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Ann Arbor, MI 48106 THE EFFECT OF HYDROLOGIC PATHWAYS AND RUNOFF EPISODES ON ALUMINUM AND MAJOR CATIONS IN TWO NORTHERN MICHIGAN STREAMS By Nancy Ellen Fegan A DISSERTATION Submitted to Michigan State University in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY Department of Geological Sciences 1993 ABSTRACT THE EFFECT OF HYDROLOGIC PATHWAYS AND RUNOFF EPISODES ON ALUMINUM AND MAJOR CATIONS IN TWO NORTHERN MICHIGAN STREAMS By Nancy Ellen Fegan Researchers precipitation control concerned effects stream have chemical with identified understanding acid many that variations, processes such as episodic discharge, controls on aluminum (Al), and mineral weathering. To represent understanding these of processes how water in predictive evolves as it specific hydrologic pathways is needed. knowledge of specific flowpaths models, travels an through Currently, detailed in watersheds is extremely limited. In this investigation, individual source water inputs traveling through specific hydrologic pathways are identified in two rivers receiving the same acidic deposition. input is directly the same, linked to differences in chemical variations geological differences. Samples obtained weekly from rivers, springs, are were and precipitation for one year to compare seasonal variations. Samples of runoff and regional groundwater were also analyzed. chemical Since Results from analyses were compared to weathering petrology to derive mineral weathering reactions to account for observed aqueous chemical trends. Significant chemical episodes occurred in response to snow melt and major storms. Increased discharge caused lower pH, decreased cations, and increased total Al in both rivers. Aluminum behaved as expected based on gibbsite solubility control, but in the Peshekee where there are numerous swamps, organic-Al carbon is inversely (DOC). directly to DOC. proportional In the same river, to dissolved organic polymeric Al corresponds Input of complex Al-organic compounds from swamps during high discharge appears to be an important aspect of Al behavior not previously identified. In the Peshekee, high cation flux is correlated with large storms flushing vadose water through mafic dikes, while in the Yellow Dog, high cation fluxes occur weeks or months after large storms as a result of flushing of thick glacial sediment. deeper infiltration and Mass balance calculations from weathering reactions for different input waters show that water chemistry is highly dependent on local geology. Based on results from this study, models of watershed acidification would be improved by considering polymeric A l , swamp overflow, and detailed geological and structural sources to surface waters. influences on input Copyright by NANCY ELLEN FEGAN 1993 ACKNOWLEDGEMENTS I wish to express sincerest appreciation to members of my guidance committee, Drs. David Long, Grahame Larson, Michael A. Velbel, and Tom Vogel, for their wealth of suggestions, and critical review of the manuscript. advice and A project of this scope could not have been accomplished without their help. Thanks are also extended to Dr. Department of Zoology and his Tom Burton of the MSU graduate students for field equipment and use of their laboratory for part of the chemical analysis. I owe a special gratitude to Tim Wilson, who spent endless hours teaching me the ropes in the geochemistry lab, and gave continual encouragement throughout the course of my work at MSU. Finally, I wish to thank my parents for their continuing support throughout my studies, and to my husband, David Hull, for providing uncommon patience, spirit and assistance. This work was supported financially by a Chevron Field Research Grant through the Department of Geological Sciences, and the Student Initiated Projects program of the CEIP Fund. TABLE OF CONTENTS LIST OF T A B L E S ............................................. vii LIST OF F I G U R E S ........................................... ix ............................................... INTRODUCTION Previous Research ................................... STUDY A R E A .................................................. Location ....................................... Geology . . . . . . . . . . . ...................... Hydrologic Setting and Climate . ................... 1 3 13 13 14 17 M E T H O D S ............... 19 Water Sampling and A n a l y s i s ....................... 19 Discharge M e a s u r e m e n t s ............................. . 25 Rock, Sediment and Soil Sampling and Analysis . . . 26 RESULTS AND DISCUSSION ................................... H y d r o l o g y ........................................... 27 Water C h e m i s t r y ............. 1. P r e c i p i t a t i o n ............. 2. River w a t e r s ............. 3. Springs, groundwater and other inputs . . . Cation Release R a t e s ................... Thermodynamic Mineral R e l a t i o n s h i p s .............. 60 Elemental Mass Balance from Weathering Reactions . . 1. Weathering petrology ................. 2. Mass balance r e a c t i o n s ..................... 73 27 31 31 35 54 57 68 68 SUMMARY AND C O N C L U S I O N S ................... 83 BIBLIOGRAPHY 90 ...................... A P P E N D I C E S ................................................. 100 Appendix A. Reverse mineral weathering reactions used in Table 6 to reconstruct source minerals for dissolved solutes ............. 100 Appendix B. Complete aqueous chemical data for all water s a m p l e s ........................... 104 vi LIST OF TABLES Table 1. Studies that have identified watershed processes that affect Al concentrations in streams . 11 Table 2. Methods of aqueous chemical analysis ........... 22 Table 3. Concentrations of major solutes in precipitation (in mg/1) . ................. 32 Table 4. Concentrations (in mg/1) of major solutes in the Peshekee and Yellow Dog R i v e r s ............... 36 Table 5. Solute concentrations (in mg/1) in different ground and surface water types in the Peshekee and Yellow Dog vicinity ..................... 55 Table 6. Reconstruction of source minerals for Northern Michigan waters (in mol/l*104) ; equations shown in Appendix A ...................... 74 Table 7. Correlation coefficients of molar concentrations for river and source waters ......... 82 Table 8. Aqueous chemical data for Peshekee River, Site 1 (1988-1989) . . . . . . . . 104 Table 9. Aqueous chemical data for Peshekee River, Site 3 ( 1 9 8 8 - 1 9 8 9 ) ................................. 106 Table 10. Aqueous chemical data for Peshekee River, Site 4 (1988-1989) 108 Table 11. Aqueous chemical data for Peshekee Spring (1988-1989) 109 Table 12. Aqueous chemical data for Yellow Dog River, Site 1 ( 1 9 8 8 - 1 9 8 9 ) ................................. 110 Table 13. Aqueous chemical data for Yellow Dog River, Site 3 ( 1 9 8 8 - 1 9 8 9 ) ................................. 112 Table 14. Aqueous chemical data for Yellow Dog River, Site 4 ( 1 9 8 8 - 1 9 8 9 ) ................................. 113 vii Table 15. Aqueous chemical data for Yellow Dog Upper Spring (1988-1989) 114 Table 16. Aqueous chemical data for Yellow Dog Lower Spring (1989) 114 Table 17. Aqueous chemical data for Precipitation (1988-1989) 115 Table 18. Aqueous chemical data for groundwater, lakes and r u n o f f ...................................... 117 viii LIST OF FIGURES Figure 1. Location of the Peshekee and Yellow Dog Rivers showing schematically the main geological features of the area; actual dike thicknesses 2-25 meters (after Sims, 1992) 15 Figure 2. Location of precipitation, stream, spring and ground water samples (Sl=Peshekee Spring; S2=Yellow Dog Upper Spring; S3=Yellow Dog Lower Spring) . . . ......... 20 Figure 3. Precipitation and discharge records for Peshekee and Yellow Dog Rivers (Van Riper=Peshekee area; Big Bay=Yellow Dog a r e a ) ...................................29 Figure 4. Typical storm event hydrograph showing the more rapid response of the Peshekee River . . . . . . . . 30 Figure 5. Weekly anion and cation variation Marquette County precipitation, 1988-1989 in western 34 Figure 6. Weekly pH variation for three sites on each river, 1988-1989 . . . . . . . . . . . .38 Figure 7a. Weekly ion concentrations, Peshekee River Site 1, 1988-1989 . . . . . . . . . . . . . . . . . . . . .41 Figure 7b. Weekly ion concentrations, Peshekee River Site 3, 1988-1989 . . . . . . . . . . . . . 42 Figure 7c. Weekly ion concentrations, Peshekee River Site 4, 1988-1989 . . . . . . . 43 Figure 8a. Weekly ion concentrations, Yellow Dog River Site 1, 1988-1989 ........................................ .. . 44 Figure 8b. Weekly ion concentrations, Yellow Dog River Site 3, 1988-1989 ........................................ .. . 45 Figure 8c. Weekly ion concentrations, Yellow Dog River Site 4, 1988-1989 46 Figure 9. Weekly variation in Al species for downstream sites in both rivers, 1988-1989 49 ix Figure 10. Relationship of individual Al species to pH for downstreams sites of both rivers .................... 50 Figure 11. Relationship of individual Al species to DOC for .................... 52 downstream sites of both rivers Figure 12. Release rates of major cations out of the Peshekee and Yellow Dog w a t e r s h e d s ............................ 58 Figure 13a. Plot of pAl (-log[inorganic monomeric Al]) versus pH for river water samples (squares=downstream sites, circles=midstream sites, triangles=upstream sites in both rivers) ........................ 62 Figure 13b. Plot of pAl (-log[inorganic monomeric Al]) versus pH for groundwater and spring s a m p l e s ............... 63 Figure 14. Activity diagram for river and ground water samples (including springs), showing mineral stability fields for 0° and 25°C in the system HC1-H20-A1203-K2065 Si02 ............. Figure 15. Activity diagram for river and ground water samples (including springs), showing line of quartz saturation at 0° and 25°C in the system HC1-H20-A1203-K20Si02 at 2 5 ° C ............................................66 Figure 16. Activity diagram for river and ground water samples (including springs), showing line of quartz saturation at 0° and 25°C for the system HC1-H20-A1203Ca0-Si02 at 2 5 ° C ....................................... 67 Figure 17. Representative x-ray diffraction patterns for clays from Peshekee and Yellow Dog s o i l s ................... 71 x INTRODUCTION Concerns about the environmental effects of acid precipitation have prompted numerous studies in the past 20 years aimed biological at understanding effects in processes surface that waters. cause Many toxic geological, chemical, climatic, and environmental factors that may affect ionic concentrations in streams have been identified by past research (Krug and Frink, 1983; Likens, 1988). One major area of investigation encompasses the study of major ion balances and changes in response to acid deposition (Neal et al., 1986; Ryan et al., events 1989; Kress et al., (Seip et al., 1989; 1990), including episodic Schaefer et al., 1990). Other lines of research focus on the study of Al behavior and the causes of toxic Al increases (Johnson et a l . , 1981; Driscoll et al., 1980, 1984, 1985; Hooper and Shoemaker, 1985; Cronan et a l . , 1986; Lawrence et a l . , 1986; Nordstrom and Ball, 1986; Manley et a l . , 1987; Neal et a l . , 1989) . Rock and soil weathering processes are major sources of ions to streams, and have also received 1992; Wright, Problems addressed are: attention (Cronan, 1985; previous approaches Velbel, 1985, 1988). with 1) developing ways of 1 that need to be identifying specific 2 hydrologic pathways and particular watershed, features; 2) geochemical reactions within a including those controlled by geologic identifying end member source water types and determining how each water attains its chemical signature; 3) determining how the contribution source changes with changing from each different water hydrologic conditions. To address these problems, rigorous geochemical studies of water types within a watershed must be conducted in conjunction with hydrogeologic petrologic survey study to to distinguish likely flowpaths, identify specific minerals involved and in chemical reactions in water as it flows through hydrologic conduits. In this investigation, individual water types flowing through specific hydrologic pathways that control the release of aluminum (Al) and major cations (calcium, Ca; magnesium, Mg; sodium, Na; potassium, K) to two streams are identified. These water types and flowpaths are identified by correlating episodic events, changes distinct in stream chemistry geological to discrete characteristics make-up of the watersheds studied. climatic and petrologic The two watersheds in this investigation are geographically adjacent to each other, and located Michigan, in an area of exposed granitic rock in northern a region that receives acid precipitation but has undergone little study. Since the initial precipitation input to is each river system the same, differences in water chemistry between rivers in the down-gradient direction must be directly linked to compositional and physical differences 3 in watershed materials. Individual runoff, sources of water to the streams, overflow from lakes and swamps, and deep groundwater, including shallow groundwater are recognized in this study based on correlations of hydrology, geology and water chemistry. The relative importance of each input in contributing ions during major discharge episodes is also discerned by evaluating how closely connected hydrologically. derived the source Finally, from weathering water specific petrologic is to mineral study the stream reactions that are account for nearly all of the geochemical variability in each system. Previous Research The basic question addressed by the research considered here is how do solutes get into stream water? To answer this question, one needs to consider what happens after rain water of a particular composition contacts earth materials inducing mineral weathering reactions, how ions released from reactions are transported to streams, streams affect solute and how reactions that occur in concentrations. Few studies have attempted to examine all conceivable aspects of geochemical and hydrological processes in a particular system, have encompassed a number of integrated facets but many in one watershed. By the mid-1970's, it became clear that large areas of North America and Europe were being affected by potentially harmful acidic precipitation caused by industrial emissions (Hornberger et a l . , 1989; Baker et al., 1991). This knowledge led to numerous surveys of precipitation chemistry across many industrialized Galloway et nations al., (e.g, 1987; USEPA, Wright, 1979; 1987; Paces, NAPAP, 1985; 1990). To understand the influence of acid rain and snowfall input on surface water chemistry, knowledge of specific mineral weathering processes in rocks and soils was required, as well as information on surface and groundwater hydrologic processes. Much of the work completed in past years by other workers has been stimulated by a need to acidification problems of the future. predict potential This work has led to the advancement of computer models that incorporate chemical and hydrologic parameters (Christophersen et a l . , 1982; to simulate predictions Chen et a l . , 1984b; Schnoor, 1984; W r ight, 1984; Cosby et a l . , 1985; Karaari et al., 1989) . Proposed models have been applied to numerous watershed systems (e.g., Schnoor et a l ., 1984; Whitehead et a l ., 1988) , with varying levels of success. watershed ILWAS, models (BIRKENES, Many of the more well known Christophersen Chen et a l ., 1984b; MAGIC, and Johnson, 1986) et a l ., 1982; Cosby et a l ., 1985; Ruess are based on key chemical reactions that are linked to submodels of soil properties and their control on water chemistry (Hendershot et a l . , 1992). These models treat the watershed as two or three homogeneous layers, not 5 generally realistic for geologically complex regions. workers have put forth a mixing model, Other conceptualizing that stream waters are generated by the mixing of chemically and spatially distinct water types (Christophersen et al., Hooper et al. , 1990; Weis et al., 1992). 1990; 1990; Hendershot et al., This approach also has inadequacies, in that it does not address the question of water flowpath identification and the chemical changes of water as it passes through specific flowpaths (Hendershot et a l ., 1992). In recent literature, some researchers have been trying to incorporate geochemical models with mixing models, notably Christophersen and Neal (1990), Hooper and Christophersen (1992). Robson et al. (1991), and All of these authors have underscored the need to assess hydrologic flow paths in order to fully understand and model watershed chemical processes and episodic control responses, any chemistry. since mechanism which hydrologic results pathways in ultimately changes in stream Many watershed studies have expressed this result (e.g., Chen et al., 1984a; Cozzarelli et a l ., 1987; Peters and Driscoll,1987; Hendershot et al., 1992). (1990) flow concluded that hydrologic Schaefer et a l . paths were critical factors in controlling the sensitivity of Adirondack lakes to acidification. Rochelle et a l . (1989) also determined that hydrologic parameters were a major control on surface water chemistry in 144 watersheds studied in the northeast U.S. Current thinking is that stream water can be considered as a mixture of specific chemical water types from within a watershed, with hydrological contributions from conditions. each depending Accordingly, a on the complete interpretation of chemical changes in stream water requires an understanding of how watershed materials, geochemical changes occur within and also how hydrologic pathways that lead to the stream influence stream chemistry. field studies must be completed More detailed in order to understand how waters evolve as they progress through the hydrologic cycle to enter streams, and in particular, studies are needed that delineate the sources of waters of different composition and how they mix before entering the stream (Neal et a l ., 1992). However, the problem is that in most watersheds knowledge of specific flowpaths Christophersen, is 1992). extremely The limited individual flow (Hooper paths and in a particular setting could depend on a large number of geologic, climatic and ecological factors, all of which may not be entirely discernable until after a large-scale study has been instituted. Most research thus flowpaths within soil layers, controls, far has concentrated but other kinds of hydrologic such as structural features, may be important. addition, while discharge or large recharge scale may be on hydrologic measurable, parameters some In like mechanisms operate on scales as small as the sub-microscopic level, and may not even be quantifiable. Because of these difficulties, researchers have tried to determine water sources and flow paths by using aqueous chemical information. One important area of study with regard to understanding 7 the geochemical through evolution flowpaths in of dilute soils and water rocks weathering reaction rates and mechanisms. as it travels concerns mineral Chemical weathering is basically the only process by which incoming acidity can be neutralized over geologic time (Galloway et a l . , 1983). While cation exchange can also cause neutralization, the supply of base cations must be continually resupplied by weathering or neutralization acidification will no occurs longer take primarily in place. areas bedrock that is chemically resistant, Surface with much water exposed particularly granite, granitic gneiss or guartzite. While it is not clear whether acid deposition actually changes the Wright, 1988), complex and rate of chemical weathering (Folster, 1985; it is apparent that reaction mechanisms are poorly understood, and that reaction rates observed in laboratory studies are not reflected by natural weathering processes (Wollast and Chou, 1988; Velbel, 1990). Many authors have used mass balance calculations to establish natural rates of weathering and cation release in watersheds in an effort to understand how specific cations are liberated and delivered to streams, and which minerals are the source for specific cations. Drever and Hurcomb (1986), for example, found the principle mineral reactions occurring in an area of the North Cascade Mountains of Washington to be calcite dissolution and alteration of biotite to vermiculite, based on mass balance calculations. calculated similar cation Cronan (1985) and Folster (1985) release rates for systems in different parts of the world, but each found broad differences between (1986) different soil types and soil horizons. Clayton found a differential weathering rate for albite and anorthite in the Idaho Batholith based in Na and Ca flux in streams. Velbel (1985, 1992) was able to relate differences in cation releases from forested watersheds of the Southern Blue Ridge to hydrologic processes and textural differences, using mass balance models. rates calculated from Further evaluation of weathering Southern Blue Ridge and Minnesota watersheds allowed Velbel (1993) to show that the magnitude of discrepancy between laboratory-derived weathering rates and those calculated minerals within weathering applied to independent from one rate watershed. "correction each of field data mineral composition hydrologic factors is In factor" in but a similar other can data likely for different words, be the same calculated set, a highly and coefficient dependent on (Velbel, 1993). In trying to elucidate weathering rate information from ion budgets in streams, workers studying watershed geochemical balances have sources of fully underscored the need to consider individual input water and specific hydrologic pathways to explain stream water variability. The link between chemical episodes in streams and large-scale hydrologic events like high runoff following major rain storms or snow melt have been recognized in numerous past studies (e.g., Neal et a l ., 1986; Seip et a l . , 1989; Ryan et a l . , 1989; Schaefer et a l . , 1990). However, the relationship between small- or even 9 microscopic-scale hydrologic processes and mineral weathering reactions that occur on scales as small or smaller than one mineral grain has not been studied. The importance of local chemical equilibria to the formation of secondary weathering products can be seen in alteration halos and rims in tiny fractures and pores observed through petrographic and electron microscopes (Meunier and Velde, 1979; Nahon, 1991). To fully explain chemical cation release weathering reactions from watershed specific to the materials, individual macro- and microscopic weathering sites within the system must be coupled to interpretations of macro- and micro-scale hydrologic mechanisms. Another major geochemical problem that has prompted many stream acidification studies relates to Numerous studies have shown that high Al waters are toxic to fish, and Leivestad, toxicity has 1980; also been documented molar ratio, important factors in surface (Baker and Schofield, Rosseland (Havas, 1986; Hall et a l . , 1987). form, levels chemistry. resulting in respiratory problems and clogging of gill structures Muniz Al et 1982; a l . , 1986) . in aquatic Al invertebrates In most cases, the chemical and the timing of release to waters are in determining biological effects or toxicity of Al and other cations in the environment. Understanding Al chemistry in streams is also necessary for discerning mineral weathering cationic weathering products processes. like Ca, Mg, While some Na and K may be delivered directly to streams and carried out of the watershed 10 upon release, other cations are less soluble then others at normal pH, notably Fe and Al, and are often redeposited in the soil column as oxides, clays, or organic compounds (Johnson et al., 1981; Bloom et al., 1979; Arp and Ouimet, 1986; Cronan et al., 1986). silicates, Thus, amorphous Al and Al-organic matter hydroxides, complexes Al (clay) precipitated in soils may be the primary source of Al to ground and surface waters. Dissolution of or leaching from these compounds is highly pH dependent, consequently elevated Al concentrations in soil and deposition surface are waters common. One in regions of the concentrations in natural waters is pH. more soluble with lower than normal affected major by controls acid on Al Aluminum becomes much pH (Hem and Roberson, 1967; May, et a l ., 1979), such as occurs in precipitation and in surface waters in much of the northeastern U.S. (Johannes et a l . , 1985). A partial compilation of research papers dealing with Al in surface water systems is presented in Table 1, which shows major observations and locations of studies. Centered mostly in watersheds in Norway and the northeast U.S., these studies and others have identified numerous processes that affect Al in streams, rivers and lakes. Some of these include release of Al from minerals by weathering, and organic matter in soils and interactions with mineral in solution, hydrologic variability, changes in precipitation chemistry, and seasonal climatic variability. In many of these watersheds, large increases in stream acidity occur in spring due to rapid 11 Table 1. Studies that have identified watershed processes that affect Al concentrations in streams. Site N ortheast U.S. (H ubbard Brook, N ew H am pshire) Author(s) Johnson et a l., 1981; L aw rence, et al., 1986, 1988; L aw rence & D riscoll, 1988; H ooper & Shoem aker, 1985 Major Observations Comments Stream cations increase, S 0 4 decrease after clear cutting forests; dilution o f Al; Al speciation is flowpath dependent, upper soil releases organic Al, low er gives inorganic Al, equilibrium w /gibbsite a series o f studies that address changes in stream chem istry due to acidification, forestry practices, soil nitrification and vegetative uptake, hydrology Al not in equilibrium o r any readily form ed mineral; high Al not during snowm elt (low pH) co ntrary to other H ubbard B rook studies; kinetic or hydrologic control; sam ples only for high flow w /A 1(OH)3 N ortheast U.S. (M assachusetts) M acA voy, 1989 Ion exchange regulates stream Al, organic acids control Al in wetlands sam ples taken only during autum n rain storm s E astern U .S. (Virginia) Cozzarelli, H erm an & Parnell, 1987 Soil Al decreases w /depth, controlled by m ineral solubility in low er soil, organics in upper soil lysim eter study o f soil w ater soils, N etherlands & H ubbard B rook (U.S) M ulder, van Breeman & Eijclc, 1989' M ost soil Al is organically complexed soil leaching experim ents soils, N ortheast U .S. & Southeast Canada C ronan, W alker & Bloom, 1986 Al explained by A l(O H )3 and humic phase com plexes lab experim ents, therm odynam ic modeling Southeast Canada (Ontario) M anley, Chesw orth & E vans, 1987 O rganic Al in upper soil, low er soil has inorganic Al; supersat. w /respect to several A l-S i0 2 phases soil extractions N ortheast A ustralia (Q ueensland) Little, 1986 Al transported through soils via organic com plexes soil leaching experim ents Scotland Bache & Sharpe, 1986 Polym eric Al com pounds readily leached from soils soil leaching experim ents Southern N orw ay (Birkenes) Seip, et al., 1989 Al controlled by variable hydrologic pathw ays, not m ineral solubility stressed th e im portance o f developing m ore complex (realistic) hydrologic models W ales (Afon H afren, Afon H ore) N eal, Smith, W alls & D unn, 1986; N eal, 1988; N eal et a l., 1989 Stream chem istry determ ined by mixing o f soil organic com ponent and products o f deep er bedrock w eathering; stream Al not controlled by simple kaolin o r Al(OH)3 stressed reappraisal of conventional stability diagram s to determ ine stream Al controls 12 melting of accumulated snow 1980; Seip et al., 1989; or after major rain storms (Seip, Schaefer et al., 1990), causing a corresponding increase in Al concentrations. Since the development of laboratory and field techniques to measure various (Barnes, 1976; behavior in chemical Driscoll, stream forms of Al 1984), waters has in natural waters detailed been studies possible. of Al Chemical equilibrium with gibbsite or some other easily formed Al-OH compound appears to control Al in certain stream systems, such as in the Hubbard Brook Experimental Watershed in New Hampshire (Johnson et a l ., 1981; Driscoll et a l . , 1984, 1985; Lawrence et a l . , 1988). Other studies have not found gibbsite solubility to be a satisfactory explanation for observed Al behavior. Hooper disequilibrium and during Shoemaker high (1985) discharge reported events in gibbsite a small watershed in Hubbard Brook, only a few kilometers away from areas in which other workers considered to exhibit gibbsite control over stream Al concentrations (Johnson et a l ., 1981). Higher than expected Al in streams during spring melt was attributed to flushing of soil-accumulated Al in the Hooper and Shoemaker (1985) study. Other researchers have given additional explanations for observed Al behavior in streams that does not coincide with gibbsite solubility control. (1986) and Mulder et al. Arp and Ouimet (1986), Bache (1989) considered organically bound Al as a primary controlling mechanism for surface water Al concentrations. Cation exchange has also been invoked to 13 explain Al behavior in certain systems (McAvoy, 1989). Some studies have indicated equilibrium with A1-S04 minerals such as jurbanite as major controlling factors on Al concentrations (Eriksson, have 1981; Arp considered and Ouiment, 1986). aluminosilicate mineral weathering important in understanding Al (Manley et al., Williams, 1988; Neal et al., 1989, 1992). clay minerals in (Walker et al., Numerous studies soils has also been as most 1987; Neal and Adsorption of Al by considered important 1988). In light of these many studies, it seems clear that no single mechanism controls Al chemistry in all watersheds. It appears that in order to understand fully the relationships between weathering processes, soil and in-stream reactions, and hydrologic factors and their effect on stream chemistry, it is necessary to evaluate each watershed individually, least until models more adaptable to specific at watershed conditions become available. STUDY AREA Location The two watersheds in this study are located in Marquette County in the Upper Peninsula of Michigan, shown in Figure 1. The Peshekee River begins near the highest elevation in the state (Mt. Curwood, 1980 feet) in the extreme eastern portion 14 of Baraga County, and flows to the southeast for approximately 30 miles through western Marquette County, draining into Lake Michigamme at its mouth. The Yellow Dog River also has its source in the highlands on the border of Baraga and Marquette Counties, but flows northeasterly for about 33 miles before draining into man-made Lake Independence near the town of Big Bay. Both rivers drain nearly uninhabited forested areas. The two rivers carry approximately the same quantity of water, but one noticeable difference between them is the color of the w a t e r . The Peshekee River, like many in northern Michigan, is colored tea brown by tannins leached from organic debris on the forest floor and the numerous bogs and swampy areas found throughout the watershed. The Yellow Dog is similarly, albeit more lightly, colored in its upper and middle reaches, but is remarkably clear by the time it reaches downstream stretches. Geology The geology of the region drained by the Peshekee and Yellow Dog rivers consists of Precambrian igneous and metamorphic bedrock, covered in places by varying thicknesses of Pleistocene glacial sediments. mostly The majority of the rocks, granitic gneiss, are considered to be at least 2.5 billion years old by Rb-Sr dating (Cannon and Simmons, 1973), a stratigraphic division known regionally as Precambrian W age (Cannon and Gair, 1970). These older rocks are overlain 15 Lake Yellow Do g P l a i n s /rflTiflif1 Superior Yellow D o g River P eshekee River mafic dikes Figure 1. Location of the Peshekee and Yellow Dog Rivers showing schematically the main geological features of the area; actual dike thicknesses 2-25 meters (after Sims, 1992). 16 unconformably by Precambrian X rocks of Early Proterozoic age, composed of metamorphosed metavolcanic rocks. sedimentary and, less commonly, Numerous diabase dikes trending nearly east-west and a few small scattered mafic plutons intrude all rocks in the Proterozoic Sims, region, age, 1992). or and are believed Precambrian Y to (Cannon be and of Middle Gair, 1970; The mineralogy and chemical composition of the dikes and plutons has been studied in detail by Wood (1962), Morris (1977) , and Shanabrook (1978) , who have shown that they contain large amounts of pyroxene, plagioclase, in places, pyrite. interpreted tholeiitic to be These related basalts and intrusive to the andesites bodies well which olivine, and known host have Keweenawan native deposits in the western Upper Peninsula of Michigan, believed by some to have been feeders been copper and are for Keweenawan lavas (Wood, 1962; Hubbard, 1975; Morris, 1977). Middle Proterozoic magmatism is associated with the opening of a continental rift system that is thought to have resulted in the positive linear gravity anomaly extending 1300 km from Lake Superior to Kansas (Chase and Gilmer, The Peshekee Precambrian W watershed outcrops tonalitic gneiss, moderate 1973). of contains granitic, numerous large granodioritic and occurring as rounded elongate ridges with foliation. Thin layers (generally less than 1.5 meters) of glacial till fill the interridge areas, which also contain extensive bogs and swamps. roadcuts, locations of mafic dikes In several places along can be identified by 17 seeping or dripping water that freezes into icicles in winter. The headwaters of the Yellow Dog River originate in similar terrain. However, the middle and lower reaches of the Yellow Dog flow through extensive glacial till and outwash, which attains a thickness of 3 00 feet or more in the area known as the Yellow Dog Plains in the central part of the watershed. Figure 1 shows the main geologic features of the region and the orientation of the rivers with respect to the mafic dikes and glacial outwash. For the most part, dikes run east- west across the entire area, intersecting the Peshekee River at nearly right angles and parallelling the Yellow Dog. small plutons of peridotite and gabbro are present middle portion of the Yellow Dog watershed. dikes shown in Figure 1 are schematic, A few in the The locations of but are based on the geologic map of the area by Sims (1992) who mapped the dikes from geophysical evidence. Wood (1962) and Shanabrook (1978) report dike thicknesses of 2 to 30 met e r s . Hydrologic Setting and Climate Although the Peshekee and Yellow Dog rivers are of similar length and transport more or less equivalent amounts of water, the nature of drainage within each watershed is not the same. The main trunk of the Peshekee drains numerous 1st through 5th order tributaries separated by rounded ridges of granitic bedrock, and morphologically represents a rather 18 typical dendritic drainage pattern. More than 50% of the low-lying areas of the Peshekee drainage basin are covered by swamps, which periods, but are are drained not by tributaries connected system during low flow. to the during surface high flow hydrologic The Yellow Dog River begins as two separate branches; each drains a small lake within the same rocky terrain as the Peshekee. However, there are very few additional tributaries that join the main trunk of the Yellow Dog for the rest of its course. asymmetric. The river flows The drainage basin overall is from west to east across the southernmost part of the sandy Yellow Dog Plains, paralleling an extensive ridge that forms a drainage divide marking the southern boundary of the basin. Few swampy areas exist within the Yellow Dog watershed. Springs are a common feature in both watersheds, and can be seen flowing into each river at many places along the banks. Some of these springs flow year-round at approximately constant discharge, while extended dry periods. flow from others subsides during These springs appear to be related to fracture systems in the bedrock. Annual rainfall in the Peshekee and Yellow Dog watersheds averages about 90 cm per year, with up to half of this amount occurring as winter snowfall. The winter season in northern Michigan is quite long and cold, and midwinter snowpack depths are typically 1.2 meters or more. Runoff is therefore generally highest during spring snow melt, especially early in the season before soils have had a chance to thaw. Rainfall 19 acidity has been monitored at several sites in Michigan over the past 15 years, and has been previously measured to average pH 4.1 to 4.6 in northern Michigan (DeGuire, 1988; Doonan and VanAlstine, 1982) . METHODS Water Sampling and Analysis To monitor these watersheds, samples of water from three sites on each river were taken weekly over the course of one year (summer, 1988 through summer, 1989). Sampling sites are shown on Figure 2, labeled Sites 1, 3, and 4 on each stream. Samples were also taken daily from Site 1 on each stream during the initial three days of the first major spring runoff in late March. The uppermost site on the Yellow Dog River (Site Y 4 ) , and occasionally other sites, during winter during those and major times. rain storms Hydrologic were and were inaccessible not measurements sampled were taken periodically at each sampling site, while Site 2 on each river was set up Precipitation for continuous was recording collected on a of hydrologic weekly basis, data. in an Aerochem-MetricsUn wet/dry precipitation collector placed in an open area between the two watersheds, away from tall trees (location in Figure 2) . Because high snowfall prevented operation of the wet/dry collector during winter, weekly snow 20 Lake Superior Yellow D og River S2 I P esh ek ee River Lake Michigamme S3 * I precipitation collector ^ — groundwater sample location stream water sample location 10 km Figure 2. Location of precipitation, stream, spring and ground water samples (Sl=Peshekee Spring; S2=Yellow Dog Upper Spring; S3=Yellow Dog Lower Spring). 21 samples including dry precipitation were collected from the same location in clean, open buckets from December through Apr i l . In addition to stream water and precipitation, groundwater from various depths and locations within the two watersheds was sampled wells. The locations of groundwater samples are noted on Figure 2. Three perennial springs, to shallow domestic one near the Peshekee and two within the Yellow Dog watershed, basis from further were define sampled the on a weekly nature of to monthly the regional groundwater. Analytical methods used to measure ion concentrations are listed in Table 2. Field methods, sample preparation techniques and further analytical details are discussed in the following paragraphs. Measurement of temperature, pH, alkalinity, and fluorine was done in the field for all water samples, which were then field processed and preserved for transport to the laboratory for storage and further analysis. Samples for major and minor elements and dissolved organic carbon (DOC) were filtered through 0.45 micron Millipore*™ mixed cellulose filters, then subsamples taken and preserved for later analyses as follows: for Ca, Mg, Na, K, Fe and Mn, 100 ml subsamples were placed in 125 ml pre-cleaned polypropylene bottles with grade concentrated nitric analysis were preserved acid; 125 ml in plastic 1 ml reagent subsamples bottles by for adding S04 1 ml formaldehyde; 100 ml subsamples for Cl and Si02 were placed in 22 Table 2. Methods of aqueous chemical analysis. Species Method Reference pH in field, combination electrode alkalinity in field, Gran titration Ca, Mg, Na, K, Fe, samples preserved w /H N 03; analysis by atomic absorption spectrophotometry (AAS) Slavin, 1968 F in field, specific ion electrode with buffer solution Orion, 1984 Al species separated in field by hydroxyquinoline/MIBK/ion exchange; analysis by AAS w/graphite furnace Barnes, 1976; Driscoll, 1984 S i0 2 automated colorimetry, molybdate blue method APHA, 1976 DOC optical absorbance measured in field, analysis in lab by catalytic oxidation Sugimura and Suzuki, 1988; Martin, pers. comm., 1991 Cl automated colorimetry, mercuric thiocyanate method APHA, 1984 so4 turbidimetric APHA, 1971 n o 2, n o 3 automated colorimetry, sulfanilamide method with Cu-Cd reduction for nitrite APHA, 1984 nh4 automated colorimetry, indophenol blue method APHA, 1976 Po 4 automated colorimetry, phosphomolybdenum blue method APHA, 1976 Orion instrument manual 23 bottles with no treatment; subsamples for nutrients N species) within a (P04 and were placed in 125 ml plastic bottles and frozen few hours; DOC subsamples placed in glass bottles. were All samples also frozen, but (except those frozen) were immediately cooled and kept refrigerated until analysis. Field processing of samples for Al speciation study followed methods to prevent contamination suggested by Barnes (1976), Driscoll (1984), and R. Aller (personal communication, 1987). To pre-clean, all bottles for storage of Al subsamples were filled with 10% HCl and heated to 95° C in a water bath for 12 h o urs, rinsed twice with distilled, deionized water, then filled with purified water and allowed to stand for 24 hours before final rinsing and drying. Samples were filtered through 0. 2 or 0. 4 /xm Nucleopore*1” polycabor.ate filters which were pre-cleaned by soaking in 50% reagent grade nitric acid for 24 hours, rinsed, then soaked in purified water for 24 hours before thorough rinsing and storage in purified water. All labware was soaked in an acid bath of 10% nitric acid and thoroughly rinsed with purified water before use. Except for transfer pipettes and volumetric flasks, no glass was used in processing Al samples. To separate Al into component species, methods of Driscoll (1984) and Barnes (1976) were modified for use in the field. For the monomeric fraction, 50 ml samples filtered through 0.2 jum filters were placed in 250 ml volumetric flasks with 50 ml purified water and 2 ml 5% 8-Hydroxyquinoline solution, and shaken vigorously for exactly 10 seconds. Ten 24 ml of methyl isobutal ketone (MIBK) were immediately added and the mixture separate was into portion, again organic and Al and bottle. separate an transferred aliquot the of simple 0.2 allowed The a reacted collected 30 ml Aim filtered using cleaned organically a storage complexed sample to organic conta i n i n g was into then layers. that molecules, micropipette To vigorously, hydrous theor e t i c a l l y singly-complexed portion, shaken was Al passed through a teflon column filled with Amberlite IR-120 exchange resin. The column was prepared to the specifications given by Driscoll (1984) . A 50 ml portion of exchanged sample was then treated using the method described above to extract the easily reactable A l . Total Al was determined from a sample prepared by passing water through a 0.4 a clean nitric bottle acid. and adding Blanks were /urn filter, collecting 50 ml in 0.1 ml double-distilled processed using speciation techniques on a monthly bas i s . in all cases was accomplished using AAS each Ultrex1™ of the Al Measurement of Al with a graphite furnace. Dissolved organic carbon was estimated within hours of sample collection filtered water. by measuring the optical absorbance of A representative suite of samples were then analyzed for DOC at Woods Hole Oceanographic Institute using a technique developed communication, (1988). 1991), Absorption coefficient = .95) by B. Martin modified readings with DOC from were and others Sugimura correlated measurements (personal and Suzuki (correlation for a final 25 approximation of concentrations. A strong correlation between color and DOC is not always detected in studies of surface waters, such as reported by Henriksen et al. in southern Norway. In this study, (1988) for lakes however, stream water color appeared to relate directly to the amount of dissolved organic carbon, a finding also reported by Merna and Alexander (1983) in previous studies of streams in northern Michigan. Estimates of DOC concentrations made in this way represent good quantitative approximations for these streams, but should not be viewed as precise measurements. Discharge Measurements To measure discharge, a Stevens continuous water level recorder was installed at one site on each river to monitor stage. Instruments were located under bridges on each river, labeled Site 2 in Figure sampling Sites 1 and 3. 2, approximately midway between Sites chosen for monitoring flow were fairly symmetric, and provided security and relative ease of access to instruments. made once flowmeter. check the weekly at Measurements these sites of flow velocity were using a Teledyne-Gurley A manual depth measurement was also made weekly to stage recorder readings. In winter, the clock mechanism of the water level recorders could not be coerced into operation, therefore manual measurements were made through holes drilled through the ice layer that covered each 26 river. Water cross-sectional depth and velocity area to calculate were combined stream with discharge, representative of flow conditions at time of sampling for each week. Rock, Sediment and Soil Sampling and Analysis Soil, sediment and rock samples were obtained from each watershed for overall mineralogical analysis. Samples from floodplain material of the Peshekee River were taken from a mid-stream location, from a depth of approximately 0.5 meter. Several samples were taken of the near-surface glacial outwash material Plains. from approximately the center of the Yellow Dog Samples of Yellow Dog outwash were also obtained at various elevations from the slope of a steep valley where the river has eroded through the glacial material to a depth of at least 75 meters. Samples of granular material were studied in two ways. First, fine settling, material then the was separated clay-sized diffraction analysis. from portion coarse prepared by gravity for X-ray Organic material was removed from dark colored clays by pre-treating with 10% hydrogen peroxide with gentle heating until reaction subsided, then clays were oriented in a thin layer on cellulose filters under moderate suction. Oriented clay layers were transferred from filters to glass slides by gently rolling a glass rod over the back of 27 a filter pressed against a slide. were obtained for untreated, X-ray diffraction patterns K-saturated, Mg-saturated, and Mg-ethylene-glycol saturated clay samples, as well as samples heated to 500° C. The second method used to determine mineralogy of watershed materials was to make thin sections of rocks and grain mounts of the coarse granular material. sections from petrographic features. each watershed techniques to were identify studied Numerous thin using microscopic standard weathering Coarse grain mineralogy was then compared to clays and previously determined bedrock compositions. RESULTS AND DISCUSSION Hydrology During the year of weekly sampling of these watersheds, a number of major hydrologic events affected stream flow and chemistry. Sampling began approximately three months Samples in late July, of unusually dry, 1988, after warm weather. from the first week of the study therefore reflect baseflow conditions. second and Heavy rain storms occurred during the fourth weeks (Aug. 3 and 17) , and also between weeks 10 and 20 (Sept. 28 - Dec. 8), resulting in significant and rapid increases in discharge in both rivers. Precipitation and hydrograph records depicting these events 28 are shown in Figure 3. Precipitation records were collected from weather stations located within each watershed, the Van Riper station near the mouth of the Peshekee River, and Big Bay station by the Yellow Dog outflow. For the most part, rivers were similar flow in the Peshekee and Yellow Dog in total flow amount and quickness of response to rainfall events, with discharge from the Yellow Dog of averaging about 8 0% that from the Peshekee. Differences in response to rainfall events are due in part to small differences watershed, in actual rainfall amounts within each and also to higher infiltration within the Yellow Dog watershed compared to the Peshekee. Hydrograph records from each watershed for an individual rain event are shown in Figure 4. Although discharge in both rivers increases rapidly with the onset of heavy rain, the recession of the hydrograph for the Peshekee is steeper than that for the Yellow Dog, indicating that the Peshekee returns more quickly to baseflow conditions, while the Yellow Dog collects water from surface runoff and interflow for a longer period of time after heavy rain. The winter season in northern Michigan was quite long and cold during 1988-89, (>20 cm) Yellow stable, and gave rise to a thick layer of ice which covered all of the Peshekee and most of the Dog. and During this consisted period, mainly of flow in both baseflow rivers inputs was flowing through the closed tube of the stream channel capped with ice. 29 15 12 -a- Van Riper Big Bay d. § CL 3 - _ * 1 5 9 13 17 21 25 2 9 33 3 7 41 45 4 9 53 w eek 18 P esh ek ee Yellow Dog 15 CO E £CO T3 f" 1 5 9 13 17 21 25 29 33 37 41 45 4 9 53 w eek Figure 3. Precipitation and discharge records for Peshekee and Yellow Dog Rivers (Van Riper=Peshekee area; Big Bay=Yellow Dog are a ) . Discharge, m3/sec 30 12 P e s h e k e e River - .Yellow D o g River 12 24 38 Time, h ou rs Figure 4. Typical storm event hydrograph rapid response of the Peshekee R i v e r . showing the more 31 Some portion of the winter stream flow was also occasionally from melted snow and ice, as the thickness of the ice layer varied from week to week. Spring snow melt and runoff occurred mainly between week numbers 35 and 4 5 (March 25 - June 1) , resulting in an abrupt increase in discharge pulses of high runoff. initially, followed by several more Runoff and high discharge from snow melt was slightly more sustained in the Peshekee watershed, reflecting the higher infiltration rates of the Yellow Dog. Another large rainstorm occurred during week number 4 6 (June 9), causing the major peak furthest to the right in both the precipitation and hydrograph records (Figure 3). Water Chemistry Results from aqueous chemical analyses of all waters in this study are tabulated in Appendix B, and are discussed in detail in the following sections. 1. Precipitation Weekly precipitation chemistry was quite variable. tabulated in Table 3 and plotted over one year's Data time in Figure 5 represent filtered (0.45 /zm) bulk samples of wet fall during spring, summer and autumn, and wet plus dry fall during winter (December through April) when bulk snow samples were 32 Table 3. Concentrations of major solutes in precipitation (in mg/1). Mean WM* Range pH 4.38 4.34 4.0-5.5 Ca 0.46 0.39 Mg 0.07 Na K Mean WM* Range S i0 2 0.005 0.01 0.0-0.1 0.0-2.0 no3 2.94 4.66 0.03-26.1 0.06 0.0-0.3 Cl 1.57 1.43 0.20-18.6 0.11 0.06 0.0-0.7 S04 0.20 0.18 0.09-0.59 0.23 0.27 0.01-3.2 Al 0.006 .005 0.00-0.03 *Volume weighted mean 33 collected. Although no distinct differences between summer and winter samples in the data are attributable to sampling methods, these data should be considered as overall estimates rather than chemistry. reported exact representations Mean values in Table for of specific precipitation 3 as arithmetic means weighted m e a n s , although for most difference between the two values. wet or dry chemistry are as well solutes there as volume is little The pH of precipitation varied between 4.0 and 5.5, and tended to be slightly higher during winter. precipitation, Of the acidic anions associated with acid N03 concentrations were high during the first large rain events after sampling commenced, events that were acidic, but also during measured. On precipitation do the a winter event when other appear to hand, be S04 related low pH's were concentrations to pH, with in higher amounts generally found in samples with low pH. Rain and snow were quite dilute with respect to major cations, as expected. components No discernable correlation among all exists, although the variability of Ca and appears somewhat similar when plotted as in Figure 5. Mg Higher concentrations of cations occur during low volume rain events, probably related to the fact that the earlier precipitation in an event "washes" most of the particles out of the atmosphere. Longer (larger) concentrated rain because events continued are thus rainfall generally is "cleaner" less and dilutes the bulk sample. Two other processes which have affected concentrations Anions in Precipitation Cations in Precipitation 25 3 Ca ■••*■■■ SQ4 20 ~e- Cl & NQ3, mg/l N03 Na 2 15 10 1. 0 - 1 5 55 0 1 5 9 13 17 21 25 29 33 37 41 45 49 53 Week Number 1 5 9 13 17 21 25 29 33 37 41 45 49 53 Week Number Figure 5. Weekly anion and cation variation Marquette County precipitation, 1988-1989. in western 35 are also reflected in the data. use of rock Although salt no salt for de-icing One of these relates to the of roads in is used on the access roads the winter. in the study area, dust in the air during winter must contain a significant amount of NaCl, as both of these ions were found in highest quantities during the winter months. Another chemical event is apparently related to the huge forest fires that consumed much of Yellowstone National Park in Wyoming during the dry summer in which this study commenced. and ash from September. plume (week the The 9, fires A large plume of smoke reached Michigan by first major rain after the Sept. 20) contained an the middle arrival of of the unusually high concentration of K, probably of biogenic origin, released to the atmosphere during burning. This K increase was accompanied by a corresponding increase in S04, as well as a decrease in other major cations. 2. River waters With certain exceptions, the major element chemistry of the Peshekee and Yellow Dog Rivers is rather similar in terms of average concentrations and overall seasonal variations. Results of chemical analyses of the most abundant solutes for 3 sites on each river are compiled in Table 4; a complete tabulation of all chemical data from river samples is given in Appendix B. Average solute concentration values reported in 36 Table 4. Concentrations (in mg/1) Peshekee and Yellow Dog Rivers. Peshekee River range of major solutes in the Yellow Dog River mean range mean pH site 1: 4.80 - 7.3 3: 5.65 - 7.4 4: 5.25 -7 .1 6.12 6.31 6.12 site 1: 5.7 - 7.8 3: 5.8 - 7.4 4: 5.7 - 7.2 6.93 6.45 6.63 Ca site 1 2.01 - 8.51 3: 2.00 -11.36 4: 2.32 -19.73 4.34 5.61 6.37 site 1: 4.59 -21.61 3: 2.71 -21.99 4: 5.65 -12.46 12.04 7.13 8.60 Mg site 1: 0.52 - 2.14 3: 0.51 - 2.31 4: 0.51 - 3.87 1.08 1.23 1.31 site 1: 0.97 - 3.94 3: 0.63 - 3.78 4: 1.33 - 2.44 2.36 1.50 1.89 Na site 1: 0.41 - 1.18 3: 0.30 - 1.08 4: 0.34 -2 .3 4 0.68 0.57 0.60 site 1: 0.49 - 1.74 3: 0.37 - 1.04 4: 0.58 -0 .9 3 0.86 0.65 0.76 K site 1: 0.17 -0 .8 2 3: 0.06 - 0.64 4: 0.04 - 0.58 0.34 0.28 0.28 site I: 0.28 - 0.81 3: 0.13 - 0.53 4: 0.38 -0 .5 5 0.48 0.35 0.46 Al, site 1: .018 - .178 3: .018 - .176 4: .012 - .175 .122 .115 .118 site 1 .022 - .137 3: .022 - .154 4: .028 - .125 .066 .085 .060 Fe site 1: 0.17 - 0.83 3: 0.10 - 0.72 4: 0.13 - 0.67 0.41 0.38 0.38 site 1: 0.10 - 0.39 3: 0.16 - 1.10 4: 0.12 - 0.51 0.20 0.44 0.29 S i0 2 site 1: 1.39 - 8.27 3: 0.85 - 8.90 4: 0.60 - 8.76 4.72 4.64 4.29 site 1: 3.67 - 9.35 3 3.00 - 7.78 4: 3.77 - 7.97 6.29 5.32 6.23 H C 03 site 1: 3.00 - 32.0 3: 5.00 - 40.0 4: 4.00 -4 0 .0 11.6 16.0 15.4 site 1: 14.35 -84.08 3: 6.00 -48.00 4: 20.00 -40.00 43.2 21.8 27.4 Cl site 1 0.93 -5 .2 5 3: 0.49 - 2.04 4: 0.63 - 3.30 1.97 0.97 1.00 site 1: 0.32 - 2.99 3: 0.49 - 2.32 4: 0.49 - 1.60 1.12 0.81 0.84 so 4 site 1: 1.62 -11.52 3: 0.67 - 5.64 4: 1.00 - 5.95 4.18 3.73 3.69 site 1: 1.00 - 6.19 3: 1.80 - 6.01 4: 1.31 -6 .8 3 4.32 3.83 5.01 N 03 site 1: .005 - 2.47 3 .016 - 5.96 4: .001 - 3.03 0.39 0.46 0.42 site I: .018 -2 .1 2 3: .001 - 0.07 4: .018 - 0.77 0.29 0.03 0.29 DOC site 1: 6.48 - 18.88 3: not measured 4: not measured 11.8 - site 1: 0.06 -22.08 3: not measured 4: not measured 9.48 - - 37 Table 4 are simple arithmetic means. Volume weighted averages were not calculated because of the difficulty of estimating 'average' discharge and the lack of discharge at individual sampling sites. of particular solutes are not information about While average amounts greatly different between rivers, certain elements are more concentrated in the Yellow Dog River, and variability. the Yellow Dog also For the purpose of displays more spatial identifying and comparing seasonal and spatial variability, annual data from both rivers were plotted and are presented in Figures 6 through 9, and are discussed in the following sections. pH: The pH range measured at river sites, shown in Figure 6, varies from 4.8 to 7.4 in the Peshekee and from 5.7 to 7.8 in the Yellow Dog. Spatial variability in pH from the headwaters to the outflow differs between the two rivers. the Peshekee, pH does not vary dramatically another, but direction. (Site 3) does decrease In contrast, is typically slightly In from one site to in the downstream the Yellow Dog midstream location the most acidic, while the pH of downstream waters (Site 1) is consistently 0.1 - 0.5 pH units higher than Sites 3 or 4. The low pH at Site 3 can be attributed to the extensive outwash plains covered with jack pine forests which are cultivated for lumber. Lawrence and Driscoll (1988), areas that have been clear cut. As shown by low pH runoff is typical from The lowest pH's were measured in each stream during initial spring snow melt and runoff; low pH episodes also occurred in response to large rainstorms in Variation in pH, Yellow Dog River Sites - iu .u liJ .i- L ix L u lu ,ljJ u X iL Variation in pH, Peshekee River Sites tE. ia r 7 6.5 site p4 6 r - U u .il L iX lllJ.i.lij-L X i-1-l.l 1 1 1, 5.5 7.5 Ia c r 7 6.5 site p3 j u sitey3 6 5.5 8 7.5 X 7 siteyl a 6.5 site pi 6 5.5 1 1 5 9 13 17 Aug Sap Oct 21 15 29 33 37 41 45 49 53 waak nutnbsr Not Dae Jan Feb Mar Apr May Ja i Aug 5 9 Sep 13 Oct 17 Nov 21 25 29 weekiunber Dsc Jan Fab 33 37 Mar 41 Apr 45 May Jul Figure 6. Weekly pH variation for three sites on each river, 1988-1989. 48 Jwi 53 .M 39 autumn and spring. Cations: Weekly variations in cation concentrations and Si02 are plotted for the two rivers in Figures 7a-c and 8a-c. The concentrations of Ca, Mg, vary in direct response Na, K and Si02 in both rivers to the proportion component present in total stream flow. of baseflow Waters are relatively concentrated during dry periods and during winter, and become diluted when there are large inputs of precipitation or melted snow. Direct amount of Ca, concentrated magnitude. precipitation Mg than and contributes Si02 to the stream an stream water, water by 1 insignificant as to it 2 is less orders of For Na and K, a few precipitation events contain the same order of magnitude concentrations as stream water and results in noticeable peaks in stream water concentrations, but for the most part rain is still much more dilute than the streams. Cations appear to be incorporated into the streams from groundwater, solutes as interflow, throughfall or or runoff from surfaces that has within picked the up forest floor debris. As in the case of downstream changes in pH, the rivers behave differently in terms of spatial variability. two In the Peshekee River, cation concentrations stay nearly the same as water travels downstream, and similar weekly or seasonal changes are reflected at all sites. In the Yellow Dog River, however, there is more variability between sites with respect to weekly or seasonal changes. Concentrations of Ca, Mg, Na and K are lowest in midstream locations, whereas by the time 40 waters have reached the mouth of the stream, cations have been concentrated by 50% or more. Anions: Both rivers exhibit similar mean concentrations of Cl, N03 and S04, but seasonal patterns of variability are inconsistent between species as well as between river systems. Data from measurement of anionic species are shown graphically in Figures 7a-c and 8a-c. differences correlated between to It is unclear the sites precipitation appears that aside overall pattern individual discharge from the major persists particular species. or on at from the data rivers in are patterns, but discrepancies, the sites if each river it same for a Large individual peaks in stream N03 are probably a direct result of input from acid precipitation, as concentrations in precipitation even from large events can be more than ten times that of river water. Sulfate concentrations, like N03 associated with acid deposition, tend to be quite similar between sites and rivers. though the between pattern of precipitation However, even S04 seasonal variation and water, stream is the concentrations of S04 in rain and snow is much similar absolute less (<10%) than that of the streams, implying that stream S04 is derived in large part episodes. large rain from watershed materials during high runoff High stream Cl also appears to be partially due to events. While F was measured in all samples, concentrations were quite low, near the detection limit of the analytical method used variation was observed. (0.02 mg/ 1 ) , and little weekly Ionic concentrations, Peshekee River site 1 (m M ol/L) 0.22 0.1S 0.1 Ca 0.03 Ci 0.04 0.04 0.1 O.OS 0.03 0.06 0.02 0.04 Mg 0.02 0.039 0.01 N 03 0.3 0.2 0.039 0.023 Na 0.1 alkalinity (a a C a C 0 3 ) 1.3 0.022 0.01 - DOC 0.3 0.15 0.12 Si 0 2 0.09 0.04 0.03 1 5 0 13 17 21 25 29 33 37 41 45 49 53 w©e« nuniLw A u g S o p O c t N ov D e c J a n F e b M ar A p r M ay J u n Ju l A u g S e p O c t NovD©c J a r ) F a b M a r A p r M ay J u n Ju l Figure 7a. Weekly ion concentrations, Peshekee River Site 1, 1988-1989. Ionic concentrations, Peshekee River site 3 (m M ol/L) 0.07 0.29 0.05 0.19 0.03 0.09 -4 0.02 0.1 ia*3 0.06 0.04 Mg 0.01 NOS 0.02 0.048 0.036 alkalinity 0.2 Na Y C a C 0 3 )_ 0 .1 fO o 0.012I0.018 0.012 0 0.15 0 .1 7E-3 S I02 0.05 total 1E-3 wee*c number A u g S e p O c t N ov D e c J a n F e b M ar A p r M ay J u n J u l 1 S 9 13 17 21 25 » 33 37 41 45 49 53 A u g S e p O c t N ov D e c J a n F e b M ar A pr M ny J u n Ju l Figure 7b. Weekly ion concentrations, Peshekee River Site 3, 1988-1989. Ionic Concentrations, Peshekee River, site 4 (m M ol/L) 0.5 0.4 0.3 0.08 0.08 0.2 0.02 0.1 0 o.ie 0.08 0.12 0.00 Mg 0.04 0 N 03 0.02 0.4 0.05 0.3 0.03 alkalinity 0.2 Na (O C Q 3 ) _ 0.1 0.01 0 5.010 0.07 5.012 0.03 6E-3 0 0.15 0.1 Ah total 0.05 0 1 5 9 A u g S e p O c t N o v D e c J a n F e b M ar A p r M ay J u n Ju l 1 5 9 13 17 21 23 29 33 37 41 wscftcnumteer 45 48 53 A u g S a p O c t N ov D oe J a n F o b M ar A p r M ay J u n J u l Figure 7c. Weekly ion concentrations, Peshekee River Site 4, 1988-1989. Ionic Concentrations, Y ello w Dog River, site 1 (m M ol/L) 0.17 0.04 0.03 0.02 N 03 0.01 0.03 0.7 0.05 0.4 ^ alkalinity (as CaCOS) 0.1 0.022 2 0.017 DOC 0.012 0.007 0.18 0.07 }— S04 1 S ® 13 17 21 25 29 33 37 41 43 4© 53 wsstc number A u g S e p O c t N o v D e c J a n F e b M & rA p rM sy Ju n Ju l 0.01 1 5 © 13 17 21 2S 29 33 87 wsg& m anfasy 41 48 48 S3 A u g S e p O c t New D@e J a n F e b M ar A p r M ay J u n J u l Figure 8a. Weekly ion concentrations, Yellow Dog River Site 1, 1988-1989. Ionic Concentrations, Yellow Dog River, site 3 (mMol/L) 0.6 0.4 0.2 Ca 0l- 0.01 0.16 0.012 0.12 006 Mg N 03 4E-3 0 0.09 0.4 0.3 alkalinity 0.2 Na 0.1 0.01 o.or 0.09 0.03 304 0.01 0.19 Si 0 2 0.1 Al, total 0.09 1 5 9 13 17 21 25 29 33 37 41 49 49 S3 A u g S a p O c t N o v D e c J a n F e b M ar A p r M ay J u n J u l 0 w w « number A u g S e p O c t N ov D e c J a n F e b M ar A p r M ay J u n J u l Figure 8b. Weekly ion concentrations, Yellow Dog River Site 3, 1988-1989. 46 •p i r r j r n r j r r n y | 5 I n i l ,i i i l i u l x i - i l t S 8? r dado J_x jL 59 d5 8S ° s l D I. 8 d 1. 8 d ■n tii » * o 3> < 5 d n * 5 a « a S a I I i z 8 asa vt m i. .«.I«■■I In«»Ii 3 < o Dog River o 5. S "5 Yellow o ion concentrations, Ionic Concentrations, Yellow Dog River, site 4 □ - north branch (mMol/L) * - east b ran ch I Figure 8c. Weekly 1988-1989. s Site C 3 fr 47 The relative changes in alkalinity from week to week are quite consistent between individual sites and between rivers, and correlate well with variations in discharge and pH. Differences in results from this measurement have to do with downstream chemical changes Site 1 on the Peshekee River, characteristic of each river. furthest downstream, has lower alkalinity than up-gradient sites, while Site 1 on the Yellow Dog is significantly more alkaline than Y3 or Y 4 . DOC: Dissolved organic carbon samples from Sites 1 of each river. it can be seen that DOC behaved downstream portions of each river. was measured only in From Figures 7a and 8a, quite similarly in the Generally, DOC was higher during times of high discharge, and low during low discharge periods. Concentrations were initially higher in the Peshekee than in the Yellow Dog during the first big rains in autumn just after the long dry summer, but were higher in the Yellow Dog for other episodes of high discharge. somewhat tannins surprising and other considering organic that acids the is always This result coloration greater Peshekee, even when DOC is higher in the Yellow Dog. DOC concentrations were higher in the Al species: samples monomeric in the From field, is from in the Winter Peshekee. the three Al species separated from total dissolved Al (Alt), (Aim), and organically complexed monomeric two other species were calculated. total (Alo), Inorganically complexed monomeric Al (Ali) is equal to the difference of Aim and Alo, and polymeric forms of Al (Alp) equals Alt minus Aim. While 48 Alt and Aim were measured from all stream samples, measured only from Site 1 of each river. Alo was Weekly variability of Al species from Sites PI and Y1 are presented in Figure 9. It is evident from Figure 9 that Al behavior is not the same in the two rivers. resulted into in relatively the Peshekee After the dry summer, autumn rains large amounts of Alt being released during weeks 3-9, concentrations stayed about the same. while Yellow Dog Al It is not until late in autumn that there is a major influx of Al into the Yellow Dog from a smaller but still significant storm (week 17), during which time Al spring, in the Peshekee stays consistently high. In both streams respond to meltwaters and storms with distinct increases in total and monomeric Al species. Overall, the Peshekee River contains more of each Al species than does the Yellow Dog. A limited correlation between Al and pH exists in both rivers, but only for some of the Al fractions, as indicated by the graphs in Figure 10 showing Al species against pH. Al in both relationship streams based is on higher at Al-hydroxide low pH, an solubility. Total expected The relationship between pH and organically complexed Al is less clear, but a similar trend with pH is present. On the other hand, no definite correlation is apparent between Ali or Alp and pH. This implies that pH is not the dominant control on inorganic monomeric Al species nor polymeric forms of Al in these streams. Other processes that may influence Ali and Alp could be complexation reactions that take place within the Concentration of Al species, mmol/l Peshekee River Yellow Dog River 0.008 total 0.004 total 0.003 0 oi- 0.008 0.003 total monomeric 0.003 monomerl 0 0.008 ^ 0.006 0.003 0.003 organic 0 ~ ■ 0 VO 0.008 0.006 monomeric, morgani me 0.003 in organ ic 0 0.008 0.003 |- 0.003 0.003 •/sA/V\TrrA-i 1 5 9 13 17 21 25 29 33 37 41 45 40 S3 vmatsmatUssr A u g S e p O c t N c v D s e J a n F o b M a rA p rM s y J u n Ju l monomeric, 0.003 0K 0 I monomeric, A °'Sanio. ■ -e*3sa©s' Saa®«- ■ a .J 0 1 5 9 13 17 21 23 29 33 37 41 45 49 53 'numasr A u g S® p Oct N ov D e e J a n F e b M ar A p r M ay J u n J u l Figure 9. Weekly variation in Al species for downstream sites in both rivers, 1988-1989. 50 Yellow Dog River Peshekee River 150 - S 150 0.120 Q. i AA AAAA . 90 79 60 P 30 4.8 5.3 5.8 6.3 6.8 7.3 5.5 7.8 6 6.5 7 7.5 8 7 7.5 8 pH pH 150 q I120 F= 60 AA P> 30 4.8 5.3 5.8 6.3 6.8 7.3 5.5 7.8 6 6.5 pH PH -Q 40 * £ 50 - *30 Q-40 Q. e 4.8 f 5.3 5.8 6.3 . « ..............6.8 7.3 7.8 o o ’« -E o " AA A § 20 In o rc « * i o - ••• 0)10 A ’ ^ 30 ~ o 9& .y 20 A 5.5 pH " AA t ^Aa a a w K a A A 6.5 7 7.5 - PH n 50 £10° Q. 80 Q. d -40 40 Q- 20 Figure 10. Relationship of individual Al species to pH for downstreams sites of both rivers. 51 stream after Al is released from watershed materials, since solubility of Al at low pH does appear to control the total amount of Al available. Exactly how all of the Al molecules are complexed at different levels of acidity is not obvious; apparently Al is partitioned amongst organic, inorganic and polymeric compounds in varying proportions in ways that are not necessarily related to proton interactions. To species examine were the nature of Al plotted against DOC. complexing The further, Al relationship of individual Al species to DOC inriver waters is not the same in these two systems, as can be seen in Figure 11. Although data points are rather scattered in these plots, there appears to be a direct correlation between Alt and DOC in each river, and no clear dependency of Aim or Ali on DOC. As for other Al species, data for Alo versus DOC are not tightly constrained, but there is an apparent inverse relationship between Alo and DOC in the Peshekee River. in concentration with In other words, as DOC increases greater discharge, the added carbon compounds in the water do not appear to be forming monomeric organic-Al correlated, The same complexes. Instead, Alp and DOC are positively suggesting a relationship between these solutes. is not true for the Yellow Dog Alo and Alp data, which tend to follow Alt and appears to be directly correlated to DOC. One explanation for the dissimilarity in the behavior of organically complexed Al in these rivers may be that the type of organic compounds supplied to the Peshekee during high flow 52 Yellow Dog River Peshekee River ... •. 6 I5 3 4 §« 3f 4 • Td 15 2 90«F * e • • 2 .21 0* 0.7 0.9 1.1 1.3 A*i * * i . . 0 1.5 ** A a A AA S - 0.5 ▲ 1 0.7 0.9 0 1.5 1.3 1.1 0.4 f 15 0.8 1.2 1.6 2 DOC, mmol/l DOC, mmol/l ■ 3 1.2 • 9 3 p h a se s: am o rp h o u s m icrocrystal line natural syn th etic Jl .... 4.5 a . i i t^i- > i i 1 » .1__t „ i 5.5 i 1 « » »--1__I » 1 !■._«_ -I 6 6.5 7.5 pH Figure 13a. Plot of pAl (-l o g [inorganic monomeric Al]) versus pH for river water samples (squares=downstream sites, circles=midstream sites, triangles=upstream sites in both rivers). 63 * Groundwater □ Springs AI(OH) 3 phases: amorphous microcrystalline natural synthetic 4.5 5 5.5 6 6.5 7 7.5 pH Figure 13b. Plot of pAl (-log[inorganic monomeric Al]) versus pH for groundwater and spring samples. 64 along a plots line suggesting quartz are shown in Figures equilibrium. 14 and 15. Two of these In Figure 14, activities of K, Ali, and H are combined to relate quartz and the main K-bearing aluminosilicates considered in this study. Two different fields are shown for each mineral, based on thermodynamic data from Bowers, et al. (1984) representing 0° and 25° C. All river water, spring, and groundwater samples plot within the kaolinite equilibrium between field, kaolinite and data do not and either imply an muscovite or K- feldspar. More specifically, the data plot almost entirely on and between the lines for the two temperatures considered, which may indicate a relationship between quartz and kaolinite that appears diffuse rather that represent a range of temperatures. appear to plot linearly in linear because samples Some of the data points do Figure 14, possibly implying quartz-kaolinite equilibrium at a temperature of around 15° C, although further analysis of those points did not show any correlation with respect to temperature. In Figure 15, activities of K, H and silica are combined. Again, nearly all data plot within the kaolinite field, implying that waters are stable with respect to that mineral. However, most of the data, especially the river water data, also fall on or between lines of quartz saturation at 0° and 2 5 °C, implying that rather than equilibrium between gibbsite and kaolinite, quartz saturation dictates where points fall on the diagram. The relationship between kaolinite stability and quartz 65 10 l K-Feld$par 8 L O G (K + /H + ) 25'C ' - W 6 Muscovite Quartz 4 o Peshekee a Yellow Dog * groundwater 2 % % 0 Kaolinite -2 4 6 8 10 12 LOG(AI3+/H+A 3) Figure 14. Activity diagram for river and ground water samples (including springs), showing mineral stability fields for 0° and 25°C in the system HCl-H20-Al203-K20-Si02. 66 - \ : \ \ X \ \ \ \ o 0 1 OI l l \ P 0 t—j j | ■T- , | , -| | Peshekee A Yellow Dog groundwater 0 \ V \ LOG(K+/H+) ]— r -|...'1 "1..... ! T ~i I" I TT....1 1 " Quartz 2 5 -1.....1TI *. Mu\covi1j( \ \ \ \ ~ t • i i \ i \ i \ i \ • \i Gibbsite \i K-Feldspar i\ i\ i \ i \ i \ i \ ! i i ** * \ i i * *o’ 0 0 ( t -6 1 1 1 1 1 -5 1 1 P y r o p h y llit e \. » Kaolinite i tl -4 \ i i i 1 -3 i i i i 1 -2 i i i i .! ... *1 L0G(H4Si04) Figure 15. Activity diagram for river and ground water samples (including springs), showing line of quartz saturation at 0° and 2 5 °C in the system HCl-H20-Al203-K20--Si02 at 25°C. 67 ( i i i i I i i i i I i f: jT—1 ii^j ' ■ r..i IP ® \ lO 14 "1 1 1 i Leonhardite ! o LOG (Ca/H ^ 2) 12 r a * j J? i* In !o i tk 4i Aj | Peshekee Yellow Dog groundwater - * * - I [0* - * 1 1° 10 * - *i i 'o % of 1* ! 8 j Gibbsite ! 0 p h i So 1 i •7 -6 25°C-j i l i i * ii -5 - kaolinite • 1 A ^ H —1—I—I— I— i—1— t_i-.-i - o |i 1 6 Pyrophyllite - , ii -- !l--- 1 L -4 - 1_ . 1 ........... 1 -3 -2 L0G(H4Si04) Figure 16. Activity diagram for river and ground water samples (including springs), showing line of quartz saturation at 0° and 2 5 °C for the system HCl-H20-Al203-Ca0-Si02 at 25°C. 68 saturation is repeated in Figure 16, which shows activities of Ca, H and silica. kaolinite field, While data again plot mainly within the it appears to be more related to quartz saturation from 0° to 25°C rather that an equilibrium reaction between gibbsite and kaolinite over the same temperature range. Elemental Mass Balance from Weathering Reactions 1. Weathering petrology To develop a set of reactions that relates the dissolved solute chemistry of water to primary and secondary minerals in the watersheds, mineralogical study of weathered sediments and clay soil particles was performed. rocks, Wood (1962), Morris (1977) and Shanabrook (1978) have studied the minerals in Peshekee and Yellow Dog rocks in considerable detail, and their work has been used here as the basis for specific compositions of olivine, pyroxene and plagioclase applied in weathering reactions. Morris (1977) and Wood (1962) do report a limited number of weathering features associated with mafic minerals, the most pronounced being the distinctive rusty brown color of the surface of mafic outcrops. (1977) Morris also found pyroxene not as weathered as olivine in thin section, fractures with or secondary cleavages, mineral and products plagioclase forming fresh to along totally 69 weathered. mafic Wood dikes (1962) from and Shanabrook give mineralogies of across the study area, but provide no observations of weathering except that much of the plagioclase and pyroxene appear rather fresh. To augment previous work, six hand samples and three thin sections of rocks from each stream evidence of primary mineral decay. area show signs Weathering textures of for but pyroxene and transformation observed studied Olivine was not observed in the few samples chosen for inspection, amphibole were in thin to section chlorite. appear as feathery or fibrous clumps in patches and along grain edges. Generally there is no discernible boundary between the altered zones and the polarized light. original pyroxene or amphibole in plane Some rocks that display moderate foliation also contain chlorite of metamorphic origin, identified as such from obvious boundaries around clumps of fibrous masses oriented in line with foliation. Other metamorphic minerals present are Ca-rich, including calcite, epidote, clinozoisite and sphene. Clusters of opaque minerals are commonly found along rims of mafic minerals and red oxide staining is present in fractures and cleavages. Plagioclase is partly weathered to clay, even in the most siliceous rocks. quartz Not surprisingly, appears quite fresh in all thin sections along with most of the potassium feldspar. Five thin sections were made from coarse grained sediments sifted out of samples from river channels and soil profiles. In unconsolidated grains, hornblende and pyroxene 70 grains are mostly decayed to fibrous clay-like material, but relict cleavages and original mineral. grain mounts reddish grain outlines give evidence of the The most obvious weathering feature seen in compared staining to rocks from is the oxidation. increased Quartz amount appears of fresh, potassium feldspars are fresh to sericitized, and plagioclase feldspars range from partly to mostly weathered. Diffraction patterns from clay separates 2fx) (< representative soil samples are given in Figure 17, from showing the major mineralogical features of Yellow Dog and Peshekee clays. Based on x-ray diffraction, clays from Peshekee soils consist of mainly chlorite and smectite with a small amount of vermiculite and possibly kaolinite. and 14.24 A The strong peaks at 7.13 are persistent in all clay treatments, indicating the presence of plentiful chlorite. dried) In the untreated clay samples, the specific peaks at together with the distinct peak at 4.77 (air 7 .13 and 14.24 A, A, indicate the particular chlorite mineral present is clinochlore, a Mg-rich chlorite containing varying amounts of A1 and Fe. the position of the 14.2 A peak saturation of the Peshekee clays, clay. was No shift in observed upon Mg- indicating an Mg-rich 2:1 A discrete shift from 14.2 to 16.98 A after treating Peshekee clays with ethylene glycol confirms the presence of expandable Mg-smectite. Upon treatment with K there is a small amount of clay in Peshekee samples that shows collapse from 14 to 10 A, which is evidence for vermiculite. The existence of kaolinite in this soil cannot be verified from 71 16.4 4 .7 7 Yellow Dog K, 550° - Mg-glyc Mg, 25° " K, 25 air dried .34 ,26 7, Peshekee K ,550° - 1 6 .9 8 M g-glyc air d r ie d ------ 30 20 (CuKa) Figure 17. Representative x-ray diffraction patterns for clays from Peshekee and Yellow Dog soils. 72 these data, nor can it be judged absent since the 7.13 A peak from chlorite would regardless be present. The Yellow Dog clays are similar to the Peshekee but show specific mineralogical differences. They appear to contain a large percentage of smectite as there is a distinct and almost complete shift from a peak of 12.5 to 16.4 A after Mg and ethylene glycol saturation in most samples, as shown in Figure 17. The smectite present partly Na-rich, marking a 12.5 saturation. as A clay air-dried d-spacing which sample expands is at exhibits to 14.5 a least peak upon Mg The most well-defined peak in all the x-ray data occur around 7.13 the the in Yellow Dog soils A, and does not shift or decline with any of treatments mineral is present. including heat, indicating a chlorite There is also evidence for vermiculite in A Yellow Dog soils since the 12.5 near 10 with K saturation. peak partially collapses to Most samples contain small amounts of illite as well, but the 10 A peak indicative of illite is always small and indistinct. In addition to petrographic analysis of solid particles, a number of samples of suspended particles collected from each stream were examined by SEM. not conducted on these made was all that water diatoms, Si02 budget. While detailed examination was samples one significant observation samples contained an abundance of fresh an important consideration in establishing a From chemical modeling it appears that most water in this study is near equilibrium with quartz, implying that free silica is readily available for any weathering 73 reactions, diatoms assuming or other that the dissolution crystalline sources of is silica not from regulated kinetically. 2. Mass balance reactions Tabulated results of mass balance calculations derived from mineral weathering reconstructions are shown in Table 6. In developing this table, primary inputs to streams guantified by this study were considered to be groundwater from springs, direct precipitation, and overland flow. follows stream. a distinct hydrologic pathway Each of these inputs before reaching the While other inputs to the streams like overflowing swamps and interflow are most definitely present in the two systems, they are not included in the reconstruction because they were not considered guantifiable by the data obtained in this study. Instead, known information was used to gain insight about such inputs; where groundwater and soil runoff do not appear to fully account for observed river chemistry, other inputs are considered to be important. Chemical reactions used are based on observed primary and secondary minerals or products identified from chemical modeling. These reactions are numbered seguentially and listed in Appendix A. For each type of water considered in Table 6, the first row of values represents the average solute concentrations of that water (arithmetic average calculated from all samples; data 74 Table 6. Reconstruction of source minerals for Northern Michigan waters (in mol/1*104) ; equations shown in Appendix A. Peshekee Spring Reaction Products Na+ Ca2+ Mg2+ K+ h c o 3- SO„2' S i0 2 Subtract precipitation .283 1.395 .786 .174 4.730 .043 .125 Kaolinite—> An5J‘ .000 1.049 .786 .174 3.755 .043 .000 Saponite—> biotite2 .000 1.049 .786 .000 3.581 .043 .000 .174 Biot .000 2.0W25E73 .629 An53 Clinochlore- > pyx3 .000 .044 .000 .000 .043 .000 Form pyrite4 .000 .044 .000 .000 .000 .000 .000 .02 Pyrite Products Yellow Dog Upper Spring Reaction Na+ Ca2+ Mg2+ K+ h c o 3- SO,,2' S i0 2 Subtract precipitation .222 1.666 .551 .146 4.392 .205 1.207 Kaolinite—> plagioclase5 .000 1.333 .551 .146 3.504 .205 .763 .555 An^ Vermiculite—> biotite6 .000 1.333 .551 .000 3.358 .205 .643 . 146 Biot Clinochlore—> pyx7 .000 .000 .481 .000 .552 .205 .000 3.6W4E5F, .14 Fa2Fo8 . 10 Pyrite Form olivine® .000 .000 .260 .000 .000 .205 .000 Form pyrite9 .000 .000 .260 .000 .000 .000 .000 Yellow Dog Lower Spring so42- S i0 2 19.53 .770 1.264 .115 18.58 .770 .195 .743 Ana, 2.226 .000 17.77 .770 .000 .115 Biot 7.461 .000 .000 13.32 .770 .000 2.2 Chlor .798 .000 .000 .000 .770 .000 6.7 Calcite .798 .000 .000 .000 .000 .000 .385 Pyrite Na+ Ca2+ Mg2+ K+ HCOj- so42- S i0 2 Products Subtract precipitation .104 .434 .218 .000 1.147 .188 .746 Kaol—> plagioclase15 .000 .394 .218 .000 .963 .188 .538 .144 Alia, Form saponite16 .000 .394 .000 .000 .527 .188 .285 .07 Sapon Na+ Ca2+ Mg2+ K+ h c o 3- so42- S i0 2 Products Subtract precipitation .152 .876 .382 .056 2.016 .276 .595 Kaolinite—> biotite17 .152 .876 .270 .000 1.736 .276 .483 .056 Biot Kaolinite—> saponite18 .000 .876 .000 .000 1.044 .276 .427 .46 Sapon Reaction Na+ Ca2+ Mg2+ K+ h c o 3- Subtract precipitation .535 7.669 2.456 .115 Kaol—> plagioclase10 .000 7.461 2.456 Kaolinite—> biotite11 .000 7.461 Talc—> clinochlore12 .000 Form calcite13 .000 Form pyrite14 .000 Products Peshekee runoff Reaction Yellow Dog runoff Reaction 75 from Appendix B) minus mean precipitation values. Because Cl and N03 were not considered in mineral reactions, they are not included in Table 6. However, this exclusion causes an imbalance in the positive versus negative charges in starting values for Table 6 entries. positive charge was bicarbonate values. this data could For this reason, balanced by initial excess arbitrarily adjusting While this approach is not the only way be handled, the discrepancies in charge balances are small, and do not significantly affect the final results. In the Peshekee watershed where soils are quite thin, springs must follow the most fractured or weathered regions in the rocks, the mafic dikes. The rationale to account for the chemical signature of the Peshekee Spring in Table 6 starts by first assuming all Na and some of the Ca is derived from the breakdown of labradorite (An55) , the predominant plagioclase in the dikes (Shanabrook, was not conclusively 1978), to kaolinite. identified While kaolinite by mineralogical study of Peshekee watershed materials, chemical modeling does show that the water kaolinite. been is Second, attributed weathering thermodynamically to to stable with respect to dissolved K in the Peshekee Spring has the saponite, release chosen of cations based on from x-ray biotite data. Clinochlore could have also been used as a weathering product of biotite, giving essentially the same result. Application of these two quite reasonable assumptions leaves Ca, Mg and bicarbonate in almost exactly the proportions required by the 76 reaction of pyroxene weathering to clinochlore, the reaction shown in Table 6 for the Peshekee Spring. (1978) third Shanabrook reports the composition of pyroxene in the Peshekee dikes as diopsidic augite, and the chlorite composition is taken from x-ray analysis of Peshekee clays. Reactions of other mafic silicates like olivine or hornblende could also produce though the cation direct concentrations observation seen supports in the spring the combinations even chosen here. Finally, a small amount of pyrite dissolution is invoked to explain unreasonable the S04 concentrations as trace amounts to in the several spring, modal not percent of pyrite have been reported in both mafic dikes and in granitic gneisses (Shanabrook, Alternately, 1978; Taylor, 1972; Wood, 1962). S04 could be derived from S04 absorbed in soils from precipitation inputs, a process known to occur in regions receiving acid precipitation (Drever, 1988; Krug, 1991). the Peshekee Spring weathering reactions (and other For water types in Table 6), there is some remaining positive charge, which could be ascribed reactions are written. to Ca or Mg depending on how the Since there is no way to balance the cationic charge in this spring or in any of the waters in this study without using S04, it may be that S04 and Ca or Mg are involved in the same reaction. No empirical evidence suggests, however, that a Ca or Mg sulfate mineral is present in the system. charge in Table Another problem with balancing the cationic 6 is that N03 and Cl are not considered 77 because they reactions. do not typically Possibly excess Ca participate is involved in mineral in interactions with organic anions. Chemical modeling data show that waters in this study are near saturation reactions or derived supersaturation for Table 6, with quartz. silica is In presumed the to precipitate or stay in the solid state except for the small amount of aqueous Si02 found in water samples. Another possibility is that excess dissolved Si02 is utilized through uptake by diatoms. The sequence of weathering reactions Peshekee Spring accounts quite well element concentrations, with only inferred for the for the observed major a little Ca left over. Another possible source for the excess Ca may be the breakdown of small amounts of epidote or other Ca-bearing metamorphic minerals present in the Peshekee rocks, like calcite, but this should produce corresponding acid anions. A similar approach was used to develop weathering reactions that lead to the composition of the Yellow Dog Upper Spring. The geology in the region of this spring is similar to that of the Peshekee, and comprises several small plutons of peridotite and gabbro; congruent dissolution of olivine (Fa20) , and incongruent weathering of labradorite (An^) , and diopside (Wo38En50Fs12) from these rocks was presumed to release much of the Mg, Ca, and Na to the spring. Specific chemical compositions of primary mafic minerals were taken from the work of Morris (1977), and the compositions of secondary 78 minerals were derived from x-ray and petrographic analyses. All Na and breakdown of vermiculite feldspar some Ca were labradorite, was assumed be derived from the and transformation of biotite to considered weathering to would the have source also of K. Potassium been an appropriate choice; probably both reactions occur in this system, although much of the microcline seen in thin section appeared fresh. The formation of clinochlore from pyroxene is used to rationalize the remaining Ca and a portion of the Mg, while the dissolution of olivine is presumed for the balance of Mg. Since x-ray data indicates Na smectite is present in soils, an alternate reaction such as An60 + Biot could also (or pyx) — — > Kaol + Na-smectite + Ca + K explain solute concentrations in water, provides that more of the Ca comes from plagioclase. and Also, the amount of pyroxene called for by this reconstruction is rather high compared to the amount of olivine or plagioclase used. Because previous work implies that olivine is more weathered than pyroxene in the Yellow Dog rocks, it would also be appropriate to allow that more of the Mg is from olivine. As in the case of the Peshekee Spring sulfate is attributed to pyrite oxidation, based on Morr i s ' (1977) notes of sulfide patches up to 1 cm in diameter in these rocks. For the Yellow Dog Lower developed Spring, weathering are distinctly different than for other reactions springs. 79 This is because outwash, the material minerals. Lower that Spring contains emanates few from glacial unweathered mafic The main source of ions from the glacial sediments are primary minerals of moderate weatherability, andesine and biotite. Another reaction that is used in Table 6 for the Yellow Dog Lower Spring is the breakdown of clinochlore to release Mg. While chlorite is relatively stable under surface conditions in soils, it may begin to break down if exposed to dilute aqueous solutions for long periods of time such as would occur if the path traveled by the spring water was quite long. The alkaline chemistry than other of the Lower Spring water in this is markedly more study, and comparatively high amounts of Ca and bicarbonate. contains Carbonate rocks are known to occur in regions immediately south and west of the Yellow Dog referred Yellow to Dog by study area Sims (1992) drainage. It (Boyum, 1975) , and have been as is occurring likely originates in similar rocks. that northwest of the Spring Lower the Discharge from this spring is two to three times greater than the Upper Spring, and unlike other springs in this study is constant year round, suggesting that waters system, follow a long flowpath through a regional flow one that is not affected by local flow patterns and near surface processes like freezing. In input, addition runoff contribution spring runoff to, was to but less considered streams. samples, To important a major account reactions than, groundwater although for ions describing episodic present in alterations of 80 secondary minerals that were determined by mineralogic study to be present calculations. in For soils were Peshekee applied runoff, to the mass balance specific smectite formed by pyroxene weathering described above (see Peshekee Spring, Table 6), was assumed to break down into kaolinite in the upper soil, releasing Ca and Mg to water. Andesine weathering was used to explain Na in Peshekee runoff. limited amounts of K were found in Peshekee Very runoff, but biotite alteration to kaolinite was used to justify the K in Yellow Dog runoff. Since Na-rich smectite was indicated by xray study of Yellow Dog soils, a reaction between Na-rich smectite and kaolinite was employed to account for all of the Na and some of the Ca and Mg present in runoff. Rather than invoking other chemical reactions to completely balance ions in runoff after samples, considering examination the above of concentrations reactions shows remaining quite results for both the Peshekee and Yellow Dog. similar This suggests similar processes may be acting in both systems to result in much of the Ca, Mg, HC03, Si02 and S04 in runoff. It appears that these ions are being leached from upper soil particles and organic debris as water runs over and through the top few inches of surface material, either by cation exchange or simple dissolution of uncharacterized mineral matter. Direct comparison of molar concentrations from each river location with chemistry from individual input sources shows that for the Peshekee River, the middle and upper portions are similar to water from springs and shallow groundwater flowing 81 through rocks from which mafic minerals are weathering, while the downstream stream water is more dilute and possibly influenced by overland flow which gains its chemical character from interactions mainly from soil minerals. This result can also be explained by considering the lakes and swamps drained within the Peshekee watershed that contribute proportionally more water downstream. Lake contributions would tend to dilute stream water while swamp input is rich in A1 and would increase Alt in the stream; both of these characteristics are seen in low elevation Peshekee w a t e r . The Yellow Dog River, for the most part, appears receive its water predominantly from groundwater sources. upper and middle stretches also reflect a runoff source, addition to groundwater. Two major types of to The in groundwater contribute to the river at different elevations. In mid to upstream areas, shallower groundwater flowing through glacial till containing mafic minerals and rocks is most important. In the downstream portion of the river, water has the chemical signature, in part, of springs that emanate from bedrock rich in carbonate. Such rocks occur at some distance away from the river; water entering the Yellow Dog River at low elevation therefore must follow the longest flowpaths of any sampled in this study. These interpretations of source waters are supported by simple statistical correlation within each watershed. of source and river waters Correlation coefficients calculated by performing multivariate statistical analyses of river water 82 chemical data and data from runoff and springs are tabulated in Table 7. Table 7. Correlation coefficients of molar concentrations for river and source waters. PESHEKEE PI P3 P4 Runoff .931 .909 .883 Spring .903 .953 .945 Correlation analysis study are chemically Y1 Y3 Y4 Runoff .993 .999 .999 Upper Spring .990 .993 .994 Lower Spring .997 .989 .991 YELLOW DOG shows all waters quite similar, an previously based on chemical modeling data. sampled in this inference made However, minor but noticable variations in correlation coefficients do exist in Table 7, and point to the same conclusions reached earlier about the nature of source water to each river location. SUMMARY AND CONCLUSIONS The purpose of this research was to identify the processes controlling concentrations of A1 species and major cations in two Northern Michigan streams. processes were identified hydrologic pathways and by Hydrogeochemical determining source water local inputs geology, in conjunction with weekly monitoring of rivers, springs and precipitation. The major findings and conclusions of this study are summarized in the following paragraphs. The most significant chemical episodes measured in the Peshekee and Yellow Dog Rivers during the one year study period occurred in response to input from 1) spring snow melt, which greatly reduced stream pH and increased total A1 concentrations; and 2) large autumn rain storms that followed an extended dry period that flushed certain cations from specific watershed locations. Precipitation pH ranged from 4.0 to 5.5; values for river water pH ranged from 4.8 during spring snowmelt to 7.8 during dry periods in summer and when rivers were frozen over in the winter. River water spatial variation. acidity showed distinct seasonal and The Peshekee River becomes slightly more acidic and dilute downstream as input from lakes and swamps increases, while the Yellow Dog is most acidic in mid-stream location, becoming alkaline downstream due to the input of deep groundwater. Aluminum speciation behavior 83 is not the same for each 84 river, and apparently is related to the composition of source waters as well as chemical interactions within the streams. Aluminum is partitioned amongst organic, inorganic and polymeric compounds in varying proportions in ways that are not necessarily related to proton interactions. Total dissolved Al (Alt) in both streams increases with acidity, as does monomeric organically inorganic monomeric Al correlate with pH. complexed (Ali) Al (Alo). and polymeric Al However, (Alp) do not Concentration levels of dissolved organic carbon are also directly correlated with Alt in both streams, but with Alo only for the Yellow Dog. In the Peshekee, Alo is inversely proportional to DOC but Alp correlates directly. Since the Peshekee receives a larger percentage of its water from swamps polymeric compared to the Yellow Dog, organically complexed Al, it is a species likely that not directly quantified in this study, is responsible for the relationship between Alp and DOC. Contradiction from expected Alo and DOC behavior may also be attributable to the analytical methods used to determine Alo, organic 1984). molecules which are designed to detect simple complexed to single Al ions (Driscoll, In the Yellow Dog system, simpler Alo compounds from soil water that interacts with organic debris may explain the association of DOC and Alo. in interpreting reactive total DOC, which does Alternately, problems may exist organic carbon based on measuring not discern organics that complex cations or those that may contribute to acidity (Krug, 1991). Other processes that may influence Ali and Alp could be 85 complexation reactions that take place within the stream after Al is released compounds of from watershed materials Al chains (inorganic to Alp), form inorganic since increased solubility of Al (OH) 3 with lower pH does appear to control the total amount of Al available. Equilibrium reactions with certain mineral phases also control Al concentrations groundwater, surface water to some extent. and river water For in this all study, activities of Ali and H are as expected for equilibrium with gibbsite. For river waters with pH less than 5.5, however, gibbsite does not control Ali activity. Instead, when pH is low during high discharge, there is less Ali than predicted by gibbsite equilibrium, probably because Al ions are being preferentially sequestered by organic molecules or are forming polymeric Al compounds. The alteration of kaolinite to gibbsite may also control Ali activities to some degree, but this relationship is not readily discernable from saturation with quartz. In any case, specific aqueous ionic concentrations resulting from both reactions are definitely temperature dependent, as the observed range of ion activities plotted on mineral stability diagrams can be explained largely by considering the range of water temperatures measured throughout the year. While base cations are, in general, diluted by runoff during high runoff events, there are distinct release rates of certain cations increases in in the Peshekee watershed when large rains follow long dry spells. This occurs because 86 pore fluids clinging to surfaces of mafic minerals throughout dry periods become increasingly leached from minerals. pyroxene dikes concentrated with In the Peshekee watershed, intersect the main trunk of the cations numerous stream at nearly right angles, and it is pore waters flushed from these dikes that are responsible for increased fluxes of Ca, Mg and Fe during such storms. Weathering of mafic dikes as a major contributor of solutes to streams has been identified in other similar systems, such as in the study by Rochette et al. (1988) . These authors found that weathering of mafic minerals in dikes cross-crossing quartzite was the most important terrestrial ionic input to West Glacier Lake in Wyoming. effect is not observed in the Yellow Dog, where dikes This and other mafic intrusive bodies exist but do not intersect the river, and therefore do not provide direct hydrologic pathways for storm runoff. In fact, once regular precipitation resumed after the summer dry spell, cation release rates progressively increased with time in the Yellow Dog watershed because of infiltration and flushing of groundwaters through deeper soil and sediment zones. A similar mechanism for cation release to streams has been proposed in other similar studies 1985). (Velbel, The same pattern of progressively increasing cation flux with time was also observed in spring after the ground had thawed and meltwaters had a chance to infiltrate to the water table. Evaluation of elemental mass balance from mineral weathering reactions for five different kinds of waters that 87 are input sources to the rivers shows that the chemical nature of the input water is highly dependent on geology. sequences developed from specific chemical Reaction compositions of primary and secondary minerals in the watershed account quite well for the observed water chemistry. The Peshekee Spring composition is directly related to the mafic minerals in the diabase dikes that it passes through, and surface runoff chemistry is produced from weathering of minerals in the upper soil zones. Runoff chemistry in the Yellow Dog basin is also from soil mineral weathering, but is the result of reactions of different mineral phases specific to the Yellow Dog soils. The two groundwater types identified in the Yellow Dog system are distinctly different from each other; the chemical signature of springs in higher elevations reflect weathering of minerals in bedrock, whereas the water of low elevation springs is of an alkaline Ca-Mg type from groundwater flowing through regional systems that pass through carbonate roc k s . Discrete sources of water to each stream at different locations can be identified by direct comparison of waters and by statistical sources of correlation input water to of chemical data. the Peshekee River The are major shallow groundwater at the middle and higher elevations, and shallow groundwater plus overland flow swamps at downstream location. in lower pH, lower cation and overflow of lakes and These distinct inputs result concentrations and concentrations at low elevation in the Peshekee. higher A1 In addition to accounting for higher overall A1 concentrations, the input 88 from swamp overflow also explains the relationship observed in the Peshekee. during high discharge has not been peculiar DOC/Alo Overflow from swamps emphasized in previous watershed studies, but is probably important in other regions that have experienced continental glaciation. Sources of water to the Yellow Dog River are from two different groundwater types; shallow groundwater draining granitic bedrock containing infrequent mafic intrusions feeds the middle and upper portion of the Yellow Dog, while deeper groundwater from carbonate rocks areas. In regional hydrologic circulation through is the major source to the lower elevation addition, during heavy rains and spring melt, overland flow and interflow flush soil water enriched in A1 to the Yellow Dog, causing decreased pH and higher Alt. Conclusions reached in this study point to the need to delineate specific sources of water to streams in order to understand how solute concentrations vary with season and with distance downstream in any watershed under investigation. Although the Peshekee and Yellow Dog Rivers receive the same initial precipitation behavior exist chemical nature input, between and and broad differences even "hydrologic within each connectedness" in chemical river. of The specific input sources dictates the chemical variability observed at different locations in each river. The pairing of watersheds receiving the same input, as in the work presented here, can be a useful method of determining specific hydrogeochemical interactions that are unique to an 89 individual watershed. Distinct differences in A1 behavior between the streams in this study could be interpreted as a function of geology and drainage characteristics because a direct comparison was available. polymeric A1 appears mainly That fact that to be associated with organic inputs, especially from swamp overflow, suggests that more attention needs to be given to understanding Al-organic complexation in relation to drainage patterns in future research. 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Wright, R.F., 1984, Norwegian models for surface water chemistry: An overview, in Modeling of Total Acid Precipitation Impacts, J. L. Schnoor, Ed. , Ann Arbor Science, p. 73-87. Wright, R.F., 1987, RAIN Project, Annual report for 1986, Acid Rain Res. Rep 13, Norwegian Institute for Water Research, Oslo, 89 pp. Wright, R.F., 1988, Influence of acid rain on weathering rates, in Lerman and Meybeck (eds.), Physical and Chemical Weathering in Geochemical Cycles, Kluwer Academic Publishers, 181-196. APPENDICES Appendix A R e v e r s e m in e r a l w e a t h e r in g r e a c t i o n s u s e d i n T a b le r e c o n s t r u c t s o u r c e m in e r a ls f o r d i s s o l v e d s o l u t e s . 6 Peshekee Spring: 1. Kaolinite--> Plagioclase: 0.488 Al Si 0 (0H 2 2 5 + 0.283 Na+ + 0.346 Ca2+ ) 4 + 0.975 HCO/ + 0.565 S i0 < — > 2 0.0629 Nao. Cao. Al, Si 4 5 5 5 5 5 2 4 5 0 8 + 0.075 C 0 + 1.465 H20 2 2. Saponite--> Biotite: 0.110 Mg . Si . Alo. 3 165 3 6 7 3 3 0 + 0.174 Fe(OH IO(OH ) 3 3 3 + 0.138 Al(OH 0.174 KMg FeAlSi O, (OH 2 + 0.174 K+ + 0.174 HCO - ) 2 0 ) 2 ) 3 + 0.118 S i0 < — > 2 + 0.174 C 0 + 0.491 HzO + 0.044 0 2 3. Clinochlore —> Pyroxene: 0.446 Mg AlSi AlO, (OH 5 3 0 ) 8 + 2.682 S i0 2 + 1.005 Ca2+ + 0.786 Mg2+ + 3.582 H C03* < — > 2.010 Cao.5Mgj Si 0 5 2 6 + 3.582 C 0 + 2.238 H20 + 0.892 Al(OH 2 4. Form Pyrite: 0.022 Fe2+ + 0.043 S 0 42' + 0.043 H+ < — > 0.022 FeS + 0.077 0 2 100 2 + 0.022 H20 ) 3 2 to 101 Yellow Dog Upper Spring: 5. Kaolinite--> Plagioclase: 0.444 Al Si 0 (0H 2 2 5 ) 4 + 0.222 Na+ + 0.333 Ca2+ + 0.888 HC03- + 0.444 S i0 2 < — > 0.555 Nao.4Cao.6Si2^Al,.6Og + 0.888 C 0 2 + 1.332 H20 6 . Vermiculite —> Biotite: 0.106 Feo.5M g 2 Si A10 (OH 7 5 3 1 0 ) 2 + 0.146 HC03‘ + 0.146 K+ + 0.093 Fe(OH)3 + 0.040 Al(OH)3 + 0.120 S i0 2 < — > 0.146 KMg FeAlSi O (OH 2 3 10 ) 2 + 0.146 C 0 + 0.233 H20 + 0.036 0 2 2 7. Clinochlore --> Pyroxene: 0.421 AlMg FeSi AlOi (OH 4 3 0 ) 8 + 2.245 S i0 + 0.070 Mg2+ 2 + 1.333 Ca2+ + 2.806 HC03’ < - - > 3.508 Ca . Mgo. Feo., Si 0 + 0.842 Al(OH 8 ) 3 3 8 5 2 + 2.806 C 0 + 1.824 H20 2 . Form Olivine: 0.221 Mg2+ + 0.055 Fe2+ + 0.139 S i02 + 0.552 H C03’ < — > 0.139 Fe04Mgi S i0 + 0.552 C 0 + 0.276 H20 6 4 2 9. Form Pyrite: 0.103 Fe2+ + 0.205 S 0 42' + 0.205 H+ < — > 0.103 FeS + 0.361 0 2 2 + 0.103 H20 0 3 102 Yellow Dog Lower Spring: 10. Kaolinite —> Plagioclase: 0.476 Al Si 0 (0H 2 2 5 + 0.535 Na+ + 0.208 Ca2+ ) 4 + 0.951 HCCV + 1.069 S i0 < — > 2 0.743 Nao. Cao. Si 7 2 2 8 Ali. Og + 0.951 C 0 + 1.429 H20 2 7 2 2 8 2 11. Kaolinite - > Biotite: 0.058 Al Si Q (OH 2 2 5 + 0.115 K+ + 0.230 Mg2+ ) 4 + 0.115 Fe2+ + 0.805 H C03' + 0.229 S i0 < — > 2 0.115 KMg FeAlSi O (OH 2 3 1 0 ) 2 + 0.805 C 0 + 0.405 H20 2 12. Talc —> Clinochlore: 2.226 Mg Si O (OH 3 4 10 + 2.226 Fe(OH ) 2 ) 3 + 2.226 Mg2+ + 4.452 HC03‘ + 4.452 Al(OH 2.226 Mg FeAlSi AlO (OH 4 3 10 ) 8 ) 3 <—> + 4.452 C 0 + 5.565 H20 + 2.783 0 2 2 13. Form Calcite: 6.663 Ca2+ + 13.326 HCO,- < — > 6.663 CaC0 + 6.663 C 0 + 6.663 H20 3 2 14. Form Pyrite: 0.385 Fe2+ + 0.770 S 0 42' + 0.770 H+ < — > 0.385 FeS + 1.348 0 2 2 + 0.385 H20 103 Peshekee Runoff: 15. Kaolinite —> Plagioclase 0.092 Al Si 0 (0H 2 2 5 ) 4 + 0.104 Na+ + 0.040 Ca2+ + 0.184 H C 03- + 0.208 S i0 < — > 2 0.144 Na^ 72Cao.28Alj gSi 7 0g "F 0.184 C 0 + 0.276 H20 2 2 2 2 16. Form Saponite: 0.218 Mg2+ + 0.436 HCCV + 0.023 Al(OH 0.069 Mg . Si 3 17 3 6 7 Alo. 0 (OH 3 3 1 0 + 0.253 S i0 < — > ) 3 2 + 0.436 C 0 + 0.183 H20 ) 2 2 Yellow Dog Runoff: 17. Kaolinite —> Biotite: 0.028 Al Si 0 (0H 2 2 5 ) 2 + 0.056 K+ + 0.112 Mg2+ + 0.280 H C 03- + 0.056 Fe(OH 0.056 KMg FeAlSi O (OH 2 3 10 ) 2 ) 3 + 0.112 S i0 < — > 2 + 0.280 C 0 + 0.224 H20 + 0.028 0 2 2 18. Kaolinite + Talc —> Na-Saponite: 0.076 Al Si 0 (0H 2 2 5 ) 4 + 0.371 Mg Si O, (OH 3 4 0 ) 2 + 0.152 Na+ + 0.270 Mg2+ + 0.692 HCCV + 0.056 S i0 < — > 2 0.461 Na . Mg Sii . Alo. 0 , (OH 0 3 3 3 6 7 3 3 0 ) 2 + 0.692 C 0 + 0.408 H20 2 Appendix B Complete aqueous chemical data for all water samples. Table 8. Aqueous chemical data for Peshekee River, Site 1 (1988-1989). Units: all solutes in mg/l, except DO C is rmol/l; temperature in ° C. Date 7/27 8/3 8/10 8/17 8/23 8/31 9/7 9/14 9/20 9/28 10/5 10/12 10/19 10/26 11/2 11/6 11/9 11/15 11/16 11/23 11/30 12/7 12/15 12/21 12/31 1/5 1/11 1/19 1/25 2/1 pH 7.3 6.8 6.5 6.2 6.6 6.5 6.7 6.7 6.5 6.3 6.0 5.4 6.0 5.9 6.1 5.7 5.7 6.1 6.1 5.6 5.9 6.1 6.0 5.8 6.4 6.3 6.0 6.1 6.1 6.0 Alt Aim 0.018 0.062 0.104 0.125 0.158 0.112 0.130 0.069 0.069 0.135 0.148 0.156 0.161 0.136 0.144 0.164 0.159 0.140 0.156 0.151 0.165 0.170 0.155 0.168 0.142 0.168 0.165 0.135 0.094 0.100 0.0015 0.0120 0.0260 0.0380 0.0890 0.0565 0.0250 0.0120 0.0120 0.0360 0.0380 0.0585 0.0445 0.0950 0.0900 0.1420 0.1010 0.1300 0.1380 0.1140 0.1040 0.1150 0.1110 0.0950 Alo 0.014 0.034 0.012 0.010 0.014 0.023 0.052 0.033 0.083 0.090 0.098 0.100 0.105 0.114 0.104 0.082 0.081 0.095 0.0930 0.093 0.1240 0.106 0.0870 0.085 0.0890 0.083 0.0870 0.087 Si 02 Ali 2.34 2.44 3.62 0.012 2.44 3.12 4.23 0.023 4.59 0.013 4.43 4.77 0.002 5.26 0.022 4.59 0.015 4.35 0.007 4.10 0.012 4.35 0.012 4.59 0.000 4.35 4.26 0.003 4.36 0.030 3.86 0.033 4.53 0.000 4.84 0.000 5.45 0.033 6.19 0.030 6.37 0.000 6.06 6.80 0.000 7.17 0.018 7.17 0.002 7.23 0.006 7.63 0.000 Alp 0.0165 0.0500 0.0780 0.0870 0.0690 0.0495 0.1050 0.0570 0.0570 0.0990 0.1100 0.0975 0.1155 0.0410 0.0540 0.0220 0.0570 0.0100 0.0180 0.0370 0.0560 0.0550 0.0440 0.0730 0.0750 0.0410 0.0480 0.0390 0.0460 Ca M g K Na 8.51 7.20 7.75 6.39 5.69 5.52 5.62 6.25 6.08 4.96 4.59 4.39 4.30 3.65 3.65 3.15 3.03 3.18 2.88 2.97 3.03 3.42 3.66 3.89 4.00 4.31 4.31 4.34 4.54 4.68 2.14 1.87 1.79 1.51 1.32 1.33 1.34 1.47 1.43 1.26 1.10 1.02 1.02 0.91 0.92 0.81 0.77 0.78 0.72 0.72 0.73 0.84 0.88 0.93 0.95 1.09 1.13 1.12 1.17 1.21 0.63 0.82 0.51 0.53 0.37 0.31 0.35 0.37 0.44 0.39 0.47 0.30 0.34 0.33 0.26 0.40 0.29 0.24 0.30 0.21 0.19 0.22 0.24 0.32 0.27 0.30 0.29 0.28 0.35 0.30 1.05 0.83 0.74 0.68 0.63 0.68 0.74 0.79 1.18 0.83 0.89 0.64 0.75 0.60 0.65 0.52 0.48 0.58 0.50 0.50 0.50 0.60 0.65 0.75 0.63 0.91 0.71 0.65 0.78 0.72 Temp 20.0 20.5 18.0 20.0 19.5 13.3 10.0 12.0 15.0 10.5 6.0 4.5 6.0 2.0 0.5 0.5 1.3 1.5 2.5 1.0 0.6 0.3 0.3 0.0 0.0 0.0 0.0 0.0 0.0 0.0 F 0.03 0.04 0.05 0.06 0.04 0.03 0.05 0.05 0.05 0.06 0.03 0.04 0.03 0.02 0.03 0.03 0.04 0.03 0.03 0.03 0.03 0.03 0.04 0.03 0.02 0.03 0.03 0.03 0.03 0.03 Cl 1.400 1.200 1.200 1.200 1.200 1.000 1.200 1.400 2.475 1.858 1.858 1.704 2.167 2.784 1.704 2.670 1.704 2.090 4.173 1.858 1.549 1.704 1.704 1.627 3.093 1.858 2.012 1.935 2.630 4.019 S04 3.50 4.80 5.10 6.00 3.00 4.50 3.00 4.71 3.47 4.65 3.60 3.72 3.65 3.47 2.23 5.33 2.85 4.59 4.15 4.59 4.40 4.96 5.14 4.28 5.02 5.08 4.71 4.71 4.09 3.84 HC03 26.246 13.122 14.736 9.842 13.123 6.561 10.662 13.123 13.123 16.404 8.202 3.280 8.202 5.249 6.561 4.921 4.101 4.921 4.101 2.460 4.921 5.741 7.381 7.381 8.202 9.022 9.022 9.842 10.662 11.482 P04 NH3 0.008 0.043 0.019 0.038 0.023 0.043 0.031 0.065 0.030 0.049 0.025 0.043 0.025 0.046 0.013 0.043 0.016 0.043 0.013 0.041 0.012 0.049 0.011 0.049 0.011 0.049 0.010 0.043 0.009 0.054 0.012 0.049 0.011 0.051 0.011 0.049 0.012 0.046 0.013 0.049 0.011 0.049 0.010 0.049 0.013 0.043 0.015 0.043 0.012 0.041 0.012 0.049 0.012 0.054 0.012 0.054 0.010 0.049 0.010 0.049 N03 0.414 1.217 0.318 1.273 0.796 1.037 0.148 2.472 0.046 0.097 0.392 0.079 0.073 0.109 0.148 0.190 0.089 0.109 0.125 0.064 0.083 1.140 0.240 0.120 0.280 1.391 0.232 0.180 0.140 0.129 Fe 0.33 0.40 0.58 0.56 0.69 0.54 0.49 0.42 0.49 0.45 0.56 0.54 0.47 0.42 0.39 0.34 0.32 0.38 0.35 0.34 0.34 0.34 0.40 0.41 0.39 0.50 0.46 0.17 0.50 0.50 M n 0.027 0.066 0.032 0.034 0.038 0.018 0.010 0.011 0.010 0.008 0.022 0.017 0.011 0.015 0.017 0.025 0.025 0.018 0.018 0.021 0.019 0.019 0.018 0.019 0.015 0.013 0.012 0.011 0.012 0.013 D O C 0.544 0.787 1.301 1.192 1.490 1.409 1.328 O 1.138 ^ 1.071 1.307 1.260 1.301 1.199 1.172 1.138 0.976 1.037 0.780 0.868 1.030 1.024 0.868 0.929 0.922 0.895 0.976 0.976 0.801 0.963 0.949 Table 8 (cont'd). 2/10 2/15 2/22 3/2 3/16 3/22 3/27 3/29 3/30 4/5 4/12 4/19 4/26 5/3 5/10 5/17 5/24 6/1 6/9 6/14 6/22 6/28 7/5 7/14 7/20 7/26 6.1 0.086 0.0995 5.9 0.082 0.0740 6.0 0.098 0.0600 6.1 0.083 0.0925 6.1 0.090 6.2 0.087 0.1130 4.8 0.110 0.0810 5.8 0.126 0.0860 5.7 0.110 0.1240 5.8 0.125 0.1610 5.9 0.124 0.1280 6.1 0.140 0.1380 5.7 0.149 0.1470 5.7 0.113 0.1020 5.9 0.117 0.1050 6.1 0.119 0.1180 6.2 0.121 6.1 0.126 0.0640 5.9 0.177 0.0740 6.2 0.178 0.0720 6.6 0.146 0.0690 6.2 0.146 0.0730 6.5 0.085 0.0430 6.5 0.105 0.0490 6.5 0.058 7.0 0.041 0.0060 0.098 0.073 0.089 0.096 0.077 0.079 0.120 0.129 0.126 0.126 0.129 0.092 0.078 0.109 0.035 0.068 0.072 0.065 0.073 0.042 0.046 0.006 7.41 7.05 6.95 7.40 6.98 8.27 7.18 5.57 6.55 5.82 3.73 4.97 3.61 3.24 2.26 1.39 1.89 1.90 2.81 2.76 2.42 3.27 3.51 4.35 3.27 4.35 0.002 0.001 0.0265 4.65 0.0580 4.70 0.0750 5.90 0.003 0.0355 4.98 4.74 0.017 0.0060 4.90 0.004 0.0290 3.55 0.007 0.0400 4.20 0.004 0.0210 3.47 0.032 3.48 0.002 0.0260 3.10 0.012 2.73 0.018 2.01 0.010 0.0110 2.15 0.027 0.0120 2.35 0.009 2.80 3.55 0.029 0.0620 3.70 0.006 0.1030 2.76 0.000 0.1060 2.69 0.004 0.0770 3.52 0.000 0.0730 3.93 0.001 0.0420 4.88 0.003 0.0560 5.98 5.48 0.000 0.0350 7.07 1.25 1.23 1.57 1.34 1.26 1.30 1.13 0.94 0.92 0.81 0.81 0.70 0.52 0.55 0.58 0.65 0.87 0.90 0.65 0.66 0.84 0.90 1.15 1.54 1.35 1.73 0.31 0.34 0.42 0.37 0.37 0.37 0.35 0.39 0.37 0.36 0.34 0.36 0.36 0.29 0.29 0.30 0.35 0.29 0.29 0.17 0.24 0.21 0.29 0.38 0.36 0.47 0.77 0.74 0.89 0.78 0.77 0.73 0.71 0.61 0.62 0.58 0.61 0.73 0.55 0.48 0.50 0.50 0.52 0.59 0.41 0.51 0.51 0.54 0.66 0.87 0.74 1.14 0.0 0.0 0.0 0.0 0.0 0.3 0.5 0.5 0.5 0.0 0.8 1.8 2.5 7.8 11.5 15.0 16.5 15.3 9.0 11.0 20.3 17.8 20.5 20.0 24.5 24.4 0.04 0.03 0.03 0.03 0.03 0.03 0.03 0.04 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.05 0.04 0.03 0.05 0.04 0.04 1.781 2.938 1.704 1.395 1.241 2.012 1.940 1.650 1.241 2.861 1.241 1.009 0.932 0.932 1.549 1.086 1.549 5.099 1.395 1.241 2.784 5.253 3.401 1.858 1.549 1.858 4.28 13.943 0.015 4.46 10.662 0.009 5.64 13.123 0.009 4.59 15.583 0.013 4.09 13.943 0.010 4.09 13.943 0.010 4.71 13.280 0.013 4.09 8.202 0.011 5.02 6.725 0.010 4.71 6.561 0.011 6.151 0.012 4.15 4.71 5.741 0.013 5.02 3.690 0.013 3.16 .4.511 0.012 4.09 4.921 0.012 3.47 7.381 0.010 2.54 9.022 0.013 9.432 0.024 2.85 1.52 5.331 0.013 3.04 4.921 0.009 2.23 9.022 0.009 1.62 9.842 0.010 2.61 13.943 0.010 3.47 16.404 0.009 3.35 18.864 0.008 3.47 22.965 0.005 0.076 0.070 0.070 0.065 0.054 0.059 0.081 0.076 0.059 0.054 0.049 0.043 0.043 0.038 0.038 0.038 0.038 0.043 0.049 0.043 0.038 0.043 0.038 0.038 0.030 0.027 0.170 0.261 0.256 0.169 0.473 0.191 0.443 0.604 0.524 0.392 0.211 0.261 0.544 0.186 0.100 0.028 0.064 0.967 1.594 0.044 0.032 0.032 0.059 0.837 0.015 0.005 0.45 0.21 0.22 0.46 0.22 0.47 0.38 0.31 0.33 0.34 0.33 0.26 0.18 0.21 0.22 0.30 0.40 0.43 0.42 0.45 0.46 0.57 0.59 0.83 0.59 0.49 0.010 0.006 0.008 0.009 0.003 0.010 0.021 0.031 0.028 0.027 0.024 0.024 0.025 0.012 0.014 0.014 0.020 0.018 0.026 0.019 0.021 0.019 0.021 0.018 0.016 0.021 0.936 0.828 0.942 0.868 0.692 0.909 0.821 0.841 0.961 0.976 0.990 0.882 0.814 0.834 0.895 1.030 1.152 1.138 1.253 1.267 1.165 1.361 1.199 0.976 0.787 0.699 Table 9. Aqueous chemical data for Peshekee River, Site 3 (1988-1989). Units: all solutes iin mg/1; tefnperature 0C. PH 7.40 6.90 6.90 6.20 6.60 6.90 6.65 7.00 6.70 6.70 6.30 6.10 6.30 6.00 6.00 5.93 5.95 5.80 6.05 6.30 6.13 5.98 6.10 6.30 6.30 6.20 6.20 6.10 6.40 6.20 6.40 6.20 6.20 6.40 5.70 6.40 6.00 5.90 5.65 5.70 5.70 Date Tenp Alt Aim F Ca M g Na 7/27 8/3 8/10 8/17 8/23 8/31 9/7 9/14 9/20 9/28 10/5 10/12 10/19 10/26 11/2 11/9 11/16 11/23 11/30 12/7 12/15 12/21 12/31 1/5 1/11 1/19 1/25 2/1 2/10 2/15 2/22 3/2 3/16 3/22 3/30 4/5 4/12 4/19 4/26 5/3 5/10 24.0 22.0 21.5 19.0 16.0 15.0 12.0 12.0 13.0 10.5 5.5 4.0 5.8 1.0 0.5 1.3 2.0 0.5 0.5 0.3 0.3 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.5 0.5 1.0 1.8 2.8 7.5 9.0 0.018 0.033 0.068 0.176 0.156 0.111 0.155 0.050 0.080 0.114 0.151 0.152 0.169 0.145 0.135 0.160 0.152 0.150 0.168 0.159 0.158 0.144 0.105 0.148 0.148 0.095 0.087 0.095 0.091 0.085 0.087 0.080 0.090 0.099 0.116 0.123 0.124 0.101 0.099 0.113 0.108 0.007 0.014 0.034 0.074 0.078 0.035 0.051 0.021 0.019 0.006 0.036 0.037 0.039 0.092 0.087 0.107 0.118 0.117 0.131 0.094 0.093 0.107 0.040 0.061 0.045 0.038 0.038 0.030 0.060 0.045 0.040 0.040 0.030 0.040 0.030 0.025 0.030 0.030 0.040 0.030 0.030 0.030 0.040 0.025 0.020 0.025 0.030 0.030 0.030 0.030 0.030 0.030 0.030 0.025 0.025 0.035 0.050 0.045 0.025 0.025 0.030 0.025 0.023 11.36 11.11 10.62 6.79 7.91 7.79 7.64 8.68 7.98 6.53 5.11 5.33 5.53 4.14 4.59 3.61 3.48 3.78 3.67 4.48 4.89 5.08 5.16 5.37 5.56 5.81 6.33 6.46 6.00 6.22 6.31 6.37 6.13 6.38 4.10 3.47 3.57 3.06 2.00 2.31 2.40 2.31 2.29 2.09 1.45 1.54 1.58 1.49 1.74 1.68 1.39 1.16 1.16 1.13 0.95 0.97 0.81 0.73 0.81 0.81 0.96 1.07 1.12 1.14 1.26 1.25 1.26 1.35 1.37 1.45 1.44 1.51 1.53 1.41 1.55 0.95 0.80 0.82 0.77 0.51 0.57 0.57 1.08 0.88 0.72 0.56 0.61 0.67 0.63 0.74 0.69 0.62 0.55 0.54 0.55 0.48 0.48 0.39 0.38 0.40 0.41 0.47 0.56 0.53 0.54 0.58 0.59 0.60 0.62 0.62 0.67 0.66 0.66 0.70 0.76 0.69 0.62 0.45 0.43 0.46 0.30 0.33 0.33 0.048 0.118 0.054 0.081 0.071 0.082 0.038 0.025 0.071 0.100 0.110 0.115 0.098 0.092 0.096 0.097 K 0.64 0.61 0.40 0.43 0.28 0.23 0.22 0.30 0.35 0.31 0.59 0.23 0.32 0.32 0.19 0.22 0.21 0.15 0.15 0.17 0.20 0.21 0.22 0.27 0.24 0.25 0.26 0.25 0.30 0.30 0.29 0.31 0.31 0.33 0.42 0.29 0.29 0.28 0.24 0.19 0.18 S04 3.200 3.000 5.200 4.500 3.700 3.200 3.000 3.595 3.966 4.090 4.300 4.832 4.399 4.720 5.220 4.466 4.090 4.214 4.337 4.709 5.637 4.585 4.090 4.832 4.152 4.090 4.709 2.605 4.275 4.709 4.832 4.523 1.924 4.090 4.709 3.904 4.090 4.894 3.595 3.966 4.090 Cl 1.000 1.000 1.000 0.990 1.000 0.800 0.900 1.335 1.335 1.896 1.408 1.190 1.471 1.896 1.335 0.900 1.045 0.765 0.620 0.765 1.045 0.765 0.900 0.832 0.767 0.908 1.049 0.767 0.626 0.626 0.767 0.767 0.626 0.626 0.767 0.767 0.626 0.626 0.485 0.767 0.767 Si P04 M H 3 N03 Fe M n HC03 2.44 3.31 2.34 3.21 4.84 4.89 3.67 4.83 5.26 5.14 3.40 2.99 2.88 4.22 3.36 2.76 2.93 4.46 4.77 5.48 6.06 6.48 5.94 5.16 7.15 6.12 7.47 7.78 8.08 7.43 7.47 8.36 8.29 8.89 6.06 5.44 5.57 4.77 3.13 3.11 2.00 0.010 0.010 0.014 0.023 0.019 0.022 0.024 0.010 0.012 0.011 0.010 0.012 0.015 0.014 0.014 0.014 0.012 0.009 0.009 0.010 0.011 0.010 0.013 0.014 0.009 0.009 0.009 0.013 0.015 0.010 0.008 0.009 0.012 0.014 0.013 0.014 0.010 0.011 0.011 0.010 0.010 0.032 0.048 0.043 0.053 0.048 0.043 0.053 0.053 0.048 0.048 0.053 0.059 0.059 0.051 0.048 0.048 0.048 0.048 0.048 0.043 0.048 0.048 0.048 0.048 0.059 0.053 0.037 0.048 0.048 0.037 0.032 0.037 0.037 0.059 0.048 0.043 0.037 0.043 0.048 0.048 0.043 0.949 0.532 0.277 0.512 0.531 0.224 0.288 0.123 0.074 0.062 0.169 0.055 0.021 0.104 0.098 0.119 0.160 0.068 0.100 0.120 0.178 0.140 0.342 0.108 0.200 0.134 0.100 0.339 0.804 0.373 0.343 0.161 0.242 0.242 0.675 0.514 5.961 0.524 0.403 5.659 0.139 0.25 0.27 0.54 0.56 0.65 0.39 0.57 0.43 0.60 0.44 0.51 0.49 0.39 0.36 0.37 0.32 0.29 0.33 0.29 0.35 0.37 0.40 0.26 0.40 0.35 0.12 0.36 0.40 0.34 0.15 0.13 0.37 0.10 0.37 0.34 0.35 0.42 0.26 0.18 0.20 0.15 0.028 0.020 0.020 0.032 0.014 0.013 0.007 0.010 0.010 0.005 0.025 0.009 0.010 0.011 0.012 0.015 0.014 0.009 0.011 0.016 0.017 0.015 0.012 0.015 0.013 0.011 0.015 0.014 0.014 0.011 0.009 0.011 0.011 0.011 0.030 0.021 0.019 0.015 0.012 0.005 0.003 29.5 26.2 16.4 9.8 13.1 16.4 13.1 19.7 32.8 16.4 8.2 8.2 4.1 5.7 8.2 4.9 4.9 4.9 6.6 9.8 9.8 10.7 11.5 13.9 13.9 16.4 14.8 15.6 17.2 15.6 16.4 17.2 18.0 18.9 8.2 7.4 8.2 7.4 4.1 4.9 4.9 Table 9 (cont'd). 6.10 6.20 6.30 5.90 6.A O 6.80 6.A O 6.70 6.70 6.70 7.10 5/17 5/2A 6/1 6/9 6/1A 6/22 6/28 7/5 7/1A 7/20 7/26 15.0 16.3 15.3 8.5 9.8 19.5 18.0 21.5 0.107 0.123 0.119 0.163 0.159 0.117 0.100 0.079 0.100 0.087 0.0A0 0.06A 0.077 0.035 0.0A7 0.013 0.030 0.025 0.030 0.030 0.030 O.OAA 0.030 0.0A O 3.17 A.20 A.65 3.28 3.22 5.10 5.7A 7.01 0.71 0.9A 1.06 0.75 0.76 1.17 1.33 1.61 0.37 0.51 0.60 0.36 0.37 0.53 0.57 0.6A 0.21 0.30 0.25 0.18 0.06 0.1A 0.20 0.23 2.5 A3 2.620 0.996 0.996 0.996 0.996 0.686 1.373 0.767 0.8A 0.908 1.A6 0.908 1.70 0.838 2.62 2.035 2.01 1.0A9 1.70 1.190 2.99 1.0A9 3.73 0.012 0.017 0.010 0.016 0.006 0.009 0.012 0.015 0.0A5 0.0A8 0.0A3 0.0A8 0.0A3 0.0A3 0.0A3 0.032 0.021 0.109 0.016 O.AOO 0.039 0.017 0.077 0.188 0.39 O.AA 0.A2 O.AA O.AA 0.A2 0.56 0.72 0.012 0.005 0.005 0.009 0.007 0.012 0.007 0.006 8.2 10.7 12.3 6.6 6.6 1A.8 15.6 20.9 25.5 2A.A 0.0A8 0.025 0.010 0.00A 0.0A2 0.0A2 8.13 8.68 1.90 2.00 0.90 0.86 0.39 0.A3 3.780 A.399 0.978 0.908 0.010 0.007 0.032 0.032 0.020 0.A5 O.OAA 0.A7 0.003 0.017 31.2 27.1 A.52 A.71 o -j Table 10. Aqueous chemical data for Peshekee River, Site 4 (1988-1989). Units: all solutes in mg/l; temperature °C. PH Date 7.10 7/28 7.00 8/3 6.70 8/10 5.25 8/17 6.50 8/24 6.50 8/31 6.10 9/7 6.60 9/14 6.40 9/21 6.60 9/28 6.00 10/5 6.10 10/1 6.20 10/19 5.45 10/26 5.70 11/9 5.80 11/16 5.50 11/23 5.90 11/30 5.85 12/7 5.80 12/21 6.30 12/31 6.10 1/5 6.10 1/11 6.03 1/19 6.10 1/25 5.85 2/1 6.10 2/10 6.20 2/22 6.10 3/22 5.70 3/30 5.90 4/5 5.85 4/12 5.95 4/19 5.70 5/10 5.90 5/17 5.80 5/24 6.15 6/1 5.90 6/15 6.50 6/22 6.00 6/28 6.40 7/5 6.70 7/20 6.65 7/26 Ca Temp 21.0 19.78 19.5 19.29 23.0 11.10 18.0 6.68 16.3 7.95 17.5 8.17 14.0 7.33 13.0 7.75 12.0 7.34 10.8 6.61 5.5 5.26 3.8 5.59 5.3 5.30 3.92 1.0 1.0 3.67 2.0 3.25 0.5 3.67 0.3 3.71 0.3 4.30 0.0 4.76 0.0 5.15 0.0 5.49 0.0 5.40 0.0 6.16 0.0 6.36 0.0 6.49 0.0 6.56 0.0 7.11 0.0 5.95 0.5 3.79 0.3 3.34 0.3 3.67 1.0 3.05 8.5 2.32 3.45 16.5 4.41 17.5 15.5 4.67 10.0 3.38 21.0 5.14 5.31 18.5 22.0 6.76 24.5 10.71 22.5 13.80 M g 3.87 2.51 2.21 1.46 1.61 1.58 1.43 1.65 1.52 1.37 1.10 1.14 1.12 0.84 0.78 0.64 0.72 0.75 0.91 1.07 1.18 1.17 1.22 1.25 1.35 1.35 1.52 1.65 1.47 0.91 0.79 0.87 0.72 0.51 0.73 0.93 1.01 0.77 1.11 1.00 1.47 2.39 2.86 Na 1.00 0.97 0.69 0.53 0.60 0.63 0.64 0.70 0.69 0.62 0.51 0.56 0.56 0.44 0.39 0.34 0.38 0.40 0.44 0.54 0.58 0.54 0.59 0.57 0.64 0.62 0.73 0.73 0.71 0.45 0.49 0.47 0.41 0.34 0.37 0.45 0.53 0.36 0.45 0.40 0.51 0.72 2.34 K 0.30 0.42 0.29 0.50 0.26 0.15 0.12 0.21 0.35 0.27 0.58 0.29 0.40 0.30 0.23 0.15 0.15 0.14 0.17 0.25 0.28 0.23 0.28 0.27 0.30 0.29 0.36 0.39 0.42 0.37 0.39 0.34 0.30 0.26 0.30 0.35 0.24 0.04 0.13 0.11 0.18 0.23 0.33 Cl 1.200 1.400 1.000 0.880 0.800 0.800 1.000 1.049 1.190 1.200 1.471 1.049 1.471 3.302 1.049 0.908 0.767 0.767 0.908 0.626 0.767 0.767 0.767 1.330 1.049 0.767 0.767 0.908 0.767 0.697 0.767 0.767 0.767 0.626 0.626 0.767 0.767 0.838 0.908 0.908 0.943 1.612 1.049 S04 1.000 1.500 2.500 4.850 3.500 4.000 4.000 3.966 4.832 5.327 5.946 5.946 5.327 4.709 4.220 4.585 4.337 3.842 4.461 3.780 4.275 4.585 4.399 4.585 4.399 4.337 5.204 5.705 3.230 4.709 5.018 4.090 4.090 3.780 2.543 1.181 0.996 1.305 1.992 1.373 1.373 1.305 1.615 Fe 0.17 0.33 0.42 0.44 0.48 0.40 0.35 0.25 0.32 0.32 0.36 0.35 0.29 0.40 0.40 0.36 0.39 0.38 0.40 0.43 0.44 0.48 0.48 0.26 0.52 0.51 0.53 0.42 0.52 0.35 0.35 0.39 0.30 0.13 0.31 0.34 0.32 0.25 0.35 0.45 0.41 0.67 0.51 Si 02 4.120 3.310 2.650 2.140 4.170 3.060 3.820 4.406 4.222 4.280 3.854 3.732 3.842 3.351 3.891 3.719 4.014 4.468 4.959 5.879 6.369 6.829 7.020 6.860 6.443 7.780 8.302 7.657 8.762 5.695 5.940 6.185 4.713 1.646 0.603 0.665 1.033 1.707 0.922 2.137 2.260 2.763 4.357 NH4 0.021 0.021 0.024 0.032 0.029 0.027 0.027 0.027 0.027 0.021 0.027 0.027 0.021 0.027 0.021 0.027 0.027 0.027 0.027 0.032 0.048 0.032 0.027 0.032 0.037 0.037 0.027 0.048 0.032 0.027 0.027 0.027 0.021 0.021 0.021 0.027 0.027 0.032 0.021 0.024 0.021 0.021 0.024 P04 0.005 0.009 0.015 0.021 0.018 0.019 0.017 0.006 0.006 0.007 0.012 0.014 0.013 0.012 0.012 0.012 0.014 0.014 0.013 0.012 0.017 0.014 0.012 0.011 0.012 0.014 0.015 0.013 0.014 0.014 0.013 0.014 0.015 0.014 0.015 0.016 0.014 0.007 0.009 0.008 0.007 0.015 0.013 Aim 0.005 0.020 0.047 0.084 0.078 0.055 0.059 0.022 0.010 0.006 0.040 0.044 0.021 0.092 0.130 0.120 0.142 0.120 0.087 0.111 0.098 0.101 0.085 0.088 0.097 0.100 0.039 0.080 0.112 0.119 0.111 0.090 0.082 0.102 0.098 0.035 0.067 0.050 0.076 0.037 0.005 F 0.03 0.06 0.05 0.04 0.03 0.03 0.03 0.08 0.04 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.02 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.02 0.03 0.03 0.03 0.03 0.04 0.04 0.03 0.04 0.04 N03 0.393 0.664 0.554 1.169 0.410 0.462 0.116 1.270 0.036 0.038 0.092 0.038 0.007 0.058 0.069 0.119 0.079 0.094 0.110 0.161 1.808 0.139 0.211 0.171 0.317 0.166 0.731 0.978 1.009 0.827 2.019 3.028 0.372 0.241 0.013 0.007 0.038 0.007 0.001 0.007 0.041 0.004 0.009 M n 0.061 0.029 0.030 0.041 0.042 0.010 0.004 0.004 0.003 0.008 0.010 0.008 0.004 0.009 0.014 0.013 0.012 0.011 0.018 0.034 0.044 0.024 0.040 0.032 0.039 0.039 0.040 0.023 0.023 0.044 0.026 0.017 0.016 0.002 0.026 0.047 0.030 0.011 0.046 0.036 0.050 0.052 0.097 Alt 0.012 0.050 0.085 0.157 0.130 0.113 0.155 0.087 0.083 0.109 0.129 0.143 0.175 0.152 0.160 0.125 0.145 0.132 0.148 0.156 0.136 0.168 0.152 0.132 0.094 0.100 0.102 0.100 0.103 0.116 0.125 0.117 0.097 0.111 0.109 0.122 0.133 0.154 0.110 0.125 0.079 0.067 0.060 Table 11. Aqueous chemical data, Peshekee Spring (1988-1989). Units: all solutes in mg/l; temperature °C. Date Temp 8/10 8/17 8/31 9/14 9/28 10/5 10/12 10/19 10/26 11/2 11/9 11/16 11/23 11/30 12/7 12/15 12/21 12/31 1/5 1/11 1/19 1/25 2/1 2/10 2/15 4/5 4/19 5/3 5/17 6/22 11. 10. 10. 8. 9. 8. 7. 7. 7. 7. 7. 6. 6. 6. 6. 4. 5. 5. 4. 4. 4. 4. 4. 3. 3. 3. 4. 6. 6. 6. PH Ca 5.20 5.64 5.55 6.00 5.85 6.53 6.75 6.57 6.30 6.25 6.30 6.29 6.20 6.65 6.20 6.65 6.20 . 6.34 6.30 6.39 6.60 6.60 6.30 6.38 6.00 6.49 6.40 6.27 6.40 6.33 6.40 6.08 6.10 6.01 6.40 5.41 6.40 5.74 6.40 5.73 6.40 6.09 6.20 6.07 6.20 5.92 6.20 5.53 6.30 5.64 6.30 5.93 6.40 5.69 6.20 5.59 6.20 5.52 6.40 5.22 M g Na K Cl S04 Fe 1.99 2.03 2.01 2.03 2.07 2.02 2.07 2.07 2.07 2.08 2.09 2.05 2.03 2.02 2.01 1.95 1.92 1.84 1.88 1.94 1.90 1.94 1.93 1.94 1.90 1.95 1.94 1.98 1.95 1.79 0.80 0.81 0.81 0.81 0.81 0.81 0.80 0.82 0.80 0.78 0.82 0.77 0.79 0.72 0.71 0.73 0.71 0.67 0.76 0.71 0.71 0.71 0.72 0.77 0.78 0.75 0.72 0.70 0.72 0.67 0.73 0.83 0.77 0.82 0.93 0.93 0.93 0.96 0.96 0.95 0.96 0.94 0.98 0.92 0.91 0.91 0.91 0.87 0.94 0.92 0.96 0.91 0.92 0.90 1..02 0.96 0.91 0.88 0.90 0.73 1.000 0.990 1.100 1.000 1.400 0.274 0.345 0.485 0.908 0.485 0.485 0.345 0.345 0.274 0.485 0.767 0.485 0.626 0.626 0.485 1.330 1.049 1.612 0.485 0.345 0.415 0.345 0.345 0.345 0.274 6.200 6.200 6.200 6.256 5.946 5.946 6.441 5.637 4.709 6.256 5.327 6.813 6.256 6.565 6.256 6.256 6.070 5.637 6.070 6.256 5.637 5.699 6.194 5.946 6.565 6.256 6.256 5.327 9.040 5.327 0.025 0.023 0.024 0.028 0.023 0.024 0.028 0.034 0.033 0.022 0.030 0.022 0.022 0.020 0.019 0.014 0.010 0.010 0.011 0.018 0.002 0.016 0.017 0.018 0.005 0.019 0.019 0.007 0.018 0.019 Si 02 HC03 NH4 6.520 4.480 4.840 6.420 7.950 8.886 8.886 9.131 8.640 8.702 8.640 8.456 8.370 8.610 8.395 8.333 8.333 7.192 8.211 8.333 2.137 8.211 8.149 8.149 8.192 8.162 8.162 8.272 8.211 8.137 20.0 32.0 26.0 20.0 24.0 24.0 24.0 24.0 26.0 30.0 26.0 24.0 24.0 24.0 22.0 22.0 26.0 24.0 24.0 22.0 24.0 22.0 24.0 24.0 22.0 24.0 22.0 24.0 24.0 22.0 0.037 0.027 0.037 0.027 0.027 0.027 0.032 0.029 0.027 0.027 0.029 0.032 0.037 0.037 0.035 0.035 0.037 0.037 0.035 0.037 0.032 0.027 0.027 0.027 0.037 0.037 0.037 0.032 0.032 0.035 P04 Aim F N03 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.00 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.008 0.010 0.014 0.004 0.002 0.001 0.004 0.002 0.005 0.010 0.014 0.015 0.016 0.013 0.007 0.008 0.008 0.040 0.032 0.035 0.035 0.040 0.030 0.030 0.040 0.025 0.020 0.050 0.030 0.035 0.025 0.025 0.030 0.030 0.020 0.025 0.020 0.025 0.025 0.030 0.030 0.025 0.025 0.020 0.030 0.015 0.035 2.112 0.949 0.109 0.135 0.050 0.122 0.035 0.030 0.038 0.042 0.030 0.023 0.027 0.031 0.013 0.035 0.030 0.038 0.020 0.023 0.601 0.038 0.037 0.045 0.125 0.085 0.099 0.102 0.052 0.045 0.009 0.007 0.001 0.007 0.019 0.025 0.001 0.017 0.022 Alt 0.03 0.03 0.03 0.01 0.01 0.01 0.01 0.03 0.03 0.04 0.03 0.03 0.03 0.05 0.03 0.03 0.03 0.02 0.02 0.02 0.02 0.02 0.03 0.03 0.01 0.02 0.02 0.01 0.03 0.04 Table 12. Aqueous chemical data, Yellow Dog River, Site 1 (1988-1989). Units: all solutes in mg/l, except DO C in mmol/I ; temperature °C. pH Alt Date 7.8 7.6 7.7 6.5 6.5 7.4 7.0 6.9 7.1 7.4 6.9 7.0 7.0 6.8 6.7 6.7 6.7 7.1 7.2 7.2 7.2 7.3 7.3 7.2 7.2 7.2 7.1 7.1 6.7 7.0 7.2 7.2 7.2 7.1 7.1 5.7 6.1 6.8 6.4 6.4 6.4 0.032 0.047 0.044 0.045 0.050 0.037 0.053 0.025 0.042 0.048 0.088 0.076 0.078 0.075 0.066 0.137 0.121 0.078 0.094 0.035 0.049 0.049 0.034 0.055 0.036 0.040 0.044 0.046 0.053 0.047 0.022 0.028 7/28 8/4 8/11 8/17 8/25 9/1 9/8 9/15 9/22 9/29 10/5 10/13 10/20 10/27 11/3 11/10 11/17 11/24 12/1 12/8 12/16 12/22 1/1 1/6 1/12 1/20 1/27 2/2 2/11 2/16 2/23 3/2 3/9 3/16 3/22 3/27 3/29 4/1 4/7 4/13 4/20 0.030 0.041 0.077 0.124 0.106 0.115 0.075 0.093 Si 02 Aim 5.540 5.050 3.670 4.560 5.610 6.520 6.880 7.657 7.559 7.473 6.155 9.344 6.093 5.584 6.247 5.204 4.492 6.124 5.928 6.566 7.351 7.044 7.228 7.903 7.473 6.836 7.749 8.160 7.792 8.148 8.026 0.010 0.007 0.014 5.790 4.840 6.308 6.063 5.572 5.339 0.006 0.010 0.007 0.007 0.006 0.006 0.008 0.005 0.011 0.025 0.022 0.044 0.124 0.056 0.035 0.008 0.013 0.015 0.015 0.016 0.019 Alo Ca M g 0.01 0.005 21.61 15.00 19.92 3.94 2.89 3.70 0.61 0.81 0.60 1.06 0.86 1.02 0.01 0.01 0.0000 0.01 0.01 0.0010 0.0005 0.00 0.00 0.03 0.02 0.04 0.12 0.05 0.03 0.01 0.01 0.01 0.0005 0.0065 15.74 17.76 16.52 18.93 16.74 15.61 9.43 12.07 10.85 8.45 10.18 6.65 4.91 9.27 8.28 10.84 12.22 11.46 13.33 13.75 13.52 13.28 14.80 16.03 15.35 16.62 10.23 3.07 3.38 3.13 3.59 3.28 3.01 1.95 2.51 2.16 1.70 2.04 1.35 0.97 1.86 1.66 2.14 2.44 2.32 2.58 2.56 2.61 2.58 2.81 2.03 2.97 3.19 3.03 0.54 0.55 0.51 0.57 0.60 0.57 0.56 0.46 0.48 0.44 0.40 0.39 0.37 0.38 0.37 0.41 0.45 0.43 0.45 0.45 0.46 0.43 0.49 0.51 0.49 0.51 0.49 8.90 6.63 7.93 7.58 9.43 6.47 1.87 1.44 1.70 1.59 2.00 1.38 0'.41 0.41 0.42 0.40 0.45 0.38 0.0005 0.0000 0.0000 0.0000 0.0040 0.0085 0.0060 0.0015 0.0000 0.0015 0.01 0.02 0.0015 0.0035 0.01 0.03 0.00 0.01 0.0020 0.0481 0.0020 0.03 0.03 0.05 0.06 0.04 0.03 0.06 0.0050 0.0170 0.0030 0.0040 0.0010 0.0375 0.0075 0.0000 0.010 0.027 0.053 0.007 0.009 0.007 0.020 0.018 0.040 0.044 0.053 0.064 0.041 0.067 0.069 K All 0.0000 Na Cl S04 F HC03 P04 NH3 N03 Fe M n DO C Alp 1.600 1.600 1.000 5.000 3.000 1.800 0.04 0.04 0.05 67.256 34.448 52.492 0.012 0.016 0.012 0.016 0.027 0.032 0.726 0.483 0.494 0.13 0.18 0.27 0.01 0.01 0.01 0.005 1.090 0.272 0.022 0.040 0.030 0.95 0.95 0.94 1.01 1.43 0.93 0.73 0.81 0.79 0.70 0.77 0.60 0.52 0.72 0.95 0.82 0.85 0.83 0.84 0.88 0.89 0.82 0.91 0.99 0.93 0.96 0.96 1.200 1.200 1.200 1.206 1.275 1.001 1.069 0.932 1.069 1.069 0.932 0.932 1.343 0.932 0.932 0.864 1.001 1.138 0.795 0.727 0.658 1.823 2.987 1.206 0.795 0.864 1.069 1.000 2.300 3.000 4.709 4.585 4.399 6.070 5.328 6.194 4.028 2.543 3.162 5.080 4.090 5.018 4.709 5.451 4.337 4.832 4.956 5.018 4.709 4.214 5.575 4.709 4.337 3.347 0.04 0.05 0.06 0.02 0.04 0.04 0.03 0.04 0.02 0.03 0.05 0.02 0.01 0.05 0.03 0.03 0.03 0.04 0.03 0.05 0.03 0.03 0.04 0.04 0.05 0.04 0.03 44.290 49.212 39.369 45.931 42.650 49.212 32.808 39.369 31.167 21.325 26.246 26.246 11.482 24.606 22.965 26.246 34.448 35.268 39.369 36.909 41.830 37.729 43.470 49.212 39.369 47.571 54.133 0.016 0.014 0.012 0.007 0.007 0.007 0.010 0.010 0.012 0.012 0.010 0.010 0.008 0.008 0.007 0.010 0.012 0.010 0.014 0.007 0.007 0.008 0.008 0.008 0.008 0.009 0.007 0.037 0.037 0.032 0.027 0.027 0.029 0.032 0.037 0.032 0.037 0.032 0.032 0.032 0.037 0.032 0.032 0.027 0.037 0.032 0.043 0.032 0.027 0.037 0.048 0.037 0.037 0.037 0.341 0.287 0.246 0.191 0.429 0.100 0.116 0.049 0.028 0.089 0.181 0.089 0.269 0.321 0.109 0.152 0.100 0.383 0.117 0.161 0.182 0.151 0.141 0.182 0.877 0.200 0.161 0.27 0.27 0.29 0.27 0.29 0.27 0.25 0.27 0.28 0.29 0.26 0.22 0.20 0.22 0.23 0.17 0.19 0.21 0.17 0.20 0.20 0.20 0.22 0.22 0.15 0.17 0.10 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.02 0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.02 0.01 0.02 0.02 1.000 0.909 0.545 0.045 0.454 0.727 1.500 0.977 1.227 1.750 1.272 1.590 1.545 1.204 1.204 0.727 0.431 0.545 0.409 0.363 0.363 0.022 0.090 0.227 0.090 0.090 0.005 0.044 0.027 0.046 0.018 0.036 0.042 0.080 0.071 0.068 0.050 0.044 0.093 0.003 0.022 0.059 0.027 0.037 0.034 0.019 0.040 0.017 0.040 0.035 0.019 0.001 0.040 0.013 0.82 0.74 0.70 0.69 0.80 0.61 0.440 0.320 1.275 0.932 1.069 0.864 5.950 5.330 5.080 4.214 4.399 4.090 0.03 0.04 0.04 0.03 0.03 0.03 16.400 18.040 22.965 22.145 27.886 18.864 0.010 0.008 0.008 0.005 0.007 0.009 0.027 0.027 0.037 0.032 0.035 0.029 0.353 0.469 0.171 0.514 0.281 0.301 0.12 0.12 0.15 0.16 0.19 0.14 0.01 0.01 0.01 0.01 0.02 0.00 0.272 0.954 1.090 1.068 0.818 1.090 0.033 0.071 0.043 0.074 0.008 0.024 Table 12 (cont'd). 6.1 6.3 6.6 6.9 6.8 6.9 6.2 6.7 7.1 7.1 7.3 7.3 7.4 6.8 0.101 0.105 0.082 0.036 0.058 0.045 0.113 0.129 0.095 0.088 0.093 0.070 0.051 0.066 4/27 5/4 5/12 5/18 5/25 6/1 6/8 6/16 6/23 6/28 7/6 7/14 7/19 7/27 4.394 4.370 4.836 5.302 5.327 6.124 5.388 5.290 6.578 0.078 0.067 0.044 0.027 0.027 0.005 0.037 0.043 0.077 0.07 0.05 0.04 0.02 0.02 0.01 0.02 0.03 0.07 7.657 0.070 0.07 7.805 7.191 0.005 0.00 0.0050 0.0195 0.0010 0.0070 0.0110 0.0000 0.0180 0.0110 0.0050 0.0000 0.0030 0.0000 0.0000 0.0040 4.59 6.30 8.34 10.47 9.24 11.54 8.00 7.67 13.61 0.99 1.34 1.74 2.12 1.86 2.40 1.63 1.64 2.55 0.34 0.38 0.39 0.50 0.60 0.49 0.50 0.28 0.46 0.49 0.57 0.67 1.74 0.74 0.88 0.77 0.67 0.84 0.658 0.658 2.713 0.932 0.795 0.727 1.275 2.576 1.001 4.709 3.780 4.214 4.585 2.605 4.709 4.090 5.018 4.399 0.03 0.03 0.03 0.03 0.03 0.04 0.05 0.03 0.04 13.123 18.044 25.016 31.987 27.886 36.088 24.606 22.965 36.088 0.009 0.009 0.005 0.007 0.007 0.006 0.008 0.008 0.009 0.035 0.032 0.027 0.037 0.037 0.043 0.048 0.048 0.043 0.190 0.150 0.443 0.060 0.084 0.039 0.089 0.017 0.090 0.10 0.10 0.13 0.19 0.19 0.21 0.15 0.19 0.21 0.00 0.01 0.01 0.01 0.01 0.01 0.02 0.01 0.01 1.227 1.022 0.909 0.977 1.318 0.886 1.295 1.840 1.068 16.76 3.09 0.53 0.94 1.549 3.471 0.03 50.852 0.005 0.037 0.100 0.39 0.01 0.886 18.47 16.39 3.46 3.01 0.54 0.62 1.01 0.94 0.795 0.727 3.780 4.709 0.04 0.03 54.133 45.931 0.005 0.004 0.037 0.037 0.070 0.099 0.20 0.17 0.01 0.01 0.090 0.340 0.023 0.038 0.038 0.009 0.031 0.040 0.076 0.086 0.018 0.088 0.023 0.070 0.051 0.061 Table 13. Aqueous chemical data, Yellow Dog River, Site 3 (1988-1989). Units: all solutes in mg/l; temperature °C. Date Temp 7/28 8/11 19.0 8/17 16.0 14.0 8/25 15.0 9/1 9/8 12.0 9/22 13.0 9/29 10.5 5.5 10/5 4.3 10/13 10/20 5.0 2.0 10/27 2.0 11/3 11/10 1.5 11/17 1.5 0.0 12/16 0.0 12/22 0.0 1/1 1/6 0.0 0.0 1/12 1/20 0.0 1/27 0.0 0.0 2/2 2/16 0.0 2/23 0.0 0.8 4/1 4/7 3.0 1.0 4/13 4/20 4.0 4/27 5.8 5/4 7.5 10.3 5/12 5/18 17.0 15.3 5/25 14.0 6/1 9.0 6/8 9.8 6/16 20.5 6/23 21.0 7/6 21.5 7/19 21.0 7/27 pH 7.1 5.9 6.4 7.1 7.3 7.0 7.4 6.7 6.7 6.8 6.0 6.5 6.1 6.4 6.4 6.5 6.8 6.6 6.6 6.4 6.4 6.4 6.5 6.5 5.9 6.1 6.3 5.9 5.8 5.9 6.2 6.3 6.7 6.4 5.9 6.3 6.2 6.7 6.7 6.4 Ca M g Na K 21.99 13.30 3.78 2.48 1.04 0.93 0.53 0.50 8.83 10.60 10.29 10.02 8.71 6.73 6.74 6.61 5.08 5.58 4.02 4.51 6.15 5.99 6.72 7.34 7.30 8.19 8.51 8.20 7.79 8.25 4.27 4.07 4.41 3.43 2.71 3.48 4.12 5.32 5.90 6.26 5.00 4.12 6.69 8.58 10.27 9.25 1.79 2.02 1.90 1.96 1.77 1.29 1.44 1.33 1.09 1.21 0.87 0.90 1.34 1.32 1.56 1.58 1.58 1.60 1.75 1.76 1.83 1.95 1.03 0.94 1.06 0.79 0.63 0.80 0.93 1.17 1.30 1.39 1.10 0.92 1.48 1.92 2.32 2.06 0.75 0.81 0.77 0.81 0.81 0.59 0.64 0.61 0.53 0.56 0.44 0.40 0.62 0.59 0.66 0.71 0.68 0.68 0.74 0.76 0.76 0.85 0.50 0.47 0.51 0.43 0.37 0.42 0.52 0.56 0.59 0.71 0.50 0.57 0.66 0.81 0.94 0.78 0.38 0.37 0.35 0.48 0.44 0.52 0.33 0.38 0.36 0.30 0.31 0.31 0.29 0.28 0.32 0.33 0.32 0.33 0.35 0.35 0.36 0.39 0.32 0.31 0.33 0.30 0.29 0.28 0.29 0.36 0.36 0.28 0.29 0.13 0.26 0.35 0.36 0.52 S04 Fe 1.200 1.000 1.800 4.000 0.16 0.67 1.200 1.000 1.200 0.626 1.000 1.049 0.767 0.908 1.049 0.767 0.626 0.626 0.626 0.767 1.049 0.485 0.485 1.049 0.626 0.697 0.626 0.697 0.767 0.626 0.485 0.485 0.626 0.767 0.485 0.485 0.626 0.626 0.626 1.049 1.190 2.316 0.485 0.767 1.900 3.000 1.900 3.347 4.709 6.008 5.204 5.080 2.048 3.162 2.852 3.842 4.523 4.399 4.523 5.018 5.204 4.214 4.090 4.832 3.966 4.090 4.090 3.966 3.471 3.780 3.162 3.780 4.894 4.709 3.904 4.090 3.347 2.852 3.595 2.048 3.471 4.461 0.48 0.33 0.56 0.56 0.45 0.42 0.50 0.45 0.40 0.39 0.34 0.25 0.41 0.41 0.46 0.51 0.50 0.50 0.49 0.52 0.51 0.45 0.32 0.32 0.41 0.27 0.18 0.18 0.24 0.31 0.47 0.46 0.42 0.41 0.51 1.10 0.77 0.62 Cl NH4 P04 Aim F N03 Hn N02 Alt 3.800 5.210 0.032 0.048 0.004 0.010 0.007 0.009 0.05 0.001 0.001 0.012 0.031 0.049 0.058 0.022 0.033 4.890 5.500 5.710 6.737 5.500 5.351 5.179 4.529 4.370 4.836 4.038 3.916 6.836 6.431 6.860 7.381 7.069 0.037 0.048 0.037 0.048 0.043 0.043 0.043 0.043 0.037 0.043 0.048 0.032 0.035 0.037 0.027 0.021 0.037 0.048 0.053 0.059 0.048 0.037 0.048 0.048 0.048 0.048 0.043 0.048 0.048 0.043 0.037 0.043 0.037 0.037 0.037 0.037 0.043 0.037 0.009 0.009 0.009 0.007 0.008 0.009 0.009 0.012 0.010 0.010 0.012 0.010 0.012 0.010 0.013 0.012 0.010 0.009 0.009 0.012 0.010 0.009 0.009 0.009 0.009 0.012 0.013 0.010 0.009 0.010 0.009 0.010 0.009 0.009 0.011 0.012 0.008 0.009 0.014 0.008 0.004 0.010 0.013 0.027 0.012 0.019 0.056 0.040 0.096 0.090 0.049 0.060 0.05 0.03 0.05 0.05 0.03 0.03 0.03 0.02 0.03 0.03 0.03 0.02 0.03 0.03 0.03 0.04 0.04 0.04 0.03 0.04 0.03 0.04 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.04 0.05 0.03 0.03 0.04 0.04 0.03 0.035 0.018 0.056 0.004 0.047 0.064 0.070 0.068 0.023 0.024 0.015 0.040 0.050 0.010 0.007 0.008 0.001 0.012 0.015 0.001 0.009 0.007 0.001 0.001 0.006 0.001 0.001 0.036 0.017 0.056 0.059 0.059 0.035 0.037 0.054 0.023 0.028 0.025 0.032 0.029 0.029 0.011 0.010 0.020 0.019 0.017 0.012 0.011 0.016 0.010 0.012 0.019 0.021 0.026 0.031 0.023 0.027 0.029 0.020 0.019 0.025 0.014 0.018 0.011 0.007 0.007 0.011 0.007 0.020 0.013 0.027 0.011 0.016 0.017 0.009 0.014 0.015 0.042 0.004 0.025 0.003 0.006 0.005 0.002 0.007 0.015 0.015 0.010 0.010 0.020 0.013 0.042 0.116 0.008 0.025 0.138 0.010 0.013 0.053 0.497 0.024 0.081 0.056 0.014 0.043 0.014 0.011 0.001 0.005 0.003 0.001 0.006 0.001 0.015 0.055 0.038 0.065 0.087 0.084 0.154 0.105 0.136 0.110 0.097 0.114 0.095 0.085 0.079 0.076 0.078 0.072 0.087 0.083 0.089 0.083 0.082 0.117 0.131 0.092 0.091 0.099 0.106 0.090 0.078 0.062 0.080 0.144 0.101 0.066 0.029 0.040 0.067 Si 02 7.535 7.719 7.780 7.473 5.535 5.265 4.897 4.505 3.707 3.364 3.216 2.996 3.609 4.345 3.977 3.486 4.590 6.063 6.921 6.308 0.070 0.065 0.060 0.051 0.056 0.055 0.046 0.076 0.074 0.060 0.079 0.080 0.076 0.074 0.068 0.047 0.017 0.030 0.047 0.060 0.026 0.003 0.003 Table 14. Aqueous chemical data, Yellow Dog River, Site 4, (1988-1989). Units: all solutes in mg/l; temperature °C. North Branch: Date 7/28 8/4 8/11 8/25 9/1 9/8 9/15 9/22 9/29 10/5 10/13 10/20 10/27 11/3 11/24 12/1 12/8 5/12 5/18 7/27 Tenp 20.00 19.00 17.50 14.00 15.00 11.00 12.00 12.00 '10.50 5.50 5.00 4.75 1.50 1.00 2.00 0.25 0.25 7.50 14.00 18.25 pH 7.1 6.8 6.8 6.5 7.1 7.1 7.2 6.6 6.9 5.7 6.7 6.7 5.9 6.5 7.0 6.9 7.0 6.2 6.6 6.6 Ca M g Na 1.86 2.44 2.20 2.29 2.16 2.35 2.14 2.11 1.50 1.99 1.79 1.59 1.80 1.68 1.64 1.78 1.33 1.66 1.50 0.79 0.93 0.84 0.88 0.89 0.91 0.86 0.83 0.65 0.82 0.74 0.66 0.73 0.69 0.68 0.71 0.58 0.68 0.61 0.55 0.51 0.47 0.48 0.45 0.48 0.55 0.52 0.49 0.46 0.50 0.42 0.42 0.40 0.38 0.40 0.38 0.45 0.44 Ca M g Na K 8.73 12.46 10.53 11.48 9.74 10.15 10.03 9.55 6.96 8.85 8.07 7.17 7.82 7.47 7.19 8.02 5.65 7.01 6.47 Cl S04 Fe Si02 NH4 P04 1.600 1.000 1.000 1.000 1.200 0.485 1.000 1.000 1.190 0.626 0.767 0.626 0.485 0.626 0.767 0.485 0.485 0.485 1.049 5.000 4.500 4.200 4.000 5.000 4.523 5.018 5.142 6.132 4.709 5.637 6.832 6.162 5.637 5.327 5.699 5.080 5.266 1.305 0.51 0.48 0.37 0.37 0.27 0.29 0.20 0.29 0.26 0.39 0.25 0.26 0.19 0.17 0.17 0.12 0.15 0.21 0.51 4.030 3.770 6.370 6.170 4.690 7.903 7.340 5.100 6.277 7.964 7.523 6.823 7.289 7.608 7.565 7.841 4.468 5.204 4.500 0.043 0.032 0.032 0.027 0.032 0.032 0.037 0.037 0.048 0.037 0.027 0.032 0.043 0.048 0.037 0.037 0.043 0.048 0.029 0.014 0.010 0.007 0.007 0.007 0.005 0.007 0.007 0.007 0.010 0.010 0.010 0.007 0.007 0.007 0.007 0.011 0.012 0.014 Cl S04 K Aim F N03 M n Alt HC03 0.009 0.005 0.005 0.004 0.005 0.007 0.003 0.005 0.012 0.010 0.004 0.004 0.006 0.006 0.005 0.004 0.005 0.007 0.031 0.047 0.040 0.053 0.032 0.052 0.030 0.067 0.053 0.125 0.063 0.092 0.076 0.054 0.050 0.053 0.028 0.057 0.060 0.107 26.2 29.5 19.7 32.8 26.2 26.2 23.0 19.7 16.4 24.6 21.3 23.0 21.3 20.5 18.0 24.6 16.4 21.3 16.4 0.034 0.006 0.011 0.003 0.004 0.003 0.007 0.010 0.010 0.009 0.006 0.029 0.029 0.036 0.043 0.010 0.035 0.029 0.038 0.042 0.045 0.062 0.048 0.050 0.040 0.040 0.030 0.040 0.040 0.020 0.050 0.030 0.055 0.030 0.030 0.030 0.035 0.028 0.267 0.563 0.765 0.280 0.603 0.538 0.169 0.765 0.068 0.077 0.442 0.079 0.109 0.130 0.139 0.346 0.036 0.017 0.097 P04 Aim F N03 East Branch: Date Temp 5/12 5/18 5/25 6/1 6/15 6/23 6/28 7/6 7/14 7/20 7/27 7.50 15.50 16.00 14.50 10.00 21.00 6.2 6.3 6.2 6.3 6.2 6.1 2.78 3.10 3.29 3.30 2.89 3.59 0.66 0.75 0.78 0.78 0.71 0.87 0.42 0.42 0.44 0.47 0.40 0.46 0.24 0.26 0.26 0.24 0.14 0.21 0.485 0.626 0.626 0.626 0.767 2.457 21.75 6.3 4.02 0.97 0.49 0.23 19.75 21.00 6.7 6.4 4.36 4.58 1.09 1.10 0.59 0.49 0.25 0.34 pH Fe Si 02 NH 4 3.904 3.904 4.399 3.657 4.709 4.461 0.14 0.12 0.16 0.11 0.14 0.18 2.873 2.137 2.076 2.161 2.444 2.321 0.070 0.016 0.024 0.024 0.010 0.016 0.010 0.010 0.012 0.012 0.012 0.012 0.071 0.058 0.052 0.019 0.044 0.036 0.030 0.031 0.030 0.040 0.030 0.030 0.119 0.017 0.033 0.033 0.006 0.017 0.006 0.007 0.006 0.005 0.006 0.006 0.093 0.136 0.061 0.075 0.068 0.046 8.20 8.20 5.74 8.61 0.908 4.337 0.27 2.137 0.045 0.012 0.015 0.035 0.073 0.013 0.059 10.66 2.035 1.049 3.719 5.946 0.22 0.26 3.241 3.486 0.032 0.102 0.011 0.010 0.020 0.013 0.030 0.028 0.048 0.178 0.010 0.007 0.042 0.070 13.94 12.30 M n Alt HC03 6.56 Table 15. Aqueous chemical data, Yellow Dog Upper Spring (1988-1989). Units: all solutes in mg/l; temperature °C. Date 9/7 9/14 9/20 9/28 10/5 10/12 10/19 10/26 11/2 11/23 11/30 12/7 5/17 6/22 Temp pH Ca M g Na K Cl S04 HC03 Si02 Aim N03 Alt 8. 10. 10. 8. 7. 6. 7. 6. 6. 6. 5. 5. 7. 9. 6.8 6.2 6.7 6.8 7.0 6.8 6.8 6.4 6.5 6.9 6.5 7.1 6.3 6.3 7.40 7.87 7.90 8.13 7.39 7.40 7.53 6.52 7.55 7.56 6.84 6.14 5.79 5.89 1.43 1.49 1.47 1.53 1.43 1.50 1.47 1.31 1.44 1.42 1.33 1.25 1.28 1.30 0.65 0.64 0.63 0.63 0.63 0.64 0.62 0.56 0.62 0.60 0.61 0.65 0.61 0.61 0.83 0.77 0.79 0.77 0.81 0.79 0.82 0.84 0.79 0.79 0.80 0.79 0.85 0.82 0.20 1.00 0.50 0.50 0.50 0.50 0.50 0.50 0.40 0.50 0.50 1.19 0.40 0.30 3.50 3.47 4.09 3.84 4.83 4.09 4.09 5.95 4.21 4.21 3.97 4.09 3.78 3.78 42.0 16.0 24.0 40.0 30.0 28.0 24.0 22.0 26.0 26.0 26.0 26.0 24.0 26.0 5.15 4.08 8.03 8.00 7.72 8.03 7.90 6.89 8.06 8.01 7.90 6.46 7.72 7.66 0.02 0.01 0.01 0.01 0.00 0.00 0.01 0.01 0.01 0.02 0.01 0.01 0.01 0.01 0.09 0.42 0.01 0.09 0.01 0.02 0.01 0.04 0.02 0.03 0.02 0.13 0.39 0.54 0.067 0.035 0.045 0.029 0.055 0.040 0.048 0.046 0.027 0.020 0.028 0.015 0.022 0.048 -P - Table 16. Aqueous chemical data, Yellow Dog Lower Spring (1989). Units: all solutes in mg/l; temperature °C. Date Temp 1/27 2/2 2/11 2/16 2/23 4/7 4/20 5/25 6/23 6.50 6.00 6.25 6.25 6.00 5.75 5.75 6.00 6.50 PH 7.5 7.5 7.2 7.5 7.3 7.7 7.5 7.5 7.5 Ca 32.00 32.07 31.92 31.78 31.80 30.74 30.45 30.66 29.46 M g 6.10 6.12 6.10 6.06 6.05 6.06 6.03 5.94 5.88 Na K 1.34 1.37 1.36 1.32 1.32 1.34 1.34 1.33 1.36 0.69 0.69 0.68 0.67 0.65 0.68 0.69 0.66 0.75 Cl 1.190 1.331 0.500 0.500 0.500 0.400 0.400 0.400 0.400 S04 HC03 Si02 8.11 8.42 7.68 8.42 5.95 8.11 8.05 5.95 7.68 116.0 118.0 102.0 101.0 114.0 115.0 112.0 109.0 102.0 10.97 10.97 10.97 10.79 10.24 10.97 10.85 10.73 10.97 F N03 0.055 0.056 0.070 0.060 0.060 0.052 0.050 0.050 0.025 0.290 0.268 0.331 0.268 0.268 0.670 0.355 0.333 0.866 Alt 0.01 0.01 0.01 0.01 0.02 0.02 0.01 0.00 Table 17. Aqueous chemical data, Precipitation (1988-1989). Units: all solutes in mg/l; precipitation amounts in inches. Date 7/27 8/3 8/10 8/17 8/23 8/31 9/7 9/14 9/20 9/28 10/5 10/12 10/19 10/26 11/2 11/9 11/16 11/23 11/30 12/7 12/15 12/21 12/31 1/5 1/11 1/19 1/25 2/1 2/10 2/15 2/22 3/2 3/9 3/16 3/22 3/30 4/5 4/12 4/19 4/26 Ca M g Na K 4.3 4.2 4.1 4.1 4.0 4.2 4.0 5.0 4.6 4.8 4.0 4.0 4.4 4.4 4.5 4.7 4.4 4.6 4.6 5.0 4.9 5.2 0.58 0.20 0.52 1.06 0.26 0.42 1.65 0.40 0.55 0.15 0.42 0.33 0.01 0.01 0.00 0.16 0.76 0.01 0.00 0.08 0.58 0.090 0.028 0.080 0.111 0.035 0.074 0.220 0.105 0.091 0.018 0.045 0.037 0.003 0.005 0.002 0.024 0.087 0.004 0.012 0.017 0.610 0.137 0.126 0.151 0.143 0.284 0.117 0.584 0.652 3.220 1.370 0.081 0.052 0.048 0.014 0.027 0.017 0.028 0.130 0.015 0.021 0.066 0.278 0.222 4.4 4.5 4.8 0.26 0.14 0.17 0.029 0.021 0.025 5.1 4.6 4.7 0.10 0.10 4.5 4.8 amount, Y amount, P pH 0.03 1.79 1.01 5.55 0.67 0.10 1.83 0.19 1.05 0.86 0.59 0.24 1.11 1.47 0.48 2.12 0.69 0.20 0.85 0.10 0.56 0.41 0.31 0.25 0.26 0.38 0.02 0.15 0.17 0.04 0.10 0.61 0.68 1.03 0.02 0.10 0.25 0.04 0.02 0.27 0.33 3.55 1.30 3.08 0.44 1.01 0.52 0.21 1.52 1.08 1.19 0.35 1.31 1.89 1.04 1.99 1.23 0.29 1.13 0.11 0.73 0.65 0.65 0.24 0.70 0.55 0.08 0.22 0.24 0.18 0.04 0.39 0.43 0.96 0.01 0.15 0.15 0.12 0.19 0.27 Si 02 N03 Cl 1.032 1.400 4.000 1.320 6.600 3.400 1.200 0.000 0.000 0.000 0.485 2.159 26.050 4.311 6.920 1.137 25.581 0.333 0.855 0.224 0.105 0.094 0.029 0.322 0.2.24 0.333 0.550 0.126 0.072 0.075 0.000 0.000 8.659 18.600 13.224 0.749 0.249 0.150 0.697 0.035 0.038 0.052 0.000 0.000 0.000 0.420 0.431 0.735 0.015 0.026 0.144 0.073 0.050 0.050 0.000 0.000 0.000 0.16 0.06 0.033 0.015 0.055 0.026 0.057 0.026 4.2 0.07 0.019 0.000 5.5 4.0 1.96 1.14 0.289 0.146 0.149 0.122 0.000 0.000 0.345 0.012 0.095 0.340 0.008 0.023 0.011 0.015 0.000 0.000 0.000 0.000 0.033 0.000 0.000 0.000 0.000 0.000 0.001 0.072 0.000 0.000 0.000 0.000 0.000 0.000 0.077 0.890 0.749 0.749 1.457 2.165 0.749 0.466 0.466 0.324 S04 0.200 0.200 0.100 0.300 0.100 0.300 0.408 0.358 0.284 0.129 0.099 0.086 0.129 0.099 0.160 0.173 Alt 0.013 0.008 0.005 0.004 0.010 0.002 0.006 0.023 0.004 0.005 0.008 0.002 0.001 0.000 0.001 0.007 0.000 0.004 0.000 0.607 0.160 0.173 0.005 0.749 0.466 0.749 0.160 0.160 0.099 0.001 0.012 0.003 0.355 0.311 0.607 0.607 0.129 0.099 0.003 0.002 0.000 0.000 0.529 0.466 0.324 0.148 0.160 0.002 0.031 0.000 0.768 0.466 0.222 0.003 0.187 0.157 0.002 1.322 1.398 0.466 0.594 0.004 0.026 0.000 Table 17 (cont'd). 5/3 5/10 5/17 5/24 6/1 6/9 6/14 6/22 6/28 7/5 7/14 7/20 7/26 0.35 0.05 0.00 1.37 0.26 2.68 1.99 0.39 1.09 0.10 0.00 0.00 0.41 0.19 0.17 0.00 0.35 1.38 2.64 0.91 0.21 0.52 0.18 0.05 0.23 0.00 4.0 1.18 0.115 0.059 0.086 0.000 1.420 0.466 0.433 0.010 4.4 4.7 5.0 4.5 4.7 4.6 1.27 0.87 0.24 0.06 0.113 0.091 0.045 0.117 0.016 0.024 0.000 0.102 0.130 0.086 0.047 0.368 0.000 0.000 0.000 0.016 1.290 0.855 1.344 0.822 0.466 0.324 0.218 0.466 0.191 0.160 0.006 0.004 0.297 0.010 1.23 0.109 0.013 0.015 0.000 1.333 0.607 0.160 0.003 0.62 0.056 0.000 .0.050 0.000 0.681 0.607 0.160 0.001 4.4 4.4 0.000 Table 18. Aqueous chemical data for groundwater, lakes and runoff. Units: all solutes in mg/l; temperature °C. GU=groundwater from well, L=lake, RO=runoff, SW=swamp. Site type mgw8/3 cgw8/4 hlgw8/23 bgw8/25 kgw8/31 vrgw9/20 wdl9/21 blsw9/21 lcg10/5 4 i110/12 sgHl1/10 yro4/26 yro6/8 pro5/3 cl5/18 sqg7/20 smgw8/4 ksgw10/7 bugw10/7 frg10/8 G U G U G W G U G W G U L SW L L G W RO R O R O L G W G W G W G U G U Temp 15. 15. 12. 9. 11. 11. 13. 14. 10. 6. 10. 6. 10. 6. 15. 6. 7. 7. 8. 8. pH Ca Hg Na 6.450 6.000 6.100 6.000 5.200 6.900 6.400 5.800 7.000 6.400 6.125 6.000 6.000 5.700 5.800 6.000 7.250 6.150 6.150 6.200 16.12 2.09 5.30 25.41 3.54 26.12 5.44 5.14 23.43 2.56 7.19 3.80 4.14 2.20 3.13 3.72 10.27 4.55 10.58 3.22 3.190 0.580 1.070 4.200 0.630 8.910 1.170 1.040 5.970 0.630 1.750 0.950 1.050 0.600 0.660 0.850 4.160 1.110 2.790 0.580 1.160 0.530 0.720 1.520 0.710 2.470 0.520 0.570 2.700 0.470 2.180 0.450 0.470 0.350 0.330 0.590 1.150 0.840 1.010 0.410 K Cl 0.700 2.400 0.440 2.000 0.360 3.000 0.970 1.800 0.570 0.700 1.560 14.288 0.270 0.626 0.300 1.330 1.320 8.373 0.270 0.485 1.470 2.176 0.410 0.415 0.500 0.767 0.150 0.767 0.180 0.767 0.320 3.302 0.560 0.908 0.480 0.626 0.680 1.471 0.360 1.049 S04 12.753 4.090 18.941 2.852 1.615 30.327 7.184 4.585 3.595 3.780 4.709 4.090 1.615 4.090 3.162 0.501 2.233 3.595 9.040 0.501 HC03 84.0 12.0 44.0 90.0 12.0 60.0 12.0 12.0 82.0 60.0 20.0 12.0 12.0 8.0 8.0 24.0 56.0 22.0 82.0 20.0 Fe Si 02 40. 8.870 0. 4.670 0. 6.730 6. 8.970 0. 6.520 0. 16.518 0. 2.260 1. 4.591 5. 21.892 0. 1.033 0. 9.254 0. 2.567 0. 4.591 0. 4.481 0. 2.751 16. 5.327 0. 3.119 1. 8.579 68. 13.916 25. 6.309 NH4 Aim F N03 M n Alt 1.132 0.074 0.113 0.035 0.035 0.055 0.035 0.035 0.035 0.035 0.035 0.038 0.030 0.043 0.035 0.074 0.035 0.094 1.367 0.231 0.008 0.003 0.004 0.001 0.038 0.002 0.007 0.021 0.000 0.012 0.004 0.050 0.025 0.042 0.054 0.030 0.026 0.050 0.040 0.040 0.025 0.025 0.035 0.023 0.020 0.040 0.040 0.050 0.040 0.040 0.030 0.937 2.007 2.449 0.355 0.094 0.485 0.155 0.046 0.010 0.874 1.006 0.677 0.427 0.191 0.025 0.360 0.015 0.043 0.380 0.017 0.465 0.002 0.034 0.460 0.006 0.002 0.001 0.006 0.001 0.039 0.075 0.210 0.050 0.348 0.033 0.064 0.016 0.022 0.002 0.083 0.003 0.021 0.162 0.002 0.056 0.009 0.122 0.187 0.160 0.117 0.141 0.001 0.072 0.151 0.087 0.010 0.015 0.005 0.000