CHLORIDE AND NITROGEN CONCENTRATIONS ALONG THE WEST SHORE OF LAKE ERIE Thesis for the Degree of M. S. MICHIGAN STATE UNIVERSITY THOMAS JOSEPH ECKER 1976 ABSTRACT CHLORIDE AND NITROGEN CONCENTRATIONS ALONG THE WEST SHORE OF LAKE ERIE By Thomas Joseph Ecker ChemicaI concentrations of chloride and seIected nitrogen parameters were measured in the area near the western shore of Lake Erie over the period May, 1970, to June, I975. SampIes were taken at six stations in Lake Erie in the vicinity of the Detroit Edison Monroe Power PIant as weII as in the Raisin River and the power plant discharge canaI. The study began one year before the power pIant began operating and continued untiI fuII operation was reached. SimiIar chemicaI data was obtained from a three year U. S. Environmentai Protection Agency sponsored study of the power pIant cooIing system. AdditionaI chemicaI data were obtained from various agencies for the Detroit and Maumee Rivers. ChIoride was used as a conservative eIement to determine the relative contributions of the three major tributaries in the study area, the Detroit, Maumee, and Raisin Rivers. Changes in nitrogen parameter concentrations were noted with respect to chIoride concentrations. Water in the near shore Take stations consisted primarin of Detroit River water. The composition ranged from 74 to 95% Detroit River water, the highest vaIue occurring in the faIT and the Iowest in the spring. The Maumee River had its greatest impact in the Spring, making up I4 to 18% of the Take water. Its contributions Thomas Joseph Ecker dr0pped to about 11% in the summer and 5% in fa11. ApparentIy Maumee River water mixes with Detroit River water and retains these proportions as the water moves northward through the study area. The impact of the Raisin River was shown to be greatest at the 1ake station c1osest to the river output, and ranged from 12% in the spring down to 5% in the fa11. Nitrate concentrations in the 1ake were determined by tributary inputs and showed a distinct maximum in spring. Nitrate decreased through the year from assimi1ation and di1ution. Organic nitrogen increased sTight1y through the growing season, but ammonia nitrogen showed much 1ess seasona1 variation than either nitrate or organic nitrogen. The most important source of nitrogen in the study area is the nitrate received from the Maumee and Raisin River watersheds during heavy winter and spring runoff. Concentrations of inorganic nitrogen measured in the 1ake did not agree we11 with ca1cu1ated va1ues. There seemed to be a deficit of from 25 to 50% in spring and fa11 and 65 to 75% in summer by the time the water entered the study area from the south. There was no compensating change in organic nitrogen. In addition, there was a continued 1055 of nitrate as the water moved through the study area a1though ammonia increased in partia1 compensation. Insufficient data exists to determine whether the nitrogen is 1ost to the atmosphere or sediments. Due to the re1ative1y high inorganic nitrogen present through a11 seasons, nitrogen fixation wou1d seem to be insignificant in the study area. The power p1ant coo1ing system has 1itt1e if any effect on the nitrogen concentrations beyond those due to mixing of Raisin River water with Lake Erie water prior to its discharge into the Thomas Joseph Ecker 1ake. There may be a s1ight 1055 of ammonia nitrogen in Spring, but 1itt1e if any change in organic, nitrate, or tota1 nitrogen. Effects of the Raisin River-discharge cana1 system are undiscernab1e more than 5 km distant as the water rapid1y mixes to ambient temperature and chemica1 concentrations. Ch1oride concentrations in the 1ake were shown to be c1ose1y re1ated to nitrate nitrogen concentration, but not to ammonia or organic nitrogen. CHLORIDE AND NITROGEN CONCENTRATIONS ALONG THE WEST SHORE OF LAKE ERIE By Thomas Joseph Ecker A THESIS Submitted to Michigan State University in partia1 fu1fi11ment of the requirements for the degree of MASTER OF SCIENCE Department of Fisheries and Wi1d1ife 1976 ACKNOWLEDGMENTS I wou1d 1ike to sincere1y express my gratitude to Professors F. M. D'Itri and R. A. Co1e for their guidance, assistance, and encouragement during the course of this investigation. I am aISo indebted to Professor N. R. Kevern for his va1uab1e suggestions. SpeciaI thanks must go to C. S. Annett and the many graduate students and staff who participated in the study for their encouragement, suggestions, and va1uab1e technica1 assistance. The schoIastic and financiaI support of the Department of Fisheries and Ni1d1ife and the Institute of Water Research is greatIy appreciated. Support of the project was provided by a grant from the Detroit Edison Company. Partia1 support for the Michigan State University computer time was provided by the Nationa1 Science Foundation. Fina11y, I wou1d 1ike to thank my parents for their mora1 support, and I especia11y thank Quentin Z. Lafarbe who made it a11 worthwhiIe. 11 r|{’D‘atfil n MW TI Se TABLE OF CONTENTS INTRODUCTION ............................ DESCRIPTION OF THE STUDY AREA . . . ................ Western Basin of Lake Erie .................. Genera1 Description ................... Hydrodynamics ...................... Hater QuaIity ...................... The Monroe Power P1ant .................... SampIing Locations ...................... The Detroit Edison Sites ................. The U.S.E.P.A. Sites ................... Other Data Sources .................... METHODS AND MATERIALS ....................... RESULTS AND DISCUSSION ....................... Ch10ride and Hydrodynamics .................. Nitrogen ........................... CONCLUSIONS ............................ LITERATURE CITED . .. ........................ APPENDICES ............. g ................ TabIE T\_) 4“ Tab1e 10 11 LIST OF TABLES Mean, maximum, and minimum discharges of the Detroit, Maumee, and Raisin Rivers . . Seasona1 and annuaI mean Ch10ride concentrations at se1ected sites in Lake Erie and its tributaries . Annua1 mean ch1oride concentrations in the discharge cana1 and p1ume . Mean re1ative composition of 1ake stations based on ch1oride concentrations . Seasona1 concentrations of nitrogen species in the Raisin River . . Ca1cu1ated and measured nitrogen parameters at 1ake stations 5 and 4 assuming that northward moving 1ake water mixes with Raisin River water . Annua1 nitrate nitrogen concentrations in the discharge cana1 Annua1 ammonia nitrogen concentrations in the discharge cana1 . . Annua1 organic nitrogen concentrations in the discharge cana1 . . . . ..... . . . . . . . . . Annua1 tota1 nitrogen concentrations in the discharge cana1 . . . ..... . . . . . . . . . . . . . . . . Seasona1 nitrate and ammonia nitrogen concentrations in the Maumee and Detroit Rivers . . iv Page 10 25 32 37 44 45 48 49 _50 51 54 IU-l‘ ..,_ {Hy P EC Tab1e Inorganic nitrogen concentrations as measured in the 1ake and as predicted from ch10ride concentrations . Nitrate nitrogen concentrations as measured in the 1ake and as predicted from ch10ride concentrations . Ammonia nitrogen concentrations as measured in the 1ake and as predicted from ch10ride concentrations . Mean concentration of ch10ride in mg/1 station Mean concentration of tota1 nitrogen in mg/1 by station . Mean concentration of nitrate nitrogen in mg/1 by station . Mean concentration of KjeIdahI nitrogen in mg/1 by station Mean concentration of ammonia nitrogen in mg/1 by station . Mean concentration of organic nitrogen in mg/1 by station . Mean concentration of inorganic nitrogen in mg/1 by station . 12 13 14 APPENDICES A1 A2 A3 A4 A5 A6 A7 A8 Seasona1 and annua1 means mg/T by stations A9 Seasona1 and annua1 means in mg/1 by stations . A10 Seasona1 and annua1 means in mg/1 by stations . A11 Seasona1 and annua1 means concentrations in mg/1 by A12 Seasona1 and annua1 means in mg/1 by stations . A13 Seasona1 and annua1 means in mg/I by stations . A14 Seasonal and annua1 means in mg/1 by stations . of ch10ride concentration in of tota1 nitrogen concentration of nitrate nitrogen concentrations of tota1 Kje1dah1 nitrogen stations . . . . . . . . . of ammonia nitrogen concentrations of organic nitrogen concentrations of inorganic nitrogen concentrations Page 55 56 57 66 72 80 88 96 - 104 - 112 - 119 - 121 - 123 - 125 - 127 - 129 - 131 F1 gun LU Figure 10 LIST OF FIGURES Map showing the 1ocation of samp1ing sites in the western basin where ch10ride and nitrogen concentrations were measured ......................... Resu1tant wind direction in tens of degrees and wind speed in km/hr during the study period .......... Montth Detroit River discharge and week1y discharge of the Maumee River ..................... WeekIy Raisin River discharge and montth precipitation at Monroe, Michigan ................... Map Showing the vicinity of the Monroe Power P1ant and samp1ing 1ocations in the coo1ing system. Locations of Stations 15 and 16 are from samp1es obtained in the therma1 p1ume which a1tered position with wind changes . . Map showing the 1ocation of the 1975 random samp1ing sites .......................... Ch1oride concentrations at 1ake Stations 1 through 6, 1970 through 1975 .................... ReIative ch10ride concentrations for Spring 1975. Con- tours were drawn for data taken on four separate dates. On each date the highest concentration was assigned a va1ue of 1.0 and a11 others ca1cu1ated as a decima1 fraction of the highest va1ue .............. Mean seasona1 ch10ride concentrations (1970 through 1974) at 1ake Stations 1 through 6 compared to seasona1 Detroit River ch10ride mean ................... Ch10ride profiTes for the Detroit River at Range 3.9, comparing data from the Michigan and Ontario Water Resources Commissions. Percentage figures represent the proportion of cross-sectiona1 f10w .......... vi Page 13 17 28 3O 34 36 Figure 11 12 13 14 15 TotaI nitrogen concentrations at 1ake stations 1 through 6, 1970 through 1975 ..... . . . . . .., ....... Nitrate nitrogen concentrations at 1ake stations 1 through 6, 1970 through 1975 . .................. Ammonia nitrogen concentrations at 1ake stations 1 through 6, 1970 through 1975 ................... Organic nitrogen concentrations at 1ake stations 1 through 6, 1970 through 1975 ............ . ....... P10ts of re1ative nitrate, organic, and ammonia nitrogen concentration vs. re1ative ch10ride concentration for the Spring, 1975, random samp1es . . . ............ Page 40 41 42 43 52 INTRODUCTION Large steam-e1ectric power p1ants with once-through cooIing systems require 1arge quantities of water to maintain their steam cyc1es. Where there is access to 1arge bodies of water, once-through coo1ing is usua11y the most economica1 means of coo1ing; and, therefore, it is used at many power p1ants on the Great Lakes. Potentia11y, these p1ants may at 1east 10ca11y redistribute and a1ter inf1uent waters of varying qua1ities which inc1ude such chemica1 e1ements associated with eutrophication as nitrogen. This paper describes the impact of the once-through cooIing system at the Monroe Power P1ant on the distribution of nitrogenous compounds a1ong the western shore of Lake Erie. The western basin of Lake Erie receives water from a dense1y popu1ated watershed. Nitrogen may enter the 1ake from numerous artificiaI as we11 as naturaI sources. The major potentia1 sources to the western basin are three tributaries, a11 of which enter the basin at the western end. By far the 1argest tributary, the Detroit River, carries nitrogenous waste from the city of Detroit. The second 1argest tributary, the Maumee River, drains nitrogen from an intensive1y farmed watershed and the city of ToIedo. Located between these two major rivers, the sma11er Raisin River contributes re1ative1y 1ess amount of nitrogen. However, the CIOSe proximity of the Raisin River to the power p1ant potentia11y has a dispr0portionate effect on the 10ca1 distribution of nitrogen. 1 The effects of any environmentaI a1terationS produced by a power p1ant or any other source are difficu1t to separate from natura1 and artificia1 background variation without some know1edge of 10ca1 hydrodynamics. Measurement of the impact on the 1oca1 coasta1 zone requires know1edge of water movements through the affected area, inc1uding the usua1 qua1ity of water that enters the study area. The re1ative impacts on water qua1ity can not be assessed without differentiating the effects of the various sources of water on the area concerned. Data coIIected over a five year period (1970-1975) Show the re1ative impact of the Monroe Power P1ant and the Detroit, Maumee and Raisin Rivers on the nitrogen concentration in the Brest Bay area of western Lake Erie. The derivation of waters in the study area was traced by the re1ative concentrations of the ch10ride ion, and the re1ative importance of di1ution was determined for the distributions of nitrate nitrogen, ammonia nitrogen and organic nitrogen. The data indicate that more than enough nitrogen enters this part of Lake Erie via tributaries to exp1ain the observed distributions. In fact, some nitrogen may be 1ost from the water cqumn as it passes through the study area a1though nitrogen distributions mostiy ref1ect the mixing of tributary waters. The Monroe Power P1ant enhanced the mixing of water from the Raisin River and the 1ake water in the vicinity but, otherwise, had 1itt1e effect on nitrogen concentrations. DESCRIPTION OF THE STUDY AREA Western Basin of Lake Erie Genera1 Description The study area is the western basin of Lake Erie near Detroit Edison's Monroe Power P1ant at Monroe, Michigan (Figure 1). The western basin of Lake Erie covers an area of about 3000 ka which is morpho1ogica11y distinguished from the rest of the 1ake by an archipe1ago that Ties rough1y a1ong a Tine drawn from Point Pe1ee to Cedar Point. The mean depth of the western basin is about 7 meters and the overa11 mean depth of Lake Erie is about 19 meters (Beeton, 1971). The western basin receives more than 90% of the tota1 water discharged into Lake Erie, but it comprises on1y about 5% of the tota1 1ake vo1ume. Therefore, the minimum possib1e f1ushing rate for the western basin is estimated to be about two months (Beeton, 1961) whi1e that for the entire 1ake is estimated to be about three years (Beeton, 1971). Because of the re1ative1y rapid f1ushing of the western basin, its water qua1ity depends primarin on the input from the tributaries. In the western basin, the temperature is moderated through the heat capacity of the 1ake; summer heating and autumn cooIing are de1ayed with respect to the air temperature. Coie (1973) Showed that the temperature regime in the near shore 1ake study area reached a R'VER' ., ’ ”WEE“ --)»2: 152,1: .90 Ikm x.“ Swan Creek - Fermi 0 Study Site RIVER l ©Monroe Water Intake - AISIN Brest Bay £3‘] 2. 5. LAKE 6. 'N"1 EEITIIE: ‘Ibledo Terminal Bridge dMAUMEE RIVER Figure 1. Map showing the 10cation of samp1ing sites in the western basin where ch10ride and nitrogen concentrations were measured. 5 minimum of 1°C in January 1971 and 1972 and a maximum of 24°C in the summers of 1970, 1971 and 1972. The mean annua1 air temperature is about 10°C (50°F). The Sha1iow western basin is genera11y vertica11y homogeneous both therma11y and chemicaIIy due to the action of wind and seiche, but temporary stratification can occur under the proper conditions (Carr et.al., 1965). Rainfa11 in the area has a Tong term average of about 73.7 cm (29 in.) per year. Precipitation for the ca1endar years 1970 through 1974 at Monroe, Michigan, averaged 73.4 cm (28.9 in.) with a minimum of 57.2 cm (22.5 in.) in 1971 and a maximum of 82.6 cm (32.5 in.) in 1973 (U. S. Weather Service). Precipitation is we11 distributed throughout the year, but the minimum usua11y occurs in February. The prevaiIing winds are from the southwest and b1ow from that direction approximate1y 23% of the time (Anon., 1965), and the month1y resu1tant wind is near1y a1ways from the southwest (Figure 2). Hydrodynamics The 1argest sing1e inf1ow of water to the western basin is the Detroit River which contributes about 95% of the annua1 input. The f10w is re1ative1y uniform over the year (Figure 3) and is determined by the re1ative heights of Lake Huron, Lake Erie, and their connecting waterways. The Maumee River contributes about 2.5% of the water discharged into the western basin whi1e the Raisin River adds 1ess than 0.5%. Both rivers have pronounced annua1 cyc1es with maxima occurring in Spring and minima in 1ate summer (Figures 3 and 4). The river f10w is not correTated directIy with precipitation because of the impact .nowgma xcapm mcu ucwcau E;\Ex cw Ummam ucwz new mmmcmmu mo mcmu cw covpumcvu use: ucmppzmmm .N mesmwd 3. MN Nb I. Ch E. mh NF 2. on 9L; Mb Nb Z. O» m» 3. wk NF Z: Ohm. 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LangIois (1954) believes that the input of a11 other tributaries to the western basin occasiona11y exceeds that of the Detroit River during so-ca11ed ”freshet" periods. Circuiation in the western basin of Lake Erie was previoust investigated by OISen (1950), Verber (1955), Herdendorf (1969), Kovacik (1972), and the Pub1ic Hea1th Service (1965). Their modeIS a110wed broad predictions of water mass movements in the near shore area. In genera1, a 1arge part of the inf1ow from the Detroit River passes directiy into the centrai basin of Lake Erie via Pe1ee passage. But Kovacik (1972) and Wa1ters et a1. (1972) Show that some Detroit River water reaches the southern shore with re1ative Chemica1 and physica1 integrity. This southward f10wing Detroit River water, combined with the northward f10wing input from the Maumee River, tends to form a 1arge c1ockwise gyre in the southwestern corner of the western basin. Day to day variations in these currents are pronounced because of such contributing factors as the changing hydrau1ic Ioadings and changing winds. Verber (1953), OISen (1950), Andrews (1948), and 0'Leary (1966) reported that surface water currents tend to directiy foIIow the wind. ResuItS in western Lake Erie (OISen, 1950; Hart1y, 1968) tend to support the assumption that bottom currents in sha110w water fo11ow the same genera1 circu1ation as surface currents. Coie (1972) estimated mean month1y water ve10cities based on 10ca11y measured wind driven currents a10ng the western share for 1970. Those estimates indicated that the prevai1ing month1y resu1tant current was northward -- >02 oumo -- >_=n oumo omom eNm_ -- nae ammo -- m=< ammo OSNS MNQP -- EQ< Doom -- poo ommo oxmm NNmP -- Dad opmm -- mz< cove comm Vkmp -- ewe omme -- »_=q os_o comm on_ --mm»flm S_ocbmo poo m ANO.OV mm.¢ m3< Amp. .oV A. 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Verber (1955) presents evidence that the 1ongitudina1 seiche of Lake Erie is a major contributing factor to these water movements. As the water rises and fa11s, it has a net westward movement south of Pe1ee Is1and and a c1ockwise progression around the western basin. Seiches can create puISeS in the discharge of the Detroit River (Herdendorf, 1969); and, at times, have been ab1e to brief1y reverse its f10w (LangIois, 1954). Water Qua1ity Both phytop1anktonic (Davis, 1964) and chemica1 (Verduin, 1969) data indicate that Lake Erie is eutrophic. The water qua1ity of the western basin is particuiar1y sensitive to the impact of its inf1uent waters because of its short f1ushing time. The qua1ities of these inf1uent rivers differ enough to p10t the movement of water by physica1 and chemica1 measurements (Herdendorf, 1969; Wa1ters et_al,, 1972; Kovacik, 1972; Andrews, 1948). Water qua1ity in the western basin is determined basica11y by the biggest contributor, the Detroit River. Compared with the sma11er tributaries in the watershed, the Detroit River has Iower conductivity, temperature, and concentrations of ch10ride and a1ka1inity. The Detroit River has been described (Har10w, 1966) as a major supp1ier of nitrogen and phosphorus to Lake Erie because of its massive discharge. However, the Maumee River has an impact much greater than indicated by discharge a10ne. According to FWPCA (1968) estimates, the Maumee contributed 25% of the phosphorus and 38% of the tota1 800 that entered the basin during the 1960's. The impact of the Maumee River has been determined by Cur1 (1957) who described the high phosphorus Toading, Chandier and 12 Weeks (1945) who noted the nitrogen inputs, and Verduin (1964) who described the high Si1t Toadings. Verduin further states that the high Si1t Ioadings, combined with increased phosphorus Ioading, is primari1y responsib1e for the eutrophic state of Lake Erie today. The Raisin River is the sma11est of the tributaries discussed here, but it neverthe1ess has a strong 1oca1 impact on the study area (Carr and Hi1tunen, 1965; Co1e, 1972). Besides draining a 1arge agricu1tura1 area, the Raisin River receives both municipa1 and industriaI eff1uent inc1uding that from paper miIIS. The Raisin is reported to have experienced anoxic conditions during summer and fa11 as ear1y as 1929 (Wright §t_a1,, 1955). Recent improvements in municipa1 and industriaT wastewater treatment may be reversing that effect. The Monroe Power P1ant In 1967 the Detroit Edison Company began buiiding a 3200 megawatt coa1 fueIed power p1ant on a fi11ed portion of the Raisin River de1ta. The intake for cooIing water was sited on the Raisin River (Figures 1 and 5) within a ki1ometer of the river mouth. A discharge cana1 was constructed to be approximate1y 2.6 kiiometers Iong and 150 meters wide. It empties into Lake Erie about 3.5 ki1ometers southwest of the mouth of the Raisin River. The design a110ws the p1ant to pump cooIing water from the Raisin River to condense steam from turbine operation with subsequent discharge of the heated water into the cana1. When the river discharge was 1ess than the p1ant pumped, water from Lake Erie wou1d provide the difference by inf1ow via the Raisin River mouth. 13 RAENN NVER PLUM CREEK DBCHARGE CANAL 0 1km V.__l A STATION 15 . ll STNHON K5 Figure 5. Map showing the vicinity of the Monroe Power P1ant and samp1ing 1ocations in the cooIing system. Locations of Stations 15 and 16 are from samp1es obtained in the therma1 p1ume which a1tered position with wind Changes. 14 Four 800 megawatt power units were bui1t and brought into Operation at a rate of about one unit per year between May, 1971 and May, 1974. Three cooIing pumps Circu1ated the cooIing water for each unit. Each pump iS rated at approximate1y 7 m3/Second, with a maximum pumping rate of approximate1y 84 m3/second for a11 four units. In 1971 and 1972, power was generated very Sporadica11y as the p1ant experienced numerous Shut-downs due to testing, maintenance, and various mechanicai adjustments. Coo1ing water was pumped more consistent1y than power was produced, but pumping averaged s1ight1y 1ess than 21 m3/second (three pumps) for the ba1ance of 1971. In May of 1972, the second power unit began pumping fo11owed by the additiona1 units in October, 1972 and September, 1973. The operation of the pumps preceeded the initiation of power production in each unit. Because of intermittant Operation, the average pumping for 1972 was on1y 29 m3/Second whi1e the means for 1973, 1974, and the first ha1f of 1975 were 50, 54, and 55 m3/second, respectiver. Pumping rates in the future are expected to average higher as power production becomes uniform1y greater. The most cooIing water was pumped in the summers of 1974 and 1975. ConverseTy, in the 1974-75 winter pumping was decreased from maximum because of the cooIer ambient temperature. In addition, winter pumping is decreased re1ative to the discharge cana1 because some of the discharge water is routed back to the river to maintain an ice-free intake. When the river f10w was high in winter or spring, the discharge water cou1d consist a1most entire1y of river water; but at times of 10w river f10w, such as in 1ate Summer and fa11, a1most a11 the water 15 came from the 1ake. Whenever p1ant pumping exceeded river discharge, essentia11y a11 of the river water passed through the p1ant. Samp1ing Locations The Detroit Edison Sites Studies of the water samp1es from the Detroit Edison samniing sites (Figures 1 and 5) were supported by the Detroit Edison ..mpany. The sites consist of stations in the power p1ant coo1ing system and in Lake Erie. The 1ake stations were samp1ed from 1970 through mid—1975 to identify the effects of the p1ant eff1uent on water masses as they foi1owed a genera11y northern course from station 6 to station 1 (Shown in Figure 1). Samp1ing stations 9, 8, and 7 were respective1y 10cated in the Raisin River, the power p1ant discharge cana1, and a sha110w embayment (P1um Creek) which adjoins the discharge cana1. Lake stations 1 to 6 were approximate1y 1.5 to 2 ki10meters from shore and 1.5 kiIOmeters apart except for station 6 which was approximate1y 3.5 ki1ometers from shore and 5.5 ki1ometers SSW of station 5. The depths at these 1ake stations ranged from 4 to 6 meters. P1um Creek (station 7) is sha110w (1ess than two meters) and discharges 1ess than 1 m3/second into the discharge cana1. The discharge cana1 itse1f (station 8) is 6 to 7 meters deep, approximate1y 150 meters wide and 2.6 ki1ometers 1ong. Station 9 is 10cated in the Raisin River, upstream from the power p1ant intake. Samp1es were c011ected from stations 1 to 9 on a biweek1y basis, weather permitting, from May 7, 1970 to June 24, 1975. Genera11y 16 unfavorab1e weather conditions prec1uded a11 except Sporadic samp1ing from November through March of each year. The samp1es were c011ected with an eight 1iter Van Dorn bott1e in trip1icate at two depths (0.5 and 2.5 meters) at eight stations and at on1y the 0.5 depth in P1um Creek, station 7. Samp1es for nitrogen ana1yses were p1aced in ponethyiene bottTeS and preserved with 42 mi11igrams per 1iter (mg/1iter) of mercuric ch10ride (Howe and Ho11y, 1969). Samp1es to be anaiyzed for ch10ride remained unpreserved. The water botties were returned to MSU for ana1ysis. In the spring of 1975, Stations 1, 2, 4, 5 and 7 were not samp1ed a1though samp1ing continued at stations 3, 6, 8 and 9. In addition, 16 stations were random1y se1ected from a grid superimposed on a map of the samp1ing area (Figure 6). Ha1f of the samp1es were taken from an area which was periodica11y warmed by the discharge p1ume of the power p1ant, and the other ha1f came from the adjacent waters beyond the direct inf1uence of the p1ume. The U.S.E.P.A. Sites A three year study on entrainment effects of the coo1ing system was undertaken in November, 1972, with a grant from the United States EnvironmentaI Protection Agency (USEPA). Seven stations were chosen (Figure 5) to samp1e the river (station 9) and 1ake (station 17) as sources of cooIing water as we11 as to foIIow its course through the discharge cana1 (stations 12, 8, and 14). In addition, two p1ume stations (stations 15 and 16) were samp1ed in order to trace the progress of the discharge water as it mixed with the 1ake. Station 15 17 eeea ¢<>+<>¢a +<><><>++<>w Ad'cet Monroe eo'in <>¢¢n . Water . o<><>¢¢+<><>3° WPQ++¢¢¢¢++u PI f++¢¢¢+¢¢46 Um} Crefik " {P 0 '¢ + ¢ ‘0 T“ Dischare + ¢+¢¢¢¢5I Cona +++++¢¢¢69 . Dischare +<>+<>A<>+¢+<><><>ao rea <>+<><>+<><>+¢¢<>m e +<>+++ 994“” <><><>¢+<><>+¢<><>m ee'eeeee‘eeeoem Ad'acent +¢<> ¢¢¢+¢<>¢¢m Water ¢¢¢¢¢¢+¢<>¢em +¢¢¢¢¢¢¢¢¢¢¢W +<>+<>+<>¢+¢<><>m <>+<>++<><><><>¢ms ,ds- ampe tohons + Q <> 0 '¢ ¢ + <> <2 'CP'V'Non-Sampled Stations <> <>¢¢<><>¢¢<>m ¢¢ {>4} 4} ¢2os rKrLOMETER Figure 6. Map showing the 1ocation of the 1975 random samp1ing sites. 18 was samp1ed a10ng the main axis of the p1ume where the temperature had fa11en ha1f way from the discharge cana1 temperature to the ambient 1ake temperature. Station 16 was a1so samp1ed a10ng the main axis of the p1ume but in a position where the temperature was on1y 1 to 2°C above ambient 1ake temperature. Therefore, stations 15 and 16 changed position in response to wind driven currents as we11 as power p1ant discharge. Figure 5 Shows the positions of stations 15 and 16 during the first year of the study. Station 18 was an artificia1 station whose composition was ca1cu1ated on the basis of the Raisin River discharge and p1ant pumping rates. It was assumed that on1y river water was drawn into the intake unti1 p1ant pumping exceeded river discharge, when additiona1 water was drawn from Lake Erie via the Raisin River mouth. At each station, five rep1icates were taken by random samp1ing at five depths except at stations 15 and 16 where samp1es were a11 from just be1ow the surface. Samp1ing was carried out on a bimonth1y basis from November, 1972, to September, 1975. Each set of samp1es inc1uded a mercury (II) preserved set for nitrogen ana1ySis and three sets of unpreserved samp1es for ch10ride anaTySiS, each designed to samp1e one of the periods: morning, afternoon, and evening. These three sets were taken over a two or three day period whi1e the nitrogen samp1es were taken at the same time as one of the ch10ride sets. Other Data Sources Ch1oride data were obtained from the Monroe Water Treatment p1ant for the days on which the study area was samp1ed (W. LePage, 19 persona1 communication). The intake is 10cated 1.5 kiIOmeterS west of Stony Point (Figure 1). Ch10ride data were a1so obtained from near Shore stations at the Swan Creek-Fermi study Site (Figure 1) during 1973. Shaffer (1975) samp1ed at the stations in trip1icate on six dates during the year. Chemica1 data for the Detroit River were obtained from two agencies. Samp1ing was conducted across the mouth of the Detroit River a10ng a transect referred to as Range 3.9 (Figure 1). The Ontario Water Resources Commission (OWRC) reported ch10ride and inorganic nitrogen concentrations for 1971. The Michigan Water Resources Commission (MWRC) reported ch10ride and inorganic nitrogen concentrations for the period 1970 through 1974. Both agencies samp1ed about six times a year during the ice—free season. ChIOride and inorganic nitrogen concentrations in the Maumee River were obtained from the ToIedo Po11ution Contro1 Agency (TPCA) for the years 1970 through 1974. Samp1es were taken from the west bank of the river at the TOIedo Termina1 Bridge (Figure 1), approxi- mate1y 1.5 ki10meters from the river mouth, on a month1y basis. Additiona1 ch10ride data for the Maumee River were obtained from the U. S. Geo1ogica1 Survey. Ch10ride va1ues were taken bimonth1y at Watervi11e, Ohio, approximate1y 34 ki1ometers from the mouth of the river. Dai1y discharge va1ues of the Raisin and Maumee Rivers were Obtained from the State Offices of the U. S. GeoIogica1 Survey. Monthiy discharge va1ues for the Detroit River were obtained from the Lake Survey Office of the U. S. Corps of Engineers. 20 Wind information was obtained from the U. S. Weather Service office at East Lansing for the To1edo Express Airport. Montth precipitation va1ues were aISO obtained for Monroe, Michigan, from this office. METHODS AND MATERIALS Laboratory ana1yses were carried out for ch10ride, tota1 Kje1dah1 nitrogen, nitrate nitrogen, ammonia nitrogen, and nitrite nitrogen. ChIOride ana1yses were accompiished with mercuric nitrate titration of a 25 mi11i1iter samp1e to the dipheny1carbazone—mercury comp1ex endpoint. A mixed indicator containing Xy1ene cyano1 FF WIS used, as out1ined in Standard Methods (Anon., 1965). Tota1 Kje1dah1 nitrogen was measured by digesting a 50 m1 samp1e with a mercury cata1yst. Ammonia formed in the digestion of nitrogen- containing organic compounds and nitrogen a1ready present as ammonia were then disti11ed and determined by the Ness1erization reaction. The micro-Kje1dah1 method that was fo110wed was out1ined in Standard Methods (Anon., 1965) and in the FWPCA (Anon., 1969) and EPA (Anon., 1971) manua1s. Nitrate nitrogen was determined by the method of Jenkins and Medsker (1964), Siight1y modified in EPA Methods (Anon., 1971) by e1imination of the ch10ride masking reagent. Samp1es containing more than the maximum standard of 0.7 mg/1iter had to be di1uted to within the standard range. Ammonia nitrogen ana1yses were carried out via disti11ation and Ness1erization. Origina11y, the disti11ation pH was buffered at 7.4 (Anon., 1965) but it was changed to 9.5 (Anon., 1969) to reduce the possibiIity of any hydro1ysis of nitrogen-containing organic compounds. 21 22 In 1972 the method for ammonia nitrogen was changed to the phenate method of Harwood and Kuhn (1970). This method e1iminated the disti11ation step comp1ete1y, was easier and faster to perform, and was more precise than previous methods. A1though the ammonia anaIySiS method was changed to insure against error, no significant differences were detected between methods when they were tested with samp1es from the study area. Nitrite ana1yses were carried out with a method simi1ar to the one provided in Standard Methods (Anon., 1965) except that acetic acid a10ne was added as a pH controi, instead of an acetate buffer. The nitrite ana1yses were discontinued in 1970 because the va1ues were usua11y insignificant (<0.01 mg/Titer). Organic nitrogen was ca1cu1ated as the difference between tota1 Kje1dah1 nitrogen and ammonia nitrogen. Inorganic nitrogen was ca1cu1ated as the sum of ammonia nitrogen and nitrate nitrogen, discounting any nitrite. Tota1 nitrogen was assumed to be the sum of nitrate nitrogen and tota1 Kje1dah1 nitrogen. This is equiva1ent to the organic nitrogen p1us inorganic nitrogen, and it is equa1 to the tota1 bound nitrogen of the samp1e. Mean va1ues for a11 stations on each samp1ing date are given in Appendix Tab1es A1 through A7 and seasona1 means in Tab1es A8 through A14. AnaIysis of variance tests were performed on each date through the 1972 samp1ing year. Where station differences were Significant (p < 0.05), Tukey's mu1tip1e range test (Stee1e and Torrie, 1960) was performed, and significance (p < 0.05) was indicated by underiining. Where Significant (p < 0.05) depth differences were present, a dagger (T) was p1aced next to the date. Asterisks (*) next to a station 23 number denote that insufficient rep1icates were avai1ab1e to inc1ude that station in the ana1ysis of variance mode1. However, the va1ue is inc1uded for comparison. After 1972, the ana1ysis of variance was discontinued. RESULTS AND DISCUSSION Chioride and Hydrodynamics On1y neg1igib1e fractions of the ch10ride concentrations in the Great Lakes are inf1uenced by chemica1 reactions of either physica1 or bioIogica1 origins. Therefore, the ch10ride concentra- tions may be used effectiveiy to trace the movements and mixing of different water masses (Hem, 1970; Kaufman and Or1ob, 1956; Spain and Andrews, 1970; Ketchum, 1951 and 1967). A mass ba1ance ca1cu1a- tion is used, and if the ch10ride concentrations of a11 sources are known, then the re1ative proportions of each source are easi1y ca1cu1ated (Hem, 1970). The va1ue of ch10ride as a tracer is iimited by the degree of difference in concentrations between sources, and by the temporaI variabiiity of each source. The conditions are best when the sources are of wide1y differing and constant concentrations. Ch1oride concentrations in the study area are characterized by wide differences among waters in the 1ake near the Monroe power p1ant, the Detroit River, and the SimiIar Maumee and Raisin Rivers (Tab1e 2). Concentrations in the Maumee and Raisin Rivers consistent1y averaged about two times the concentration in the 1ake from 1970 to 1974 and more than twice the concentrations reported for the Detroit River. Data presented in Tab1e 2 Show that the 1ake concentrations most strong1y ref1ect the input of Detroit River water even though the Maumee and Raisin Rivers are re1ative1y c1ose to the 1ake stations that were samp1ed. 24 25 v.np o.NN mpwm PELmd-xmmcu cmzm _ Pm m.m_ m.m~ o.mp pamFQ “cospmmch moccoz o.mm F.vm n.¢m ¢._¢ o.mm Lm>wm :wmwmm m.o¢ m.mm m.mm m.om o.~¢ cm>wm amaze: ¢.q_ N.mp m.m_ m.¢_ m.- Lm>Vm “wocpmo _.m_ N.m_ n.¢_ w.op w._~ Ao-_ meowpmpmV :mmz mxmb mm «.m_ II «.m— I- -- mpvm waged-xmmcu swam N.m_ o.¢_ ¢.¢_ o.m_ N.m_ pew—a pcmspmmgh moccoz _.wm m.m¢ w.©m “.mm m.mm Lm>wm cwmwmm o.mm m.qq m.mm o.Nm o.Pm Lm>wm mosses o.o~ N.m_ 0.0? N.m_ m.wF Lm>wm “wocpmo m.mF N.wp m.mp m.o~ N.¢N Ao-P mcovpmpmV com: mme “waamw m.o_ - w.m_ -- -- mpwm wagon-xmmcu cmzm m.NF m.m_ o.op m.m_ o.m_ pampa pcmEpmmLH moccoz N.Nm w.mm m.m~ m._¢ m.mm cm>wm :wmwmm «.mm m.mm N.mm m.~m o.NN cm>wa amaze: m.op N.m_ o.ap m.m_ o.om _ Lm>wm gwocpwo m.m_ m.m_ m.m_ m.mm N.ow Ao-_ meowumpmV :wmz axe; mmmumw :mmz Pacemmmm enm_ mump NmmF ommF cemmmm .mmecmpznwcp my? use mwcm mxmb c? mmpwm umpumme pm mcowpmcpcmucoo muwcopcu cams szccm vcw Pacemmmm .N mfinmh 26 m.mp I- w.n— -- -- mpwm wacdexmeu cmzm m.mp o.mF _.mp P.m~ P.0N “cm—m ucmspmmgh mogcoz v.mm m.mm m.mm m.ov o.mm Lm>wm :wmwwm m.mm F.m¢ m.mm m.Pm o.mm Lm>wm mm53mz N.m— ¢.¢P —.o_ o.mp _.NF Lm>wm awocpmo ©.m_ m.m_ m.©~ ©.m~ P.mm Ao-F mcowumpmv :mwz mme mmmz flmmmmm :mwz FmCOmmmm qmmr mnmp Nmmr onmp cemmmm A.S.:ouV .N SFDSP 27 Chioride concentrations at the 1ake stations varied wide1y over the study period from 1970 to 1974 (Figure 7). The differences in ch10ride concentrations at station 1 through 6 in the study area were frequentIy Significant (p < 0.05) on any one particu1ar date, but the differences were not particu1ar1y consistent from one samp1ing date to another. This inconsistency cou1d have resu1ted from the changing ch10ride concentrations introduced to the 1ake from the tributaries and other sources as we11 as by a changing composition caused by mass movements of water. Figure 7 indicates that ear1y Spring ch10ride concentrations in the 1ake tend to exceed those at other times of the year, but the seasona1 variations are not marked. During the high Spring runoff, Ch1oride residua1s from winter street saitings may contribute to higher concentrations in the 1ake. Part of the seasona1 variabi1ity in 1ake ch10ride concentrations may resu1t from the re1ative variabi1ity of annua1 inputs of water from the Detroit, Maumee and Raisin Rivers (Figures 3 and 4). These three tributaries contribute a1most 99% of the f10w to the western basin of Lake Erie whi1e most of the remainder f10ws in from the Huron River near the mouth of the Detroit River. The Detroit River contributes about 95% of the annua1 f10w into the basin. However, the proportion and amount varies considerab1y according to the season. A1though the Detroit River contributes a stab1e f10w, particu1ar1y during the ice-free seasons, the mean month1y f10w of the remaining tributaries typica11y varies by one order of magnitude. A1though the Maumee River discharge averages on1y two to three percent of that from the Detroit River, it usua11y contributes eight to 15 percent of the winter or spring discharge and 0.2 to 0.4% of 28 .mNGV cmsoecb ONSV .0 Senate“ _ meowpmpm weep “a meowumEpcmueoo mewco_;u .N menace was — R2 L g? g _ _ N3. L — :2 Re p5§< ZIpD-mp<_\a-\H:p< O»WL<»\¢L\J»2-¢W .2.O»WL<.WP\4.‘ e_ covpmom op m_ cowbmpm EOE» mucmumwo Ezerxwz new cmmz .mE:_Q new Pmcmu mmcmcumvv esp cw mcovumcpcmucou wnwcopzo came szcc< .m mrnmp 33 Previous studies of currents in the western basin, taken co11ective1y, indicate that the wind is the primary determinant for water movements, and the currents are predominant1y northward a10ng the west shore (Andrews, 1948; Verber, 1953 and 1955; O1sen, 1950; and O'Leary, 1966). Re1ative1y rare northeasterIy winds or ca1m weather foster a particu1ar1y strong intrusion of Detroit River water into the study area. Brisk souther1y winds enhance any effect of the Maumee River on the study area, particu1ar1y at times of high discharge. A1though the wind frequent1y Shifts, month1y resu1tant winds are a1most a1ways souther1y. Therefore, the net water movements were expected to traverse the study area from station 5 to station 1, whi1e in the process mixing with Raisin River water and other minor shore1ine sources. The vaci11ating winds cause current reversais which obscure concentration gradients, but 1ong term averages revea1 consistent trends for the re1ative impact of Maumee, Detroit, and Raisin River waters (Tab1e 2). In Figure 9, it iS assumed from data reported in Tab1e A8 that Raisin River water has no inf1uence beyond station 5 to the south or station 3 to the north. The mean rise in ch10ride concentration observed at stations 5, 4 and 3 is be1ieved to have been caused entire1y by the Raisin River input just west of station 4 except in 1970 when it was west of station 3. There are no other potentia1 sources a10ng the shore in that vicinity except the extensive human settiement on the northern Shore of Brest Bay. Therefore, water at station 6 and station 2 is be1ieved to ref1ect measurab1e mixtures of Detroit and Maumee River water, whereas station 1 may 34 .cmms mcwgo_:u Lm>wm pwogpmo Fm:0mmmm op vmcmaeou 0 Senate“ _ meowpmpm axes pm A vnmr sauces“ okmFV mcowpmgucmocoo muwgopgo chommmm :mmz :82 8:25 :8 52m :23 .I.I. II. 1.. .I..I.. .L-Voulmcomz 82on axe-V ' 0" '0'.‘ 0'0'.' 0'. m mi ............. 522 02520 .66an 82¢ :otmo coEEam I .282 5:06 axe-V N II Icmmz- mammo- damawIc-omm-mmmoii 05.8 19.692 :0:on axe-V . I..- . I .I. N m v .m weaned 6.2 .09 do. ION. .09 Se do. d: .09 6.9 6.8 do. 6.: -09 3.9 .08 To._~ aptlomo Bur/6w 35 be 1oca11y inf1uenced by cu1tura11y enriched tributaries and direct inputs from Shore zone settIements. The re1ative contributions of Maumee and Detroit River waters that mix in the study area can be estimated from data gathered on chemica1 concentrations in the Detroit and Maumee Rivers by govern- menta1 agencies over the period of study. Detroit River ch10ride data was obtained both by the Ontario Water Resources Commission (OWRC) and the Michigan Water Resources Commission (MWRC) a10ng the same cross-river transect (Figure 1) but at different samp1ing times in 1971. The Michigan Water Resources Commission measured ch10ride throughout the study period. A11 of the profiIeS compared in Figure 10 agree c1ose1y and revea1 the stab1e annua1 contributions of ch10ride to Lake Erie. Data were obtained by the Toiedo Po11ution Controi Agency (TPCA) on ch10ride concentrations at one 10cation on the west Shore near the mouth of the Maumee River. This part of the river is inf1uenced by 1ake seiches which can conceivab1y mix 1ake and river water at this 1ocation. These data, however, were assumed to be representative of 1ower Maumee River concentrations, and they agreed c1ose1y with ch10ride data obtained 34 ki1ometers upstream by the United States Geo1ogica1 Survey. Assuming, then, that stations 2 and 6 are composed of Detroit and Maumee River water, and that stations 3, 4 and 5 contain Raisin River water in addition, a mass ba1ance equation can be formuIated and the re1ative contribution of each source determined. These ca1cu1ations indicate that the Maumee River is particu1ar1y inf1uentia1 in the Spring and 1ess so in times of 10w water input during the fa11 (Tab1e 4). In fact, fa11 contributions from the Maumee ref1ect 36 .3o_m chowpomm-mmoco we cowpgoaoca mcp .m:o_mmwssou mmoc30mma memz owcmpco use camecovz .o_ menace pcmmmcawc macsmwm mmmpcmucma esp Eoce mumu mewcmaeou .m.m magma um Lm>wm “wocpmo mg» Low mmeeoca muweo_;u mmoxw mmozm 5m 5m; 52 000.8 000.9 008. 88 o — p — pi _ . . p P _ b - _ p p L _ F r _ O _I0\oo_ It. V I-O\oomI.+IIIo\oom III-TO\oo_Iv_+lo\oo_Iv_IIIo\oo_I-rllv .wo_ .I.-: I..--- :I. -o_ /. -o~ lo I w b V m. “6 1| \ 8 m V m“ V. :9 28 226 ..... w V.V .5 28 82,2 2.... -mm V. 39.05. 28 0mg: 11 .V m roe .V .V _ .._ fine 37 II mmo.o Fmo.o Feo.o II Lm>wm :wmwem meo.o “mo.o «op.o mo~.o pmo.o Lm>vm messes me.o 500.0 mem.o nmw.o mmm.o Le>wm “wecumo Ppeu II moo.o Foo.o mmo.o II Lm>wm cwmwem opp.o P_~.o woF.o o__.o epF.o Lm>wm messes —mw.o emw.o Fom.o me.o owm.o Lm>wm pwegpeo Lessem II oeo.o mmp.o Foo.o II Lm>wm :wmwex mn—.o mmp.o om~.o oep.o m¢_.o Lm>wm messes me.o mom.o Fem.o mom.o mmm.o Lm>wm pwegpeo mcwcqm m m e m N seepage meme .mcewuecpceecee mewcepge :e eemee mcewpepm exep we :ewpwmeeEee e>wpepec new: .e mPeeh 38 an exceptionaI Spate during the fa11 of 1972. Without that exceptionaiiy high runoff, the Maumee River wou1d not have had more than trace effects. At certain times of very high discharge, which might exceed the mean spring seasona1 discharge by five or ten times, a1most a11 of the water in the study area cou1d have come from the Maumee River. The prOportion of Maumee River water remains fair1y constant as the water masses proceed northward through the study area. Apparent1y Detroit and Maumee River water mix to the proportions found in the study area near the mouth of the Maumee River, and those proportions tend to be retained unti1 after the water passes Stony Point. There it cou1d be di1uted to concentrations approaching the mean Detroit River concentrations, as indicated by Monroe city water. Water from the Raisin River mixes into this northward moving vaci11ating mass. On1y at station 4 is the impact of the Raisin River as important as the impact of the Maumee River a10ng this samp1ing transect. But, by far, the major source of water in the study area is the Detroit River, particu1ar1y during the 1ate summer and fa11. This a1so has been indicated by synaptic surveys conducted over a few days by Hart1ey, Herdendorf, and Ke11er (1966). These observations aiso support those of other workers who have suggested that a c1ock- wise gyre usua11y dominates the circu1ation in the southwestern corner of western Lake Erie. Nitrogen Nitrogen potentia11y cou1d enter the gyre of southweStern Lake Erie from the Detroit, Maumee and Raisin Rivers as we11 as from the atmosphere. It may be Iost to deep sediments or to the atmosphere as 39 water passes through the western basin. This study genera11y indicates that the most important source of nitrogen to the study area is the watershed. Nitrogen fixation in the 1ake did not appear to be an important source. The nitrogen concentrations usua11y f1uctuated wide1y in the study area (Figure 11) with the comp1exity of the changing tributary discharges and vaci11ating, wind-driven 1ake currents. But there were discernib1e seasona1 trends. The nitrate nitrogen concentration (Figure 12), in particu1ar, was high in Spring and 10w in 1ate summer and ear1y fa11. The ammonia nitrogen (Figure 13) was seasona11y 1ess variab1e than either nitrate nitrogen or organic nitrogen (Figure 14); the 1atter tended to increase through the growing season and peak during 1ate summer and ear1y fa11. The concentrations of nitrogen measured in the Raisin River aISo exhibited the same seasona1 trends (Tab1e 5). These trends have been wide1y recognized by others (VoIIenweider, 1968; Feth, 1966; and Hutchinson, 1957). Assuming that the net movement of water through the study area is northward and, therefore, that Raisin River water mixes with water moving northward from station 6, the re1ative proportion of Raisin River water can be ca1cu1ated from the ch10ride concentration of the sources for stations 4 and 5. The percentage compositions Shown in Tab1e 6 were ca1cu1ated from ch10ride concentrations by assuming that Raisin River water and station 6 water combine to form station 5 water, and that station 5 and Raisin River water combine to produce station 4 water. As shown in Tab1e 6, measured tota1 nitrogen was usua11y 1ess than had been predicted by this mixing scheme. The difference was most consistent1y due to nitrate nitrogen 40 was _ .mkseL 2. .mmmp smeecge Dump .0 sweets» P mcewpeem exe— we mcewuegpceecee cemeguwc Fepeh .F— mcemwe Rm» Ohm Pem gemwmm e cavemem emcemeez empoweece emcemeez empoweece “smegma eeeecee cemeepwz eweemco cemecpwz Fepep eegeem .Lepez Le>wm :wmwem sew; mexwe Lewes exep mew>ee ecechcee page mewssmme e ece m mceweepm exep we mgeueEegee :emeguwc emcemeee ece empepeepeo .e epeeh 46 0F.0 FN.0 Pe.0 mm.0 FFeu __.0 F_.0 mm.0 em.0 Leasem e_.e “0.0 m_._ RN._ esteem _\0E F\0E _\0E F\0E emcemeez empoweeee emcemeez empoweece cemeepwz eweeesq cemegpvz meecpwz em.0 «0.0 NF._ 00., _.N 0.xm P_em N0.0 00.0 e0._ N_.P N.m m.n0 Leggem mm.e Ne.e ew._ mm.V F.m m._m eceegm mmflwwmmamm-m-mmflmmw _\eE F\ee _\me _\e5 ee>em cemwea e :eeemem emcemeez empoweece emcemeez empoweece uceecee “emote; :emecpwz eecemco cemegpwz Feuek eeceem A.u_cooV .0 wpeeh 47 differences with 1itt1e, if any, compensation from other forms of nitrogen. The Raisin River, therefore, has s1ight1y 1ess of an impact on tota1 nitrogen concentration at the 1ake stations than Simp1e di1ution of river water by 1ake water wou1d indicate. There was very 1itt1e indication that mean annua1 nitrate nitrogen (Tab1e 7) changed in concentration as river and 1ake water mixed and passed through the coo1ing system of the Monroe Power P1ant. There may have been a SIight 1055 of ammonia nitrogen in Spring (Tab1e 8), but 1itt1e change in organic nitrogen (Tab1e 9) during passage. But overa11, there was 1itt1e change in tota1 nitrogen (Tab1e 10). The nitrogen data obtained random1y from the study area in 1975 were piotted against the re1ative ch10ride concentrations (Figure 15). Concentrations of nitrate nitrogen were c1ose1y re1ated to the ch10ride concentrations, probab1y ref1ecting coincidentaI Shore zone inputs. The concentrations of organic nitrogen varied indepen- dentiy of the ch10ride concentrations, and concentrations of ammonia nitrogen were not as c1ear1y re1ated to ch10ride concentrations as were the concentrations of nitrate nitrogen. Most of the nitrogen that enters the 1ake from the tributaries comes in the form of nitrate nitrogen. Both ammonia and organic nitrogen are readiiy' formed by bio1ogica1 processes in the 1ake proper from some portion of the nitrate nitrogen that enters the 1ake. Therefore, neither ammonia or organic nitrogen are as 1ike1y to be direct1y associated with shore zone inputs that have re1ative1y high ch10ride concentra- tions. m_._ mm.F 00.m __.N m0.m mw.P 0m.m mm._ 000: ececw ..... fi-------w._------M------M.-------mm-------.-w--------m_..m------w._----------wm--- -- -.-H.-------M-.-M._-------w.-------N---aw. ..... M._------M.-------N. ..... --.-._--- -----._m._ ....... w....-------w-m ....... N ....... w-------w ....... wm-------.-m .......... we 0_ m_ 0F 0 NF mp m up Lem> cowemem meme .Fecee emcegemwe exp :0 mcewuecpcmecee cemegpwc epecuw: _e:::< .N mpeeh 49 -.0 N_.0 0N.0 0m.0 0N.0 0_.0 00.0 ep.0 000: 0:000 0_.0 0F.0 NN.0 0_.0 0—.0 0F.0 00.0 e_.0 0NOP 00.0 _—.0 _N.0 PN.0 0F.0 0F.0 0m.0 No.0 emmfi 0F.0 mm.0 mm.0 mm.0 mm.0 mm.0 nm.0 0N.0 mmmfi 0P 0? e_ 0 NF 0_ 0 m— 000> cavemem axes .Feeee emeecemwe ecu cw mcewueceeeecee cemecuw: eecesse Feecc< .0 mFeeh 50 00.0 F0.0 00.0 00.0 00.0 0m.0 N0.~ 0m.0 :00: 0:000 00.0 N0.0 00.0 00.0 00.0 mm.0 0~.F 00.0 0NOF 00.0 00.0 00.0 00.0 0n.0 00.0 No._ 00.0 «NOF 0m.0 00.0 m—.F 00._ NF.F 00.P ~0._ 00.F mm0_ 0P 0F 0— 0 N— 0_ 0 up Lem> :e0emem exme .Fecee m0cegemwv exp :0 meewuegpceecee :mmeepw: ewcemce _e:::< .0 epnep 51 00.0 m0.m 00.0 00.0 0N.m 00.0 00.0 00.0 :00: 0:000 00.0 00.0 00.0 00.0 00.0 50.0 00.0 0N.F 0N0. 0¢.F m0.F 00.0 mm.m 00.0 N~.m 00.0 00.— «n0p Fm.m 00.0 00.0 00.0 00.0 0_.¢ 00.0 Fm.m 0NOF 0F 0F 0— 0 0— 0p 0 NF Lem> cewpmem wee; .Fecee e0gecemwu 0:0 :0 mcevuecp:ee:ee :e0eeuw: Pepe“ Fe:::< Io— mfineh .me_:Eem Eeuce: .0m0_ .0:0:00 0:0 Lew :e_uecu:ee:ee eewce_0e e>wue_eg .m> :eweececeecee cemegpw: ewcesse 0:0 .ewce0ee .epegpwc e>wpepeg we mpeFQ .0F 003000 52 Zmoombi 4.20224 zwwomtz O_Z<0mo meomtz whdmki 0.0 I who E0 L N.O F 0.0 bf. » who I 0.0 I #m NO 0.0 IO»; . MO I who II 30 I No I 0.0 I . I - II- - . . ed 4 I - . . .Ne 00.": r $0.": V. .Vm u: ND. u.— . E. + xme. L . 8.1569 L . 3:81; .3 . I . V . . I I I I I I I I ‘ I .- I I I I. I f®.0 I I I I I I” III II w .I a I I v I In II In I I.IPI\\\I\\\\\ II II I IIIIIuH\\IIII\ r II ‘ III I I I ~\flW\II\I\\ I a I I I I I II II III I I I I II III. I II \II\I II II I I I I I I I \I\\b\ I I I I I V. \IIII I IQO I I I I I I I I I I n I - II I I I I I I I I - I I I I I I V- I II I - I I r0.— BOIHO‘IHO 53 Some data were collected on nitrogen concentrations for the Detroit and Maumee Rivers in conjunction with chloride measurements by the Michigan Water Resources Commission and the Toledo Pollution Control Agency. Only estimates of nitrate and ammonia nitrogen are available, however (Table ll). The predicted concentrations of inorganic nitrogen in the study area were not manifested as predicted by the mixing of different source waters alone (Table 4). Inorganic nitrogen (Table l2) was always less concentrated than predicted; 25 to 50 percent less in spring and fall, and 65 to 75 percent less in summer. The one exception was station 6 in the fall which showed only a six percent discrepancy. There also appeared to be a further decline as the water masses moved northward through the study area even though this decline was not predicted by any mixing phenomena. Both nitrate (Table 13) and ammonia nitrogen (Table 14) were less concentrated than predicted at station 6, but only nitrate nitrogen continued to decline in concentration as the water progressed northward through the study area. The ammonia concentrations may have increased slightly in partial compensation. Seasonal concentrations of organic nitrogen (Table Al3) varied through the study area but with no indication of any trend up or down. Substantial quantities of nitrogen seem to be lost from the water column mostly before it enters the study area during all seasons. Some nitrogen may be lost directly to the atmosphere as ammonia, although the usual pH encountered in western Lake Erie (less than 9.0) would seem to be too low to foster this loss. Organic nitrogen may settle to the bottom where denitrification 54 Table 11. Seasonal nitrate and ammonia nitrogen concentrations in the Maumee and Detroit Rivers. 1970 1972 1973 1974 Mean Nitrate nitrogen concentrations Spring Detroit River 0.37 0.35 0.28 0.36 0.34 Spring Maumee River 3.25 9.15 4.27 1.28 4.49 Summer Detroit River 0.37 0.29 0.21 0.22 0.27 Summer Maumee River 4.05 8.05 3.10 2.60 4.45 Fa11 Detroit River 0.13 0.19 0.25 0.22 0.20 Fell Maumee River 1.60 4.23 2.07 2.75 2.66 Ammonia nitrogen concentrations Spring Detroit River 0.50 0.52 0.38 0.48 0.47 Spring Maumee River 1.80 2.45 1.23 2.15 1.90 Summer Detroit River 0.46 0.46 0.37 0.35 0.41 Summer Maumee River 2.60 1.20 1.20 1.75 1.69 Fa11 Detroit River 0.29 0.31 0.40 0.35 0.33 Fa11 Maumee River 3.85 0.70 3.23 2.10 2.47 55 Fn.o on.o m¢.o mm.o —.mm 00.0 mm.. mq.o mm.. .messm 0m.. om.. mm.. a... mc.tam m m 00.0 N... em.o 00.. om.o mm.o ..ma m¢.o mm.. qm.o .m.. mm.o .m.. amassm mm.. mm.. .... .... mm.o 00.. m:.cam vmcsmmmz umpuwvmca vmcsmmwz napowumcm vmczmmmz vmpuwumca v m N cemmmm co.pmbm axes .mcowpmgpcwucou mc..o.;u Eocw vmpu.umLa mm new mxm. asp :. nmgsmmms mm mco.um.#:mucoo :wmocpw: owcmmcoc. .N. m.nmh 56 .m.o mm.o mm.o o¢.o Fgmu mm.o nu.o mm.o ou.o Lmaszm «N.. mo.. mo.. 0... mc.cam o m Fv.o «m.o mm.o mm.o mm.o mm.o Fpm. mm.o om.o mm.o mm.o mm.o mm.o LmEEDm m... NN.. No.. 0... mw.o mm.o mcwcqm vmgzmmmz umpu.vmca umczmmmz umwuwumga umgzmmmz vapo.umga w m N cemmmm co..wpm axes mvwco.;u soc; vmpuwnmca mm ucm mxm. .mcowpmgucmocoo mcp :. vmczmmme mm mcowpmgucmocoo camogam: mpmcpmz .mp mpnmh 57 om.o 00.0 om.o .¢.o ..ma N..o om.o o..o om.o amassm o..o N..o q..o m©.o m:.cam o m m..o mm.o .N.o .m.o mN.o m¢.o ..m. ...o om.o mo.o om.o m..o om.o Lasagm e..o 80.0 m..o .m.o m..o .o.o m:.tam vmgsmmmz umpo.vm.a nmcsmmwz cmpuwvmca umczmmmz umpu.vwga v m N cemmmm :o..a.m axes .mcowpmggcmocoo mv..o.:u Eocm vmpuwnmca mm ucm wxm. mcp :. wwgzmmms mm mcowpmgucmucou :mmocpw: mwcoEE< .v. mfiamp 58 could take place. Although atmospheric nitrogen fixation probab1y takes place in western Lake Erie at least for short periods of time (Mague and Burris, 1972; Howard et__l., 1969), these data indicate that it is not likely to be a primary source of nitrogen in the study area because seasona1 concentrations of inorganic nitrogen tend to be relatively high even during the summer. Because of high concentrations, the Maumee and Raisin Rivers contribute inordinately higher masses of nitrogen to southwestern Lake Erie than indicated by their discharge. Therefore, nitrogen fixation may be relatively uncommon in this part of the western basin. The Monroe Power Plant seems to have little effect on the dynamics of nitrogen other than to enhance the mixing of Raisin River water with waters derived almost entirely from the Detroit and Maumee Rivers. There appears to be a slight decrease in nitrogen concentration as water passes through the cooling system and into the lake. However, such decreases also seem to occur naturally on a much larger scale as water moves northward through the study area. CONCLUSIONS From calculations based on the chloride concentrations in major inf1uents, water in the study area was shown to be composed of Detroit, Maumee, and Raisin River waters. The relative pr0portions are a function of tributary discharge and wind driven currents. The Detroit River has a relatively high quality and uniform discharge that consists of water from the upper Great Lakes and wastewaters from the Detroit and Windsor municipalities. The Maumee and Raisin Rivers, on the other hand, receive municipa1 effluent in addition to runoff from an intensely farmed area. The difference in source waters coupled with the seasonal discharge characteristics of the Maumee and Raisin makes their impact on the study area highly variable over the ice-free seasons. The chloride concentrations show that the tributary input remains in the near shore area, because chloride concentrations remain higher than that of the Detroit River. On a short term basis, the shore region can be flushed with low chloride lake water when the proper conditions are achieved. However, on a seasonal basis, the near shore waters seem to consist of tributary input other than the Detroit River. This water probab1y moves in either direction along the shore in response to wind, river input, and seiche activity. Most of the nitrogen is contributed to the study area by the Maumee and Raisin Rivers as well as other small tributaries that 59 6O drain land in the area. The great majority of this nitrogen is input as nitrate during periods of high discharge in winter and spring and occasionally in fall. This is a considerable prOportion of the total nitrogen input to Lake Erie and its origin in the watershed is of considerable importance to those wishing to control nutrient inputs. Based on chloride behavior, which is considered conservative, nitrogen in the study area shows a consistent net decrease from the values calculated from river inputs. Insufficient data are available to evaluate the mechanism of these losses; however, they are probably due to some combination of sedimentation and denitrifi— cation. The main impact of the Monroe Power Plant, as traced by chloride ion, seems to be the movement of Raisin River waters to a new input site on Lake Erie and the dilution of that water by lake water prior to discharge to the lake. Discharge canal studies show a rapid mixing of discharge water with lake water, such that chloride concen- trations are usually diluted to ambient 1ake values within five kilometers. Some nitrogen may be lost on transit through the discharge cana1, possibly controlled by the same factors that Operate in the lake proper. The elevated temperature in the canal would also tend to accelerate any biological processes occurring therein. This long term investigation into the seasonal impact of major tributaries in the study area, provides important background data needed to understand the biological processes in the ecosystem. Hopefully, it will contribute to the evaluation of present 61 perturbations to the system, as well as provide meaningful methods and criteria for future planning, including power plant siting. To be most helpful, continuing studies of this area should include year around monitoring of the major tributaries. With this information, Lake Erie's nitrogen and hydrodynamic systems couldjbe modeled more accurately. Continuous monitoring would also provide1 better evaluation of both long and short term tributary effects. Studies over the area might be expanded to investigate how mixing gradients are affected by the distance from shore. Hydro- dynamics could also be more accurately ascertained by evaluating at least two independent conservative quantities. Chloride has been amply proven to be the best natural tracer so far, but perhaps sodium or sulfate could also be demonstrated to be useful as conservative tracers. With two conservative tracers the pr0portions of water consisting of three sources could be unambiguously defined. In addition, investigations nearer the shore might reveal some previously unrecognized source explaining the anomalously high chloride values at station 1. LITERATURE CITED LITERATURE CITED Andrews, T.F. 1948. Temporary changes of certain limnological conditions in western Lake Erie produced by a windstorm. Ecology 29(4): 501—505. Anon. 1965. Standard Methods for the Examination of Water and Wastewater. 12th Edition. American Public Health Association, New York. 769 pp. Anon. 1968. Lake Erie environmental summary, 1963-64. U.S. Dept. of the Interior, Great Lakes Region. Federal Water Pollution Control Admin- istration. Cleveland, Ohio. 170 pp. Anon. 1969. FWPCA methods for chemical analysis of water and wastes. U.S. Dept. of the Interior. Federal Water Pollution Control Admin— istration. Cincinnati, Ohio. 280 pp. Anon. 1971. Methods for chemical analysis of water and wastes. U.S. Environmental Protection Agency, Washington, D.C. 312 pp. Beeton, A.M. 1961. Environmental changes in Lake Erie. Trans. Am. Fish. Soc. 90:153-159. Beeton, A.M. 1971. Chemical characteristics of the Laurentian Great Lakes, In; Proceedings of the conference on changes in the chemistry of Lakes Erie and Ontario. Bull. Buffalo Soc. Nat. Sci. 25(2):l-21. Carr, J.F., V.C. Applegate, and M. Keller. 1965. A recent occurrence of thermal stratification and low dissolved oxygen in western Lake Erie. Ohio J. Sci. 65(6):319-327. Carr, J.F., and J.K. Hiltunen. 1965. Changes in the bottom fauna of western Lake Erie from 1930-1961. Limnol. 0ceanogr., 10:551-569. Chandler, D.C. and 0.B. Weeks. .1945. Limnological studies of western Lake Erie. V. Relation of limnological and meteorological condi- tions to the production of phytoplankton in 1942. Ecol. Monogr. 15:435-457. Cole, R.A. 1972. Physical and chemical limnology along the western shore of Lake Erie. Tech. Rep. 13. Institute of Water Res. Michigan State Univ., East Lansing, Mich. 120 pp. Cole, R.A. 1973. An ecological evaluation of a thermal discharge: summary of early postoperational studies. Tech. Rep. 32.0. Institute of Water Res., Michigan State Univ., East Lansing, Mich. 43 pp. 62 63 Cole, R.A. and R. Freeman. 1972. An ecological evaluation of a thermal discharge. Part IV: Preoperational Studies, 1970-1971. Tech. Rep. 16. Institute of Water Res., Michigan State Univ., East Lansing, Mich. 98 pp. Cur1, H.C. 1957. A source of phosphorus for the western basin of Lake Erie. Limnol. Oceanogr. 2:315-320. Davis, Charles C. 1964. Evidence for the eutrophication of Lake Erie from phytoplankton records. Limnol. Oceanogr. 9:275-283. Eaton, U.S., G.E. Likens, and F.H. Bormann. 1969. Use of membrane filters in gravimetric analyses of particulate matter in natural waters. Water Resour. Res. 5(5):1151-1156. Feth, J.H. 1966. Nitrogen compounds in natural water -- a review. Water Resour. Res. 2:41-58. Harlow, G.L. 1966. Major sources of nutrients for algal growth in western Lake Erie. Univ. Michigan. Great Lakes Res. Div. Proc. 9th Conf. on Great Lakes Res. Pub. no. 15. p. 389-394. Hart1ey, R.P. 1968. Bottom currents in Lake Erie. Univ. Michigan. Great Lakes Res. Div. Proc. 11th Conf. on Great Lakes Res. p. 398-405. Hart1ey, R.P., C.E. Herdendorf, and M. Keller. 1966. Synoptic water samp1ing survey in the western basin of Lake Erie. Univ. Michigan Great Lakes Res. Div. Proc. 9th Conf. on Great Lakes Res. Pub. 15, p. 301-322. Harwood, J.E. and A.L. Kuhn. 1970. A colorimetric method for ammonia in natural waters. Water Res. 4:805-811. Hem, J.D. 1970. Study and interpretation of the chemical characteris- tics of natural water 2nd edition. Geological survey water supply paper 1473. U.S. Geological Survey. U.S. Government Printing Office. Washington, D.C. 363 pp. Herdendorf, C.E. 1969. Water masses and their movements in western Lake Erie. Ohio Div. Geol. Survey Dept. No. 74. Columbus, Ohio. 7 pp. Howe, L.H. and C.W. Holley. 1969. Comparisons of mercury (II) chloride and sulfuric acid as preservatives for nitrogen forms in water samples. Environ. Sci. and Technol. 32478-481. Hutchinson, G.E. 1957. A treatise on limnology. Vol. 1. Geography, Physics, and Chemistry. John Wiley, New York. 1015 pp. Jenkins, 0. and L.L. Medsker. 1964. A brucine method for the determina- tion of nitrate in ocean, estuarine, and fresh waters. Anal. Chem. 36:610-612. 64 Kaufman, W.J. and G.T. Orlob. 1956. Measuring ground water movement with radioactive and chemical tracers. J. Am. Water Works Assoc. 48 559- 572. Ketchum, B.H. 1951. The exchanges of fresh and salt water tidal estuaries. J. Mar. Res. 10:18-38. Ketchum, B.H. 1967. Phytoplankton nutrients in estuaries. In; G.H. Lauff (ed.) The Estuaries, Pub. No. 83, Amer. Assoc. Adv. Sci., 757 pp. Kovacik, T.L. 1972. Information on the velocity and flow pattern of Detroit River water in western Lake Erie revealed by an accidental salt spill. Ohio J. Sci., 72(3):81-86. Langlois, T.H. 1954. The western end of Lake Erie and its ecology. U.W. Edwards, Pub. Ann Arbor, Mich. 479 pp. O'Leary, L.B. 1966. Synoptic vector method for measuring water mass movements in western Lake Erie. Univ. Michigan Great Lakes Res. Div. Proc. 9th Conf. on Great Lakes Res. Pub. 15:337-344. Olsen, F.C.W. 1950. The currents of western Lake Erie. Ph.D. thesis, Ohio State Univ., Columbus, Ohio. Public Health Service. 1965. Proceedings Vol. 2: Conference in the matter of pollution of navigable waters of the Detroit River and Lake Erie and their tributaries in the State of Michigan. Washington, D.C. 304 pp. Shaffer, P.W. 1974. An ecological evaluation of the fate of radioisotopes from Fermi II nuclear power plant in western Lake Erie: trace elements and background gamma levels in water and sediments near the western shore of Lake Erie. M.S. thesis. Michigan State University, East Lansing, Mich. 125 pp. Spain, J.D. and S.C. Andrews. 1970. Water mass identification in a small lake using conserved chemical constituents. Univ. Michigan Great Lakes Res. Div. Proc. 13th Conf. on Great Lakes Res. p. 733- 743. Steele, R.G.D. and J.H. Torrie. 1960. Principles and procedures of statistics. McGraw-Hill Co., New York. 481 pp. Verber, J.L. 1953. Surface water movement, western Lake Erie. Ohio J. Sci. 51(1):42-46. Verber, J.L. 1955. Surface water movement in western Lake Erie. Int. Assoc. Theor. Appl. Limnol. Proc. 12:97-104. Verduin, J. 1969. Man's influence on Lake Erie. Ohio J. Sci. 69:65-69. 65 Vollenweider, R.A. 1968. Scientific fundamentals of the eutrophication of lakes and flowing waters, with particular reference to nitrogen and phosphorus as factors in eutrophication. Organ. Econ. Coop. and Dev. Rep., Paris. Walters, L.V. Jr., C.E. Herdendorf, L.J. Charlesworth, Jr., H.K. Anders, W.B. Jackson, E.J. Skoch, D.K. Webb, T.L. Kovacik, and C.S. Sikes. 1972. Mercury contamination and its relation to other physico- chemical parameters in the western basin of Lake Erie. Univ. Michigan Great Lakes Res. Div. Proc. 15th Conf. on Great Lakes Res. p. 306-316. Wright, S., L.H. Tiffany, and W.M. Tidd. 1955. Limnological survey of western Lake Erie. U.S. Fish. Wildl. Serv. Spec. Sci. Fish Rep. 139. Washington, D.C. 341 pp. APPENDICES 66 Table A1. Mean concentration of chloride in mg/l by station. 1 May 70 19.1 19.8 21.1 21.4 21.9 23.3 29.3 33.2 33.5 . 15 May 70I 19.1 19.8 19.9 20.4 20.5 21.8 24.2 25.3 29.4 27 May 70 16.5 17.8 17.9 18.8 19.7 22.4 27.5 28.4 29.8 . 10 June 70 18.4 19.2 19.6 19.8 20.3 20.9 22.4 24.3 31.5 23 June 70. 20.3 20.4 20.8 21.1 21.9 22.2 31.6 32.1 36.8 7 July 70+ 14.5 17.3 18.8 18.9 19.1 19.3 23.0 23.9 31.3 21 July 70 17.3 19.0 19.5 20.1 20.1 20.4 30.1 30.7 32.5 4 Aug 70 23.8 27.8 28.3 29.3 30.7 31.8 32.3 35.4 35.9 18 Aug 70 25.5 33.6 34.2 34.3 34.5 34.7 39.8 40.3 67 Table A1 (con't.) 1 Sept 70 22.4 23.1 24.1 25.5 25.7 26.2 27.5 28.0 36.6 15 Sept 70 21.9 23.2 23.9 24.7 24.7 25.0 26.2 30.0 32.0 27 Sept 70 20.9 22.7 23.5 24.3 24.9 25.0 26.3 27.4 40.2 10 Oct 70 17.6 18.0 18.7 18.7 19.4 20.1 20.3 36.6 39.0 25 Oct 70 18.8 19.3 19.4 19.5 20.0 21.5 22.3 22.6 26.3 7 Nov 70 15.2 20.8 21.9 22.5 23.4 24.1 24.3 29.3 30.3 22 Apr 72 32.7 35.0 38.2 40.3 44.0 44.0 46.2 61.3 11 May 72 14.7 16.3 24.8 25.1 26.1 26.3 41.8 42.2 50.0 31 May 72 19.6 21.0 23.4 24.1 24.3 24.5 29.3 31.2 33.8 13 June 72 19.3 19.8 19.8 20.0 20.3 20.4 24.9 25.8 45.5 Table A1 (con't.) 27 June 72 12 July 72 25 July 72 16 Aug 72 29 Aug 72 12 Sept 72 29 Sept 72 6 Oct 72 13 Oct 72 27 Oct 72 15 Nov 72 68 5 3 4 l 2 6 8 7* 9 9.6 9.9 11.1 11.2 11.4 12.8 18.7 25.0 46.0 6 1 2 3 5 4 8 9 14.5 14.9 15.2 17.9 19.1 19.5 23.1 45.6 1 4 2 3 5 6 7* 8 9 12.4 13.0 13.1 13.3 14.4 15.9 16.7 17.5 24.2 5 1 2 4 3 6 7* 8 9 14.4 14.9 15.0 15.0 16.4 17.4 20.5 20.9 40.3 2 6 3 1 5 8 4 7* 9 15.7 16.1 16.7 20.9 21.8 23.8 24.0 24.1 46.6 2 4 5 1 3 6 8 7* 9 17.4 17.4 18.0 18.3 18.7 19.2 24.0 24.5 41.8 2 6 1 4 3 5 7* 8 9 15.2 16.3 18.3 18.4 18.5 19.1 30.6 30.8 42.5 3 8 9 17.2 30.8 43.0 2 3 6 5 1 4 8 7* 9 14.7 17.9 18.0 18.1 18.3 19.2 31.8 33.3 44.2 5 3 4 6 1 2 8 7* 9 12.3 16.3 16.9 17.2 18.2 21.8 35.0 37.2 43.1 2 3 1 4 5 6 8 7* 9 9.0 12.8 15.5 15.6 17.0 18.2 30.5 33.7 34.1 Table A1 (con't.) 7 Feb 73 24 April 73 11 May 73 30 May 73 20 June 73 6 July 73 17 July 73 1 Aug 73 15 Aug 73 28 Aug 73 10 Sept 73 24 Sept 73 8 Oct 73 20. 20. 29. 20. 16. 16. 14. 14. 69 29. 20. 30. 22. 27. 24. 28. 22. 20. 20. 26. 20. 18. 20. 15. 31. 25. 29. 22. 20. 20. 27. 20. 20. 20. 18. 29. 29. 26. 33. 30. 39. 43. 34. 46. 32. 31. Table A1 (con't ) 13 Nov 73 14 Mar 74 3 April 74 17 April 74 7 May 74 22 May 74 31 July 74 13 Aug 74 11 Sept 74 27 Sept 74 7 Oct 74 24 Oct 74 7 Nov 74 18 Mar 75 25. 25. 22. 18. 19. 70 25. 22. 18. 21. 19. 19. 17. 12. 12. 13. 25. 32. 28. 27. 20. 19. 22. 19. 20. 17. 14. 14. 26. 28. 20. 22. 20. 24. 14. 27. 30. 29. 26. 25. 24. 20. 20. 21. 18. 14. 20. 27. 30. 31. 28. 26. 24. 21. 21. 22. 18. 14. 21. 27. 30. 33. 28. 36. 25. 42. 44. 39. 45. 23. 27. 40. 71 Table A1 (con't.) 6 May 75 3 6 8 9 15.4 22.2 28.3 28.5 4 June 75 6 3 8 9 19.3 24.1 29.2 38.3 24 June 75 3 6 8 9 17.7 18.0 20.8 33.8 Tab1e A2. Mean concentration of total nitrogen in mg/l by station. 1 May 70 15 May 70 27 May 70 10 June 70+ 23 June 70 7 July 701 21 Ju1y 70 4 Aug 70 18 Aug 70 6 1 2 9 3 8 4 7* 5 2.18 2.20 3.24 3.64 3.74 3.75 3.97 4.13 4.66 l 2 6 3 4 5 7* 8 9 0.93 1.07 1.53 1.63 2.01 2.14 2.21 2.27 2.44 2 l 3 5 6 4 7* 8 9 0.43 0.54 0.89 1.33 1.42 2.07 2.90 3.47 5.93 l 2 9 7* 3 8 6 4 5 1.43 1.88 2.08 2.10 2.25 2.34 2.48 3.00 3.53 6 5 1 4 2 3 8 7* 9 1.42 1.48 1.62 1.81 1.90 1.92 3.28 3.76 6.08 2 3 1 6 5 4 8 9 7* 0.71 0.88 0.94 0.96 1.12 1.22 1.78 1.89 1.98 2 3 1 4 6 5 8 7* 9 0.70 0.71 0.82 0.87 0.92 1.00 1.46 1.98 2.15 2 1 6 4 3 5 7* 8 9 0.65 0.71 0.72 0.73 0.75 0.76 1.76 1.83 2.08 6 1 3 2 4 5 8 9 7* 0.53 0.57 0.58 0.62 0.67 0.77 1.45 1.52 1.95 73 Table A2 (con't.) 4 5 6 2 1 3 9 8 7* 1 Sept 70 0.58 0.60 0.63 0.67 0.67 0.72 1.27 1.39 1.56 3 2 1 6 5 4 9 8 7* 15 Sept 70 0.46 0.46 0.51 0.51 0.53 0.58 1.04 1.21 1.35 3 2 1 5 6 4 9 7* 8 27 Sept 70 0.56 0.60 0.65 0.74 0.74 0.77 1.33 1.43 1.51 4 3 1 6 7* 5 2 8 9 10 Oct 70, 0.80 0.89 0.92 0.93 1.00 1.02 1.09 1.46 1.47 5 4 3 1 2 6 7* 8 9 25 Oct 70 0.93 0.93 0.99 0.99 1.06 1.07 1.61 1.61 1.69 4 2 3 5 6 7* 1 8 9 7 Nov 70 0.88 0.91 0.92 1.04 1.04 1.10 1.15 1.25 1.90 2 8 7* 23 Jan 71 0.60 1.37 1.79 1 7* 18 Feb 71 0.52 1.95 6 2 5 1 3 4 9 8 7* 16 Apr 71 0.50 0.87 0.92 0.98 1.15 1.34 2.68 2.84 3.28 1 2 6 4 3 5 8 9 7* 1 May 71 1.89 2.10 2.20 3.27 3.45 3.56 3.93 3.99 5.10 Table A2 (con't.) 20 May 71 1 June 71 18 June 71 2 July 71* 15 July 71 29 July 71 17 Aug 71 2 Sept 71 16 Sept 71 2 Oct 71 1 2 6 3 5 4 8 9* 7* 0.98 1.28 1.31 1.46 1.49 1.66 2.13 2.48 2.58 2 3 1 6 5 4 7* 8 9 0.52 0.74 0.77 0.78 0.88 1.51 2.45 3.72 4.72 1 2 3 9 6 8 4 7* 5 1.31 1.85 1.97 2.54 2.64 2.65 2.71 3.35 3.66 6 5 4 3 8 2 7* 1 9 0.96 1.07 1.29 1.33 1.48 1.56 1.65 1.98 2.13 6 1 5 4 8 2 3 9 7* 0.80 0.82 1.12 1.15 1.20 1.25 1.25 1.35 1.40 3 6 2 5 1 8 4 9 7* 0.78 0.79 0.84 0.84 0.85 0.88 0.90 1.19 1.33 4 5 3 6 1 2 8 7* 9 0.68 0.71 0.76 0.81 0.82 0.89 1.27 1.37 1.44 3 2 4 1 6 5 9 8 7* 0.71 0.77 0.79 0.81 0.84 0.93 1.03 1.07 1.28 6 2 3 5 1 4 7* 8 9 0.61 0.66 0.66 0.76 0.79 0.85 1.04 1.06 1.26 5 6 3 7* 1 4 8 9 2 0.75 0.76 0.99 1.08 1.09 1.15 1.20 1.46 1.74 Table A2 (con't.) 15 Oct 71+ 30 Oct 71 12 Nov 71 2 Dec 71 19 Dec 71 11 Jan 72 18 Feb 72 22 Apr 72 11 May 72 31 May 72 13 June 72 5 6 3 4 1 2 8 7* 9 0.59 0.65 0.70 0.71 0.73 0.74 1.26 1.39 1.73 5 3 6 2 4 l 8 7* 9 0.94 1.00 1.01 1.05 1.11 1.15 1.43 1.89 1.96 3 2 1 4 5 6 8 7* 9 0.81 1.02 1.02 1.05 1.26 1.51 1.74 2.52 4.06 7* 8 9 1.44 1.48 2.33 3 4 1 7* 8 9 0.90 0.91 0.96 3.09 3.19 4.76 3 4 9 8 7* 1 81 3.37 7.15 7.77 9.66 3 1 8 7* 9 1.40 1.46 2.89 3.08 4.32 2 1 3 4 5 9 8 7* 1.65 1.75 1.84 2.02 2.31 10.68 12.44 17.08 3 2 1 4 5 6 9 8 7* 0.60 0.74 0.94 0.94 0.96 1.73 8.40 9.00 9.46 6 5 7* 3 4 8 1 2 9 1.61 1.61 1.86 2.04 2.13 2.28 2.62 2.72 3.03 4 2 6 5 8 1 7* 3 9 1.95 2.16 2.21 2.25 2.46 2.46 2.63 3.00 4.70 76 Table A2 (con't.) 5 3 2 1 6 4 8 7* 9 27 June 72 0.62 0.64 0.67 0.84 0.84 0.92 2.95 3.63 7.00 6 3 7* 1 2 8 4 5 9 12 July 72 0.91 1.10 1.16 1.24 1.28 1.34 1.66 1.78 1.90 2 3 6 1 4 5 8 7* 9 25 July 72 0.60 0.70 0.79 0.83 0.89 0.99 1.04 1.10 1.27 1 4 2 5 3 6 7* 8 9 16 Aug 72 0.67 0.72 0.75 0.77 0.82 1.02 1.03 1.05 1.44 6 1 2 3 4 5 7* 8 9 29 Aug 72 0.72 0.84 0.93 1.08 1.24 1.79 2.32 2.34 7.00 4 3 5 2 6 1 7* 8 9 12 Sept 72 1.12 1.12 1.16 1.32 1.34 1.48 1.94 2.21 3.83 2 5 3 1 4 6 7* 8 9 29 Sept 72 1.14 2.00 2.07 2.27 2.38 4.03 7.30 7.97 8.79 3 8 9 6 Oct 72 2.32 6.55 10.46 2 1 3 5 4 6 8 7* 9 13 Oct 72 1.79 1.93 2.08 2.15 2.60 2.74 4.86 4.92 5.62 5 3 4 6 1 2 8 7* 9 27 Oct 72 0.97 1.65 1.70 1.72 1.95 2.16 6.38 6.46 7.04 77 Table A2 (con't.) 2 3 1 5 6 4 8 7* 9 15 Nov 72 0.70 0.88 1.21 1.30 1.46 1.89 9.16 9.41 9.68 3 1 8 7 9 7 Feb 73 0.89 1.23 5.80 6.08 7.44 5 3 2 4 1 7 8 9 24 Apr 73 1.32 1.63 1.84 1.97 2.01 3.11 3.30 4.20 6 5 1 2 4 3 8 7 9 11 May 73 0.70 0.73 1.07 1.10 1.13 1.55 2.15 2.41 2.54 5 2 6 4 1 3 8 9 7 30 May 73 1.06 1.10 1.20 1.38 1.41 1.50 5.50 5.63 5.81 1 4 5 2 3 6 8 7 9 20 June 73 1.27 1.39 1.64 1.76 2.17 3.30 3.36 3.40 4.87 1 6 2 5 4 3 7 8 9 6 July 73 1.13 1.50 1.45 1.85 3.11 3.33 7.29 7.35 7.38 3 4 2 5 1 6 7 8 9 17 July 73 0.97 1.03 1.20 1.25 1.46 1.63 1.94 2.01 2.70 6 3 5 1 2 4 8 7 9 1 Aug 73 1.31 1.39 1.43 1.45 1.49 1.60 2.26 2.42 4.09 3 1 5 2 6 4 7 8 9 15 Aug 73 1.31 1.36 1.42 1.43 1.47 1.72 1.72 1.73 3.09 6 2 3 1 5 4 8 7 9 28 Aug 73 0.88 0.88 0.88 0.91 1.01 1.03 1.25 1.28 1.89 3 5 4 2 6 1 7 8 9 10 Sept 73 0.86 0.87 0.94 0.95 1.02 1.04 1.45 1.51 3.31 Table A2 (con't.) 24 Sept 73 8 Oct 73 13 Nov 73 3 Apr 74 17 Apr 74 7 May 74 22 May 74 16 July 74 31 July 74 13 Aug 74 11 Sept 74 27 Sept 74 0.71 0.80 0.82 0.88 1.07 0.73 1.07 0.54 0.83 0.69 0.81 0.50 0.74 0.86 0.88 1.08 1.58 0.87 1.61 0.62 0.88 0.72 1.01 0.55 0.75 0.86 1.63 1.30 1.64 0.93 1.66 0.66 0.91 0.86 1.04 0.56 0.76 0.87 1.69 1.45 1.64 1.02 1.68 0.72 0.97 0.95 1.05 0.62 0.82 0.88 0.74 0.84 0.90 0.79 1.04 1.36 1.38 2.76 2.79 Table A2 (con't.) 7 Oct 74 24 Oct 74 7 Nov 74 18 Mar 75 22 Apr 75 6 May 75 4 June 75 24 June 75 2 0.45 0.63 0.85 1.52 1.59 1.70 1.81 2.17 2.12 3.54 80 Table A3. Mean concentration of nitrate nitrogen in mg/l by station. 1 6 9 2 8 7* 3 4 5 1 May 70 1.43 1.63 .32 2.47 2.70 2.80 2.97 .07 3.62 2 l 3 9 7* 6 8 5 4 15 May 70 0.40 0.45 .97 1.07 1.13 1.13 1.43 .57 1.58 2 l 3 5 6 4 7* 8 9 27 May 70 0.18 0.22 .50 0.62 0.93 1.60 1.63 .32 4.83 7* 9 1 8 2 3 6 4 5 10 June 70 0.47 0.58 .77 1.37 1.37 1.47 1.97 .47 2.88 6 5 l 4 3 2 7* 8 9 23 June 70 0.90 0.97 .98 1.12 1.37 1.40 1.70 .70 4.67 2 7* 1 8 9 3 6 5 4 7 July 70 0.20 0.23 .33 0.40 0.45 0.45 0.48 .60 0.67 8 7* 2 1 3 6 4 5 9 21 July 70 0.15 0.17 .22 0.25 0.28 0.30 0.30 .37 0.88 5 6 2 3 1 7* 4 8 9 4 Aug 70 0.12 0.12 .16 0.18 0.18 0.20 0.23 .55 0.73 l 5 4 3 8 2 7* 9 18 Aug 70 0.08 0.09 .10 0.12 0.13 0.14 0.19 .21 Table A3 (con't.) 1 Sept 70 15 Sept 70 27 Sept 70 10 Oct 70 25 Oct 70 7 Nov 70 23 Jan 71 18 Feb 71 16 Apr 71 1 May 71 81 3 1 5 2 6 4 7* 8 9 0.07 0.07 0.08 0.08 0.09 0.09 0.12 0.13 0.26 2 1 6 7* 5 3 8 9 4 0.06 0.06 0.08 0.08 0.09 0.10 0.10 0.14 0.18 9 3 2 5 4 6 7* 1 8 0.13 0.13 0.14 0.15 0.15 0.16 0.16 0.16 0.17 9 4 3 7* 8 2 1 6 5 0.14 0.19 0.21 0.24 0.25 0.26 0.27 0.27 0.35 8 1 5 3 7* 4 2 6 9 0.24 0.24 0.24 0.24 0.24 0.25 0.28 0.31 0.46 7* 4 8 2 5 3 6 1 9 0.25 0.25 0.26 0.26 0.27 0.27 0.30 0.31 0.58 2 8 7* 0.55 0.99 1.10 1 7* 0.45 0.27 6 1 2 5 3 4 9 8 7* 0.30 0.47 0.50 0.64 0.67 0.96 1.47 1.75 2.43 1 6 2 9 8 4 3 5 7* 1.30 1.75 1.92 2.48 2.55 2.87 2.92 3.12 3.65 Table A3 (con't.) 20 May 71 1 June 71 18 June 71* 2 July 71 15 July 71’r 29 July 71 17 Aug 71 2 Sept 71 16 Sept 71 82 1 2 9 3 8 6 5 4 7* 0.51 0.71 0.87 0.88 0.89 0.96 1.04 1.12 1.48 2 3 1 5 6 7* 4 8 9 0.21 0.31 0.45 0.52 0.52 0.93 1.17 2.48 3.66 1 8 9 2 3 7* 4 6 5 0.68 0.84 10.1 1.18 1.27 1.43 1.96 2.00 3.03 8 5 9 6 4 7* 3 2 1 0.49 0.53 0.54 0.55 0.57 0.59 0.62 0.68 0.95 4 7* 6 8 1 9 3 5 2 0.26 0.27 0.27 0.34 0.35 0.40 0.45 0.56 0.56 1 8 3 4 2 9 5 7* 6 0.08 0.08 0.08 0.10 0.12 0.13 0.14 0.16 0.16 1 3 2 4 6 5 8 9 7* '0.07 0.08 0.08 0.08 0.09 0.10 0.11 0.14 0.16 5 2 3 9 1 8 6 4 7* 0.07 0.07 0.08 0.09 0.10 0.11 0.11 0.12 0.16 1 8 6 9 7* 5 3 2 4 0.10 0.11 0.11 0.13 0.13 0.14 0.19 0.20 0.23 Table A3 (con't.) 2 Oct 711 15 Oct 71 30 Oct 71 12 Nov 71 2 Dec 71 19 Dec 71 11 Jan 72 18 Feb 72 22 Apr 72 83 6 4 3 5 8 7* 9 2 1 0.04 0.09 0.09 0.10 0.12 0.15 0.17 0.19 0.25 2 l 3 5 6 4 8 7* 9 0.05 0.05 0.05 0.05 0.07 0.09 0.11 0.13 0.16 5 6 3 9 4 7* 8 2 1 0.19 0.20 0.24 0.26 0.26 0.29 0.31 0.37 0.37 2 3 1 5 6 4 7* 8 9 0.10 0.12 0.17 0.19 0.25 0.26 0.31 0.33 0.70 7* 8 9* 0.97 4.78 8.35 3 4 1 7* 8 9 0.35 0.36 0.37 2.22 2.27 3.72 3 4 9 8 7* 1 19 2.60 5.51 6.23 7.95 1 3 7* 8 9 0.72 0.74 1.48 1.54 2.35 1 5 4 3 2 9 8 7* 0.74 0.75 0.82 0.86 0.89 9.37 11.12 15.4 Table A3 (con't.) 11 31 13 27 12 25 16 29 12 29 84 3 2 4 5 1 6 9 8 7* May 72 0.31 0.32 0.50 0.54 0.60 1.34 7.16 7.97 8.50 7* 9 8 6 3 4 5 1 2 May 721 1.00 1.14 1.14 1 37 1.54 1.59 1 72 2.03 2.11 4 7* 8 9 2 5 1 6 3 June 72 1.41 1.41 1.52 1.57 1.61 1.81 1.90 1.96 2.42 5 2 3 1 6 4 8 7* 9 June 72 0.26 0.27 0.29 0.34 0.38 0.48 1 90 2.60 4.49 1 2 8 6 3 9 4 5 July 72 0.20 0.25 0.46 0.54 0.54 0.57 0.94 1.22 1 8 7* 9 3 2 6 5 4 July 72+ 0.22 0.22 0.23 0.23 0.23 0.23 0.27 0.30 0.30 1 2 5 4 8 3 7* 9 6 Aug 721 0.20 0.21 0.23 0.28 0.32 0.32 0.33 0.40 0.48 2 1 6 3 4 5 8 7* 9 Aug 72 0.08 0.10 0.14 0.18 0.26 0.38 0.79 0.83 3.28 1 4 3 5 2 6 8 7* 9 Sept 72 0.06 0.07 0.07 0.07 0.08 0.09 0.16 0.17 0.38 2 1 5 3 4 6 7* 9 8 Sept 721 0.34 0.57 0.62 0.76 0.96 2.74 5.37 5.99 6.09 Table A3 (con't.) 6 Oct 72 13 Oct 72 27 Oct 72 15 Nov 72 7 Feb 73 24 Apr 73 11 May 73 30 May 73 20 June 73 6 July 73 17 July 73 1 Aug 73 85 3 8 9 0.97 4.78 8.34 2 3 1 5 0.51 0.67 0.90 1.03 5 4 3 6 0.41 0.82 0.82 0.88 2 3 5 1 0.36 0.51 0.51 0.57 3 1 8 7 0.55 0.71 4.51 4.54 5 3 2 1 0.72 0.97 1.10 1.22 5 6 1 2 0.28 0.31 0.42 0.47 2 1 5 3 0.34 0.36 0.37 0.39 1 4 2 5 0.25 0.44 0.44 0.74 1 2 6 5 0.50 0.61 0.67 1.12 4 3 2- 5 0.31 0.38 0.46 0.52 1 6 3 5 0.64 0.70 0.72 0.74 1.25 6.02 1.24 0.48 0.42 0.74 1.97 0.59 0.77 1.83 0.68 0.54 1.94 2.24 0.79 0.80 8 7* 9 3.16 3.28 3.33 8 7* 9 4.86 4.87 5.15 8 7* 9 7.67 7.78 8.23 8 9 2.05 2.67 8 7 9 1.00 1.12 1.31 8 9 7 3.75 3.90 3.91 8 6 9 1.99 2.22 2.83 9 7 8 5.70 5.82 5.84 8 6 9 0.84 0.85 1.17 8 7 9 0.98 1.01 1.28 Table A3 (con't.) 15 Aug 73 28 Aug 73 10 Sept 73 24 Sept 73 8 Oct 73 13 Nov 73 3 Apr 74 17 Apr 74 7 May 74 22 May 74 16 July 74 31 July 74 86 0.61 0.28 0.15 0.24 0.50 0.85 0.29 0.17 0.25 0.53 0.86 0.56 0.48 0.43 0.94 Table A3 (con't.) 13 Aug 74 0.05 11 Sept 74 0.10 27 Sept 74 0.05 7 Oct 74 0.06 24 Oct 74 0.09 7 Nov 74 0.20 18 Mar 75 0.93 22 Apr 75 0.96 6 May 75 ’ 0.60 4 June 75 1.07 24 June 75 1.14 0.77 2.26 1.84 2.79 2.52 2.52 87 88 Table A4. Mean concentration of total Kje1dah1 nitrogen in mg/l by station. 6 3 1 2 4 8 5 9 7* 1 May 70 0.51 0.77 0.77 0.77 0.90 0.91 1.04 1.32 1.33 6 4 1 5 3 2 8 7* 9 15 May 70 0.40 0.43 0.48 0.57 0.66 0.67 0.94 1.08 1.38 2 1 3 4 6 5 8 9 7* 27 May 70 0.24 0.32 0.39 0.47 0.48 0.71 1.12 1.16 1.26 2 6 5 1 4 3 8 9 7* 10 June 70 0.51 0.52 0.65 0.66 0.73 0.78 0.98 1.50 1.64 2 6 5 1 4 3 9 8 7* 23 June 70 0.50 0.52 0.53 0.64 0.70 0.97 1.41 1.58 2.06 3 6 2 5 4 1 8 9 7* 7 July 7O+ 0.43 0.48 0.51 0.52 0.55 0.61 1.38 0.44 1.74 3 2 1 4 6 5 9 8 7* 21 July 70 0.43 0.49 0.57 0.57 0.62 0.63 1.30 1.31 1.81 4 2 1 3 6 5 9 8 7* 4 Aug 70+ 0.49 0.50 0.53 0.57 0.60 0.65 1.18 1.27 1.56 3 1 2 4 5 9 8 7* 18 Aug 70 0.47 0.48 0.49 0.55 0.68 1.31 1.33 1.76 Table A4 (con't.) 1 Sept 70 15 Sept 70 27 Sept 70 10 Oct 70* 25 Oct 70 7 Nov 70 23 Jan 71 18 Feb 71 16 Apr 71 1 May 71 20 May 71 89 4 5 6 2 1 3 9 8 7* 0.49 0.52 0.54 0.59 0.60 0.64 1.01 .26 1.43 3 4 2 6 5 1 9 8 7* 0.36 0.40 0.41 0.43 0.44 0.45 0.90 .11 1.26 3 2 1 5 6 4 9 7* 8 0.42 0.46 0.48 0.59 0.60 0.62 1.20 .27 1.34 5 4 6 1 3 7* 2 8 9 0.60 0.60 0.66 0.66 0.68 0.76 0.82 .21 1.34 4 5 3 6 1 2 9 7* 8 0.68 0.69 0.75 0.75 0.76 0.78 1.24 .36 1.38 4 3 2 6 5 1 7* 8 99 0.62 0.65 0.65 0.73 0.77 0.83 0.85 .00 1.32 2 8 7* 0.05 0.37 0.69 1 7* 0.09 0.67 6 5 2 4 3 1 8 9 7* 0.20 0.28 0.38 0.39 0.48 0.50 0.75 .21 1.23 2 4 5 6 3 1 8 7* 9 0.35 0.41 0.44 0.46 0.51 0.59 1.37 .45 0.51 6 5 1 4 2 3 7* 8 9 0.36 0.45 0.47 0.50 0.57 0.58 1.10 .41 1.63 Table A4 (con't.) 1 June 71 18 June 71+ 2 July 71 15 July 71 29 July 71 17 Aug 71 2 Sept 71 16 Sept 71 2 Oct 71 15 Oct 71 90 6 2 1 4 5 3 9 8 7* 0.26 0.31 0.33 0.34 0.37 0.44 1.09 1.42 1.52 5 1 6 2 3 4 9 8 7* 0.63 0.63 0.64 0.68 0.71 0.75 1.53 1.81 1.92 6 5 3 4 2 8 1 7* 9 0.41 0.55 0.71 0.72 0.87 1.00 1.03 1.07 1.59 1 6 5 2 3 8 4 9 7* 0.47 0.51 0.57 0.69 0.81 0.86 0.90 0.95 1.12 6 3 5 2 1 8 4 9 7* 0.63 0.69 0.70 0.72 0.78 0.80 0.81 1.06 1.17 4 5 3 6 1 2 8 7* 9 0.59 0.62 0.66 0.72 0.75 0.81 1.16 1.22 1.30 3 4 2 1 6 5 9 8 7* 0.64 0.67 0.70 0.71 0.73 0.86 0.94 0.96 1.12 2 3 6 4 5 1 7* 8 9 0.45 0.47 0.53 0.61 0.62 0.69 0.90 0.95 1.13 5 6 1 3 7* 4 8 9 2 0.65 0.72 0.88 0.89 0.93 1.06 1.08 1.29 1.55 5 6 4 3 1 2 8 7* 9 0.54 0.58 0.62 0.65 0.68 0.69 1.14 1.27 1.57 Table A4 (con't.) 30 Oct 71 12 Nov 71 2 Dec 71 19 Dec 71 11 Jan 72 18 Feb 72 22 Apr 72 11 May 72 31 May 72 13 June 72 91 2 1 5 3 6 4 8 7* 9 0.69 0.75 0.76 0.76 0.81 0.85 1.12 1.61 1.70 3 4 1 2 5 6 8 7* 9* 0.69 0.79 0.85 0.92 1.08 1.26 1.41 2.21 3.36 7* 8 9 0.80 0.95 1.76 4 3 1 8 7* 9 0.55 0.55 0.59 0.94 0.94 1.04 3 4 8 9 7* 0.61 0.77 1.54 1.64 1.71 3 1 8 7* 9 0.66 0.74 1.35 1.60 1.98 2 3 1 4 9 8 5 7* 0.77 0.98 1.02 1.20 1.31 1.49 1.56 1.68 3 1 6 2 5 4 7* 8 9 0.29 0.34 0.39 0.42 0.43 0.45 0.96 1.03 1.25 6 5 3 4 1 2 7* 8 9 0.24 0.29 0.50 0.54 0.59 0.62 0.86 1.16 1.89 6 5 4 2 1 3 8 7* 9 0.41 0.44 0.55 0.56 0.56 0.58 1.10 1.21 3.13 Table A4 (con't.) 27 June 72* 12 July 72 25 July 72 16 Aug 72 29 Aug 72 12 Sept 72 29 Sept 72 6 Oct 72 13 Oct 72 92 5 3 2 4 6 1 8 7* 9 0.35 0.36 0.40 0.44 0.46 0.50 0.86 1.03 2.50 6 5 3 4 8 2 1 9 0.38 0.56 0.56 0.72 0.88 1.03 1.04 1.32 2 3 6 4 1 5 8 7* 9 0.37 0.47 0.53 0.59 0.61 0.69 0.82 0.88 1.05 4 3 1 5 6 2 7* 8 9 0.45 0.50 0.54 0.54 0.55 0.55 0.71 0.73 1.04 6 1 2 3 4 5 7* 8 9 0.57 0.74 0.85 0.90 0.98 1.41 1.49 1.56 3.72 4 3 5 2 6 1 7* 8 9 1.06 1.06 1.09 1.23 1.25 1.42 1.77 2.05 3.45 2 6 3 5 4 1 8 7* 9 0.80 1.27 1.32 1.32 1.41 1.70 1.88 1.93 2.81 3 8 9 1.35 1.77 2.11 1 5 6 2 4 3 7* 8 9 1.04 1.12 1.12 1.29 1.35 1.41 1.64 1.70 2.34 Table A4 (con't.) 27 Oct 72 15 Nov 72 7 Feb 73 24 Apr 73 11 May 73 30 May 73 20 June 73 6 July 73 17 July 73 1 Aug 73 15 Aug 73 28 Aug 73 93 5 3 6 4 1 2 0.57 0.83 0.84 0.88 0.94 1.04 2 3 4 1 6 5 0.34 0.37 0.51 0.64 0.74 0.79 3 1 8 9 7 0.34 0.51 1.29 1.42 1.54 5 3 4 2 1 8 0.60 0.65 0.73 0.74 0.79 1.26 6 5 2 1 4 3 0.39 0.45 0.63 0.65 0.65 0.87 5 2 6 4 1 3 0.69 0.76 0.79 0.85 1.05 1.11 5 4 1 6 2 8 0.90 0.96 1.02 1.09 1.32 1.37 1 5 6 2 3, 4 0.64 0.73 0.83 0.84 1.09 1.15 3 4 5 2 6 1 0.59 0.73 0.73 0.74 0.78 0.87 6 3 5 2 4 1 0.61 0.67 0.70 0.72 0.80 0.81 5 6 4 3 2 1 0.85 0.86 0.87 0.88 0.98 1.06 2 1 3 6 4 8 0.75 0.80 0.81 0.84 0.87 0.96 8 7* 9 1.52 1.59 1.89 9 8 7* 1.42 1.49 1.63 7 9 1.28 1.53 8 9 7 1.15 1.23 1.29 9 8 7 1.73 1.75 1.90 3 7 9 1.43 1.46 2.04 7 8 9 1.46 1.51 1.68 7 8 9 1.15 1.17 1.53 8 7 9 1.28 1.41 2.81 8 7 9 1.22 1.33 2.23 5 7 9 0.97 1.00 1.33 Table A4 (con't.) 10 Sept 73 24 Sept 73 8 Oct 73 13 Nov 73 14 Mar 74 3 Apr 74 17 Apr 74 7 May 74 22 May 74 16 July 74 31 July 74 13 Aug 74 3 0.79 3 0.53 0.55 0.57 0.66 0.37 0.32 0.49 0.57 0.39 0.74 0.57 0.79 0.55 0.60 0.58 0.74 0.40 0.41 0.50 0.63 0.41 0.79 0.60 0.87 0.58 0.61 1.16 0.79 0.43 0.45 0.64 0.71 0.41 0.81 0.79 94 0.88 0.58 0.61 1.23 0.84 0.53 0.53 0.64 0.86 0.51 0.83 0.85 0.92 0.63 0.62 1.51 0.97 0.59 0.56 0.66 0.95 0.52 0.88 0.91 0.99 0.70 0.69 1.29 0.73 0.65 0.69 0.97 0.71 0.91 1.08 1.28 0.81 0.83 1.39 0.92 0.93 1.06 1.13 0.78 0.94 1.08 1.36 0.86 0.88 1.43 0.95 1.00 1.28 0.84 0.96 1.19 2.84 2.33 1.85 1.47 1.07 1.03 1.80 1.33 1.49 2.35 2.83 Table A4 (con't.) 11 Sept 74 0.67 27 Sept 74 0.38 7 Oct 74 0.38 24 Oct 74 0.49 7 Nov 74 0.59 18 Mar 75 0.60 22 Apr 75 0.60 6 May 75 0.53 4 June 75 0.63 24 June 75 0.44 95 1.82 2.04 1.41 2.82 4.24 1.84 1.85 3.02 96 Table A5. Mean concentration of ammonia nitrogen in mg/l by station. 8 4 5 3 9 6 7* 2 1 1 May 70 0.10 .11 .12 0.12 .21 0.23 0.27 0.51 .63 1 5 6 8 3 4 7* 9 2 15 May 70 0.06 .08 .08 0.09 .09 0.11 0.11 0.12 .17 1 2 7* 6 3 4 9 8 5 27 May 70 0.15 .19 .22 0.29 .31 0.35 0.38 0.51 .54 2 1 6 4 5 3 8 7* 9 10 June 70 0.20 .29 .33 0.35 .37 0.37 0.47 0.59 .60 3 5 2 6 4 8 1 9 7* 23 June 70 0.25 .27 .27 0.28 .33 0.44 0.51 0.51 .79 7* 4 8 3 5 l 6 9 2 7 July 70 0.14 .16 .18 0.18 .20 0.22 0.23 0.29 .30 4 5 1 6 3 7* 2 9 8 10 Oct 70 0.47 .50 .53 0.59 .63 0.71 0.75 0.88 .95 5 4 8 6 2 3 7* 1 9 25 Oct 70 0.56 .59 .67 0.69 .69 0.69 0.73 0.74 .08 4 3 2 6 5 1 7* 8 9 7 Nov 70 0.56 .57 .59 0.64 .70 0.72 0.78 0.91 .23 97 Table A5 (con't.) 23 Jan 71 0.01 0.12 0.13 18 Feb 71 0.01 0.12 16 Apr 71 0.11 0.17 0.17 0.17 0.17 0.33 0.37 0.39 0.44 1 May 71 0.13 0.18 0.18 0.19 0.20 0.23 0.38 0.44 0.60 20 May 71 0.09 0.11 0.11 0.12 0.18 0.23 0.49 0.50 0.52 1 June 71* 0.12 0.14 0.17 0.19 0.20 0.23 0.44 0.49 0.70 18 June 71 0.21 0.21 0.24 0.32 0.32 0.33 0.35 0.43 0.59 2 July 71* 0.14 0.18 0.18 0.27 0.27 0.27 0.33 0.42 0.50 15 July 71 0.15 0.15 0.16 0.18 0.19 0.24 0.32 0.35 0.41 Table A5 (con't.) 29 July 71 17 Aug 71 2 Sept 71 16 Sept 71 2 Oct 71+ 15 Oct 71 30 Oct 71 12 Nov 71 2 Dec 71 19 Dec 71 11 Jan 72 5 6 3 2 1 4 8 9 7* 0.09 0.09 0.11 0.14 0.14 0.15 0.24 0.51 0.53 2 6 1 5 3 4 8 7* 9 0.04 0.07 0.08 0.08 0.08 0.10 0.47 0.52 0.61 2 6 5 3 1 4 9 7* 8 0.10 0.11 0.18 0.18 0.19 0.21 0.40 0.45 0.51 2 3 6 5 4 7* 1 8 9 0.22 0.24 0.25 0.26 0.31 0.35 0.36 0.43 0.55 6 3 5 1 4 2 7* 8 9 0.25 0.30 0.31 0.34 0.45 0.45 0.50 0.52 0.60 6 5 3 2 1 4 7* 8 9 0.13 0.16 0.16 0.18 0.21 0.24 0.50 0.64 0.67 5 2 6 3 1 4 8 7* 9 0.22 0.26 0.27 0.28 0.31 0.31 0.60 0.60 0.68 1 2 3 4 5 6 7* 8 9 0.23 0.25 0.26 0.27 0.28 0.31 0.55 0.55 1.04 7* 8 9* 0.50 0.56 0.94 4 3 1 8 7* 9 0.27 0.28 0.36 0.57 0.58 0.63 4 3 9 8 7* 0.36 0.39 0.72 0.88 0.93 Table A5 (con't.) 18 22 11 31 13 27 12 25 16 29 Feb 72 Apr 72 May 72 May 72 June 72 June 72 July 72 July 72 Aug 72 Aug 72 99 3 1 7* 8 9 0.53 0.64 0.65 0.65 1.12 3 2 4 1 5 9 8 7* 0.45 0.47 0.51 0.53 0.55 0.57 0.60 0.70 3 4 1 6 2 5 7* 8 9 0.15 0.15 0.16 0.17 0.18 0.22 0.52 0.53 0.59 6 5 4 3 1 2 7* 8 9 0.13 0.14 0.22 0.26 0.26 0.27 0.36 0.59 1.08 6 5 4 1 3 2 8 7* 9 0.01 0.02 0.03 0.09 0.09 0.11 0.54 0.54 1 46 3 4 5 2 1 6 8 7* 9 0.01 0.02 0.03 0.03 0.03 0.08 0.38 0.41 1 44 6 5 3 4 7* 8 2 1 9 0.15 0.16 0.23 0.31 0.35 0.36 0.36 0.42 0.51 3 2 6 4 1 5 8 9 7* 0.10 0.13 0.24 0.24 0.29 0.31 0.47 0.50 0.51 5 4 6 3 1 2 7* 8 9 0.08 0.10 0.11 0.12 0.12 0.14 0.18 0.22 0.60 4 3 1 6 5 2 7* 8 9 0.01 0.02 0.02 0.03 0.04 0.04 0.20 0.34 1 14 Table A5 (con't.) 12 Sept 72 29 Sept 72* 6 Oct 72 13 Oct 72 27 Oct 72 15 Nov 72 7 Feb 73 24 Apr 73 11 May 73 30 May 73 20 June 73 100 6 5 1 4 3 2 7* 8 9 0.01 0.01 0.02 0.02 0.04 0.05 0.41 0.44 1.31 4 6 5 3 1 8 7* 2 9 0.02 0.03 0.03 0.03 0.03 0.20 0.22 0.25 0.60 3 8 9 0.01 0.23 0.48 2 1 4 5 6 3 8 9 7* 0.02 0.02 0.02 0.03 0.03 0.04 0.17 0.57 0.73 5 6 4 1 3 2 7* 8 9 0.02 0.02 0.02 0.03 0.04 0.06 0.24 0.25 0.41 3 8 2 4 9 6 1 5 7* 0.12 0.14 0.17 0.20 ' 0.22 0.22 0.22 0.25 0.25 3 1 8 7 9 0.04 0.10 0.29 0.32 0.38 4 1 2 5 3 8 7 9 0.02 0.06 0.06 0.09 0.10 0.20 0.21 0.27 6 5 4 2 3 1 7 8 9 0.01 0.01 0.01 0.02 0.02 0.03 0.19 0.22 0.26 2 4 5 6 3 1 8 7 9 0.01 0.01 0.01 0.01 0.03 0.08 0.31 0.32 0.35 4 5 3 2 6 1 8 7 9 0.00 0.00 0.01 0.02 0.03 0.08 0.22 0.28 0.36 Table A5 (con't.) 6 July 73 17 July 73 1 Aug 73 15 Aug 73 28 Aug 73 10 Sept 73 24 Sept 73 8 Oct 73 13 Nov 73 3 Apr 74 17 Apr 74 7 May 74 6 0.01 0.02 0.03 0.01 0.01 0.01 0.00 0.01 0.01 0.01 0.12 0.00 0.02 0.03 0.04 0.01 0.02 0.02 0.01 0.02 0.03 0.05 0.13 0.00 0.02 101 0.07 0.08 0.13 0.09 0.32 0.23 0.13 0.04 0.11 0.21 0.19 0.08 0.31 0.22 0.08 0.11 0.25 0.32 0.18 0.33 0.18 Table A5 (con't.) 22 May 74 16 July 74 31 July 74 13 Aug 74 11 Sept 74 27 Sept 74 7 Oct 74 24 Oct 74 7 Nov 74 18 Mar 75 22 Apr 75 6 May 75 4 June 75 0.03 0.04 0.01 0.02 0.06 0.01 0.01 0.01 0.21 0.29 0.03 0.06 0.02 0.03 0.06 0.01 0.01 0.01 0.35 0.40 0.23 0.18 0.31 102 0.04 0.06 0.02 0.04 0.07 0.02 0.01 0.02 0.36 0.41 0.30 0.22 0.37 0.05 0.08 0.03 0.04 0.09 0.02 0.01 0.02 0.37 0.38 0.31 0.45 0.38 1.67 2.49 0.68 0.39 1.26 103 Table A5 (con't.) 3 6 8 9 24 June 75 0.01 0.01 0.05 0.24 104 Table A6. Mean concentration of organic nitrogen in mg/l by station. 6 2 3 l 4 8 5 7* 9 1 May 70 0.29 0.34 0.54 0.59 0.78 0.86 0.92 1.06 1.07 6 4 1 5 2 3 8 7* 9 15 May 70 0.31 0.32 0.43 0.49 0.50 0.57 0.85 0.96 1.25 27 May 70 0.05 0.09 0.12 0.17 0.17 0.19 0.63 0.75 1.04 10 June 70 0.21 0.28 0.32 0.37 0.38 0.41 0.50 0.90 1.04 23 June 70 0.23 0.24 0.26 0.27 0.36 0.72 0.72 1.14 1.27 7 July 70+ 0.21 0.25 0.26 0.32 0.39 0.40 1.14 1.20 1.61 7* 3 2 6 5 4 1 8 9 10 Oct 70 0.04 0.07 0.07 0.10 0.11 0.14 0.15 0.26 0.46 25 Oct 70 0.06 0.06 0.07 0.09 0.10 0.13 0.39 0.54 0.64 7 Nov 70 0.06 0.06 0.07 0.08 0.09 0.09 0.09 0.09 0.11 23 Jan 71 0.04 0.24 0.57 Table A6 (con't.) 7 May 74 22 May 74 16 July 74 31 July 74 13 Aug 74 11 Sept 74 27 Sept 74 7 Oct 74 24 Oct 74 7 Nov 74 18 Mar 75 22 Apr 75 6 May 75 3 0.32 0.52 0.35 0.72 0.54 0.59 0.36 0.37 0.48 0.32 0.35 0.46 0.37 2 4 0.47 0.48 4 5 0.60 0.69 5 4 0.35 0.36 4 2 0.78 0.79 2 4 0.57 0.75 1 5 0.83 0.84 5 2 0.37 0.50 2 4 0.38 0.40 1 5 0.49 0.51 6 4 0.38 0.40 6 8 0.57 0.65 3 8 0.53 1.50 9 6 0.89 0.91 105 0.60 0.83 0.39 0.81 0.79 0.85 0.51 0.40 0.52 0.51 0.71 1.59 0.97 0.64 0.86 0.43 0.81 0.89 0.89 0.67 0.47 0.53 0.57 0.64 0.88 0.45 0.82 0.95 0.96 0.69 0.56 0.60 0.57 1.01 0.99 0.59 0.90 1.07 0.98 0.84 0.60 0.78 0.66 1.05 1.23 0.80 0.92 1.08 1.04 0.64 0.88 0.73 1.72 1.26 1.90 2.45 1.75 1.45 1.75 Table A6 (con't.) 18 Feb 71 16 Apr 71 1 May 71 20 May 71 1 June 71 18 June 71 2 July 71+ 15 July 71 29 July 71 106 l 7* 0.04 0.55 6 5 1 2 4 3 8 7* 9 0.09 0.13 0.20 0.21 0.22 0.31 0.52 0.79 0.88 2 4 6 5 3 1 9 8 7* 0.17 0.22 0.23 0.27 0.34 0.46 0.91 0.94 1.05 6 5 3 l 4 2 7* 8 9 0.24 0.33 0.36 0.37 0.42 0.48 0.60 0.93 1.11 6 5 4 2 1 3 9 8 7* 0.10 0.14 0.16 0.17 0.21 0.22 0.60 0.72 1.71 1 6 5 4 3 2 9 8 7* 0.30 0.32 0.43 0.45 0.46 0.47 1.10 1.33 1.58 6 5 3 4 2 7* 8 1 9 0.28 0.37 0.44 0.54 0.61 0.65 0.66 0.76 1.09 l 6 5 2 8 9 3 4 7* 0.32 0.36 0.42 0.51 0.54 0.60 0.62 0.66 0.72 6 9 8 2 3 5 1 7* 4 0.54 0.54 0.56 0.58 0.58 0.61 0.63 0.64 0.66 Table A6 (con't.) 17 Aug 71 2 Sept 71 16 Sept 71 2 Oct 71 15 Oct 71 30 Oct 71 12 Nov 71 2 Dec 71 19 Dec 71 11 Jan 72 107 4 5 3 6 1 8 7* 9 2 0.49 0.54 0.58 0.66 0.68 0.69 0.69 0.70 0.78 8 3 4 1 9 6 2 7* 5 0.45 0.46 0.46 0.52 0.54 0.58 0.59 0.67 0.68 3 2 6 4 1 5 8 7* 9 0.24 0.24 0.28 0.31 0.33 0.36 0.53 0.56 0.58 5 7* 6 1 8 3 4 9 2 0.35 0.44 0.47 0.55 0.56 0.59 0.61 0.70 1.09 5 4 6 1 3 8 2 7* 9 0.38 0.38 0.45 0.47 0.49 0.50 0.51 0.77 0.90 2 1 3 8 5 6 4 7* 9 0.42 0.45 0.51 0.52 0.54 0.54 0.55 1.00 1.02 3 4 1 2 5 8 6 7* 9 0.43 0.52 0.62 0.70 0.80 0.86 0.95 1.67 2.33 7* 8 9 0.30 0.31 1.48 1 3 4 8 7* 9 0.23 0.27 0.27 0.36 0.36 0.42 3 4 8 7* 9 0.22 0.41 0.66 0.78 0.92 Table A6 (con't.) 18 22 11 31 13 27 12 25 16 Feb 72 Apr 72 May 72 May 72 June 72 June 72 July 72 July 72 Aug 72 108 3 1 8 9 7* 0.13 0.15 0.70 0.85 0.95 2 1 3 4 9 8 7* 5 0.45 0.49 0.53 0.69 0.74 0.89 0.98 1.02 3 1 5 6 2 4 7* 8 9 0.14 0.18 0.20 0.22 0.24 0.30 0.44 0.50 0.67 6 5 3 4 1 2 7* 8 9 0.11 0.15 0.24 0.32 0.33 0.35 0.50 0.55 0.81 6 5 2 1 3 4 8 7* 9 0.40 0.42 0.44 0.48 0.49 0.51 0.57 0.67 1.67 5 3 2 6 4 1 8 7* 9 0.33 0.34 0.37 0.39 0.42 0.47 0.49 0.62 1.07 6 3 5 4 8 1 2 9 0.23 0.33 0.40 0.42 0.52 0.62 0.67 0.81 2 6 1 8 4 3 7* 5 9 0.24 0.29 0.32 0.34 0.35 0.37 0.37 0.38 0.55 4 3 2 1 6 9 5 8 7* 0.34 0.38 0.41 0.42 0.43 0.44 0.46 0.50 0.53 Table A6 (con't.) 29 Aug 72 12 Sept 72 29 Sept 72 6 Oct 72 13 Oct 72 27 Oct 72 15 Nov 72 7 Feb 73 24 Apr 73 11 May 73 109 6 1 2 3 4 8 7* 5 9 0.55 0.72 0.80 0.88 0.96 1.22 1.29 1.38 2.58 3 4 5 2 6 7* 1 8 9 1.02 1.04 1.08 1.19 1.24 1.36 1.40 1.61 2.14 2 6 3 5 4 1 8 7* 9 0.55 1.24 1.28 1.35 1.40 1.67 1.68 1.71 2.20 3 8 9 1.33 1.54 1.63 7* 1 5 6 2 4 3 8 9 0.90 1.01 1.09 1.09 1.27 1.33 1.38 1.53 1.77 5 3 6 4 1 2 8 7* 9 0 55 0.79 0.83 0.86 0.91 0.99 1.27 1.35 1.49 2 3 4 1 6 5 9 8 7* 0.17 0.25 0.31 0.42 0.52 0.54 1.21 1.35 1.39 3 1 8 9 7 0.30 0.41 1.00 1.04 1.22 5 3 2 4 1 8 7 9 0.50 0.56 0.69 0.71 0.73 1.05 1.07 1.26 6 5 2 1 4 3 8 9 7 0.39 0.44 0.61 0.63 0.64 0.85 0.93 0.97 1.09 Table A6 (con't.) 30 May 73 20 June 73 6 July 73 17 July 73 1 Aug 73 15 Aug 73 28 Aug 73 10 Sept 73 24 Sept 73 8 Oct 73 13 Nov 73 3 Apr 74 17 Apr 74 5 0.67 0.75 0.93 0.71 0.69 0.62 0.82 0.72 0.77 0.55 0.57 0.56 0.34 0.29 0.78 0.95 0.74 0.71 0.65 0.83 0.73 0.80 0.58 0.58 0.93 0.43 0.32 110 0.83 1.06 0.82 0.71 0.66 0.86 0.77 0.85 0.59 0.58 0.99 0.43 0.38 0.97 0.90 0.73 0.72 0.93 0.78 0.90 0.61 0.61 1.09 0.54 0.43 1.07 0.97 0.78 0.74 1.04 0.79 0.99 0.68 0.62 0.57 0.46 1.38 1.29 1.34 0.96 0.97 0.83 0.76 0.73 0.67 0.62 1.44 1.42 1.38 1.06 1.08 1.23 0.94 0.78 0.77 0.86 0.67 1.58 1.68 1.55 1.17 2.14 1.85 1.02 2.20 1.89 1.33 0.89 0.89 111 Table A6 (con't.) 6 3 8 9 4 June 75 0.44 0.70 0.83 1.67 8 6 3 9 24 June 75 0.39 0.54 0.66 1.16 112 Table A7. Mean concentration of inorganic nitrogen in mg/l by station. 6 1 9 8 2 7* 3 4 5 1 May 70 1.86 2.06 2.53 2.79 2.97 3.07 3.09 3.18 3.73 1 2 3 9 6 7* 8 5 4 15 May 70 0.51 0.57 1.06 1.19 1.22 1.24 1.52 1.65 1.69 27 May 70 0.37 0.38 0.81 1.16 1.22 1.85 1.95 2.82 5.17 .i. 10 June 70 1.06 1.06 1.18 1.56 1.84 1.84 2.29 2.75 3.25 23 June 70 1.18 1.22 1.45 1.49 1.61 1.67 2.14 2.49 5.18 7* 2 8 1 3 6 9 5 4 7 Ju1y 70 0.37 0.50 0.54 0.56 0.63 0.71 0.74 0.80 0.82 10 Oct 70 0.66 0.79 0.84 0.86 0.89 1.02 1.02 1.19 25 Oct 70 0.80 0.84 0.91 0.93 0.97 0.97 0.98 1.00 1.54 7 Nov 70 0.81 0.84 0.85 0.95 0.96 1.03 1.04 1.17 1.81 Table A7 (con't.) 23 Jan 71 18 Feb 71 16 Apr 71 1 May 71 20 May 71 1 June 71 18 June 71 2 July 71 15 July 71 29 Ju1y 71 113 1 8 7* 0.56 1.11 1.22 1 7* 0.46 1.39 6 2 5 3 1 4 9 8 7* 0.41 0.67 0.81 0.85 0.87 1.12 1.80 2.11 2.87 1 6 2 8 9 4 3 5 7* 1.40 1.97 2.12 2.99 3.05 3.06 3.13 3.30 4.03 l 2 3 6 5 4 8 9 7* 0.62 0.80 1.10 1.14 1.16 1.22 1.38 1.39 1.98 2 3 1 5 6 4 7* 8 9 0.35 0.51 0.57 0.74 1.19 1.36 1.37 3.19 4.15 1 2 8 9 3 7* 4 6 5 1.00 1.39 1.44 1.44 1.51 1.78 2.28 2.32 3.23 6 5 4 8 3 2 7* 9 1 0.69 0.70 0.75 0.82 0.89 0.96 1.00 1.05 1.22 6 4 1 3 8 7* 5 2 9 0.43 0.50 0.51 0.63 0.66 0.68 0.71 0.74 0.74 3 1 5 4 6 2 8 9 7* 0.19 0.22 0.23 0.25 0.25 0.26 0.32 0.65 0.69 Table A7 (con't.) 17 Aug 71 2 Sept 71 16 Sept 71 2 Oct 71 15 Oct 71 - 30 Oct 71 12 Nov 71 2 Dec 71 19 Dec 71 11 Jan 72 18 Feb 72 114 2 1 6 3 5 4 8 7* 9 0.12 0.14 0.16 0.16 0.17 0.19 0.59 0.68 0.74 2 5 3 6 l 4 9 7* 8 0.17 0.25 0.26 0.26 0.29 0.33 0.49 0.61 0.62 6 5 2 3 1 7* 8 4 9 0.36 0.41 0.42 0.43 0.46 0.48 0.53 0.54 0.68 6 3 5 4 1 8 2 7* 9 0.29 0.39 0.41 0.54 0.58 0.64 0.65 0.65 0.76 6 5 3 2 1 4 7* 8 9 0.20 0.21 0.21 0.23 0.26 0.33 0.63 0.76 0.83 5 6 3 4 2 1 7* 8 9 0.41 0.47 0.52 0.57 0.63 0.68 0.89 0.91 0.94 2 3 1 5 4 6 7* 8 9* 0.36 0.38 0.40 0.46 0.53 0.56 0.85 0.88 1.73 7* 8 9* 1.47 5.34 9.28 3 4 1 7* 8 9 0.63 0.64 0.73 2.79 2.84 4.35 3 4 9 8 7* 1.59 2.96 6.23 7.11 8.88 3 1 7* 8 9 1.27 1.31 2.12 2.23 3.47 Table A7 (con't.) 22 11 31 13 27 12 25 16 29 12 Apr 72 May 72 May 72 June 72 June 72 July 72 July 72 Aug 72* Aug 72 Sept 72 115 1 5 3 4 2 9 8 7* 1.27 1.29 1.31 1.33 1.36 9.94 10.59 16.10 3 2 4 1 5 6 9 8 7* 0.46 0.50 0.65 0.75 0.76 1 51 7.75 8.51 9.02 7* 6 8 3 4 5 9 1 2 1.36 1.49 1.73 1.80 1.81 1.86 2.22 2.29 2.38 4 2 5 7* 6 1 8 3 9 1.44 1.72 1.83 1.95 1.97 1.99 2.06 2.51 3.03 5 3 2 1 6 4 8 7* 9 0.29 0.30 0.30 0.37 0.45 0.50 2.27 3.01 5.93 2 7* 1 6 3 8 9 4 5 0.61 0.62 0.62 0.68 0.77 0.82 1.08 1.25 1.38 3 2 6 1 4 5 8 9 7* 0.33 0.36 0.50 0.51 0.55 0.61 0.70 0.73 0.74 5 1 2 4 3 7* 8 6 9 0.31 0.32 0.35 0.38 0.44 0.50 0.54 0.59 1.00 1 2 6 3 4 5 7* 8 9 0.12 0.12 0.17 0.21 0.27 0.42 1.03 1.12 4.42 1 5 4 6 3 2 7* 8 9 0.08 0.08 0.09 0.10 0.11 0.13 0.58 0.60 1.70 Table A7 (con't.) 29 Sept 72 6 Oct 72 13 Oct 72 27 Oct 72 15 Nov 72 7 Feb 73 24 Apr 73 11 May 73 30 May 73 20 June 73 6 July 73 116 2 1 5 3 4 6 0.59 0.60 0.65 0.80 0.98 2.77 3 8 9 0.99 5.01 8.41 2 3 1 5 4 6 0.52 0.71 0.92 1.06 1.27 1.65 5 4 3 6 1 2 0.42 0.84 0.86 0.89 1.04 1.04 2 3 5 1 6 4 0.53 0.63 0.76 0.79 0.94 1.59 3 1 8 7 4 0.60 0.82 4.80 4.86 6.40 5 3 2 4 1 7 0.81 1.07 1.15 1.26 1.28 2.04 5 6 1 2 4 3 0.29 0.32 0.45 0.49 0.49 0.70 2 5 3 6 1 4 0.35 0.38 0.42 0.42 0.44 0.55 1 4 2 5 3 8 0.33 0.44 0.47 0.74 0.76 2.21 1 6 2 5 4 3 0.61 0.68 0.71 1.13 2.14 2.43 7* 8 9 5.59 6.29 6.59 8 9 7* 3.33 3.91 4.02 8 7* 9 5.11 5.11 5.56 8 7* 9 .82 8.03 8.47 8 9 2.25 2.94 8 7 9 1.22 1.31 1.57 8 7 9 4.06 4.23 4.25 7 6 9 2.22 2.25 3.19 9 7 8 5.83 5.95 5.97 Table A7 (con't.) 17 July 73 1 Aug 73 15 Aug 73 28 Aug 73 10 Sept 73 24 Sept 73 8 Oct 73 13 Nov 73 3 Apr 74 17 Apr 74 7 May 74 22 May 74 16 July 74 0.40 0.43 0.20 117 1.66 0.45 1.08 0.31 1.22 2.24 0.59 3.34 0.33 1.52 1.95 1.24 0.87 0.88 1.46 3.82 3.60 4.51 0.67 Table A7 (con't.) 31 July 74 13 Aug 74 11 Sept 74 27 Sept 74 7 Oct 74 24 Oct 74 7 Nov 74 18 Mar 75 22 Apr 75 6 May 75 4 June 75 24 June 75 2 0.09 0.06 1.06 0.76 1.26 0.91 2.56 1.89 118 0.68 0.25 0.26 0.65 0.40 0.33 0.46 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