40 (0.0368N) Titration of Organic Aclda with Ca(0H ) 2 50 80 Fotentlometrlc (pH) Titrat ton of In Figure 14, the change In phate Phosphates pH for solutions of the three phos­ forms titrated with NaOH la shown, and d lsodlum phosphates ITe formation of the mono are observed In the typical S curve described by Odajlrl and Nickerson (1964), The titration of the phosphates with base between pH 2.5 and 11,0 represents the weak-acid consumption of the phosphates by neutralization, The titration of N a 3 pO^ was done at two rates to compare the effect of rate of titration with taCCFOj on the formation of Ca-PO^ complexes. The curves are shown poly-forms with Ca(0 H > 2 is shown In figure 15. The titration of the in Figure 16. The presence of pre­ cipitation and a decrease In pH indicated the formation of Insoluble phosphate forms. in pH occurred. On further addition of alkali, only a small change The results of complete forms are given In Tables titration of the phosphate 24 and 25. The Influence of calcium on the titration of the phosphate waa forms followed by adding C a C l 2 to the solutions before neutralization with Na O H (Figure 17). In this way, the involvement of calcium ion In possible calcium^phosphate-organic acid complexatlon could be measured from two directions with calcium. In all cases, the pre­ sence of CaCl 2 in the phosphate solutions resulted in an increase In the amount of NaOH needed to reach the weak-acid function equi­ valency, This was more pronounced for orthophosphate where the solu­ bility of dlcalclum phosphate formed was depressed by the calcium present in the solution. When the phosphate forms were titrated with NaOH In the pre­ sence of CaCljt the formation of Insoluble calcium phosphate occurred above pH of 6 , When natural organic acid concentrates were added to 81 12 10 8 pH 6 4 2 N* 4 P 2 0 7 (1.06x10'JM) N a r P , 0 Tn (1 19x10-3M> 0 5 10 Volume Figure 14. 15 20 (ml) of NaOH (0 0911M) Titration of Linear Phosphate Forma with NaOH 25 FAST _$Z SLOW 83 14 N a 4 P 2 0 7 (1.17x10"JM) X 10 20 Volume Figure 16. N a eF.,Otn (1.19x10*3M) 30 (ml) of C a ( 0 H > 2 40 (0.0368N) Titration of Pyrophosphate and Tripolyphoaphate wl th Ca (OH) 2 50 84 Table 24 The pH Measurement a ot Phoaphatea irlth N aOH Cone Sample N a 3 P0 4 Na5P3010 V o lN *?li 0 . 201 0.195 0. 248 0 225 0 189 0 .218 0.237 0,216 + 0.022 0.0912 0.0886 0.0886 1.155x10"2 1.06x10" 3 0.0994 0.0911 1.8 2,5 C. 179 0.215 1,25x10"2 1.13x10"3 0.0994 0.0911 1.6 0.159 0.226 0.1000 0.0994 0.0911 0.0911 .2 ml .2 2.7 1 95 1 ,9 2.4 meq .0 2 x 1 0 " ^ .0 2 x 1 0 "* 1 .0 2 x l 0 ~£ 1 .0 2 x 1 0 ' 1 .0 2 x 1 0 1.17x10.-3 1 17x10" 3 1 1 2^7 (NaOH) 2 2 2.6 2.8 85 Table 25 pH Meaaureme nta of Phosphates vlth Ca(0H)? Con e . Sample Na3 P0A 1 1 1 1 N a 3P04 faat 1 Ha ,P 0 4 •low 1 M a 4p 2°7 n »5 p 3°10 .0 2 x 1 0 * 3 .0 2 x 1 0 ' 3 .0 2 xl 0 -J .0 2 x 1 0 ' 2 (Ca(OH)2 > .0263H .0263 .0263 .0097 Vol r«rrn'J7 7.2 ml 7.5 8.7 25.0 fm - me<| 0.189 0.197 0.230 0.243 0.215 + 0.026 0. 224 0.294 .0 2 x 1 0 ' 3 1.17x10-3 .0263 .0368 .0 2 x 1 0 - 3 1.17x10" 3 .0263 .0368 6.6 0.151 0.242 1.155x10" 2 1.06x10" 3 .0097 .0368 23.5 6.3 0.141 0.232 1.25x10" 2 1.13x10“ 3 .0097 .0368 23.5 5.4 o. 141 8.6 8.0 5. 75 0.200 86 14 10 8 6 4 2 CaCl 2 CaCl- + Acids 0 3 6 Vol Figure 17. 12 9 <«1) of N a O H (0.0 9 IN) Titration of Na^PO^, CaCl 2 and Main Branch Organic Acids with NaOH 15 87 the mixtures, the cloudiness was reduced, dependent upon the quantity of organic material added to the mixture. The comparison of the milliequlvslente of the weak-acid function for the phosphate expected from the mixture of calcium chloride and phosphates with organic acids and that actually measured is given in Table 26. Potentlometrlc (PH) Titration of O r g a n ic Acid-Phosphate Mixtures When the titrations of phosphate forms were carried out in the presence of both calc iu m and natural organic acids. less volume of N a O H was needed to attain curves similar to that of the pure phos­ phate (Figure 17). The equivalent amount of base used was reduced and the precipitation of calcium phosphates was inhibited and some­ times eliminated. The maximum effect of the organic acids on the formation of Insoluble calcium phosphates would depend on the number of acid groups which can be neutralized on the organic colloid. These Interactions are shown In Figures 18 and 19. The influence on complexatlon of organic acids from different sources Is shown in Figures 20 and 21. The determination of the amount of anticipated mllllequlvalence for phosphate-organic acid mixtures also resulted in a reduction of the equivalent values when Ca( 0 H > 2 was used. The orthophosphate showed the greatest difference and the most noticeable reduction In cloudiness of the calcium phosphate mixtures with organic acids (Fig­ ure 22), With m a i n branch organic extract (Figure 23) and with tri­ polyphosphate (Table 2 7 ) t the volume of base used was greater. There was a general trend In the increase in the amount of base needed as the number of phosphorus atoms increased. titration results are given In Table 28. Additional mllllequlvalence T a b la 26 Maan Equlvalant Maaturamanti of Fhoiphata Mixture* with NaOH Organic Acid Sourca Maq Phoaphataa Soln. Hao Maaaurad Maq P + CaCl2 Total Maq Maaaurad Maq P + C a C b + Org Acid Maq Changa 0.246 Na3P04 0.221 0.321 0.567 0.416 0.151 0.164 Na3P04 0.213 0.263 0.427 0.292 0.135 0,096 Na3P04 0.228 0.356 0.452 0.292 0.160 Main Branch 0.223 Na3P04 0.201 0.305 0.528 0.337 0.191 0.249 Na3P04 0.221 0.313 0.562 0.426 0.136 Wolf Craak 0.304 Na3P04 0.201 0.250 0.554 0.421 0.133 North Branch 0.164 Na4P2° ? 0.196 0.209 0.373 0.337 0.036 North Branch 0.164 0.202 0.237 0.366 0.337 0.029 North Branch N#5P3°10 89 1A 12 10 8 pH 6 A 2 CaCl CaCl-, + Acids 0 3 Figure 18. 9 (ml) of NsOH 12 6 VotuM (0.0911N) Titration of Na^PjO/* CaClj and Main Branch Organic Acids with NaOH 15 90 10 pH CaCl ^ a5^3®10 + CaClj + Acids 6 9 Volume (ml) of NaOH Figure 19. 12 (0.09U N ) Titration of N a 5 P 3 0 1Q, CaCl^ and Main Branch Organic Acids with NaOH 15 91 14 12 10 8 pH 6 4 2 CaCl- + Acids 0 4 Volume Figure 20. 12 8 (ml) of N a O H 16 (0.0911N) Titration of Na-jPO^, CaCl^ and North Branch Organic Acids with NaOH 20 92 14 10 CaCl ® Na 4 P 20 X N*4 P 2 0 7 • N*5 P3° 10 + CaC l 2 + Acids + CaCl 2 -^■NagPgOjg + CaCl 2 + Acids 8 Volume Figure 21,. 12 16 20 eratures that gave a reproducible response wa s from 15C to 35C. The more dilute solutions were more constant. normal, natural range occurs part of the year. This In other cases, the samples were allowed to come to room temperature. POTENTIAL-COMPARISON METHODS From the potential-comparison results, the association- constant values increased with the pH value which would indicate the Involvement of precipitation in the reduction of the free calcium ions. This precipitation was Indicated by the appearance of cloudiness in the solutions at high pH with a more negative potential. Also evident is the Increased complexatlon by the more condensed phosphates because of the Increased number of negative sites In the chain. In the p H range of natural water systems, the N a 3 P0 ^ complexatlon with CaCl 2 was comparable with Chughtal £t a l . (1968) from p H values of 6.5 to 7.5. The assoc1 ation-constants found by titration from either direction were nearly reproducible 106 at 9-0 to 10.5 pH, had a naan value of 1.50 z l O ^ while at 6.5 to 7.5 pH, Kf averaged 465. The Influence of natural organic acid on the complexatlon wee Indicated b y an Increaae In the aeount of free calcium apparently removed from the aolutlon and an Increaae In the conatant at p H 6.5 to 7.5 to an average of 6 8 8 . In the caae of pyro- and trlpolyphoephatea, the associationconatant again lncreaeed with p H value aa precipitation occurred to alao reduce the free calcium in aolutlon. In the pH range of 8.5 to 10.0, the precipitation waa reduced and the reaulta were comparable to those found by Watters and Lambert (1959). In the natural p H range of 6.5 to 7.5, the conatant waa lower than that found by Irani and Callla (1960) b y a factor of 1C, however, their ionic strength was higher. In the presence of organic acida, the effect on the aasoclatlon-conatanta again showed an Increaae. The change waa greater than that for orthophosphate. POTENTIAL-TITRATION METHODS The potential-titration results compared favorably with those found by potential-comparison. There waa a definite relationship between the p H of the solution and the associationconstant. A comparison of the means of the results is given In Table 29. The specific reduction of free calcltmi In orthophosphate complex mixtures by the addition of Wolf Creek acid averaged 107 Table 29 Association-Constant Means for Potential-Comparison and Potential-Tltration Methods Phosphates J>h Pot. Comp. Pot. Titr. Organic Acid Source - Kf “ .0 xl 0 9.5-10.5 N a 3 P0 4 1.24x10** 1.49xl0 4 Main Branch 6 8.5- 9.5 N a 3 P0 4 4.50xl03 4.50xl03 Main Branch e.oxio3 8.5- 9.5 Na4P 2 °7 3.80xl04 2.90xl04 Main Branch 4.4xl0 4 8.5- 9.5 N a 5P3°10 4 . 10xl0 3 9 . 50xl03 Main Branch 7.5xl0 3 6.5- 7.5 N a 3 P0 6.5- 7.5 6.7- 7.5 507 515 Main Branch 613 N a 4 p 2°7 596 650 Main Branch Wolf Creek 1000 N a 5 P 3O l 0 657 Main Branch Wolf Creek 1212 830 4 720 680 3 108 8.8 isg/1. This change in association-constant and the decrease In apparent free calcium In solution showed that the organic acids were becoming Involved in calcium complexatlon either separately or with the phosphate. The pH-titration method attempted to resolve this. In the natural water samples, there was apparently some calcium fixation b y oxldlzlble matter In the samples. The bay and river samples taken at selected sites showed a rather Irregular amount of calcium being involved, ranging from 1 to 65 mg of calcium, with the average calcium released by oxida­ tion being 13.5 mg. This again shows that all the calcium In the natural waters of Thunder Bay Is not free, but covtplexed In an organic and phosphate system. NATURAL COLORED ORGANIC ACIDS The extraction of the organic acids from the natural samples was one on four streams of highest fluorescence response. The concentration process was somewhat time-consuming, especially In removing the last traces of salt crystals. In selected cases, purification was not carried out completely when potentiometrie titration by pH was done. the case of potential In (nrv) measurement of calcium, It was essential that the sodium concentration be reduced to a minimal amount. In these cases, satisfactory samples were obtained after repeated evaporation and dissolution In alcohol. 109 The identification and characteristics of the natural organic acids was accomplished by fluorescence response and Infrared absorbance. The natural water samples showed a fluorescent excitation and emission at wave lengths similar to that observed by Christman and Ghasaeml (1966) and Packham (1969) who used similar extraction procedures. The maln-branch water continued to Increase in the amount (mg/1) of organic carbon throughout the study. Bean Creek and the North Branch of Thunder Bay River also showed high values throughout the investigation, with Wolf Creek shoving mediuxorange values. IDENTIFICATION O F NATURAL ORGANIC ACIDS Organic color in natural water has its origin in the multitude of organic molecules comprising the forest vegetation and varies in composition and amount with season and source. This color could arise from the aqueous extraction of living woody substances, decaying wood, the solution of degradation products in and the solution of organic soil matter. The infrared spectrum for the Thunder Bay River naturalorganlc-concentrate in alcohol was similar to that recorded by Black and Christman (196 3) and by Mldwood and Felbesk (1968). Infrared spectra for the Thunder Bay organic fractions showed carboxyllc acid and hydroxy absorption maxima in the 2.5 to 3.5 micron range. 6.0 A strong absorption band was located at micron which is the region characteristic of carbonyl- 110 group stretchlng-frequency and the double-bounded carbons In conjugated phenyl groups. Absorption In the 3.5 to 7.0 micron range In the samples was probably due to alkane groups and alkyl branches. The broad absorption regions between 7.0 and 8.0 micron, 9.0 and 10.0 micron are possibly due to combination of C-C and C-O stretching frequencies. The strong bands at 9 to 10 micron and 11 to 12 micron Indicate the C-H out-of-plane deformation frequencies of free hydrogen atoms on substituted benzene rings in a polymer chain. The functional groups identified (Table 17) were R-0H, C-H, - O O O H , Ar-OH, Ar-X, Ar-Xn , and R-O-Ar. Christman (1963) characteristic Black and found peaks in fulvic acid amnples which were of carboxyl groups, -OH, C-H, conjugated phenyl groups, and substituted phenyl groups. Midwood and Felbest (1968) found that most of the spectra of organic fractions show peaks of alcoholic and phenolic -OH groups, CH^- and -CH 2 - groups, C-C, - OOO ~ , and -COOH. The natural colored organic materials extracted from the waters of Thunder Bay Watershed have a definite acid nature. The adjustment of the p H of their solutions with hydrogen Ion results In a conjugate base that can be neutralized with standard hydroxide. for Ca( 0 H ) 2 The neutralization was somewhat lower indicating a possible complexatlon of the divalent metal ion by neighboring negative groups. The measurement of the equivalence reaction of the phosphate forms gives a definite weak-acid fraction that could be used to Indicate the effect of organic acids on the neutralization Ill process. The niI \ *.eqi'i'-'.i1.ec~p -'/.id vs,. directly related to the concentration of the pboephat* solution u:?eJ. Titration setv^d to be an accu’*at? raeasuremer *■ of f*oio"'lc phosphate aval, lab To for cationic interaction (h?c ;?/n or calc *.««). The calcium ion ie involved in reaction with the pho*ph.-?':f forms in precipitation that c.-r.n occur at alValine pH value*? according to the equation: Ca(H 2 P 0 4 )2 t <:*+"► - + 2 H+ and slow conversion of precipitated iicalcium phosphate tertiary salt. CarjpO^, Inj These calcium reactions with tne p h o s ­ phates also occurred when calcium was added separately ttn CaCl 2 and titration carried rr.t with NaOH. The maxim um quantify of soluble calcium phosphates fovn-d depends on the number of acid pr^upa (anionic) which can c** neutralized on the organic molt'cule. in weak-acid equivalent The apparent -eduction reaction by the addition of natural organic acids to the calcluro-phosphate reaction solution wsj shown by the presence of a reduction in the mil li equ iv ale nts „ The reduction was measured in the mixtures by the sunmatirm of the anticipated equivalence found for separate reactant*'. The formation of apparent soluble calcium phosphate could a! involve a chemical corip!e-ration as a result of certain chemically active groups preseni: iu the organic molecule. The soluble cal'-ium phosphates could be formed as a r?nult of the colloidal properties of the organic matter. The overall, phenomena of this interaction could be possibly allied with rhf combined occurrence of both active anionic groups. a colloid and one or more chernfc**1 1 v. In the absence of metal, only a slight 112 reaction took place between the phosphates and natural organic acids used. POTEKTTOMETRIC (t>rf) TITRATION METHOD The concentrated organic acids from the Main Branch and North Branch of Thunder Bay River were titrated potentlometrlcally with NaOH and Ca(OH)j. Tne curve with NaOH showed two equivalence points, one at acidic p H and the other at slight basic conditions. 2.5 The titration curves, between pH and 11.0, represent the actual alkali consumption by the anionic colored material through neutralization of acidic sites. In the case of Ca(OH) 2 , the curve was a simple neutral­ ization curve with no Indication of the presence of more than one type of acidic group. The titration process has indicated that anionic sites are available In a basic solution. for reaction with cations The Inflections on the curve using NaOH would seem to reflect the presence of more than one type of functional group. After the were acidified salt solution of the standard phosphate to apd of 2.5, titration was NaOH and Ca( 0 H ) 2 > The formation of mono- forms carried out with and di-metalllc salts were Indicated by the S curve obtained in the neutral­ ization process. The tertiary salt can exist only in such a strong alkaline environment that Its formation below pH of 11.0 does not occur in any measurable amounts. In the titration of the starting at pH 2.5, phosphate forms with C a C O H ^ t there is a similarity In curves up to 113 Che monophosphate stage at p H 6 . After addition of sore Ca( 0 H) 2 > there was a slight non-linear change at pH of 7.0 possibly because of the presence of a secondary calcium phosphate along with partial precipitation, /bive a p H of 8 .0 , secondary calcium phosphate was converted Into the insoluble tertiary salt. The presence of calcium Ions seem to Influence the course of the pH change. The titration of the phosphate forms with NaO H In the presence of a Vnown and constant amount of C a C ^ * showed a drop In p H after the formation of monocalcium phosphate is apparent. The calcium concentration seema to depress the solubility of the dlcalclum phosphate to such an extent that the transformation Into trlcalclum phosphate was not observed initially but did occur with time as precipitation Increased In the calcium-phosphate solutions. The titration of the phosphate In the presence of CaCl 2 and organic acids with NaOH was conducted under identical conditions as previous reactions. When the phosphate forms were cosblned with CaClj, the dlcalclum phosphates were formed. The formation of soluble trlcalclum phosphates took place when the organic acid was present. The precipitate which was noticed above pH of 7.0 In the phosphate solutions was reduced when the organic acids were present. W h e n the amount of reacting species was increased, the formation of the precipitate was noticed at pH values above 8.0. Therefore, the amount of trlcalclum phosphate which can be formed in solution depends on the quantity of organic acid present in the system. 114 Whe n Ca( 0 H ) 2 was used as the tltrant, the dlcalclum phosphate precipitate again formed above a pH of 6.0 as a non­ linear portion of the curve at pH of 7.0. While, above pH 8.0, In the presence of organic acids, the precipitates seemed to decrease In quantity. In addition, the amount of base used to reach pH of 11.0 was greater than that for NaOH, Ibe influence of organic carbon on this amount of base was more pronounced than the effect during NaOH titration. phosphate titration with CaCOH)^, In the the presence of the free carboxyl and phenolic groups Is necessary for the formation of the soluble trlcalclum phosphate as long as the phosphate originally was in solution. In all cases of titration with base, the pH of the phosphate- calcium-organic acid reaction system decreased phosphate for the three forms from 1 to 2 pH units on standing. seem to indicate that on continual contact This would the calcium is replacing the hydrogen Ions on the acidic groups by ionexchange and serving as a bridging site for the phosphate forms in solution. In evaluating the equivalent reaction ability of the phosphate forms, the pH of the sodium phosphate solution was adjusted to 2.5 with H C 1 . The pH readings per unit volume of added standard alkali were plotted to obtain a phosphate titration curve. Hydrolysis was avoided by conducting the reaction at room temperature and as rapidly as possible. distance between the two equivalence points was considered equivalent to the weak acid Nickerson (1964). function (fw ) of Odaglri and The 115 In the caie of titration of orthophosphate with NaOH, both the presence of CaCl.2 and Main branch organic acids adds to the equivalence of the phosphate solution. When the three components were combined only a slight decrease In the mlllleqvlvalency was observed. W he n Ca(OH ) 2 was used as the tltrant, the reduction was much more pronounced which would be attributable to involve­ ment of the divalent calcium In an Ionic reaction other than neutralization. After chemically blocking the acid groups In casein, Vlsser (1962) concluded that where the organic material does not possess free carboxyllc groups, It has no Influence on the course of normal phosphate titration In the presence of calcium. This would Indicate that the max imu m quantities of soluble trlcalcltsB orthophosphate formed depends on the number of acidic groups which can be neutralized on the natural organic acid molecule. According to Vlsser, the formation of the calcium orthophosphate is probably related to the combined occurrence of both a colloid and one or more chemically active groups. In the pH range used, the primary ions present In the calcium-phosphate mixtures would be CaH 2 P04+ , CaH 3 P 20 7+ * C a 2 ‘^P0 4 + and C a 2 H 2 P 3 0 . The phosphates In the metal complexes could be bonded through the calcium to the acidic groups of the organic matter. When the amount of calcium Increases as In the titration with Ca(OH)2 , a considerable aaiount of the phosphate could occur as calcium phosphates which are physically mixed with the organic acld-metal phosphates. 116 Vlsser be a major (1962) proposed that the humlc acid of organic soils would factor In the transport of calcium phosphates by Involving the colloidal matrix and the carboxyl groups should both be present in the one substance, The general structural according to Christman and Ghasaeml formula for the acids (1966) involves: COOH COOH HOOC These structures could be part of a natural complex as: 0 0 II H Ca - 0 - P - OH i OH COLLOID - C V 0 COLLOID I\ Ca 0 S 0 K COLLOID - C S 0 - $ - 0 II / / 0 — Ca 0 0 II * Ca - O - P i - O - P I - O/ OH 0 — Ca(2H) The phenol groups in the molecule m ay be Involved as well complexatlon. In either case, In this the Interaction makes possible the movement of calcium phosphates In soils and natural water as a calcium-phosphate-organic acid complex. The phosphorus cycle in a natural water environment can be In­ fluenced by chemical complexatlon with calcium Ions and soluble or­ ganic matter. Moreover, the physical occulsion of phosphates on natural colloidal organic material could Involve calcium. Potentio- metrlc titration by either millivolt or pH response showed a definite Involvement of organic material extracted In the complexatlon of the three phosphate from the Thunder Bay waters forms by calcium through the acidic sites on the natural organic polymer aK>lecule. SUMMARY The water quality of the Thunder Bay Watershed has been found to be relatively high. Much of the 1250 square wile drainage basin la still In its natural state. The regional Inventory of this w a t e r ­ shed showed Instances of dowestlc, agricultural, and industrial influ­ ences on the quality of the water,, character of the watershed resources and composition of aquatic species. Both the sewage effluent and the discharges from wood-products industries contain significant organic materials. Eighty per cent of the local primary-treatment sewage effluent was determined to be composed of the simple linear phosphates: ortho, pyro, and trlpoly. These phosphates are Involved in the phosphorus cycle of Thunder Bay and associated with accelerated eutrophlcatlon of natural waters when temperature, light, and other necessary nutrients are present. Suspended and settleable solids can serve as adsorption sites for linear phosphate forms in natural waters. In the Thunder Bay at Alpena, Michigan, calcareous particles are present from natural lime­ stone sources and as cement dust emitted from a local Industry. The composition of the cement dust and the domestic sewage efflu­ ent entering the bay indicates that constituents action are available. for possible inter­ The suspended solids level In Thunder Bay water along with total and acld-extractable phosphates from solids were measured to determine the extent of the fixation occurring In waters of the bay. In the removal of phosphorus from standard phosphate solutions, cement dust showed a definite uptake of ortho, pyro, and 117 118 tripolyphosphate fomi. In river water, phate was lower, Indicating the possible involvement of soluble n atu­ ral organic acids and metal the adsorption of orthophos­ ions In the complexatlon. Chemical oxidation of natural samples shoved that in Thunder Bay, an Interaction exists between calcium and natural organic material. The colored organic materials are acidic In nature and were recovered in sufficient concentration to determine metal-organic acid-phosphate interactions. The three linear forms of phosphorus were combined with the organic acids extracted from the natural colored water of selected tributaries of the Thunder Bay system In the presence of soluble calcium. ial, In the presence of the concentrated organic colored m a t e r ­ there was a reduction In the milllequlvalence of calclum-phos- phate mixtures. In identical solution m i x t u r e s „ increases in the association constants for calcium-phosphate complexes Indicated involvement of the phosphates with calcium and natural organic acids. Calcium and hydrogen electrodes were adequate for following this complexatlon in natural waters by potentiometric titration. It has been shown that the natural organic material of the Thunder Bay Watershed form soluble cosq>lexes with the calcium-phos­ phate systems and the suspended calcareous particles adsorbing p h o s ­ phates. These phenomena are Important factors In the transport and availability of phosphorus in the Thunder Bay aquatic ecosystem. RECOMMENDATIONS FOR CEMENT DUST If the dust from the cement operation has a fairly consistent composition during Its production and dispersion over the bay, it could serve as an agent to fix phosphates in the natural eutrophlc water system. Hynes and Greiv (1970) showed that preventing the release of nutrient ions from the mud-surface can cause the water above sediments to be a less suitable m edi um for the growth of algae. The use of cement dust as a phosphorus adsorbing material In an eutrophlc system could lead to Interruption of the phosphorus cycle, thereby slowing the release of nutrients so that undesirable algals blooms do not occur or cease to re-occur. The reversibility (phos­ phate- release) of the dust-phosphate particles has been found to average 7.0 mg/g above the original phosphorus in the solution. Moreover, phosphorus could be removed in sewage oxidation lagoons by applying the appropriate amount of dust to reduce the phosphate level to the desired value. and Sawyer In their work on sewage lagoons, Burrell (1967) found that lime-treatment of raw wastewater can effect a 97% removal of soluble Inorganic phosphorus forms. The lime requirement is independent of the phosphorus content and can be esti­ mated in terms of the alkalinity (controlled by pH). Since the 1ism treatment of wastewater produces effluents with N:F ratios of 30 or above, It appears that properly managed stabl 1 lzation ponds could provide very suitable secondary treatment of sewage with the dust. Another specialized application of the dust in the sewage area could be as s substitute for lime in the chemical treatment of the 119 120 domestic •>««{§, To Institute this proposal, adequate equipment would be needed to remove the moist dust material by sediment at loti and sludge draw-off in the final clarlfers. O'Farrell treatment of the secondary effluent (1969) found that the from a modified aeration plant can consist of single or two-stage lime precipitation and the two-stage high lime process, filtration. In lime is added to a p H of 11,5 in the fiist stage and then is recarbonated to a pH of 9.5 to 10.0 with flocculating additivea in the second stage. The two-stage process w i t h flocculants has maintained ninety per cent removals of phosphorus. Hie chemical phosphate removal techniques can be accomplished by conversion of soluble phosphates to an insoluble form by either p r e ­ cipitation or adsorption with the metallic salts added to wastewater. The pH of the water la usually increased with lime to permit the form­ ation of Insoluble metal phosphate salts. The cement dust has been found to cause a 0.02 pH change for each milligram o f dust used, with a m a x i m u m of 10.70. With an excess of cement dust, higher values can be reached up to 12.00 pH. Wlrkasch (1968) has found these suspended me ta l l i c phosphates are fine and well-dispersed In submlcron-mlcron size. The precipi­ tates can be flocculated with organic polyelectrolytes, coalescing into large quickly-settling floes. The cement dust could be an economical precipitating agent, especially with small amounts of ferric Ion added as a coagulant aid. Moreover, the dust could be discarded along with the adsorbed nutrients which wo u l d involve removal and disposal without reclamation. CONCLUSIONS The water quality of the Thunder Bay River and lta tributaries la at high levels above the population centers. basi n progresses toward Lake Huron, the water accumulates Increasing concentration of pollutants especially nutrients and domestic sources. As the drainage frost agricultural The industrial and domestic waste-waters discharged into the watershed are contributing synthetic additives to Thunder Bay and lead to degradation of the bay waters. The quality of the basin waters and the character of the stream resources need to be regulated at a level which will not allow further degradation o f the system to occur. Highly diversified benthlc communities containing many clean water forms have been found In substantial areas of Thunder Bay near shore (Fetterolf, e£ a l . , 1968). Only In the areas near discharge of wood-products operations is a highly degraded ecosystem existing under the prevailing sewage conditions and presence of cement dust. The wind di r e c t i o n s , current patterns, river and the movement of the flow into the bay aid in the distribution of the high phos­ phate contribution of the sewage plant. The presence of cement dust In the natural water environment of Thunder Bay has an Influence on the availability of phosphorus to the ecosystem of the bay through Its adsorption and subsequent sedimentation. The calcium Iona in Thunder Bay waters Interact with phosphates and this Interaction Is Influenced by the presence of natural organic acids. The involvement of the organic acids in the complexatlon is 121 122 directly related to the anionic nature of the colloidal polymer. The carboxyllc groups In the natural colored organic acids form stable metal-organic complexes as well as water soluble multl-dentate chelates with calcium. In the watershed, the organic color observed In selected tribu­ taries was high enough to acquire a sufficient amount of concentrated extract. In the case of the measurement of the amount of soluble calcium fixed by oxldlzable organic material, a mean value of 15 mg/1 was Measured. This Indicated that there Is an Interaction between calcium and the natural organic acids occurring In Thunder Bay system. The Thunder Bay River and its branches have been found to contain significant organic color. With the natural organic acids of the Thunder Bay Watershed forming a soluble complex in the calcium-phos­ phate system, this phenomenon will most certainly be of importance In the transport and availability of calcium phosphates in the bay aquatic environment. The apparent reduction In milllequlvalence of calcium-phosphate mixtures by the presence of the organic acids sup­ ports this Involvement. The Increase in association constants for calcium-phosphate complexes when organic acids are added further substantiates this conclusion. The interactions of the calcium constituents (soluble and solids) wi th phosphorus and natural organic acids should be considered as controlling system. factors In the over-all equilibria In the Thunder Bay Evaluation of other physical and chemical complexatlon sys­ tems that may exist should be done In order to attain a more complete Pi cture of the eco-processes operating In Thunder Bay. The Thunder Bay water system Is a vital part of the natural resources of North­ eastern Michigan and should be protected present and future generations. for use and enjoyment of BIBLIOGRAPHY BIBLIOGRAPHY Anon, Anon. 1963. Great Lakes Rea. D l v . ,Univ. of Michigan, Introduction. 1971, Science Neva, Alpena Neva, The. 1961, ago. May 25:8-12. Pub. No. 10. 99:370. Geology of Alpena County - Written 70 years Alpena Power Company. 1971. Personal comsmnication and Company records. Alpena, Michigan. Alpena Soil Conservation District, 1969. General Soli Map, An Appraisal of Potentials for Outdoor Recreational Development, Alpena County, Michigan. 60 p. American Chemical Society. and Eng. Neva. Sept. 8 1969. Cleaning our environment, Report. S58. Chem. American Public Health Association, American Water Works Association, Water Pollution Control Federation. 1965. Standard Methods for the examination of water and wastewater Including bottom sedi­ ments and sludges. Amer. Publ. 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As well, the nutrient levels can be regulated by biochemical, chemical, and physical processes occurring within the aquatic system. W i t h i n a body of water, the primary regulatory processes are assimilation of Inorganic forma ^> 3 '* HjPO^" , and HPO^") by microorganisms and aquatic plants, mineralisation or organic forms by microorganisms, and uptake and release by sediments. Transformations of condensed, Inorganic phosphorus forms appear to be restricted to the chemical and biochemical hydrolysis of these phosphates to orthophosphate. The forms and amounts of phosphorus in waters have been described by Jenkins <1968), according to analytically defined fractions, namely: micron filter), (1) particulate phosphorus (retained by 0.45 (2 ) dissolved phosphorus - orthophosphate (reactive in reduced phosphomolybdate colorimetric procedure) and condensed phosphate (contains F-O-P linkages hydrolyzed by m il d acid), and (3) dissolved organic phosphorus (contains P-O-C and P-C linkages degraded to orthophosphate by acid digestion). 133 134 The biological productivity of a body of water haa been directly related to the degree of fertilization by plant nutrient*, especially phosphorus. Phosphorus enters surface waters primarily from land-run-off, percolation through soil, and waste waters. Prink (1967) found that an isolated lake which supported a large population of rooted aquatic and planktonlc algae had a high Inorganic nitrogen and phosphorus concentration coming from land drainage. Engelbrecht and Morgan (1961) considered the source of phosphorus in Illinois surface waters from land-drainage to be in the form of simple orthophosphate or as soluble, hydrolyzable forms of phosphate. These phosphates could be adsorbed on clay particles which enter water during erosion. Engelbrecht and Morgan (1959) found the phosphorus present in natural waters from surface drainage amounted to 0.036 m g /1 as orthophosphate and 0.081 mg/1 as total phosphates (P2O 5 ), Samples from streams with significant amounts of treated and untreated wastes had an average of 0.411 mg/1 orthophosphate and a maximum inorganic-condensedhydrolyzable- phosphate concentration equal to 0.657 mg/1. They found that a sewage plant, with activated-sludge treatment, had an average 18 m g /1 as P ^ 5 effluent. MissIngham (1967) found that the phosphorus content of domestic sewage Is four times what it was before the advent of synthetic detergents. These detergents are composed of 30 to 50 percent phosphate builders (primarily polyphosphates). Herold (1967) found that the phosphate builders in detergents, such as Tide, were composed of 5X-ortho, 25%-pyro, and 70X-tripolyphosphates. 135 In his discussion of the overall picture of eutrophication, Fruh (1967) proposed that the type and intensity of the eutro­ phication problem depends on the frequency (5 x 10^ ^elle/llter), algal blooms The frequency la related to the respec­ tive genera and species of algae present and phosphate concen­ tration, Shapiro (1967) has Indicated that there are either ionic or organic reactions systems Involved In phosphate uptake which should be measured in the evaluation of eutrophication of natural water by phosphorus. The high phosphorus concentrations are associated with accel­ erated eutrophication of waters when other factors such as: temperature, sunlight, size and shape of water body, type of stratiflcation, and level of other nutrients are adequate to support aquatic growth. To prevent production of biological nuisances, Mackenthun (1968) suggested that total phosphorus concentration should not exceed 0 , 1 0 m g /1 at any point within a flowing stream and should not exceed 0,05 mg/1 in a lake or reservoir, Rigler (1964) indicated that phosphorus concentration In a water body depends on a dynamic equilibrium between the bacteria and plants and the solution phases. Natural amounts of total phosphorus are conmonly less than 0.05 to 0.10 mg/1 and usually not greater than 0,50 mg/1. exceeds dissolved phosphorus. The particulate phosphorus usually The dissolved organic phosphorus is about 15 to 30 percent, and, the dissolved orthophosphate is about 10 percent of the total phosphorus in natural waters. 136 The availability of phosphorus tn natural ay sterna frcna nan's activities depends upon the conversion of polyphosphates to biologically assimilable phosphorus ferns by hydrolysis. The structures of the polyphosphate ions and their respective hydrolysis to orthophosphate have been studied to determine the rates of decomposition, Karl-Kroupa, ^t. al. (1957) found sterilized aqueous solutions that the condensed phosphates have half-lives of several months at pH 7 and 20C, at.d are eventually hydrolyzed at the s1ov rate to orthophosphate. Factors Karl-Kroupa found that affect hydrolytic degradation were: pH, temperature, enzymes, colloidal gels, concentration of phosphates, and the solution's Ionic state. Shannon and Lee (1966) studied the rates of hydrolysis of pyro­ phosphate and tripolyphosphate Into orthophosphate under laboratory conditions using various natural waters. They showed that the rates of hydrolysis of pyrophosphate was 0.08 mg P/1 per 500 hours at 4C and varied from 0.23 to 0.47 mg P/1 per 500 hours at 20C. Vripoly­ phosphate averaged 0,15 mg P/1 per 500 hours at 4C and varied from 0.34 to 0.50 mg P/1 per 500 hours at 20C. Studies In a natural stream showed the presence of an apparently natural condensed phos­ phate that hydrolyzed at approximately the same rate as tripolyphoaphate did under laboratory conditions. Cleacerl and Lee (1965) found the hydrolysis degradation of all chain and ring phosphates is affected by Increasing hydrogen ion con­ centration, as well as, the amount of certain metal ions, and the presence of specific enzymes. In general, divalent cations (Ca, Mg) were found to have a pronounced effect on the enzymatic hydrolysis of P-O-P linkages. Van Wazer, e_t al,. (1952) studying hydrolysis of 13 7 pyro and trlpolyphcjphatee found that the tre*smce of calcium Ions increased the hydrolysis rates. Biologic systems (bacteria, algae) definitely Influence the rate of degr erdsf lc of the condensed phos­ phates, v*. tti tr ipolyphosphate degrading at a more rapid rate than pyrophosphate. Crowther and Weston (1953) have determined that the hydrolysis of the pyrophosphate anion is a first-order reaction at constant hydr ogen-ion concentration. The iate- constant at pH 6.0 was 1.25 x 10“^, while at pH 9.3V the r ate- c-. nsr ant was 1.00 x 10'^. First- order rate-constants for the hydrolysis of the tripolyphosphate anion depended upon the initial phosphate concentration. The rate-constant at pH 5,0 was 2.9 x 10~^ and at pH 9.3, it was 1.50 x 10“^. Aquatic plants generally utilize inorganic phosphate and show little tendency to assimilate organic phosphorus. Zoop lank ton and higher invertebrates can obtain, phosphorus through digestion of par­ ticulate matter but do n^t appear to assimilate soluble inorganic or organic phosphorus directly from natural water ("Phillips, 1964). The transformations of organic phosphorus to inorganic phosphorus can be carried out by bacteria in the mineralization process. Stums and Morgan (1962) have shown vith laboratory algal studies that phosphorus may be the key element in the fertilization of natural bodies of water. Studies involving the addition of artificial fertilizers to nat­ ural systems, Tanner (1960), McTotire and Bond (1962), and Hooper and Ball (1964 and 1966) The results of these studies indicate a defin­ ite relationship between the aquatic life of a body of water and the amounts of nutrients added. Hepner (1959) studying the dynamics of phosphorus added to fishponds in Tsresl, found a direct relationship 138 between the alkalinity and the amount of sdded phosphate that was removed from the water. These findings were related to both the calcium concentration in the water, a* w e t 1, as that found ir. the bottom mu da. Pomeroy ^t _al. (1965) have suggested that the amount of phosphate involved in adsorptive chemical exchanges between sediments and water is large enough to be significant in regulating biological processes. Fruh (1967) in his discussion on the over­ all pi cture of eutrophication proposed that, depending on the type of sediment fixation prevalent, the recycling of available nutrients within a lake might be sufficient to sustain highly productive conditions over a period of years. In the case of soils and land areas, phosphorus is removed more by erosion than by leaching, because phosphorus is usually fixed and held by the soil in some form of a metal-phosphorus compound. Bailey (1968) established that Inorganic and organic phosphorus compounds are retained largely by the calcium, and aluminum components of soils, iron, The iron and aluminum phosphates predominate in acid soils and the calcium phosphates in alkaline soils, Hortenstine (1966) found that liming can be effective in increasing phosphorus fixation on sandy soils. The release or uptake of phosphates by sediments from land and water sources is dependent on pH, aerobic conditions, temperature and the movement of overlying water. The properties of the sediments that affect this exchange of phosphorus have been considered from various aspects, Sommers et a l c (1970) found that the phosphorus 139 retention capacity of a sediment is largelv determined by Its mineral composition. Calcareous and non-calcareous sediments differ in phosphorus retention, with the retention property related to the aaorphous iron and aluminum components and the calcareous carbonate fraction. Malquori and Radclelli (1967) studied the Influence of calcium compounds on reaction of polyphosphates with soil particles and found that limestone fixed the simple linear phosphates to a greater degree than the complex ones. The sediments of an eutrophic lake may have a high nutrient concentration which becomes available to planktonic algae on lake destratiflcation. Sedimentation and phosphorus-release, at the bottom, influence the soluble phosphorus content of water and control the nature and rate of biological growth when phosphorus is less than the 0.10 rag/1 limiting concentration (Mackenthum, 1964). Mortimer (1941 ar.d 1942) has done the basic study of exchange between mud and waters in lakes which showed a definite relationship between the rate of supply of nutrients and seasonal changes. Holden (1959) studied the location of the phosphate in the deposits at the bottom of lakes and found most of the adsorbed phosphate remained in the upper aerobic rone of the mud and may be converted to non-usable organic forms. These may be released during periods of temporary anaerobic conditions. With high phosphate concentrat ion, the penetra­ tion in mud is up to fifteen centimeters. Sylvester and Anderson (1964) indicated that adsorption of phosphate proceeds during degradation and oxidation. Under reducing conditions, phosphate solutes are released to overlying water. Therefore, it appears that redox conditions are involved in phosphate adsorption on the suspended and settleable par­ ticles . 140 Harter (1968) found that there may be two types of adsorption on sediments. One is a strong, chemically-bonded mechanism while the other is of a more loosely-bonded nature when high amounts of phosphorus were present. Pomeroy e_t _al. (1965) also identified two adsorption reactions which occurred at different rates. He suggested that the more rapid process is an initial surface adsorption. The slower process may be a secondary combination of phosphate into the crystal lattice of clay. The effectiveness of the adsorption process would depend on: 1. The exchange capacity of the sediments; 2. the exchange rate between water and sediments; 3. the rapidity of vertical Suspended solids can provide mixing (flushing) in the water. adsorption sites forphosphate forms and thereby are an important consideration in the movement of phos­ phorus in natural ecosystems. The extent to which sediments will regulate nutrient levels In natural waters is partially dependent on the process controlling nutrie.it-transport to and from the sedtmentwater interface, in particular, water movement and physical settling of particulate material. Chemical diffusion plays a minor role. Lee (1970) found that sediments can serve as a buffer for phos­ phorus, with the net flux of phosphorus from lake water to the sedi­ ments. The determination of the mixing process and a better under­ standing of the hydrodynamics of water bodies will give an indication of the relative flux of phosphorus from the sediments. A thorough understanding of the water circulation patterns in a lake is essential in determining the influence of water-sediment inter­ actions. With sediments acting as a major 'sink' for nutrients enter­ ing the Great Lakes, the success of efforts to reverse eutrophication 141 by controlling nutrient sources will depend In particular on the extent of nutrient re-supply by the aediaients (Harlow, 1966). The Influence of calcium compounds on the phosphate adsorption Is of concern In areas that have limestone and calcareous materials. Studies by Hasler (1957) and Mlsra (1963) Indicate that the application of Lise to water or sediments, reduces the amount of soluble phosphorus released. This release is dependent on both pH and the amount of circulation in the water. Williams _et al. (1969) suggested that the phosphorus retention capacity of a sediment is an important factor In determining the levels of phosphorus which accumulate in lake sediments under natural conditions In summary, McKee _et _al. (1969) have reached the following conclusions concerning sediment-water nutrient relationships: 1. A portion of the nutrients, soluble and insoluble, In a water body are ultimately destined to become part of the sediments. The extent of deposition depends upon the nature of the particle and Its role In the aquatic system. 2. The lnitlsl area of deposition may be only temporary, the nutrient containing sediments or stay be physically transported or the nutrient re-dissolved. 3. Wind-induced currents are a major factor that deter­ mines the rate and area of final deposition and the contact time between suspended sediments and water. 4. Suspension of sediments increases their effect on the overlying water. 5. The sediments act as reservoirs of nutrients for the overlying water. 6 . The rapidness of sediment build-up will affect the degree of Influence on the overlying water. Deeper sediments exhibit very little Influence on the water. The role of the sediments In the phosphate cycle in natural waters is a full study in Itself, so this study will only evaluate 142 the Influence of suspended calcareous solids from a cement-dust discharge and natural sources, The phosphate-sediment adsorption considered In this study will be that of three phosphate forms with the calcareous cement dust as suspended material In water. The Identification of these phosphate forms (orthov pyro, and tripoly) can be accomplished by chromatographic separation. Both paper and column chromatography have been used to separate polyphosphates into identifiable Ira:tions. Ion-exchange chroma­ tography has developed as a methoj fcr recoverable separation of the various phosphate species by the use of proper elution solutions and rates. Grande and Beukenkamp (1956) and Shiralshl and Iba (1964) have used various buffered potassium chloride combinations as eluants for the separation of polyphosphates. Matsuura e_t _al. (1967) have separated the three phosphate forma being considered in thlj project by elution with KCl-buffered solutions, and their procedure was used in this study. Herold (1967) used Dowex-l-X 8 anion resin in the chloride form to determine the phosphate components in detergents. Specific volumes of a KCl-buffeted solution were used to separate the phos­ phates. The eluents were acidified and the phosphorus concentrations determined color imetrlcally,. The method was adequate to separate milligram quantities of detergents. Peters and Pieman (1956) found that the lon-exchange methods require less time and yield more accurate results. The analytical procedures used in this study for measuring interactions of suspended-calcium compounds with these phosphates have been primarily taken from soi1-analysis methods. Wentz and 143 Lee (1969) have described procedures for determining sedimentary phosphorus in lake cores. They used a dilute HCI-H 2 SO 4 extraction procedure for the removal of *available' pn.sphorua from lake sediments The sediment sample size, pH of the sediment-extractant mixture and aasq>le pre-treatment effects the amount of phosphorus removed. They measured the rate of available phosphorus deposition and found it to be constant In the marl sediments. The deposition reached a maximum at about 30 centimeters below the water-sediment interface and Increased proportionately as the sediments change from marl to sludge. The available phosphorus appears to be associated with the carbonate portion of the sediments studied. Livingstone and Boykin (1962) examined bottom-sediment cores by extraction with acid-digest ion. They concluded that the ionic activity of the water would be directly proportional to the lonexchange capacity of the sediments. Biological productivity would be inversely proportionate to the adsorptive capacity of the sediments. Williams jst a l . (1967) found that one-hour extraction with 0.5N acid will completely dissolve samples of pure apatite identified by Chang and Jackson (1937) as 'first HC1-P'. A second extraction with acid was found to remove additional amounts of phosphate from soils high in first HC1-F, The phosphate in both HC1 extracts seemed to originate from apatite. The summation of the first HC1-P and second HC1-P was denoted by the expression, During the total *acid-extractable Ca-P'. fractionation process no appreciable dissolution of apatite occurred prior to the determination of acld-extractable Ca-P. This fraction would not contain any aluminum or iron-bound phosphate. 144 4 practical application of these compilations and adsorption have been applied to phosphorus removal from waste water. The class­ ical objectives of primary and secondary *e*teweter treatment are the removal of oxygen-demanding material and suspended matter. Phosphorus removal by primary sedimentation Is Influenced by particulate matter, as well as, by the presence of metal ions that form insoluble salts with ortho and polyphosphates. The addition of sufficient amounts of lime serves the dual purpose ot providing calcium lens, as well as, Increasing the pH to facilitate precipitation,. The final concentra­ tions of soluble orthophosphate in secondary sewage effluent has been postulated by Jenkins and Menar (1968) as a combination of: 1, Biological incorporation into activated sludge cells; 2. collodlal precipitation with calcium similar to CaHPO^ (Ksp ■ 2,2 x 10-71 followed by adsorption on the sludge floe. Most of the research on phosphate precipitation has been concerned with the fundamental mechanisms of cat ion-phosphate reactions and with the evaluation of the effects of pH and cation concentration on the extent of phosphate removal. Buzzell and Sawyer (1967) suggested a pH-controlled-lime addition cculd reduce phosphate in sewage by 80 to 90 per cent, Berg ^t _al. ^1970) resioved phosphorus and suspended solids from secondary effluent of conventional water-treatment system by clarification with lime. pH of 9.5. Sufficient lime was added to maintain a Dickerson and Farrell (1969) found lime (CaO) most effec­ tive in reducing phosphate in waste water of a Michigan flour industry. In a pilot plant operation, 1340 mg/1 lime as CaO were required to re­ duce the phosphate level in a primary effluent from 295 mg/1 to 5.6 mg/1 at a pH of 9,5. The suspended solids level was reduced from 3740 mg/1 to a mean of 193 m g / 1 , 145 Rebhum and Manka (1971' foc^d that the effect and behavior of organic matter from secondary sewage effluents which has undergone chemical treatment to be similar to that cf humlc compounds In natu­ ral waters and soil. Forty to fifty per cent of the organic composi­ tion of these effluents was reported to be humlc substances (humlc, fulvlc and hymatcraelanlc acids'. The use of calcium for phosphorus removal from natural water and sewage would be influenced by this organic material, Harter (19691 has fctnd that organic matter may be important In the Initial bonding of phosphorus by soils. Phosphorus is Initially bonded to anion exchange sites of organic as well as inorganic matter and subsequently transformed Into less soluble metal phosphates. Anderson (1967) suggested that feme mineral soils normally contain in the range of 1 0 0 0 ppm total phosphorus of which approximately thirty to seventy per cent la associated with organic material. Scharpenseel (196 7) used humlc and fulvlc acids together with Ca(0 H )2 to show that particles from clay soils can form a metal-acid complex. The calcium can act as a bridge Ion between organic acids and clay material. Pherefore. the tctal picture of phosphate fixation must Include these organic materials. Many surface waters have a characteristic, yellow-brown color which Is caused by the presence of complex organic compounds of natu­ ral origin. The organic compounds producing color in water, fall within a broad category collectively termed humlc substances. The general origin of colored organic sK>lecules Is from soil run-off and the decomposition of vegetable material. The formation of humlc acid is a result of polymerization of polyphenollc units 146 derived either from bacterial synthesis or the break-down of llgnln reaiduea formed during the plant decomposition. Origin of organic matter may be al locbthoncma from decomposing terrestial vegetation and soil-humus material. The second source is autochthonous organic* which are released from aquatic vegetation decomposition and extraction from bottom sediments of lakes. The concentration of organic acids In lakes has been found higher nearer the bottom*, and below any thermocllne that may be present (Buck, 1968). Steelink (1953) found that the structure of numlc acid has a molecular weight range of 20.000 to 50,000„ The macromolecule con­ tains an easily hydrolyzable protein and carbohydrate fraction at­ tached to a highly condensed 'core'. This core Is partly aromatic, with structural elements derived from llgnln phenols and resorclnol phenols. In addition, alcohol, carboxyl, and carbonyl groups are present together with heterocyclic nitrogen structures. In the molecular structure of the chemical components which con­ tribute to natural color, the structural units are probably linked through C-C alkyl-aryl and aryl-aryl bonds and through ether bridges. Packhsm (1969) shoved that humlc substances in water are In true solu­ tion, but a proportion of the molecules are large enough to exhibit colloidal properties In the natural water. Midwood and Felbest (1968) found that the structural units In humlc acids and fulvlc acid* are similar, although fulvlc acid Is of lower molecular weight and has more reactive groups than humlc acid. Black {1963) identified fulvlc acid as the most water-soluble fraction of natural soil humus. This acid would be expected to be found In colored, natural waters in higher concentrations than either humlc or 147 hymatomelanic acids. Lew BOD results Indicated that these organic substances normally considered responsible for color in water are apparently In their final state of mlcrobioiogic decomposition. The humlc substances present in water would be expected to be confined to humlc, hymatomelanic, and fulvlc acids, with properties: Humlc acid - Soluble In sodium hydroxide, Insoluble in mineral acid and alcohol. Hymatomelanic acid Fulvic acid - - Soluble In sodium hydroxide and alcohol, insoluble in mineral acid. Soluble in sodium hydroxide, mineral acid, and alcohol. In these natural organic aclda, Wagner and Stevenson (1965) found one-third of the total -COOH groups were close enough to form cyclic anhydrides, and two-thirds of the total -OH groups were phenolic; a definite ionic environment suitable for complexation of metal ions. Analysis by Black and Christman (1963) characterised fulvlc acids as polymeric-hydroxy-methoxy-carboxyl1c-aronatlc acids with the nega­ tive charges of the color particles because of the ionization of the carboxyl and aromatic hydroxyl groups. The groups characterized as fulvic acids have equivalent weights of 89 to 133 together with strong indications of unsaturation and aromaclty. The fulvic acids, as water-soluble, relatively low molecular weight humlc substances, can form stable complexes with metal ions and hydrous oxides (Ogner and Schnitzer, 1970). Fulvic acid was found to be a chemically and biologically stable polyelectrolyte with a number-average molecular weight of 951 and 9„1 milliequivalence for - 000H with 6.9 milllequlvalence of total phenolic -OH. Therefore, fulvic acid, in an aquatic environment, may act as a vehicle for the mobilization, transport, and complexatton of natural organic and in­ organic compounds. 148 Shapiro (1958) has done work on the complexatlon of iron by yellow organic acids In lake water and found that the humlns of organic matter in lakes cause color and stimulate the growth of certain limnetic algae. Prakash and Rashid (1968) indicated that the yellow soluble organic material In natural waters is of interest because of its influence on photosynthesis by the reduction of available light and its share in the biochemical oxygen demand. Its capacity for binding cations and phosphate has a specific Influence on growth of aquatic vegetation. Buck (1968) found that the addition of yellow organic acids to natural waters in Northern M ic hig an ponds, produced changes in pH, conductivity, alkalinity, and color intensity of water. The first three m a y be explained by a hypothetical union between these acids and calcium carbonate. The change in color absorbance m ay be a result of the change in pH. Wilson (1959) found the absorbance of light by the organic color increased when the wave length of light passed through the sample, decreased from 350 to 250 mu. This response has been used for measurement of the level of colored organic matter in natural waters. Packham (1969) found an optical density (absorbance) response for the colored water at 350 and 450 mu. Christman and Ghasseml (1966) noted a fluorescence excitation in natural colored water at 361 mu. Semenov et _al. (1963) have measured the humic acid content of surface waters in milligrams of carbon per liter, by the difference in fluorescence absorbance at 340 and 440 mu respectively. H9 The two coaaon a d v e n t s that have been used for the elution and concentration of these colored organlcs chloroform and ethyl alcohol. Ryckman (1961) froe natural water are With these solvents, Sproul and found that the organic compounds extracted Into the chloroform fraction were more odorous than those extracted into the polar, alcohol fraction. Daniels jet a_l. (1963) sampled organic compounds In waters of Lake Huron by adsorption on activated carbon and extraction with chloroform and ethanol. The choice of solvents, and the order of use, was based primarily upon the polarity of the adsorbed materials. The eluates were evaporated and the chloroform extracts were assumed to represent less polar compounds from industrial sources. The alcohol extracts were associated with the sore polar varieties of natural origin. Comparison of the organic material extracted by chloroform and alcohol eluates appeared to be useful In Judging water quality. From these data of Daniels £t _al. (1963), the waters of northern Lake Huron were found relatively free from pollution. their data Indicated that the ratio of extracts Moreover, fluctuated seasonally, since the alcohol to chloroform ratio was 3.77 for the s u m e r 3.70 In winter. and The periodicity of the fluctuations In the ratio was related to those of lake level, temperature and sampling location. The actual composition of this organic matter has been studied by various procedures and in different natural locations. and Lee (1967) Gjesslng fractionated moderately-colored creek water using Sephadex columns by gel-permeatlon procedures. Various streams showed different organic carbon elution patterns, Moed (1971) used the adsorption of soluble organic yellow material on aluminum oxide 150 to separate organlcs by the elution of yellow material with buffer* of varying molar strengths. of yellow material without The procedure allows the concentration exposure to the action of organic solvents and acids. In the demineralization of water by ion-exchange, Packham (1969) found that humlc substances can create considerable difficulties by fouling the anion-exchange reain. The strongly-baalc anion exchangers have a high-chemical affinity for organic acids together with an open structure In the reain bed (Wilson, 1959). The organic matter was removed when the resin was regenerated with sodium chloride. Christman and Ghasaeml (1966) Identified the sources of natural organic color as the aqueous extraction of living woody substances, as well as, vegetation. the dissolution of degradation products In decaying They Isolated the organic matter by lon-exchange separation and elution of the colored material from the anion resin with 2M NaCl and extraction with normal-butanol. Buck (1968) has adapted an anion-exchange procedure for the separation of yellow organic acids from Michigan ponds by elution from the resin with sodium hydroxide. resins, In the use of these macroporous the ion-exchange procedure may not be quantitative. It does permit relatively large quantities of the various natural organicacid fractions to be Isolated readily even from waters of low color. Packham (1969) found that more complete recovery could be obtained using 2M sodium chloride with IM sodium hydroxide solution as regenerant, at a slow rate of diffusion within the resin. The acid filtrate from the humlc acid separation contained a high concentrat Ion of salts and a fulvic acid fraction. The aqueous 151 solutions were extracted with alcohol or acetone and the extract filtered and evaporated to dryness. The solid residue of fulvlc acid recovered can be stored or dissolved In alcohol. The involvement of these anionic-acidic organic structures with metals in natural waters results In the formation of soluble metalio-organic complexes (Khanna and Stevenson, 1962). They suggested that the retention of mlcronutrlents added to soli as fertilizers may be due, In part, to the formation of stable complexes with the polycarboxylic and hydroxy sites of the organic matter. Phosphate binding to the natural organic acid material has been found by Gupta (1967) not to be a simple adsorption phenomenon but one related to the amount of humlc acid present and the type of soil (calcareous or non-calcareous). Khanna and Bajwa (1967) used potentiometrie titration of humlc acid from two soils to measure the formation of stable metalorganic complexes. The humlc acid was found to have two definite carboxylic groups per-molecular-weight in the calcium complex. Weir and Soper (1963) studying the reactions of phosphates and iron with the active groups of lon-exchange resins found that only small amounts of phosphate held by the complex were releasable. Chemical analysis showed that the complexes can exist as P0^‘ ^ bonded through the metal of the acid group on the cationic resin. There may be two types of binding between the humlc acids and the anion resins. The normal electrovalent bonding between the humic acid carboxylate groups and the functional groups of the lonexchange resins would be present. A second type of bonding appears to be dependent on the pH of the solution: the bonding is much weaker 152 In alkaline solution than In acid solution, possibly due to wan derWaal forces or dipole Interactions of the very large, essentially aromatic molecules. The involvement of calcium In these complexes was studied in clay soils by D'yakonova (1964) who found that with humlc acids extracted from clay-humus complexes, an Indirect relationship existed between the calcium content and the organic natter. In selected, molecular metal-to-fulvlc ratios prepared by Levesque and Schnltzer (1967), it was found that in the absence of metal, no reaction can take place between added phosphates and fulvic acid, Visser (1962) studied the Interaction of the different Ionic states of orthophosphate with calcium and organic matter (proteins, polysaccharides, and organic acids). He found that between pH values of 5 and 12, calcium caseinate and tricalclum phosphate will occur together as a soluble chemical complex. The formation of this complex was thought possiole between colloids which have free carboxyl groups present within the organic structure and the calcium phosphate. Shapiro (1964) found that the yellow organic acids were capable of chelating iron and keeping it In solution up to a pH of 9,5. He determined that the color was suspended in a colloidal form in direct proportion to the iron concentration. The coagulation and reactions of colored material involved colloids with an average diameter between 3.5 and 10 mu. The formation of soluble calcium-phosphate-organic acid complexes would influence the transport and deposit of these components in soils ard natural waters -- the major area of study in this project. 153 The conrplexir.g ability of the linear polyphosphates would be due to the formation of chelate rings. On consideration of the stn-iLure of chains of Interlinked phosphate tetrahedra, It appeared ;n*t a chelate ring might be completed between any two sd]«:ent FO 4 tetrahedra (Van Wazer and Campanella? 1950). The cjmplexiwg ability of a linear phosphate would be proportional to the total number of phosphorus atoms in the polyphosphate structure; 0 (I P - 0 - P - 0 0 M The total number of positions along the chain where a metal Ion can form a complex, could be one less than the number of phosphorus atoms In the chain. Since the weakly-acid hydrogen 1 b associated with the terminal PO 4 groups of polyphosphate molecules, the only type of complex formation that can effect the strength of the weakacid function must involve these terminal groups. Watters and Lam­ bert (1959) measured the stabilities of calcium complexes formed with pyrophosphate and tripolyphosphate Ions by means of the neutraliza­ tion reactions involving titration of the salts with hydrogen Ion, Irani and Callls (1960^ studied the effect of pH, temperature„ 1 c n i ' strengtti, and length of phosphate chain on the calcium complexes, Tre tetramethyl a m o n l u m polyphosphates were prepared by lon-exchange reaction of the tod turn salts with the hydrogen form of Dowex 50W-X2, followed by neutral 1 zatIon of the resulting acids with tetramethyl ammonium hydroxide at 2.5C and pH of 12. Under varying conditions, they found a direct relationship between the length of the phosphate .heln and the stability of calcium complexes. '1 ;i 155 In aqueous solutions, numerous studies have been conducted Inves­ tigating the Interactions between calcium and phosphorus under natural water conditions. Schnofield (1964) Indicated that the normal precipi­ tation ot calcium from water as CaCO^ at a pH of 12 was Inhibited by the presence of as little as 1.0 to 1.5 ppm ortho or pyrophosphate. Baiba (1966) measuring the concentration of the three forms of ortho­ phosphate Ions by titration of phosphoric acid with calcium hydroxide found that HjPO^" was the Ion in greatest abundance In a pH range of 2.4 to 12.0 and would form CaH 2 PC>4 + with calcium. An evaluation of natural Interactions can be based on the pH measurement of the change In the weak-acid function (Odagiri and Nickerson, 1964) of the phosphate forms In the presence of calcium and natural organic acids. In order to measure possible complexa- tion between calcium and anionic organic colloids, Vlsser (1962) used different forms of orthophosphate. These forms were determined by titrating phosphoric acid with alkali In the presence of calcium and observing complexes resulting with selected organic substances Machen plexes (1967) studied m a g n e s i u m and c a l c i u m te traphosphate c o m ­ as a function of p H lowering. lity of the tetraphosphate ton first Part of the Increase In st ab i­ ion complexes m a y be attributed forming a single bond with any to a metal terminal oxyg en before rear ­ ranging into a chelating p o s i t i o n to form a ring with phosphorus, oxygen, and metal ions. The calcium select-ion electrode was used to measure the activity of the free calcium ion. This activity can be applied to the ligands forming a soluble compound. Cation-sensitive glass electrodes offer the possibility of specificity and make possible activity measurement 156 in the presence of other cations and anions (Elsensan, 1967), This neans that Ion-assoclatIon studies can be carried out conventiently In mult 1-component systems. In the past few years, the development of a calcium select-lon electrode has resulted In the measurement of calcium Ion rapidly and reproducible In the pH range of 3,5 to 10.0 (Schultz, jit. _al., 1968). For example, Rechnitz and Hseu (1969) have demonstrated that a solId-membrance calcium select-lon electrode gives a satisfactory response with respect to changes In calcium ion concentration. They found the electrode was suitable for indicating the course of potentlometric titration Involving the Ca**""^ ion. Through direct selective measurement of the free calcium activity at equilibrium, the stability constants of calcium complexes with polycarboxyllc acids were determined. The select-ion calcium electrodes measure the single ion activity of the calcium ion in solution, rather than the concent rat ion of the ion. Since, activity of the calcium Ion in solution is the measure of the reactivity of the Ion, the extent and rate to which the calcium ion takes part in a chemical reaction can be established. In dilute solution, the activity of the calcium ion approaches calcium ion con­ centration. Therefore, in these cases, the activity is proportional to the concentration, and the electrode can be calibrated with respect to concentration. Ihe activity of the C a * * ion is measured by the potential devel­ oped across the liquid-liquid Junction of the electrode's exchanger fluid and test solution. The integrity of the Junction is maintained by a ceramic plug through which the exchanger in the electrode fluid flows. The silver-silver chloride internal electrode element provides 157 a stable potential between all Inner electrode Interface*, assuring that variations In potential are related only to changes In ionic activities of the test solution. The water- l^is c l b l e organic phase In the electrode forms a liquid lon-exchange 'membrane' whose lonexchange properties for cations are similar to amchanlsma to liquid Ion-exchanger concentration cells. The electrode is Insensitive to chemicalty-bound or unionized calcium. The transport number of calcium Ions across the organic phase has been found to be unity (Corning, 1968). Under these conditions, the equilibrium potential across the membrane is described by the following form of the Nernst Equation: E - E° + 2.303 RT Log (aca++> 2F The activity (a) of an ion can be related to its concentration (c) by the activity coefficient (^Y Ca"*"*"). The Nernst equation at 25C for Ca"*""*" can be rewritten using the activity coefficients and con­ centrations of Ca++ instead of activity as: E - E° + 29.6 Log . Throughout the remainder of the basin, area wells In bedrock six Inches or more in diameter will yield over 100 G P M . The zones are shown in Figure 31 and described in Table 36. PRESENT FOREST RESOURCES In the Thunder Bay Watershed, over half of the forest acreage Is now of the upland forest types Including: white and Norway pine, Jack pine, maples, white birch, aspen, oaks and hemlock. About 25 percent of the land is cleared farmed land, pastured land, and land that is idle. Approximately 20 percent of the forest cover Is of lowlandforest type including: elm, and tamarack. ash, maples, cedar, spruce, balsam fir, The remainder of the forest resources are of marsh and bog types, such as alder, willow, and sedges, and open wildland types which include, fire (pin) cherry, sumac and ferna. The forest types along the major tributaries are given in Table 37. The descriptions of the major cover types Is given in Table 38 (Michigan Department Conservation, 1924). 183 F1GURK 31 . WATER THUNDER AVAILABILITY OF BAY WATERSHED 184 Table Water 36 Availability Zo ne 1 W e l l s 6 I nc h e s o r m o r e In d i a m e t e r w i l l t h a n 10 g a l l o n s p e r m i n u t e (GPM), yield l es s Zone 2 W e l l s 6 I nc h e s o r m o r e 10 to 1 00 GPM. In d i a m e t e r w i l l yield fr om Zone 3 W e l l s 8 Inches or m o r e 1 0 0 to 5 0 0 G P M. in d i a m e t e r yield from Zone 4 Note: W e l l s 10 i nc h e s o r m o r e m o r e t h a n 50 0 G P M. will in d i a m e t e r w i l l y i e l d I n ibII a r e a s w h e r e s a n d and g r a v e l d e p o s i t s o c c u r a l o n g s t r e a m s , t h e o u t p u t in g a l l o n s p e r m i n u t e w ill be increased considerably. 185 Table 37 _ F,ireat Types along Principal Thunder Bay Stream* Lover South Branch Lowland foreat typea - Maple and apruce Stands of hardwoods - Jack Pine and white birch Poplar (aspen) and some elms Wolf Creek White cedar, spruce, poplar, and white birch Upper South Branch Lowland forest types - Maple, cedar, and spruce North Branch Thunder Bay Poplar, white birch, maple, cedar, and balsam fir Bean Creek Poplar, white birch, maple, spruce, and cedar Main Branch Thunder Bay River Poplar and white birch; elm and maple, Jack Pine, balsam fir, oak, and pine. Cedar and willow Percentages In Alpena County (Michigan Conservation Department, Forest Types Aspen and Birch Jack Pine Cedar and Spruce Maple, Hemlock, Ash Norway and White Pine Northern Oak Balsam Fir Willow Wildland Per Cent 42.3 1.2 10,2 13.9 1.0 8.4 0.1 1.2 0.5 1924) 186 Table 38 Foreat Cover Type* of Thunder Bay Watershed Aapen(Popl a r ) , Populua trawuloldea or Populua grandldentata The atanda occur In n a i l , even-aged clmmpa. Depending on alta, the Aapen reachea M a t u r i t y In AO-50 yeara. Much of It dlea after that and other apeclea take Ita place ao that It la aaaoclated vlth a large niaaber of other apeclea, Located along the North B r a n c h , Bean Creek and the Main Branch, White Birch, Betula papyrifera Speclea la aaaoclated with Jack Pine and Aapen. The tree aaturea In 60 to 75 yeara. W h e n It haa reached Maturity, It will be replaced by other apeclea. Located along Lower South Branch, Wolf Creek, North Branch, Bean Creek, and Main Branch, Jack Pine, Plnua bankalana Standa occur in amall, aged clumpa. Maturity la in 60 to 70 yeara. It la alao aaaoclated with a large ntmdier of other apeclea In drier areaa. Located along Lower South Branch, and Main Branch. Northern White Cedar, Thuja occldentalla Speclea la found on wet altea in pure atend, or generally acattered under Jack Pine and Aapen. The treea mature In 100 to 110 yeara. Located along W o l f Creek, North Branch, Bean Creek, and Main Branch,, White Spruce, Plcea glaoca Speclea la found aaaoclated with fir and cedar on wet altea. It maturea In 60 to 70 yeara. Located along B e a n Creek, Hunt Creek, and Main Branch. Red Maple, Acer rubrum Speclea la generally found on wet altea aa medium-age tree, maturing In 100 to 110 yeara. Located along Upper South Branch, Bean Creek, Gllchriat Creek, and Main Branch. White Pine, Plnua atrobua Nearly all haa been lumbered and found mi x e d with other apeclea. Maturity la reached In 170 to 180 yeara. Some located along Main Branch. Balaam Fir, Ablaa balaamaa Speclea la found on wet altea In limited quantltlea and maturea In 40 to 50 yeara. Located on North Branch and Main Branch. Northern Oak, Queroua elllpaoldalla Thla apeclea la found In drier altea aaaoclated with man y other treea. Located on Main Branch. 186a Table 38 (Cont'd.) Alder, Ainua Incana Brush speclea Willow, Sallx >p„ Speclea found as brush or small trees on wet sites scattered among other species. Alder and W i l l o w with Sedges along most stream banks. Open Wildland Types - Flrecherry, Suaiac, and Ferns 187 CLIMATIC CONDITIONS The a i d - c o n t i n e n t , aid-latitude position occupied by the Great Lakes area reeults In varying extreme? in weather conditions. The climate along the immediate Lake Huron shore la seal-aarltlae and lacks most of the temperature-variations shown In sumy cases only a few allee inland (U. S. Department of Cbaaerce, 1967). Teaperature The early winter temperatures are higher than are c o w o n to this latitude but, as the Great Lakes freeze, the temperature coassonly approaches zero Fahrenheit. Thunder Bay and the Thunder Bay River are usually free of ice by the first week in April. average date of the last killing frost la May 12, season Is 100 days. The The growing The average date of the first killing frost In autumn Is October 4. The m a n annual temperature la 43, 6 F with a high of +106F and a low of -36F over the past ten years (Table 39) (U. S, Department of Cosswrce, 1971). Precipitation Precipitation Is well-distributed throughout the year. The most probable annual mean-precipitation In northern Michigan Is 30.60 Inches (Water Resources C o m i s s i o n , 1968). For the Alpena area, the annual mean-precipitation Is 28.80 Inches, with 16.8 Inches from May to October (Velz and Gannon, 1960). The spring thaw and run-off seldom offer any flood danger because o f the operation of hydroelectric dams. The annual snow-fall averages 50 to 90 Inches, The mean temperature, total precipitation, and wind direction for Thunder Bay, tog* her with high and low yearly temperatures for duration of this study, are given In Table 40. The monthly range-and-amen 1R8 Table 39 Cllaatologlcal Date for Thunder Bay A r e * fu. S. Department of C o M i r c i , 1971) Meaaureaant Airport El«vatlon(ft) 690 1966 Hean Teap(F) Tot Prec(ln) Teap HI-Low 42.5 27.32 98,-15 Sewage Plant 585 43.7 26.51 95,-11 Atlanta 940 Rogera City 1015 43.9 22.46 101t-18 43.4 31.21 96,-6 1967 Mean Teap(F) Tot Free(In) Teap HI-Low 41.2 35.17 88,-20 42.5 31.69 88,-9 42.7 33.17 89,-24 41.6 29.85 85,-13 1968 M e a n Taap(F) Tot Prec(ln) Te^p HI-Low 43.1 34.05 95,-21 43.9 32.43 92,-11 32.58 93,-29 30.40 93,-10 1969 Mean Teap(F) Tot Prac(in) Trap Hi-Low 42.2 31.42 94,-10 43.5 30.22 94,-7 28.77 94,- 43.3 31.31 91,-8 1970 Mean Teap(F) Tot Prec(ln) Teap Hi-Low Mean Mean Teap(F) Tot Prec(ln) Teap Hi-Low 42.6 27.12 92,-23 42.3 31.01 93,-18 43.8 25.66 92,-12 43.5 29.30 92,-10 26,73 91,- 23 32.10 89,-18 43.3 29.34 94,-24 42.8 30.96 91,-11 189 Table 40 Prevailing Weather Conditions of TTiunder Bay 1960-1970 (U. S, Department of Coomerce, Month 1971) Temperature Mean Preclpi tatlon Wind Direction Min Mean Max Jan 12.9 19.9 26.8 1.83 in Feb 10.8 18.8 26.8 1.56 NW Mar 18.6 26 .5 34.3 1.92 NW Apr 31.4 39.4 47.4 2.28 W May 41.6 50.6 59.6 2.92 SE Jun 51.6 60.9 70.1 3.03 SE Jul 57.1 66.5 75 .9 2.63 NW Aug 55.8 64.9 73.9 2.87 SW Sep 49.3 58.0 t)6 .6 3.11 NW Oct 39.6 47.4 55.2 2. 70 NW Nov 29.4 35.4 41.3 2.41 W Dec 19.4 25.2 30.9 1.90 N-W 34.8 42.8 50 7°F 29.16 In Snow - 79 r4 I n . N-W W -NW (8 i 190 for precipitation recorded at. the Alpena NCAA veather station is shown In Figure 32. The monthly total discharge range-and-mean of the Thunder Bay River 1* shown in Figure 33. Wind The winds on the Great Lakes are generally from western quadrants. Across northern Michigan, west-northwest winds are prevalent. On Lake Huron, prevailing winds are frost the northwest with the exception of May and June, when southeasterly winds pre­ dominate. During July and August., w h e n lake surface temperatures are near their maxlansn, southeasterly winds occur during the warmest hours of the day. Over Thunder Bay, the winds may, and often do, blow from several directions because of the frequent passage of cyclones and a n t 1 - cyclo n e s . northwest The wind direction is predominantly from southwest- for eight months of the year. For approximately 250 days of the year, the wind is blowing off-ahore over Thunder Bay (U, S. Department of Comeerce, 1971). Generally, easterly winds off the bay occur during spring and late summer when temperature conditions are favorable. CURRENT PATTERNS IN BAY The surface circulations which exists In Lake Huron, appear to be the result of an equilibrium between the flow-through of Lake Michigan and Lake Superior waters and the wind-driven transport of surface water. The fundamental surface circulation pattern in the upper and central portions of the Lake appeared to reflect the direction and velocity of the winds of the preceding twelve years (Ayers, et al,, 1956), Jan Figure Feb 32 Mar Apr Monthly Tun -Tul Precipitation May 161 Total Precipitation (Inches) oo Sep Alpena, Aug for O-t Nov Michigan Dec (1960-19701 192 5 4 3 Total Dlacharge (million cubic feet) 8 2 1 Jan Feb Figure 33, Mar Apr May Jun Jul Atig Sep Oct Nov Dec Monthly Total Discharge of the Thunder Bay River at the Ninth Street Dam (1960-1970) 193 Lake Huron has certain pseudo-oceanic charaete r l a t i c e , Include: These (1 ) the tendency of the strongest currents to swing to their own right (Corloll's Force); (2) the apparent tendency of wind-direction surface water to sove to the right of the wind direction; and (3) the distribution of upvelling and sinking of water on both upwind and downwind shores according to the relation­ ship of current streamlines and the shore. Current velocities In Lake Huron range frow 0.1 m.p.h. nearly 0.5 si.p.h. to The fundamental surface circulation patterns In the upper and central portions of the Lake is counterclockwise. A counterclockwise current with a ■ ” <■■■ velocity o f 0.47 m.p.h. is located off Alpe n a (Figure 34). There is a smaller northern current contributing to a clockwise eddy centered off Thunder Bay. This current is apparently a simple equilibrium adjustment of the field of density, with its rotation produced by friction of the adjacent rapid current. The equilibrium eddy off Thunder B a y Indicates that it acquired wind-driven, warm, surface water from close inshore, through both north and west quadrants of Its center. The currents within the bay have been shown by drift bottle data to be counter­ clockwise because of this flow (Ayers, er _al. 1956). The portion of water apparently moving northward along the Oscoda-Alpena shore appeared to be circulating around an elongated eddy and turns back south on the offshore side of the eddy. 0.26 m.p.h. The thermocllne was 5 to 6 This flow averaged about C at 23 feet off Alpena. A tongue of surface water with temperature greater than 20C extended southeasterly from Thunder Bay, F I G U R E 34. SU R FA CE WATER CURRENTS IN LAKE HURON SURFACE CURRENTS tfmome i MMGW KM a*HDIT 0»(CTOI •%-u«c o o to so* o »*C wt vEuxirr - \ w «LD C ^T» t O IIK C T O * ESTIMATED GRAPH FOR CURRENT v El OCITY BAY CITY PORT HURON 84' 43* 195 THE WATERSHED CULTURAL DISCHARGES In Alpena County, ground water pollution in limestone areaa 1* caused by septic tanks and tile fields. Inadequate land drainage la present In the County and In Presque Isle County. Ground water and watershed management can be used to alleviate these problems. Wood-Flber Industry Effluents Abltlbl Corporation has an average discharge of 2.4 m.g.d. This contains organic solids (BOD - 32,000-35,000 lbs/day), suspended solids (5000 lbs/day) and elevated temperature (125F ) . The Fletcher Paper Company discharges cooling water (75F) and process water. additives (Ti0 2 The process water contains fiber fines and » dyes, binders, etc.). Huron Portland Cement Corporation The local cement plant haa a maximum production capacity of 18 mill i o n barrels or 3.4 million tons of cement per year. This amount is produced by three new computer-operated kilns and 16 older kilns. Ten other older kilns are on stand-by. The collection ability of the kilns is 90% efficient using precipitators and dust bags. Over 1000 tons of dust are collected dally in computerized kilns. The same amount Is retained in the older kilns that axe operating. The emission of dust amounts to an over-all discharge of at least 100 tons per day. This has been aonltored by the company and the air pollution division of Michigan Department of Public Health (Dowd, 1971). The composition of the cement dust used in this study contained the ranges given in Table 41 (Galer, 1970), The distribution of the material over Thunder Bay la dependent upon the direction of local 196 Table 41 The Mean C o ^ o a l t l o n of E a l t U d Cement Duet M a t erial (Galar, 1970) Subetance Height Percentage Rang) CaO 40-44 A 1 2°3 f *2°3 3.5-6.0 1.5-3.0 K jO 3.5-6.0 MgO 1-2 Na20 0 . 2- 0,3 20 Sillcatea 12 ) (S10 2 Sulfatea 18 (S0 3 2.5-3.0) Phoaphatea 0 .5-0.6 197 prevailing winds during the year (Table 42, U. S. NOAA Weather Bureau, 19 71). I’nce in the water, the phyaical transfer of material Is dependent on tne hydrodynamics of the aqueous ayateia. Mixing of sediments In the water arises primarily from wind-induced currents and flow of water from the Influent streams and domestic discharges. The cement plant generates its own power so that there is a cooling-water discharge into the p l a n t ’s shipping channel. into the bay occurs from an abandoned quarry where dust A run-off from the collectors is disposed of. Alpena Sew erage System The sewage system handles an average of 2.5 million gallons per day serving a population of 15,000 in 3600 residential homes with a total 4500 dwelling units. of There is a combined system of sanitary and storm sewers with six lift stations. 72 miles of sewer line* with 60 miles combined. There are Since 1961, all new construction (16 . 7X) of sanitary and storm sewer lines has been separ at e d . There ate four interceptors located near the river; two on the north aide and two on the south side. diverted to the river after the plant haa o<.juried. High storm flows are an initial flush of the sewage flow to The induatrial plants supply only sanitary sewage and some cooling waters to the sewage system. The plant was completed in 1958 and has a nominal capacity ot t M e e m illion gallons per day and a ma x i m u m of six million gallora per day to serve 18,000 persons in the city and township. Currently, a sewage plant expansion is under construction to expand service and capacity and to Introduce secondary treatment together with chemical phosphate removal. 198 Table 42 Prtvillltig M ean Wind ConditIona of Thunder (0, S. H O A A Weather B u r e a u , 1971) Month 1960-1970 Wi n d Direction 1969-1970 Wind Direction _®*Z 1970-1971 Wind Direction Teaperature Mean a F Jan IfW W NW 19.9 Feb NW NW W 18.8 Mar NW NW W-NW 26.5 Apr NW W-SE S-SE 39.4 May SE E W-NW 50.6 Jun SE S-W S-SE 60.9 Jul NW S-W E-SE 66.5 Aug NW S-SE S-S W 64.9 Sep NW SE N-NW 58.0 Oct NW W S-SW 47.4 Nov NW W Dec NW SW Mean W-NW( 8 bo .) S-SE(4 W W-NW b o .) S W - N W < 6 Mo.) M ean Precipitation (1960-1970) - 29.16 inchee Snov - 79,4 lnchea 35.4 25.2 42.8 199 The watte*viter treatment plant how operates as a primary treatment facility with grinders and a grit chamber, sedimentation in holding tanks and bacterial digestion of the raw sewage sludge. The digester sludge is pumped onto outdoor beds several times during the year, allowed to dry, and used for soil rehabilitation. The resulting effluent Is disinfected with chlorine and discharged into the river near the bay mouth. The Influent has been estimated to contain a m e a n total phosphate of 26 p p m (520 lbs/day) and the effluent has a mean of 16 ppm as total phosphate (365 lbs/day). The Influent BOD has a m e a n of 1100 lbe/day while the effluent has a BOD aetn of 600 lbs/day (LaMarre, 1971). THUNDER BAY W A T E R QUALITY AND RESOURCES Much of the Inorganic materials and some organic matter in natural water arise from the chemical alteration of minerals; e.g. calcium and magnesium are derived from reactions involving, carbon­ ates, feldspars and some clays. and sulfate Phosphates are derived from pyrite and gypsusi. from apatites Carbon dioxide in water, dissoci­ ates to bicarbonate and carbonate depending on pH and important variables determining the alkalinity of the water. The quality of the water in the main body of Lake Huron excellent, as Is that of its two principal sources of Superior and Northern Lake Michigan. Is one of the Is water, Lake Since Lake Huron derives its water initially from these lakes, it is assumed much of its chemical character should be determined by the rates of mixing of Michigan and Superior waters. 73,300 c.f.s. Lake Superior has an average discharge of through St. Mary's River, while Lake Michigan has an average discharge through the Straits of Mackinaw of 55,000 c.f.s. 200 Lake Huron waters are low In turbidity end moderate In hard­ ness. For the most part, ICO percent saturation. the dissolved oxygen content la nearly In northern Michigan, effective change It land use. there has been no These lands nave remained for the most part forested, with second growth having replaced most of the original timber. The soils of the region have low water-holding capacity and maximum filtration rates. The streams draining this area are stable throughout the year, mostly very clear, and are low In concentrations of chemical constituents. This continues to provide a source of high quality waters to Northern Lake Huron. Calcium, magnesium, and alkalinity account for 75 to 80 percent of the Ions in Lake Huron waters. This is due directly to the approach to equilibrium of carbon dioxide from the air and CaCO^ In the sediments (Kramer, 1964), Lake Huron water tends towards partial equilibrium along its length and attains a true equilibrium after passing into the Lake St. Clair system. The Lake appears to be unsaturated with respect to sodium and silica. There is excess phosphorus in the lake compared to that which Is needed to saturate apatite. Excess phosphorus Increases with biological use of the lake with the difference of actual phosphate and 'hydroxy-spat 1 te phosphate' being an empirical index of biological activity. Hydroxy apa t i t e , although relatively quite insoluble in aqueous medium, exists in chemical equilibrium with orthophosphate ions. If other chemical and physical environmental requirements of algae are satisfied, the utilisation of orthophosphate ions by a growing 201. Algal culture can bring about the continual release of soluble phosphate from hydroxyapatlte as chemical equilibrium la maintained. Chemically 'insoluble' phosphate materials can be sources of biologically available phosphate ions. As an increasing algal population utilizes the soluble phosphate, chemical equilibrium is maintained by the release from the parent compound of additional phosphate ions into solution. In Ihunder Bay. trawling temperatures range from 10C to 20C at 5 fathoms, and 5C to 10C at 10 fathoms (60 feetj. Temperature apparently does not rise above 6 .5C at 15 fathoms or beyond (KAHO, 1969). Ayers at al. (1956) has found a temperature range of 5.8C to 20.0C in Thunder Bay. Ayers _et jsl. (1956) Thunder Bay. They found a calcium mean of 22,20 mea n of 6.4 mg. while Kramer found a swan secchl value of 7 Inches in mg and a magnesium They found a conductivity mea n of 161 micromhos/cm (1964) steasured a conductivity range of 140 to 145 in Lake Huron. Results for analysis In Thunder Bay Table 43 and the results for study of Lake Huron are given In parameters Is given In Table 44. The plume of Thunder Bay River into the bay can be seen visually and from aerial photographs over the bay as shown In Figure 35 at an altitude of 3000 feet. Living Systems in Thunder Bay and River Highly diversified benthlc communities containing many clean water forms have been found in the majority of Thunder Bay. May­ flies. caddisflies and amphipods, common inhabitants of natural inshore populations In Lake Huron near Alpena, are widespread. 20? Tab la 43 Thundar Bay W t t i r Quality Study Sacchl (ft) Ayara I Ayara II Currant (ft/«in) Papth TTtT 0 7 12 Ayara III 50 75 - Ca (■g) 12.4 11.9 10.6 23.50 23.40 24.20 21.50 20.60 20.60 HE 0 20 50 73 19.5 17.9 16.8 0 20.0 50 10.0 HE 9 Taap "TEf 5.8 68 Michigan Watar Raiourcei C w a l i f t o g Tea i Sifci'hi Temp ream 'TTcr 19571965 1967 ua Ca pa H 2-12 - 9.0 26.00 7.8 113 -A? («g> 6.6 6.7 6.7 5.7 5.8 6.0 6.2 22.45 21.35 7.6 6.3 Cond (uohm/cn) 161 162 166 159 156 157 155 16 7 166 203 Table 44 Lake Huron Water Quality (Kramer, 1964) Parameter Calcium Mean Value 23,0 ppm Magnesium 6 .3 ppm Sodium 2 .4 ppm Potassium 1.1 ppm Sul fate 9.0 ppm Alkalinity 82 ppm Phosphorus 10 ppb Silica 2 .3 ppm pH 8.1 204 Figure 35. Areal Photograph of Thunder Bay 205 The population* of bottom animals In the bay, around the Abitlbl discharge off the river mouth, were composed almost exclusively of pollution tolerant organisms, primarily tublflclds (sludgeworms) (Fetterlcf, jet a_l, ( 1968). Species diversity and percent of sludgeworms in the area outside of the river influence, substantiates that environmental condition# are adequate for intolerant, clean-water forms. In the river, benthlc samples, taken above the main sources of organic wastes, consistently contained normal of a large variety of organisms. faunal communities composed Certain components of these consnunltles indicated clean-water conditions. Samples from the river, below Fletcher Paper Company waste discharge and below sewage plant discharge show a definite decline in the quality of the benthic fauna between 1957 and 1965 (Fetterlof, e_t , 1968). In the KAHO (1969) studies, a thermocline often appeared in the echo tracings. Fish concentrations were evident where the thermocline touched bottom. Yearlings and adult alevlfe were abundant in Thunder Bay (4000 to 9000 for 10-minute trawl catches). The spawning of alewife occurred frequently in the well-defined protected areas of the bay. Both adults and yearlings were at most depths, but were segregated spatially from one another, perhaps in schools. Small numbers of smelt were captured in the Thunder Bay proper, but the catch increased to 1200 for a 10-minute trawl at 40 fathoms. The size of smelt Increased with depth, and lakeward movement of the various size groups took place throughout the summer. Only 150 yearlings were netted, and 7500 adults were taken in deeper water. 2 Seth fv. .iter: -i.-.j *1 ln.y s'.uipi.^a were observed, with the fourhorn «|ecief beir^ ::re prevalent (4j-, to 145 for 10-minute trawls). The trawl c f ilneaplne stickleback were extremely variable. The o:^s>lons. peak* f 4C0C to 7Cvi> per 10-mirute trawl were the largest catches recorded In Thunder there appeared a distinct offshore, oeeper shift et the large populations as the l u m t r progressed. Other fish co :as lonai iy ibeerved were spot-tail shiner (C tl 24 per 10-minute tr i«.' ■r.d tr:ut per.h .138 tt 456 per 10-minute trawl). dual species recc/ered w r t : round white lish Indivi­ bloater* (74) , ehortr.ose cisco (4), white suckers (7>P and Johnny darters (19), the Department of Natural Resources has planted Coho and Chinook salmcd rat.-bow trout, and brown trout in the river and in the bay during the past (r._ •i : four year*., The Fisheries Department of Alpena Com- . Cc.-ege has planted the Donaldson strain of Chinook salmon during thi' per led During the sptlng and fall for the past two years, a we11-estsbi1sheu migrations! run has been occurring for both trout Mean and salmcn in the river and along bay shoreline. ''a# studied the living systems of the Oxbow reser­ voir a n d Besser bake water* behind the Ninth Street Dam. He found a t'v's. of nineteen genera of aquatic plants Including three algae Thirty-four families, thirty-nine genera, and fourteen speji«s of invertebrate animals were collected. Tendipedldae were the most cotmacr.ly collected organisms, while Coenagrionldae were aecnnd in aburdar.ee. Several invertebrate taxa were collected. Fresr.w*te; sponge colonies were numerous and large in size. IY.e *pe:ifs of fish In the waters were typical of a backwaters imp ou:.dment ar.d lrcluded: pumpk: *.#frJ_ Northern pike yellow perch, rockbasi, red horse, carp, bluck crappie, bluegill, bowfin, bullhead 207 (yellow and brown), smallmouth and largemcuth baaa, white sucker, burbot, mudmlnnow, northern redbelly dace, golden shiner, creek chub, banded klllitlsh, brook stickleback, and Johnny darter. Many of these species have been caught or observed In the river, Impoundments, lakes and tributaries of the Thunder Bay Basin during the course of the study. These organisms should be typical of those present throughout the watershed. SUMMARY OF THUNDER BAY WATERSHED RESOURCES The watershed or drainage basin of a river comprises all the land that contributes to the river's flow. The Thunder Bay Watershed has its aurtace water sources from both swampy land areas and ground­ water springs. The groundwater flows from both limestone and shale formations, resulting In fairly hard water with significant amounts of soluble calcium. The presence of highly mineralized water from wells In the watershed adds to the hardness and alkalinity of water reaching the river. The land resources of the watershed reflect the variety of nat­ ural and cultural development that has progressed In northern Michigan. The soils In the rhunder Bay Basin are as varied as most watersheds, ranging from porous sands to Impervious clays. used for farm purposes. The loams are being These soils determine the water quality of the natural water that reaches the watershed. Organic soils, with a fair amount of humus and low waterholdlng capacity, are present along several main tributaries (North Branch, Bean and Wolf Creek). With over one-fourth of the vegetation being swamp and marsh type, streams of highly colored natural water are pre­ valent (Table 45). There Is a substantial amount of colored water reaching the main river and Thunder Bay. T a b I t 45 Tha Color of Thunder Bay Yellow Organic Natural Aclde itte Stream 1 Main Branch Mouth 2 Main Br. 9th St. 4 6 Location Method Fall/70 Win/70 Sum/71 Fall/71 Mean 42.0 - 7.0 7.2 21.9 35.6 57.1 24.5 23.0 Semen - 3.2 50.1 29,4 10.9 23.2 Lo.So, Br . M32 Semen - 2.8 3.0 12.7 17.5 9.0 Wolf Cr. Fluor Semen 40.0 - 15.5 21.3 25.3 18.8 40.7 30.7 25.1 Mouth Fluor* Semen# Fall/69 . • Bean Cr. M32 Semen 44.0 58.0 56.0 59.0 48.2 53.0 8 Up.So, Br. M32 Semen - 11.3 22.0 10.0 14.4 14,4 10 Main Br, Semen - 3.5 21.9 31,4 46.5 25.8 13 Gilchrist Semen - 8.0 13.2 6,0 8.8 9,0 15 Main Br. Atlanta Semen - 11.1 26.3 22.0 33.8 23.3 17 No. Br. Rueh Lake Semen - 12.0 * 65.0 14.4 30.5 18 No. Br. Semen • 9.0 53.8 55.0 58.5 49.8 Hillman M33 Mouth * Turner Fluorometer # Semenov, at , 1963 (Color at Carbon In mg/1) 208 7 209 The climate of the Thunder Bay Basin is typical of northern lati­ tudes and reflects the moderating effects of the large water masses of the Great Lakes. the year. The precipitation Is well-distributed throughout The water run-off in the major streams is controlled by hydroelectric and lake-leve1ing dams (Table 96). The major current patterns in Thunder Bay and the river plume tend to distribute the constituents of the air and water out into the bay waters and south from the The mouth of the main brancti. cement plant emission has a significant amount of particu­ late matter that reaches the bay and river. The westerly wind direc­ tion carries the cement dust over Thunder Bay, the majority of the year. The high calcium composition of the cement dust contributes to the fixation ability of the particles. The sewage effluent is a major contributor of nutrients and or­ ganic materials (Tables47 and 48) to the river and Thunder Bay. The phosphate levels are typical of a primary treatment plant and could lead to accelerated eutrophication of the bay when available to the aquatic organisms. Both wood-products industries are currently con­ tributing a high organic load to the river but their discharges are being corrected as to unnatural Even with B a y ha s specific remained fairly instances charges si de of these prevalent composition. discharges, h i gh e x c e p t of benthos influence of for c o l i f o r m c o u n t d e g r a d a t i o n near Intolerant, clean water the the q u a l i t y o f the these ( Ta b l e 4 9) t he w o o d - p r o d u c t s forms h a v e b e e n discharges Thunder found a b o v e in the r i v e r and and and dis­ out­ bay. The fish populations of Thunder Bay reflect the Influence of the aLewlfe and the spawning habits of small and large lake-run species. T a b l e 46 Total and Mean Discharge of Thunder Bay River at Ninth Street Dam (Alpena Power Co., 1971) Year 1967 1968 1970 Turbines Spillways Total Ann, 30,137 9,326 Mon. 2,511 Ann. Mean Discharge (CFS) Hydro KWH (106) Turbinea Spillways Total 39,463 11,484 3,578 15,063 40.6 777 3,288 957 298 1,222 3.4 28,963 2,479 31,422 10,983 936 11,940 39.1 Mon. 2,616 207 2,620 917 78 995 3.3 Ann. 30,362 6,786 37,148 11,568 2,568 14,160 41,7 Mon. 2,530 566 3,096 964 214 1,180 3.5 Ann. 24,640 3,200 27,840 9,400 1,234 10,634 33.7 Mon. 2,053 267 2,320 783 103 886 2.6 67.5 8.8 76.3 26 4.0 30 Daily 1971 River Plow (Cu.Ft ,xl06) 0.092 Ann. 27,372 10,983 38,355 10,387 4,188 14,575 37.7 Mon. 2,280 915 3,196 866 350 1,215 3.1 75 30 105 28.4 11.5 40 Dai ly 0.103 210 1969 Mean 211 Tdbi 9th St. Dam 1080 II It 4-Mile D a m 1550 •1 M 7-Mile Dam 2420 11 H Hillman Dam •* n rt rt tr it fi ii ii ii tr Herron Rd, M 32 11 Up. So. Br. rt it r* Lo. So, Br. 11 If 11 438 102 Head 11 M 32 108 M 32 168 Hubbard Lake 11 104 95 Wolf Creek Wolf Cr. Rd, 70 Bean Creek Bean C r . R d . 15 Gilchrist Cr. M 33 26 Hunt Creek Mouth 27 *Local 11 Local* U, 3, G e o l . Servicf II IT II Local 21 Male Corners M 11 135 63 Head Alpena Power Co, 150 208 Atlanta No, Branch 11 »i Information Source (Measured In this study) U. S, Ceol. Service Local U, S. Geol. Service Local U. S, Geol. Local Service Table 52 Water Reaource Comnlsalon Water Quality Data for Thunder Bay Rlvtr Watershed Veer Range Temp (C) P.O. (®g/l) Su». Solid (mg/1) £H Cond BOD^ COD (pohm/cm)(mg/1) NCh (mg/1) (mg/1j (mg/i) P0> Cl~ (mg/1) Deter. (pp») 0.0 0.1 0,0 Main Branch of Thunder Bay River at Breakwall 1965 1966 1967 Year Min Max Med -2 7.4 6 23 4 12.4 29 15 7.5 8.3 7.9 270 500 350 2.4 5.4 3.2 Min Max Med 0 24 4 3 15 9 7.6 8.4 7.9 280 400 250 Min Max Med 0 22 11 0.5 40.0 7.5 7.6 8.5 234 400 340 0.8 _ 3.8 - 2.6 - 11,5 6.2 12.2 10.3 5.2 11.6 8.2 Coloform Temp (HPN/100) (C) D.O. (mg/1) 8.0 Flow (cfe) Suap. Sid. (mg/1) Ca - 14 35 0.00 0.00 0.00 0.30 0.40 22 0.10 1.30 0.30 0 6 0.00 3 2.1 10 0.00 0.00 0.00 6.4 3.2 37 O.BO 0.30 0.34 0.60 0 8 0.10 0.01 3 0.0 0.2 0.0 0.05 0.35 0.15 0.00 0.20 0.10 0.00 0 m 0.40 15 0.00 6 22 PH PO/ NO 3 _NH* Hard Cl" •(all measured in ■g/ 1)- - - * Aik SQy, Fe North Branch Thunder Bay River 1967 300 7 10.8 40 9.0 52 8,2 0.05 0,10 0.00 0 185 180 12 0.2 7 10.8 88 6.0 58 8.8 0.05 0.10 0.00 4 210 210 10 0.2 Wolf Creek 1967 800 218 Table 53 Water Reaource Co— liaaion Phyaleal and Chemical Water Quality Data Mai n Branch Thunder Bay Rivet at Breakvall Phyaleal Year Range Turb ~Jc) Max Min Mean 27.0 Max Kin Mean 23.0 0.0 8.8 12 1 5 1970 Max Min Mean 23.0 0.0 10.8 1971 Max Min Mean 10.0 0.0 2.4 1968 1969 0.0 Cond D gO 4 (uohma) (mg/l) cm (mg/l'j BOD («£7i> 11 .8 5 e2 8.4 8.10 7.60 7.93 14 0 7 3 70 310 337 15.6 7. 2 10.2 8.40 7,50 8.00 44 0 11 3.8 13 1 4.9 470 210 362 14.0 7.2 9.7 8.30 7.80 8.10 23 0 7.5 6.4 1.8 4.2 5 3 4.4 400 270 352 12.8 9 .8 11,2 8,10 7. 70 7.95 15 3 3.2 1.0 2.1 - - 9.9 4,3 0 1 :,o Col 1 46,000 230 23,115 6,5 1.4 1 - - - 40,000 600 14,000 - - - Chemical lmg/ 1) Year Range Allt 1968 Max Min Mean - Org N NH 3 W0? P0* OrgPOi 0.900 0.40 0.150 0.010 0,058 208 188 200 57 21 34 5 44 13 52 17 11 27 16 20 0.80 0.00 0. 20 0.032 0,10 0.17 0,03 0.08 0.000 0.00 Hard Ca Mg Cl" SO, 1969 Max Min Mean 182 153 169 0.90 0.20 0.58 0,30 0.02 0.10 1 25 0.00 0, 20 0,33 0,02 0,02 0.120 0.010 0.010 488 160 215 60 15 11 46 7 2 7 52 12 34 18 24 Max Min Mean 220 100 166 1.10 0.20 0.60 0.48 0.05 0.22 0.20 0.00 0.09 0.48 0.03 0.17 0.200 1970 0.089 235 120 182 58 16 11 4 54 12 56 15 8 20 Max Min Mean 185 155 170 0.80 0.50 0.65 0.220 0.20 0.040 0.10 0.016 0,15 0.07 0.04 0,05 0.050 0,010 0.026 200 170 185 14 5 56 15 10 21 1971 0.000 219 The mean dissolved oxygen values were similar at 10.2 ppm and 9.9 ppm. The mean BOD by the commission was 3.0 ppm and 00D was 2.3 mg. In the measurement of chemical parameters at the breakwall, phos­ phate,. ammonia, nitrate, and chloride were similar except when smsplea were taken in close proximity of the sewage plant effluent discharge, Michigan Water Resources Commission measurements indicated significant levels of organic nitrogen and phosphorus at the river mouth. Their data showed higher values for alkalinity, hardness, sulfate, calcium, and magnesium,. The coll form count was significant in the river and along Thunder Bay beaches (Table 54) especially when the river plume carried the domestic effluents in the southerly direction. The Michigan Water Resources Commission (1971) has sampled the North Branch and Wolf Creek. The data for dissolved oxygen, dis­ charge, calcium, sulfate, hardness, and alkalinity were comparable to results of this study. nla) The nutrients (phosphates, nitrate, simao- levels found in the continual measurement at these stations were higher in value. The four year seasonal study on the watershed has indicated that the natural water Is of medium to high hardness, with significant soluble calcium present (Tables 55, 56 and 57), calcium carbonate was more prominent fairly high total solid content was highest in the main river. all waters day, The alkalinity as than sulfate or chloride, found. A Suspended solids were There is adequate dissolved oxygen in for natural clean water aquatic organisms. During the the nutrient levels showed only scattered Instances of cultural Influence They were sufficient to support aquatic vegetation that was extensive in several locations In streams and reservoirs. Three tributaries and the lower reaches of the main river had a high natural color, 220 Table 54 Thunder Bay River and Bay Sawpllng Data Alpena Health Department and Local Analyele Year Location Range P0A Collform* M.F.M. Fecal Tew (F) HH, MO, /i •8 C1‘ “ Main Branch Thunder Bay River 1970 1971 Fish Dock Max Min Mean 78 67 71 14500 1500 7190 Cemet wry Ptiap Station Max Min Mean 78 66 71 2500 100 970 Fish Dock Max Min Mean 74 62 67 11000 800 5500 2800 10 720 8.10 0.72 8.00 0.28 8.05 0.52 0.62 0.12 0. 33 0, 26 22,5 7.0 0.01 0.11 12.5 Ceatentery Puap Station Max Min Mean 75 62 67 12000 100 3100 790 10 205 8.10 0.56 7.88 0.30 8.00 0.42 0.25 neg 0.11 0.22 15.0 0.01 10.0 0,12 12.0 Ch I s ho 1m Bridge Max Min Mean 75 60 68 700 80 245 10V 8.14 0.68 10V 8,00 0.34 10V 8.07 0.52 0.17 neg 0.10 0.17 17.5 0.01 6.0 0,10 11.0 R.R, Car Bridge Max Min Mean 68 61 66 2700 200 1100 Breakwater Max Min Mean 69 62 65 40000 600 4000 Hatchery Max Min Mean 58 49 55 450 150 250 10V 10V 10V - - - - - - - - - - 60 10V 30 - 0.64 0.50 0.57 0.60 0.01 0.30 0.30 0,11 0.20 - 50 10 30 - 0.76 0.70 0. 73 0.32 0.15 0.23 0.22 0.07 0.14 - 2800 300 1420 7.85 0. 70 330 10V 7.82 0.30 30V 7.84 0.50 0.17 neg 0.06 0.36 0.02 0.19 8.0 6.0 7.0 V100 V10 8.02 0. 20 7.88 0 15 7.95 0,18 0,40 0 20 0 30 0,18 0.01 0.09 8.5 8.5 8.5 V10 8.07 0.22 8.04 0.12 8.06 0.17 0.43 0.12 0.28 0.20 0.01 0.11 8 8 8 tr Bay Svlwwlng Beaches 1971 Starllte Bale View Max Min Mean 70 67 68 Max Min Mean 70 67 68 * Mich. Public Health Dept. VI00 (Greer, 1971) 221 Table 55 1967-1968 Local Analyala fmg/l? of Tb ur.der Bay Watershed Si te I 2 Cl~ 64 1 16 6 61.6 8 3 62. 8 12 4 28.8 198 1,0 145 11,8 174 9.0 487 240 253 95.0 44 8 26 4 193 1 0 147 9 5 166 5 0 96.1 51 6 45.6 12 0 b 7 C. 34, 7 24 2 191 1 5 166 10 5 181 31 0 43.1 28.4 31,3 166 14 2 7 1 0.2 158 12.6 162 10 6 Har d 288 234 254 8,0 71 7,5 44d 2vi> 316 Max Min Mean 30b 196 23 3 8.0 7.1 7.5 Range Mai n B r . Max Mi a Mean Main Br, Aik _L?_ Stream Tot Solid Ca Mg so^ M- Lo So B r . Max Mi n Mean 612 152 300 7.9 7, i. 7 5- 354 228 30 7 5 Lo,So„ Br, Max Mi n Mean 216 1 78 196 8,2 7. J 7,7 46 2 204 323 Wolf Cr . Max Min Mean 292 170 242 7 9 7,0 7. 5 420 258 332 - - 22.0 224 29 2 7,0 110 10. 7 12.7 169 20,0 Max Min Mean 716 166 381 7 7 6,8 7 2 414 348 378 - - 26 4 266 6 „0 152 14 ,9 221 - Max Min Me an 576 147 292 7,, 3 6.9 7,0 522 224 323 162,4 34.2 49 3 13.4 8 7 4 30,1 31.3 192 1.0 155 12,7 168 - 392 6.9 270 54.6 23 2 3.0 189 - Max Min Mean 592 138 264 7 4 6 9 7. 2 444 192 343 60,4 30,6 51.0 27,4 55, 7 29,0 19,2 185 0.8 127 6,5 152 3 5 Max Ml n Mean 5?4 1VO 334 8,0 6 8 7 4 468 230 331 - - 9 .6 202 1 0 135 4 0 169 Max Min Mean 334 254 2 ?8 7 8 6 7 ^ 2 462 235 298 - - 19 2 208 7.0 199 11 0 203 Max Min Mean 318 164 231 8,0 6 8 7 .3 444 235 300 - - 21 -7 194 4 7 189 9,8 192 - Max Min Mean 222 180 207 7 6 6 9 7 3 409 222 321 14. 7 194 neg 163 7.9 184 - Max Mi n Mean 216 144 189 7 ,7 6 8 7 4 456 228 355 - - 19. 2 174 0 5 172 8-5 173 - Max Min Mean 174 68 121 8 0 6 9 7 4 678 353 515 - - 19 2 139 97 neg 9,6 118 - 6 7 8 9 10 11 13 14 15 16 18 Bean Cr, U p .S o , Br, Up.. So Br. Matn Br, Brush Cr , Gilchrist Hunt Cr,. Main Br, Main Br„ No Br . 130. 7 29,6 61. 6 15 ,3 96 ,1 22 5 - 221a Table 55 (Cont’d.) Stream Range S o l ,PCA To t ,PO^ NH^ Fa Tannin 0.24 0 02 0 15 2 ,4 1 1 1 ,9 1 Mein Br. Me* Min Me an 0 270 0.006 0, 180 0 30 0 ,25 0.28 0,67 0 21 0 45 J®33 12 0. 24 1 ,18 2 Mein B r . Max Min Mean 0 14 0 05 0 13 0,50 0.10 0, 25 0. 75 0. 18 0.45 1.55 0.09 0.61 0,20 0 .01 0,11 2,3 0.9 1,6 4 Lo.So, Br Max Min Mean 0. 08 0 02 0 06 0 50 0,08 0.25 0 85 0 12 0,35 1.30 0.13 0.65 0 22 0 01 0, 12 2 4 1 5 1 9 5 Lo.So. Br Max Min Mean 0. 03 neg 0 02 0.14 C .05 0.08 0.08 0,80 0.0b 0.43 0, 24 0 01 0.12 1.3 4,10 0,05 1.37 0.55 0.11 0.26 0,18 0.01 0.09 2.1 1.8 2.0 0,35 0.01 0.19 3,4 3.2 3,3 6 Wolf Cr. Max Min Mean 0 08 0.01 0.03 0.16 0. 15 0.16 7 Bean Cr. Max Min Mean 0. 24 0.01 0.12 0,50 0.30 0.40 1.10 3.01 0.13 1.19 1,00 0.02 0. 31 1 ,28 0.24 0.67 1,10 0,46 0,88 1 17 0.35 0.64 0.40 0.01 0.14 2.4 1.6 1.9 0,57 0.13 0,06 1.0 1.77 0.13 0. 76 0.69 0.16 0.40 0. 24 0 01 0. 16 2.2 0, 7 1,4 0.89 1.42 0.27 0.86 0,27 0.03 0.25 1 ,6 1.6 1-6 0.47 0.10 0. 29 0. 24 0.02 0.12 2,2 1 2 1 ,7 8 Up.So. Br Max Min Mean 9 Up.So, Br Max 10 Mein Br, Max Min Mean 0 15 0.01 0.05 9.40 0.16 4.80 11 Brush Cr. Max Min Mean 0 .20 0. 12 0.16 2,60 0,12 1,36 Max Min Mean 0 10 0 07 0 08 1 34 0 30 0,82 0 26 neg 0,13 Max Min Mean 0 .18 neg 0.05 0 .28 0, 28 0, 28 0,46 0, 36 0.42 0 49 0.08 0,22 0,38 0.02 0.14 1.5 13 14 Gilchrist Hunt C r „ neg - 15 Mein Br. Max Min Mean 0 26 neg 0.09 1 54 0 20 0,87 1.03 0,11 0,48 0,27 0,07 0.15 0- 31 0-02 0.14 2.0 0,4 1 2 16 Mein Br. Max Min Mean 0 16 neg 0,05 0,89 neg 0 45 1,00 0 34 0,6 7 1,11 0,03 0,57 0,13 0.01 0.03 2,0 1.1 1,5 18 N o . Br . Max Min Mean 0.05 neg 0,03 0. 73 0, 26 0 50 112 0. 27 0.13 0 20 0 16 0.13 0. 14 1,1 Table 56 1970 -1971 Local Physical Data at Thunder Bay Watershed Stations ilte I 2 3 5 6 7 8 Main Br. Main B r , Main Br. Lo.So. Br Lo.So, Br. Wolf Cr. Bean Cr, Up.So. Br. Air Temp H?0 Temp Discharge Susp Solid Total Solid Color DO, (C) H Aik Hard Ca SO4 Cl" Tot. POa Fe Main Br * Max Min Mean 8. 09 7. 56 7.,82 170 162 166 240 166 198 39.0 17.1 28.0 17.2 4.4 11.7 12.0 7.5 9.9 1.12 0.26 0.67 1. 37 0 .06 0 .53 0 .28 0 .08 0 .,18 0.13 neg 0.06 2 Main Br Max Min Mean 8. 35 7..92 8 .12 188 165 177 235 169 195 78.0 17.1 42.8 14.3 9.0 11.9 10.3 5.5 8.2 0.33 0.22 0.28 1.,04 0 .20 0 .53 0 .40 0 .05 0, .21 0.13 0.03 0.08 3 Main Br * Max Min Mean 8 .36 8 .14 8 .24 191 172 180 235 187 207 60.0 23.1 40.3 12.5 6.0 9.2 9.0 5.0 ’'.0 0.31 0.19 0.26 0 .48 0 .46 0 .47 0 ,36 0 ,05 0 .19 0.16 0.025 0.09 45.0 30.5 36.8 12.2 4.4 6.9 10.3 7.2 8.4 0.56 0.15 0.30 0 .30 0 .01 0 .11 0.05 neg 0.02 48.0 16.0 29.6 13.8 6.4 9.2 11.5 5.4 7.6 0.60 0.06 0.33 0 .06 0 .04 0 .05 0 .07 0 .01 0 .04 0 .34 0 .06 0 .20 neg 4 Lo.So. Br Max Min Mean 8 .10 7 .08 7 .76 186 168 178 5 Lo .So. Br Max Min Mean 8 .33 7 .13 7 .80 172 160 168 222 170 200 204 154 186 Max Min Mean 8 .20 7 .26 7 .77 212 160 195 266 208 228 48.0 20.0 34.1 9.0 3.2 6 4 13.5 6.3 10.1 0.60 0.08 0.36 0 .10 0 .0 0 .04 0 .28 0 .08 0 .18 0.08 Max Min Mean 8 .02 7 .71 7 .86 268 238 255 358 237 298 75.5 26.0 51.0 23 5 5.0 13 3 7.0 5.0 5.8 1.80 0.21 0.74 0 .20 0 .10 0 .12 0 .42 0 01 0 .18 0.08 Up.So. Br . Max Min Mean 8 ,12 7 .50 7 .89 144 128 137 187 152 164 26.8 15.0 21.3 22.0 3.0 10.0 19.2 3.5 8.1 1,36 0.13 0.43 1 .60 0 .01 0 .53 0 .15 0 03 0 .09 0.06 Up.So. Br . Max Min Mean 8 .21 8 .02 8 .14 246 197 218 330 208 260 56.0 34,0 45,0 R 2 7.2 7.4 8.0 5 0 6.1 0.58 0.005 0.29 0 .23 0 .01 0 .12 0 ,17 0.11 3,5 1.37 (Color - 147 0) 6 7 8 9 Wolf Cr Bean Cr Truax Cr 2 23 I T a b l e 57 ( C o n t ' d . ) Site Stream 10 Main Br. 11 12 13 15 16 17 18 SOz. cr 60.0 35.0 43,0 10.6 8.5 3.0 5,1 1.10 0.22 297 148 194 68.0 9.5 26.0 45.0 1.2 8.0 1.0 0.66 0.01 6.5 3.6 60.0 30.5 43.0 8,2 193 198 305 198 226 3.3 272 193 217 302 204 230 8.26 197 186 193 Max Min Mean 8.31 7,86 8.16 Max Min Mean PH Aik Hard Max Min Mean 8.37 7.92 8,18 246 191 208 288 191 Bruah O r , Max Min Mean 8.40 150 140 148 Max Min Mean 8.42 7.84 8.24 202 Max Min Mean 8.36 Max Min Mean 8,35 Main Br, Gllchrlat Hunt Cr. Main Br. Main Br No. Br, No Br- Tot.PO/. NO^ Fe ™3 0.32 0.03 0.18 0.19 0.05 0.10 0.12 0.12 0.12 0.44 0.32 0.09 0.19 0.30 0.07 0.17 0.10 8.0 0.72 0.45 0.165 0.15 2.5 4.8 0.22 0.02 0.01 68 0,51 0.24 0.08 0.10 0.12 62.0 23.1 42.0 8.5 6.2 1.0 6.1 3.0 4.1 0,41 0.075 0.25 0 46 0.018 0.24 0,15 0.015 0 11 0.12 272 196 219 68.0 7.2 30.5 51.0 4.9 3.1 2 5 2.9 0.53 0.15 0.32 0.60 0.033 0.26 0.175 0.008 0.09 0.09 206 186 196 262 198 217 59.2 30.5 45.4 10,0 2,2 0.28 0.18 0.65 0.028 0,32 0.15 0.007 0.08 0.12 7.2 8.5 3.0 4.9 8.34 8.06 206 192 267 202 9.8 7.2 8,7 7.6 3.5 4.9 0,23 0.08 0.17 0 40 0.028 0.23 0.13 0.005 0 08 0.10 8.22 87.5 40.0 62.9 Max Min Mean 7.96 7.80 7.85 170 152 162 8,0 9.4 0,30 6.5 7.2 0.2 0.10 0.21 0.32 0.005 0.115 0.16 0,034 Max Min Mean 8.22 8.00 8.10 196 150 176 14,6 1,5 9.2 6.7 3.0 4.0 0.42 0.31 0 72 0.36 0.51 0,38 0.054 0,205 - 0.76 (Color * 23 2) Devlla River 8.12 8.26 8.10 8.26 8,22 8 20 221 200 222 200 183 192 54 0 94.0 250 166 203 20.1 153 30,4 50 5 3.7 7.8 1,0 3.4 0.63 0.10 0.22 0 10 223a H Ca Range 0.04 0.08 0,03 0.06 0.13 0.008 0.07 0.17 0.08 0,12 2 24 Analysis of specific parameters relative to the major portion of research in this ttudy was done at selected sampling sites in the river and Thunder Bay at Alpena (Table 58), The phosphate data showed a high total phosphate level in the river below the sewage outfall (Br3) and near the discharges (Brl and Ba2) of the wood-products plant (Tables 59 and 60), This phosphate composition Is carried down to the river mouth and diluted by the river water until It reaches the bay. As the river flow? out into the shipping channel, dilution. there Is further The prevailing wind and currents causes the river to swing south along the shoreline as shown by phosphate levels. Selected soluble phosphate measurements showed that orthophosphate constitutes from fifty to ninety per cent of the total phosphate measured. This may reflect the degree and rate of hydrolysis occurring in Thunder Bay waters The chloride and anmonia levels followod the same move­ ment Into the bay and the same dilution patterns. The calcium levels reflect the contribution of groundwater from limestone sources In the river basin (Table 61). The river plume can be clearly distinguished visually or through colorimetric measurement at the sampling sites in the bay. The natural color would be composed of yellow organic acids which could interact with the soluble calcium. The measurement of oxldlzable calcium at sampling sites revealed that a significant amount of calcium was being bound up by the organic material, together with acld-extractable phosphate. is lower at bay sites This interaction (Ba and Bu) because of the dilution and lower levels of calcium and organic material In the main river, this in­ volvement is highest where organic color was at a high level. The suspended solids also play a role in the movement of nutrients In Thunder Bay waters The river had a high level of suspended solids. T a b l e 58 Distribution of Selected Parameters at Specific Sites Thunder Bay River and Thunder Bey Year Rang* River Brl Br2 Br3 Mol Mo 2 Mo 3 Bel Ba2 - 0.20 - - - Ba3 B? - 0*5 t^6 S'V i| . . - 11.1 Soluble Phosphate (mg/1) 1971 Mu Min Mean 0.22 0.06 0.14 - 0.75 0.20 Total Phosphate (mg/1) 0.165 0 100 0.142 0.62 0 10 0.31 3.70 0.43 1 19 0.50 0.20 0.33 1.00 0.21 0.44 0.82 0.13 0.43 0.35 0.18 0.26 0.56 0.09 0.32 0.37 0.12 0.27 0 47 0.14 0.28 0 .35 0 18 0 .29 0,47 0,18 0.29 43J ll.i 27 J 1971 Max Min Mean 1.04 0.15 0.43 4.84 0.26 1.93 1 10 0.15 0.48 1.55 0.29 0.87 0.54 0.10 0,33 1.62 0.08 0.58 1.10 0.09 0.48 0.82 0.25 0.59 1.25 0.18 0.54 1.66 0 18 0.46 0 97 0.29 0.56 1 10 0 31 0 .70 1.12 0.18 0.53 - - - - - - - 225 Max Min Mean 0.62 1970 A monla Nitrogen (mg/'l) 1970 1971 Mu Min Mean 0.022 0.095 0.010 0.017 0.052 Max Min Mean 0.30 0.10 0.16 1.15 0.018 0 0 1 2 0.660 - neg 1.48 neg 0.74 0.035 0.018 0.026 - 8. 0.015 0.022 neg Nitrate Nitrogen (mg/1) - 1970 - 0.025 - 0.006 - - - - 9.8 9.4 11.2 4.0 6,0 4 5 5.2 6.5 5 0 7 5 6.5 4.0 5 2 0.010 - - - Chloride (mg/1) 1970 1971 Max Min Mean 8.9 - 16.6 5.0 3.5 4,5 12.5 4 0 6 8 8 0 4 0 6.2 - 10.3 12.5 5 0 6.0 4 0 4.8 60 4.5 5.2 - 9.8 96 - 4 0 4 5 Table Year Range River Brl Br2 Br3 Hoi 84.0 30.4 52.0 84.0 24,0 43.6 24.0 49.0 8.0 20 4 17.0 5.0 10.9 Mo2 58 < C o n t ' d Mo3 Bel ) 8*2 B*3 B*4 Be 5 100.0 64.0 19.6 22.0 44.4 24.2 71.0 22,0 48.5 75.0 18.7 37.2 75 0 22.0 41.4 54.0 - 48.0 2.0 22.1 27.5 12.0 18.5 16,0 4,0 11.8 29.6 3,0 15 6 50,0 - 4.0 12.0 4.0 7.2 7,9 4.4 5.7 22.0 5.2 10.7 15,0 4.0 7.4 16.0 3,2 7,9 6 0 - . . Bab Soluble Calcium (mg/1) 1971 Ma x Min Mean 71.0 20.0 41.8 1971 Max Min Mean 40.0 8.0 21.8 38.2 31.8 35 0 - 65 0 4 2 24 2 Suspended Solids (mg/1) 1971 Max Min Mean - 14 0 17.0 3.6 8.0 18.0 3.2 8.3 15.0 6.0 8.7 - 8.0 - 18.0 4.8 9.6 14.0 4.4 8.7 225a 1970 Max Min Mean Acid-Extractablc Phoaphate (mg/1) 1970 1971 ......................... Max Min Mean 1.10 0.05 0.46 Max Min Mean 8.17 7.85 8.03 0.08 - • 0.10 • - 0.28 0.04 0.14 1.35 neg 0.40 1.35 0.05 0.40 1.16 neg 0.27 0.93 0.11 0.43 0.32 neg 0.16 0.40 0.22 027 8.12 8.00 8.06 8.30 7.94 8.11 8.25 7 38 7.92 8.20 7.90 8.04 8.20 7.84 8.00 7.90 7.88 7.89 8.23 7.92 8.09 7.78 7 73 7.75 - - 5 0 00 2.5 * - 0.17 - -EM1971 7.80 - Color (mg-Carbon/l1) 1971 Max Min Mean 56.4 5,0 40 4 38.8 20 0 29.4 56.5 4 4 38,9 55.8 3.8 25.3 0 0 50 0 10,0 30 0 42,6 8 2 27.2 23.2 21,9 22,5 35,1 2 5 217 Table 58 v'7ont1d.) Year Range River Bui Bu2 Bu 3 Bu4 Bu5 Bu6 Bu7 - - Bu8 Bu9 BulO Sewagi - 11.0 Soluble Phcephate (mg/1) 1971 - 0.14 0,13 - Total Phoaphate (mg/1) 1970 Max Min Mean 0.165 0.100 0.28 0.140 1.70 0.30 0.84 0.39 0.07 0.25 0.39 0.37 0.38 0.47 0.10 0.26 1971 Max Mn Mean 1.04 0.15 0.43 0.78 0.16 0.44 2.26 0.23 0.84 1.16 0.28 0.62 1.72 0.37 0.7b 0,07 0.58 0,25 0.44 0.37 0.37 - 0.26 0.18 0.22 0.28 0.22 0.25 0.16 - 0.42 0.25 0.32 0.38 0.18 0.28 0.23 0.20 0.22 43.0 11.0 27.0 Anmonia Nitrogen (mg/1) 0.022 - - • - - - 9.0 • - - 3.5 6.0 3.5 4.8 4.0 4.5 4.0 26.4 22.0 24.4 50.0 17.9 26.9 26.4 19.0 22.7 26.0 24.4 25.1 18.0 4.3 11.8 17.0 1.1 9.3 23.0 21.0 10.0 15.3 107.0 23.2 n e 54.5 0,0 26 2 56.3 0.0 28.2 - o.ooe t 8,1 Chloride (mg/1) 1970 1971 8.9 Max Min Mean 5.0 3.5 4.5 4.5 9.4 - 96.0 4.0 6.0 5.0 5.5 * 4.5 a* 50.0 - 24.0 15.2 42.0 25.0 33.5 - 12.0 - f ,0 17.0 - 36.9 - 25.0 neg • - Soluble Calcium (mg/1) 1971 Max Min Maan 71.0 20,0 41.8 Oxldlzable Calcium (mg/1) 1971 Max Min Maan 40,0 8.0 21.8 Color (mg-Carbon/1) 1971 Max Min Mean 56.4 5.0 40.4 23.2 10.0 5.0 - 225b 1970 T a b l e 58 ( C a n t ’ d . ) Year Range River Suspended So U d a 1970 Max Min Maan 1371 MAX Min Mean Bui B u2 Bu3 Bu 4 Bu6 Bu5 Bu7 Bu8 Bu9 BulO (mg/1) - 17.0 3.6 8.0 5.6 9.0 5.0 6.3 9.0 3 0 5 8 8.0 2 0 4.3 11.0 4.0 8.0 15.0 3.0 7.3 - 4.0 11.6 5.0 5 1 9.2 2.8 6 7 5.6 5 0 5 3 7.0 4.0 5.0 7.6 4,0 8.0 4.0 6.0 * * - 6.0 2.8 4.4 5.2 4.0 4.6 - - 0.426 m - 0 25 0.11 0 18 m - 8.38 ACid- Extractable Phosphate (mg/1) - 1970 Max Min Mean 1.10 0 05 0.46 Max Min Mean 8.17 7.85 8.03 0 *5 0 19 0.16 0.18 0 12 0 15 0.84 0.0? 0.21 7 98 7.55 7 72 8,36 7.75 8.11 7.70 7.72 - Ba2 Ba3 Ba4 0.25 0.25 0.39 0.25 0.28 0.28 0.28 0.37 0.32 L ~ 0 .2 i 1 - 0.025 0.01 o o; 0.03 0 06 0.06 _2iL 1971 Total Phoaphatei at Selected Depths Depth (ft; Mol Surf a :a 0 30 0.30 3 6 0.38 9 0.25 Me 2 Mol Bal ■» 0.43 0.42 0 33 0.43 0.28 0.23 0.20 0,18 * (mg/1) - - - * 225c 1971 - - cr 3 pa sC 1 4 * o O m w ri j' o (n oc vn -o D CM l-i tQ c 3 £| pa N O' O I t > i in ■m O o 4t F 4 l C O O ro 4 fa o pa d o 4 pa rH i. o r on o O VC *-> 4 C n in 4 t3 pa <* i a o « a o rO' 00 O' ^4 C M i 0 in 4 0 £ vC pa v 4 c -4 P. O' «N o •I it CJ t CM cn Mf a o 44 m a o o -n mt a o Csl 3 pa 1 o oo i O X * o O O d c r4 4 « X i m ■ 1-4 a o o 4J o o a o r1 r r 4 --- f=> 00 n V - 1 -M » 3 pa i— 1 t c CO Csl o o> 4 o o o r- r- r V < Q Q 00 C'J , 'j o a X c- O *-i m CM > o 4 4) J PH River Br2 Br 3 Mo 2 Mo 3 Ba2 Ba3 Ba4 Bu3 Bu5 Bu8 BulO 76. 0 84.5 83,0 85. 5 60. 2 74.0 67.0 b4 5 32. 3 25. 5 24.0 33.5 34.0 16 0 18.0 21.4 18. 7 5.3 8 8 8 1 7, 2 15, 5 9,2 8.5 Mean 59.2 14,2 8. 20 River Br2 Br3 Mo 2 Mo 3 Ba3 Ba4 Bu2 Bu3 Bu5 30,6 37.3 36.5 31.5 36, 3 29.7 24,0 25,6 23,0 24, 4 15.6 8.3 4.3 12.5 7 3 8.7 16.0 8. 7 4,3 15.0 8.01 8.11 8.07 8.05 8.02 8.10 7.73 7.52 7.98 7. 72 Mean 29. 9 10. 1 7.93 - 8. 10 8 20 - - 8.16 - 8, 36 - - Watershed Location Range Natural Ca (m r ) Oxidized Ca (mg) PH E x t ,P0i Main River Max Min Mean 80.0 38 0 48. 1 61.8 9. 7 25,4 8. 36 7.60 8.19 1. 39 0,09 0,41 Main Trlh. Max Min Mean 54,0 26,8 38,0 37. 5 4.4 18.1 8, 22 7.96 8.09 0 85 neg 0.43 Stream Max Min Mean 43.0 36,4 40,5 16.2 3,0 9.3 8,40 7.97 8.19 0.82 neg 0.27 229 Comparable levels were found In Thunder Bay (Bu3, B u 5 , Ba3, Ba4, M o 2, and M o 3 ) , possibly from the cement dust fallout. These solids did contain acid-extractable phosphate,, especially in the areas (Bu3 and M o 2) where dissolved phosphate levels were high (Table 62). The amount of phosphate extracted with acid was constant over a two-year period (0.24 mg). The milligrams of phosphate extracted for each milligram of suspended solids recovered was also constant at 0.033 mg. Most of the oxygen-temperature profile results (Table 63), indic­ ated the lack of a thermocline In the inner bay and river where the river current has an influence. (mean of 7.3 ppm) There was sufficient dissolved oxygen for intolerant cold-water fish species and intoler­ ant organisms according to Michigan Water Resources C o ^ l a s i o n Water Quality Standards (Appendix IV). (1967), The measurement at various depths reflected the slight depletion of oxygen as depth increases and the cooling of water with depth. The phosphate measurements at similar depths (Table 64) showed that the selection of the three to six feet depths as sampling area would represent the uniform composi­ tion of the water at the sampling site. The sewage plant data (Tables 47, 48, 65, and 66), indicated that the amount of plant effluent and its composition varies with season, day and amount of rainfall. The highest flows were recorded during the spring and early summer of the year and did not appreciably affect the levels of the chemical parameters. the week had the highest sewage samples. The beginning and middle of level of components measured In the composite The removal of BOO and suspended solids reflect that of a primary treatment facility. The nutrient levels Indicate that the treatment is not affecting nitrogen levels and Is enhancing the amount of phosphate that is present in the discharge of the effluent. 230 Table 62 Acid-Extractable Phosphate ot Thunder Bay Suspended SolIda Date Site 9/70 B&3 Bu3 Bu5 Bu 6 Bu9 10/70 11/70 Mo 2 3 Ba3 Bui Bj3 Bu5 Bu7 Ba3 Bui Bu3 Bu5 Mean 6/71 7/71 8/71 9/71 10/71 Mean Mo 2 Ba2 Ba4 Bu2 Bu3 Bu4 Bu 8 Mo 3 Ba4 Bu3 Bu5 BulO Mo? Ba3 Ba4 B a5 Bu3 Bu 6 Ext; ac .PO a “ W " FO a ,/Solid ^ogfing) .28 .23 .18 .26 .28 .30 .14 .24 .36 .040 .10 .024 .060 .025 7.3 5.0 4.0 8.3 9.5 .32 .32 . 70 .?& .3+ .54 .28 .24 .035 .034 .10 .020 .21 .050 .024 .038 Suap.Solids ■fe7iT 7.5 7.0 10.0 6.0 4.0 8.0 Tot. PO 4 (mg/I) .20 .36 .020 7.5 .35 .33 6.0 .28 .21 7.0 4.0 .38 .28 .10 .12 .044 .035 .014 .030 7.0 0.34 0.24 0.033 .44 .42 .54 .38 .57 .52 .39 .05 .007 .16 .020 .26 .05 .04 .040 6.8 8.1 6.4 5.1 4.9 5.3 6.0 12.5 12.5 8.0 .12 .18 .38 .33 .23 .37 .23 .19 .27 .08 .010 .008 .023 .030 .017 .021 .010 .10 .014 .08 .020 .58 ,43 .35 .19 ,68 .22 6.0 1 .10 6.0 1.05 1.05 .17 .15 .07 .058 .038 .056 .028 .025 7.0 4.0 5.9 5.1 4.8 5.8 Mo 2 Ba3 Bu3 8.2 Mo 2 Ba3 Bu3 10.0 6.6 9.2 5.9 8.4 6.8 .010 .57 .92 2.26 .84 .024 .030 .090 .91 .30 .37 1.05 .25 .57 .105 .042 .068 0.62 0.24 0.033 .20 .20 231 Table 63 Dissolved Oxyften(mg/l) and Tcmperature(C) Profile In Thunder Bay Surface 3 ft. 6 ft. DO Temp 7.5 21.5 7.5 22.0 7.5 22.0 DO Temp 7.4 21.0 DO Temp 7.5 21.0 7.6 21.5 7.6 22.0 DO Temp 7.4 20.0 7.5 19.5 7.5 20.0 - DO Temp 7.5 19.5 7.4 18.5 - DO Temp 6.9 16.0 7.2 16.5 7.3 16.5 DO Temp DO Temp 7.1 18.4 7.1 18.8 7.0 18.2 7.0 18.5 7.0 18.0 7.0 18.0 Mo 2 DO Temp 7.3 18.4 7.3 18.2 7.3 18.2 - Ba3 DO Temp 7.3 18.2 - - 7.3 18.0 DO Temp 7.9 17.7 - 7.9 17.5 DO Temp 7.5 19.2 DO Temp 7.3 18.5 - Temp 20.0 - Temp 17.0 Site 8/11/71 9th St. River Br3 Mo 3 Ba3 Ba6 - _ - 7.2 22.0 9 ft. - 12 ft. - 18 ft. - Bottoi - 7.4 21.0 7.5 18.0 7.3 17.5 7.5 20.5 7.4 19.5 7.2 18.0 7.5 19.5 7.6 19.5 7.4 18.0 7.5 18.5 7.3 17.0 7.2 16.0 7.2 16.5 7.2 16.0 7.2 16.0 6.9 15.5 7.0 18.2 7.0 18.2 7.0 18.0 7.0 18.2 6.9 17.8 7.0 18.2 6.8 1 /.ft - 7.2 18.0 7.1 17.8 6.7 17.6 7.3 18.0 7.2 18.0 7.1 17.5 8.0 17.5 7.9 17.3 7.8 17.3 7.1 17.8 17.2 6.6 17.0 _ - - 8/28/71 River Br2 Bu3 Bu8 BulO _ - - 7.3 18.5 - 7.3 18.2 - 7.3 17.8 7.0 17.2 6. 7 17.0 19.0 18.0 17.5 17.0 17.0 17.0 16.0 16.0 16.0 15.0 - 9/15/70 B a2 .0/15/70 Bu5 232 Table 64 Phosphate Measurement(mg/1) at Various Depths In Thunder Bay Date 8/28/70 9/8/70 10/12/70 1 s* ll/i. 11/5/70 Mean Site Surface River Br 3 River Br 2 Br 3 Bal Ba2 Ba3 Ba4 Mo 2 Mo 3 Ba2 Ba3 Ba4 Mol Mo 2 Mo 3 River Br 2 Br 3 Mol Mo 2 Mo 3 Bal Ba2 Ba3 Ba4 - - - - - - - - 0.25 0.25 0.28 _ - - - 0.25 0.28 0.28 3 ft. 6 ft . 0.10 0.60 0.05 0.70 0.15 0.20 0.85 0.16 0.23 1.05 0.25 0.27 0.37 0.18 0.35 0.33 0.31 0.50 0.51 0.54 0.47 0.25 0.28 0.37 0.23 0.23 0.30 0.30 0.37 0.25 0.28 0.30 0.18 0.12 0.20 0. 72 0.30 0.44 0.43 0.11 0.23 0.88 0.28 0.42 0.28 0.18 0.29 0.28 0.32 - - 0.25 0.28 0.37 9 ft. - - Mean 0.075 0.650 0.15C 0.215 0.950 - 0.18 0. 30 0.30 0.34 - 0.52 0.49 - - - 0.243 0.253 0.317 0,25 0.33 0.23 0. 276 0.333 0.220 - - 0.25 0.33 0.23 ... - 0.116 0.215 0.800 0.276 0.40C 0. 360 0.180 0.263 0. 280 0.323 233 Table 65 Monthly Means Month M.G.D. ci- (mg/1) by Day Sol.POji; for Alpena Sewage Effluent Tot.POi Hard _i™3_ Aik Sunday 9/70 10/70 12/70 1.70 2.36 1/71 2/71 3/71 A/71 5/71 6/71 7/71 8/71 9/71 10/71 12/71 1.67 1.95 4.29 4.30 2.88 3.40 4.10 2.39 2.92 1.55 2.49 Mean 2.55 3.6 14.0 198 140 240 212 161 235 120 85 80 90 265 12.8 14.5 10.8 6.2 9.8 9.8 5.8 10.0 8.4 12.7 8.9 22.0 20.5 18.0 11.6 16.2 12.8 26.4 13.2 24.5 20.1 11.8 10.8 15.8 5.4 1.7 5.2 8.5 6.2 6.2 8.0 15.8 9.2 0.37 0.92 0.90 1.26 0.77 0.90 0.25 0.07 0.25 0.20 0.40 185 280 318 322 320 ■ 2 78 232 201 244 156 9.3 17.7 8.7 0.52 264 - 8.0 ■HL. 6.7 0.46 - 14.8 26.1 10.3 96 97 - - - - — - 238 216 * * 224 226 Tuesday 18 .0 9/69 9/70 12/70 2.47 2.62 89 - 8.0 12.8 20.6 25.2 9.6 7.1 0.30 0.56 1/71 2/71 3/71 A/71 5/71 7/71 8/71 10/71 11/71 12/71 1.88 1.99 3.51 5.20 4.48 2.97 3.56 2.20 1.85 2.22 125 102 215 180 160 90 175 80 160 140 11.7 18.5 16.0 5.2 9.2 9.8 15.5 12.8 16.5 16.1 25.0 26.0 25.0 12.0 18.6 21.5 18.7 16.7 28.3 17.9 5.2 15.5 8.4 1.8 5.0 6.7 15.7 13.7 10. 7 7.5 0.36 0.39 0. 76 0.96 0.78 0.31 0.28 0.23 0.86 0.21 14b 271 318 324 270 202 226 249 2 76 348 192 203 Mean 2.84 138 12.7 21.0 8.9 0.50 263 21? - * - - 220 232 2$3a Table 65 (Cont'd.) Month M.G.D. ci- Sol.PO/. Tot.PO, J0?j_ NO 0.68 Hard Aik Wednesday 9/70 10/70 12/7G 2.31 1.86 2.62 103 - 16.0 11.3 25.0 30.5 24.4 S.l 1/71 2/71 3/71 4/71 5/71 6/71 7/71 8/71 9/71 1 1/71 12/71 1.94 2.02 3.92 5.10 4.01 4.72 2.84 2.83 2.52 1.79 5.68 228 246 175 185 193 16 7 90 170 75 245 90 12.3 17.0 8.0 5.3 8.6 8.6 12.8 15,7 8.4 15.0 4.4 19.5 26.2 15.5 11.6 16.2 15.1 2C .4 21 .8 2-1.6 28.0 5.5 6.5 17.2 5.0 0.8 5.4 6.3 10.0 8.5 7.7 10.3 1.5 0.78 0.62 1.03 1.42 1.85 0.22 0.21 0.26 1.12 0.58 254 313 328 326 242 223 195 283 233 194 212 136 Mean 3.15 163 11.0 20.3 7.5 0.80 266 181 - - - - Thursday 9/69 9/70 10/70 11/70 12/70 1/71 2/71 3/71 4/71 5/71 7/71 8/71 9/71 10/71 11/71 12/71 Me an - - 2.33 2.00 2.17 2.70 102 1.95 2.00 2.86 4.42 3.43 3.92 3.28 2.92 1.69 1 .56 2.98 2.68 312 106 248 230 170 100 120 100 100 110 150 154 - - - - 11.4 19.0 13.5 11.2 12.7 18.0 10.5 6.1 8.6 13.7 8.0 6.7 16.5 20.6 12.2 12.7 18.1 32.0 30.0 27.0 21.0 5.5 0.59 31.5 27.0 18.0 12.0 20.5 18.0 22.6 18.2 25 „0 32.8 15.9 23.1 10.5 17.0 6.1 1.8 4.0 6.7 4.0 6.5 15.8 11.4 4.0 7.8 0.34 0.94 0.78 1.06 0.62 1.07 0.08 0.13 0.25 0.50 0.48 0.57 - 5.7 - - - - - - - » - - - - - 204 229 290 296 270 277 254 222 249 246 36 5 263 — - - - 210 - 218 23? 220 234 Table 66 Alpena Sewage Effluent H e ana (mg/1) for Specific Days 19 yo Day Sol.P04 Tot. PO, _ c jr o .6 14.0 0.27 1.80 7.8 0,34 100 39 0. 75 1.50 8.5 8.2 0, 36 0,60 23.6 - - - 116 1.40 1.26 Sun 8.0 20.5 Mon 15,5 26.8 Tues 13,5 24.2 89 Wed Thur 12,2 9 06 25.6 24.6 Fri - jm*3_ -»°30.46 Sat 17,0 31.7 Mean 12.6 25.3 97 118.5 93.3 _ C 1 20.86 - Deter„ 1.10 • 2. 00 - - - 9. C 0.41 1.55 1971 Day S o l .P0/( Tot.PO^ ci- NHn NO 3 PH Aik Hard Det, *e Sun 10. 7 18.4 188 7.6 0.91 7.42 224 292 Tues 9.3 21.1 137 7.2 0.60 7.30 201 256 - 0.77 Wed 11.6 25.8 190 8.0 1.12 7.50 223 301 - 0.91 Thur 10.8 19.8 200 6 8 0.85 7,37 201 266 1 ,20 0,80 Mean 10.6 21.3 179 7.4 0.87 7.40 212 2 79 0.97 0,83 IN 8.4 13,2 134 6.8 0.87 7.40 215 280 - - OUT 8,7 16 .7 160 7.1 1,2 2 7.45 215 280 .. _ 0. 73 _ Appendix III. R e s o u r c e s of T h u n d e r G e o g r a p h i c Sites and Bay Watershed Sampling Locations, THUNDER BAY WATERSHED SAMPLING LOCATIONS 235 APPENDIX III. Figure 36 236 Table 67 Description of Thunder Bay Baeln Geographic Sltee Site Geographic Location Description A City of Alpena Located on Thunder Bay, main river and Beaser Lake are within city limits. B Village of Hillman Located near the county line with a population of 450. C Village of Atlanta Located at the Junction of M32 and M33 with a population of 1000 D Rush Lake The floodwatera of the Rush Lake flow Into North Branch which is controlled by a dam In Montmorency County. E McConelck Lake The main branch flows through the lake where the original dam is In dis-repair. F Fletcher Pond The backwaters of the d a m on the Upper South Branch has formed an expansive floodwatera In Alpena and Montmorency Co. G Beaver Lake A deep, spring- fed lake that has a natural flow into Beaver Creek. H Hubbard Lake A large natural lake, 3 by 7 miles in size, whose level Is controlled by a dam where flow is into Lower South Branch. J Devils Lake A bog, marsh lake with much sedimentation and a dam controlling level, with over­ flow entering North Branch Devils River. Main Branch Thunder Bay River In Montmorency County, the river is 13.0 miles in length, flowing through brushwood and cleared areas, passing from McCormick Lake through Lake Fifteen Into backwaters at Atlanta. Elevation 875-1100. In Alpena, County, the river Is 25,5 miles long before It reaches the 7-mile dam pond. The remainder o f the river passing through the three reservoirs of the 7-mlle, 4 - m i l e , and 9th St. dams 237 Table 67 (Zont'd.) Site Geographic Location D e a crlpt1 on la 11.0 miles long. All types of terrain Is along the shores forest, bruin, marsh, cleared areas. Elevation is 650 to 7 75 feet. K Devils River Swiftly moving stream, clear water (2-3 ft.) over gravel-rock bottom, sand banks, 10 to 12 feet wide with holes near mouth. Appendix III: Table 68 Description of Limnologies! Sampling Stations In Thunder Ray BaaIn Site Water Resource Location Station Deacrlptlon 1 Main Branch 2 Main Branch Ninth Street Bridge Depth: 4 to 10 feet. Width: 100 to 150 feet. Current Is dependent on dam operation, rocky bottom; and extensive growth on stonesand large boulders. 3 Main Branch Four Mile Dam Depth: 2 to 4 feet. Width: 50 to 100 feat. Bottom type: Rocky with gravel and rock slabs. Vegetation: Some aquatic growth and algae. Current flow depends on operation of dam. 4 Lower South Branch M-32 Bridge Depth: 6 to 8 feet. Width: 20 to 25 feet. Bottom type: Sllt-sand bottoms In holes and gravel and sandy in fast water. Vegetation: Heavy in clear, swift water and on sandbanks. Current Is moderate-to-fast in ripples and shallow-rocky areas. Most deep holes have a large accumulation of wood and some vegetation on muddy-sandy bottoms. Lower South Hubbard Lake Depth: 2 to 4 feet. Width; 30 to 50 feet. Bottom type: Sand and gravel marl. Vegetation: Some submerged growth and algae on rocks Swift current below dam as clear water. (Above Hubbard Lake, river has a moderate flow and Is somewhat turbid from swamp areas - 3 to 4 feet deep.) Alpena Depth: 15 to 20 feet. Width: 150 to 175 feet. At the mouth of the main branch of the river the water drops off quickly at the breakwall where sample was taken five feet off shore. The shipping channelis dredged periodically so that the bottom and sides are silted and sparse of vegetation. 238 6R ( C o n t ' d . ) Water Resource Location Station Description Hubbard Lake Road Bridge Depth: 4 to 8 feet. Width: 40 to 60 feet. Bottom type: Soft mud-slit and sand, littleaquatic life and vegetation. Slight turbidity, with brown color and slow current. Bean Creek M-32 Bridge Depth: 2 to 4 feet. Width: 10 to 15 feet. Silt bottom, very slow current, abundant vegetation as a drainage stream from swamp areas with brown color, Bean Creek Road Bridge Depth; 1 to 3 feet. Width: 12 to 18 feet. Moderate current over rock* into intermittent holes, with sllt-sand bottoms, clear and colored, few aquatic animals and little vegetation. Upper South Branch M-32 Bridge Depth: 3 to 5 feet. Width: 40 to 60 feet. The level of this branch is controlled by a dam on Fletcher Pond. Flows swiftly over gravel-rocky bottom Somewhat turbid with aquatic growth on rocks. (Mud-sand bottom at mouth, 4 to 6 feet deep.) Upper South Branch Turtle Lake Bridge Depth: 4 to 6 feet. Width: 20 to 30 feet. Above Fletcher Pond, the stream has a swift current with a sand, gravel-rocky bottom and vegetation In slltatlon at bottom and sides of pools. Main Branch Hillman Dam Depth: 3 to 6 feet. Width: 40 to 60 feet. Clear water and swift current below dam, with clay-slit bottom and gravel with algae. Crayfish are abundant. Brush Lake and Creek Dam at Hillman Depth: Flows directly from lake over dam into main branch. Fast over rock* with algae growth, clear and colored Main Branch M-32 Bridge Depth* 3 to 6 feet. Width; 30 to 50 feet. Turbid water with large amounts of sedimentation Rockclay bottom. River becomea turbid below the mouth* of Gilchrist and Hunt Creeks as It flows Into Hillman Pond. 239 Wolf Creek T a b 1e Site 13 Water Resource Gilchrist Creek - (C o n t 'd .) Location M-33 Bridge Station Description Depth: 2 to 4 feet. Width: 20 to 30 feet. Swift current in raplda over gravel-rocky bottoms. Holes at stream curves with sand-fine gravel bottom. Aquatic growth and slltatlon along banks. Hunt Creek At Mouth Depth: 1 to 3 feet. Width: 15 to 20 feet. Rapid stream flow over rocks and gravel. Clear non-turbld water with slltatlon and vegetation along shore. 15 Main Branch Atlanta Dam Depth: 2 to 4 feet. Width: 30 to 40 feet. River flows from the Atlanta Pond over a dam used to control lake level. Current Is swift over a rock-gravel bottom. Some aquatic growth on the stones. 16 Main Branch McCormick Lake Depth: 2 to 3 feet. Width: 15 to 20 feet. The headwaters of the Thunder Bay River is at the lake. Lake level-controlling dam is In disrepair. River flows swiftly over a clay-marl bottom with gravel and sand. Water is clear and has chalky color. Vegetation along lowlands and floodplalns Isextensive. 17 North Branch 18 North Branch Rush Lake Male Corners Bridge Depth: 1 to 2 feet. Width: 10 to 15 feet. A dam controls the Rush Lake Flood Area, so stream flows moderately fast through a swampy area over a sand bottom with slltatlon and vegetation along the shore. (Above Sunken Lake, river has a rocky, gravel bottom. Below the lake, the bottom la sand-muck with clay banks and hard outcrop bottom.) Depth: 6 to 8 feet. Width: 50 to 60 feet. Slowly moving, clear and colored, over sand bottom with some vegetation. Highly variable flow derived almost entirely from direct surface run-off draining fine, imperivous soils. 240 14 Appendix IV. Michigan Water Quality Standards 241 Appendix IV Michigan Water Q u a l i t y Standards (Michigan Water Resources C o M l i s l o n , 1967) D I S S O L V E D OXYGEN (mg/1) D o m e s t i c Water Supply - Present at all times in sufficient quantities to prevent nuisance. Recreat i o n (Body Contact) - Present at all times In sufficient Quantities to prevent nuisance. Agri cultural-Comserctal - Average dally not less than 2.5, nor any single value leas than 2.0. Fish and Aquptic Life - At the average low river flow of 7-day duration expected to occur in 10 years the following D.O. values shall be: Intolerant fish-cold water species - Not less than 6 at any time. Intolerant fish-warm water species - Average daily D.O. not less than 5, nor shall any single value be less than 4. Tolerant fish-warm water species - Average dally D.O. not l*>ss than 4, nor any single value less than 3, TOXIC A N D DELETERIOUS SUBSTANCES D o m e s t i c Water Supply - Conform to current USPHS Drinking Water and Agricultural Standards as related to toxicants. Recreat i o n (Body Contact) - Lim i t e d to concentrations less than those which are or m a y become Injur­ ious to the designated use. Fish and Aquatic Life - Not to exceed 1/10 of the 96-hour median tolerance limit obtained from continuous flow bio-assays where the dilution water and toxicant are continuously renewed except that other application factors may be used In specific cases when justified on the basis of available evidence and approved by the appropriate agency. TOTAL DISSOLVED SOLIDS (mg/1) D o m e s t i c Water Supply - Shall not exceed 500 as a monthly mean nor exceed 750 at any time. Chloride monthly mean shall not exceed 75, nor shall any single value exceed 125. Re c r e a t i o n (Body Contact) - Limited to concentrations less than those which are or m a y become injur­ ious to the designated use. Fish and Aquatic Life - Standards to be established when Informa­ tion be c o m e s available on deleterious effects. 242 APPENDIX TV (Cont'd.) NUTRIENTS ( S u e for all Uses) Nutrients originating from Industrial, Municipal, or domestic animal sources shall be limited to the extent necessary to prevent the stimulation of growths of algae, weeds and slimes which are or may become injurious to the designated use. TEMPERATURE