ABSTRACT Deborah D. Noltemeier. COMPARISON OF WATER QUALITY IN COASTAL PLAIN STREA_MS OF NORTH CAROLINA (Under the direction of Mark M. Brinson) Department of Biology, November, 1984. A one year study was conducted in the central Coastal Plain of North Carolina to examine water chemistry in a Piedmont-draining alluvial river (and its floodplain), and in ten Coastal Plain-draining streams which were further subdivided into two general categories based on their geologic origin: (1) peat-draining streams and (2) mineral soil-draining streams (including a channelized stream). Objectives of this research were to demonstrate similarities and differences in water chemistry and to determine if streams could be distinguished and categorized on the basis of the chemical composition of their waters. The results of this study elucidated differences in the chemical composition of streamwater v/hich can be used to distinguish the geologic origin of Coastal Plain-draining streams. The characteristics of peat-draining streams that distinctively separate them from, mineral soil-draining streams are higher concentrations of organic carbon and lower levels of dissolved oxygen, biochemical oxygen demand, pH, total alkalinity, conductivity, cations (Ca, Mg, Na, K and Fe) , inorganic nitrogen, and phosphorus. V7hen compared to the two categories of streams originating in the Coastal Plain, the Piedmont-draining alluvial river had higher levels of dissolved oxygen and cations; lower concentrations of organic carbon; and levels of biochemical oxygen demand, pH, total alkalinity, conductivity, iron, inorganic and organic nitrogen, and phosphorus that were between those of the other two categories. Categorical separations of streams, based on their geologic origin, are basically sound; however, large watersheds often possess diverse lithology which results in overlapping stream types. Anthropogenic influence was superimposed on Coastal Plain-draining streams as a result of v/astewater discharges, agricultural activities, animal husbandry operations, and channelization. Localized loadings of nitrogen and phosphorus in Chicod Creek and Grindle Creek resulted in high concentrations of these nutrients in streamwater, which indicated that the assimilative capacity of these streams had been exceeded. Channelized Grindle Creek had perennial flow; higher levels of cations, conductivity, and nutrients; and lower dissolved organic carbon concentrations, which clearly distinguished it from the natural streams. COMPARISON OF WATER QUALITY IN COASTAL PLAIN STREAMS OF NORTH CAROLINA A Thesis Presented to the Faculty of the Department of Biology East Carolina University In Partial Fulfillment of the Requirements for the Degree Master of Science in Biology by Deborah D. Noltemeier November, 1984 3. T. iOYNKH LIBSARÜ M a fw Á’ T7WTVWO 4o Cj:>r G B /J ? COMPARISON OF WATER QUALITY A] IN COASTAL PLAIN STREAMS OF /9Si NORTH CAROLINA by Deborah D. Noltemeier APPROVED BY: SUPERVISOR OF THESIS /Ćx 07). Mark M. Brinson, Ph.D. DEAN OF GRADUATE SCHOOL ACKNOWLEDGEMENTS This study represents the combined efforts of a number of people to whom I am indebted. I express my sincere appreciation to my thesis chairman, Dr. Mark M. Brinson, for his guidance, assistance, and patience throughout this project. His support and encouragement, as well as critical reviews of this thesis, have ultimately lead to com.pletion of this project. I also thank the other members of my thesis committee. Dr. Lee Otte, Dr. Robert Christian, and Dr. Graham Davis, for critically reviewing this manuscript and for providing valuable suggestions. Martha Jones deserves special recognition and thanks for supervising and performing the laboratory analyses and for her assistance in various aspects of this project. David Bradshaw collected the Tar Swamp rainfall samples and provided technical advice. Jerry Freeman maintained and repaired equipment involved in this project. Steve Nelson assisted in performing nutrient analyses. Randy Creech deserves special recognition for computer programming. Tim Charles and Laddie Crisp provided technical assistance. Bruce Payne drafted the figures. Teresa Smith and Ben Loftin provided assistance in various aspects of this project. Mary Grace Pate deserves special recognition for professional excellence in word processing. This study was supported in part by the U.S. Environmental Protection Agency, grant R-805881. I am especially grateful to my father, Al Noltemeier, for accompanying me on many field collections and providing assistance in field work. I dedicate this thesis to my parents with special thanks for their support and encouragement throughout this study and in all of my academic endeavors. TABLE OF CONTENTS Page LIST OF TABLES V LIST OF FIGURES vi LIST OF APPENDIX TABLES vii INTRODUCTION 1 Factors Affecting Water Quality of Streams ... 3 Features of this Study 12 STUDY AREA 17 Coastal Plain-draining Streams 22 Peat-draining streams 23 Mineral soil-draining streams 27 Alluvial River and Swamp 31 METHODS 3 5 Field Measurements, Collections, and Samiple Preparations 35 Chemical Analyses 41 Data Processing and Analysis 44 RESULTS 47 Dissolved Oxygen and Biochemical Oxygen Demand . 48 pH, Total Alkalinity and Conductivity 51 Cations 58 Nitrogen 66 Inorganic forms 66 Organic forms 70 Phosphorus 7 3 Organic Carbon 77 DISCUSSION 81 Seasonal Trends 81 Characteristics of Peat-draining Streams .... 86 Comparison of Water Chemistry Between North Carolina and Minnesota Peatlands 92 Characteristics of Natural Mineral Soil-draining Streams 96 Effects of Channelization on a Mineral Soil- draining Stream 99 Characteristics of a Mineral Soil-draining Stream Associated with Limestone Formations . . 103 Characteristics of a Piedmont-draining Alluvial River 105 iii TABLE OF CONTENTS Page DISCUSSION (cont'd.) Exports to Downstream Ecosystems 108 Conclusions 112 LITERATURE CITED 116 APPENDIX 124 IV LIST OF TABLES Page 1. Stream categories with representative sampling sites and watershed areas 13 2. Annual arithmetic means (A), with standard errors, and annual weighted means (W) of concentrations of rainfall constituents in the Croatan (RGC) and Tar Swamp (RGT) rain gauge collections 54 3. Comparison of water chem.istry in North Carolina streams and Minnesota bogs and fens 93 4. Annual runoff and export of nitrate-nitogen, ammonium-nitrogen, dissolved organic nitrogen, particulate organic nitrogen, total phosphorus, total organic carbon, and dissolved organic carbon from September 1978 through August 1979 109 LIST OF FIGURES Page 1. Map of North Carolina showing the location of the study areas 18 2. Preparation of field samples for chemical analyses 39 3. Annual arithmetic means and weighted m.eans for (a) dissolved oxygen (0_) and (b) biochemical oxygen demand (BOD ) from September 1978 through August 1979 49 4. Annual arithmetic means and weighted means for (a) pH and (b) total alkalinity (TA) from September 1978 through August 1979 52 5. Annual arithmetic means and weighted m.eans for (a) conductivity (COND) and (b) calcium (Ca) from September 1978 through August 1979 56 6. Annual arithmetic means and weighted means for (a) magnesium (Mg) and (b) sodium (Na) from September 1978 through August 1979 60 7. Annual arithmetic means and weighted means for (a) potassium (K) and (b) iron (Fe) from September 1978 through August 1979 63 8. Annual arithmetic means and weighted m.eans for nitrate-nitrogen (NO^-N), (b) ammonium-nitrogen (NH .-N) , and (c) nitrite-nitrogen (NO„-N) from September 1978 through August 1979 67 9. Annual arithmetic means and weighted means for (a) dissolved organic nitrogen (DON) and (b) particulate organic nitrogen (PON) from Septem.ber 197 8 through August 1979 71 10. Annual arithmetic means and weighted means for (a) total phosphorus (TP), (b) filterable reactive phosphorus (FRP), and (c) particulate phosphorus (PP) from September 1978 through August 1979 .. . 74 11. Annual arithmetic means and weighted means for (a) dissolved organic carbon (DOC) and (b) particulate organic carbon (POC) from September 1978 through August 1979 78 12. Seasonal patterns of dissolved organic carbon (DOC) and discharge (Q) at (a) East Brice Creek (EB), (b) Island Creek (IS), (c) Palmetto Swamp (PA), and (d) Tar River (TR) from September 1978 through August 1979 83 VI 1ST OF APPENDIX TABLES Page 1. Annual arithmetic mean concentrations (A), with standard errors, and weighted mean concentrations (W) for nitrogen and phosphorus (in mg/1) from September 1978 through August 1979 125 2. Annual arithmetic mean concentrations (A), with standard errors, and weighted means concentrations (W) for total organic carbon, dissolved organic carbon, calcium, magnesium, sodium, potassium and iron (in mg/1) from September 1978 through August 1979 126 3. Annual arithmetic mean concentrations (A), with standard errors, and weighted means concentrations (W) for pH, total alkalinity (in meq/1), conducti- vity (in um.ho/cm), temperature, dissolved oxygen (in mg/1), biochemical oxygen dem.and (in mg/1) and discharge (in m^/sec) from September 1978 through August 1979 127 4. Linear correlations (r) between chemical and physical factors for East Brice Creek (EB) .... 128 5. Linear correlations (r) between chem.ical and physical factors for West Brice Creek (WB) .... 129 6. Linear correlations (r) between chemical and physical factors for Black Swamp (BL) 130 7. Linear correlations (r) between chemical and physical factors for Mill Creek (MI) 131 8. Linear correlations (r) between chemical and physical factors for Catfish Lake drainage canal (CL) 132 9. Linear correlations (r) between chemical and physical factors for Island Creek (IS) 133 10. Linear correlations (r) between chemical and physical factors for Creeping Swamp (CS) 134 11. Linear correlations (r) between chemical and physical factors for Palmetto Swamp (PA) 135 12. Linear correlations (r) between chemical and physical factors for Chicod Creek (CH) 136 13. Linear correlations (r) between chemical and physical factors for Grindle Creek (GR) 137 Vll LIST GF APPENDIX TABLES (continued) Page 14. Linear correlations (r) between chemical and physical factors for Tar River (TR) 138 15. Linear correlations (r) between chemical and physical factors for Tar Swamp (TS) 139 viii INTRODUCTION The Coastal Plain of North Carolina is characterized by a diversity of wetland ecosystems due to the low topography, poor drainage, and abundant rainfall typical of the area (Kuenzler et al. 1977). At the time of Wilson's (1962) report, it was estimated the areas of v/etland types were: bogs (9,160 km^), sounds and bays (6,050 km^), wooded swamps (4,000 km2), seasonally flooded bottomlands (1,860 km^), coastal open fresh water (1,560 km^) , irregularly flooded salt marsh (406 km^), inland open fresh water (357 km^), regularly flooded salt marsh (236 km^), and fresh marsh (192 km2 ) . Wetlands identified by Wilson (1962) as bogs are now recognized by the descriptive name pocosin, which is derived from an Indian word meaning "swamp on a hill" (Richardson 1981). Pocosin wetlands comprise over 50% of North Carolina wetlands in the Coastal Plain; however, they are under severe developmental pressure with only 31%, or less, left in their natural state (Richardson 1983). Pocosins are blocked drainage systems which formed along the Coastal Plain, approximately 10,000 years ago, as a result of a complex interaction of climatic, hydrologic, geologic, and biological processes (Otte 1981). Pocosins typically have a shrub-dominated vegetational structure situated on a broad topographic plateau and are characterized by an accumulation of autochthonous organic matter as peat, a water table vihich 2 remains at the surface of the pocosin throughout most of the year (resulting in a waterlogged substrate and predominately anaerobic edaphic conditions), acidic soils, and periodic fires (Snyder 1978, Christensen et al. 1981, Otte 1981, Richardson et al. 1981, Sharitz and Gibbons 1982, Ash et al. 1983). Only a few studies (Kirby-Smith and Barber 1979, Skaggs et al. 1980, Daniels 1981) have been conducted on the water chemistry of streams draining pocosin wetlands. The question arises, how does the water chemistry of peat- draining streams differ from the water chemistry of stream.s draining mineral soils? This study v./ill attempt to answer that question. Why is the study of stream water chemistry important? Streams are the circulatory system in an ecosystem which transport nutrients and organic matter from upstream eco- systems along a gradient to downstream aquatic ecosystems. In this hydrological circulatory system, tributaries are capillaries, streams are venules, and rivers represent veins returning water to the heart of the system--the estuary, and ultimately, the sea. Water is continuously circulated in this solar-powered system by evaporation and precipitation. Knowing that our very existence is intricately linked to the hydrological cycle, and that the quality of water in streams regulates our use of this water, makes the study of water chemistry of paramount importance. 3 Factors Affecting Water Quality of Streams Lotie ecosystems are open, primarily heterotrophic ecosystems (Odum 1971, Wetzel 1983) that are energetically dependent on allochthonous input from longitudinal coupling (upstream-downstream) and lateral coupling (stream-flood- plain) (Wharton and Brinson 1978) . Allochthonous energy input is usually in the form of particulate and dissolved organic matter (Wetzel 1983). Sources of stream water are direct rainfall, overland runoff, and groundwater seepage (base flow) (Wetzel 1983). The chemical constituents in stream water are influenced by: (1) precipitation input, (2) the regional geology, (3) the amount and chemical composition of base flow contributions to the stream channel, (4) interaction with the biotic components of the lotie ecosystem, (5) riparian vegetation (which provides a source of allochthonous energy influx into the stream and shading), (6) organic productivity and the photosynthesis-respiration balance in the stream, and (7) land and water utilization in the watershed and hum.an activities in the stream channel (Kuenzler et al. 1977). Aquatic and terrestrial ecosystems are coupled by the hydrologic cycle such that chemical and physical charac- teristics of lotie ecosystems are largely dependent upon the biological, lithological, and topographical attributes of the watershed. The biotic community of the watershed contributes allochthonous energy to the stream in the form 4 of litterfall and other organic debris. The soil biotic community plays an essential role in decomposition and nutrient cycling in the terrestrial environment of the watershed which, in turn, affects the chemical composition of runoff and base flow reaching the stream. Energy flow in small streams with forested watersheds is primarily depen- dent upon allochthonous energy input, since shading, as v/ell as current, tends to limit autochthonous primary production (Goldman and Horne 1983 , V7etzel 1983). Although the major energy input pathway in small streams is exogenous, autoch- thonous primary production by aguatic macrophytes, algae, aquatic mosses, and encrusted diatoms (in illuminated reaches of the stream) may also contribute to stream ener- getics on a seasonal basis (Goldman and Horne 1983). Detritus serves as the major energy source for heterctrophic metabolism in lotie ecosystems (Wetzel 1983). Lithological attributes of the watershed largely determine the inorganic chemical com.position of streamwater as well as controlling the amount of runoff reaching the stream. The chemical composition of streamwater is influ- enced by weathering and erosion of parent material and soils in the watershed (Hem 1970). The chemical composition of streamwater is also influenced by climate, gases and aero- sols from the atmosphere, activities of humans in the stream and surrounding watershed, and biogeochemical cycling. 5 Runoff, erosion, and subsurface infiltrating water (base flow) are agents of physical weathering which contrib- ute minerals to streamwater. Rates of weathering are determined by temperature, the amount of precipitation, the chemical constitution of parent and soil minerals, as well as the influence of vegetation. The chemical composition of parent material and soil minerals governs their solubility and ion-exchange capacities with groundwater and with streamwater (Hem 1970) . The infiltration capacity of the watershed for pre- cipitation partially depends on the composition of the soils. Sandy soils have a low field capacity and readily allow precipitation to infiltrate, thereby minimizing runoff and providing an opportunity for aquifer recharge. Alterna- tively, clayey soils, with a high field capacity, possess small pore spaces that restrict rainfall infiltration, especially when dehydrated (or conversely, saturated). This results in increased runoff to streams which limits the potential aquifer recharge in clay-dominated regions (Heath 1980). Peats are organic soils that are characterized by a great capacity to retain water and maintain an exceptionally high moisture content (Ingram and Otte 1981). For these reasons, peat accumulation also involves the accumulation of a significant amount of water within an ecosystem. The seasonal precipitation/evapotranspiration balance controls the v/ater table level and hence, the infiltration capacity of wetlands for precipitation. The amount of 6 runoff to streams is also affected by the time of year rainfall occurs due to the influence of évapotranspiration on water table levels. In summer and fall, vegetation effectively removes water by évapotranspiration, which subsequently lowers the groundwater table resulting in increased infiltration capacity for precipitation. During this time of the year, overland runoff to streams from the watershed is minimal. In winter and early spring, when deciduous vegetation is in a leafless condition, precipita- tion exceeds évapotranspiration output resulting in high water tables and hence, rainfall rejection since the soil is saturated. Runoff rates would be highest during these seasons. Local topographic conditions may influence stream, v/ater quality. Topographic lows, along stream margins, form floodplains for streams. These seasonally flooded bottom- lands are important in removing sedim.ent from floodwaters, thereby enhancing the quality of water transported to downstream^ ecosystems. Within the floodplain, various biogeochemical interactions between floodwaters and the swamp forest ecosystem occur which significantly affect stream water quality as floodwaters are gradually released back into the stream (Wharton et al. 1982, Brinson et al. 1983, Yarboro 1983). 7 Conversely, topographic highs along stream margins minimize interaction with the adjoining terrestrial water- shed (when compared to streams with broad floodplains). In- creased water velocity during spates, due to flow contain- ment by high banks, would result in increased erosion and hence, increased transport of suspended sediments as in channelized streams. However, the high suspended sedim.ent load characteristic of Piedmont-draining streams is more a function of steeper stream gradients in the Piedmont and the greater susceptibility of soils there to erode because of the rolling topography. The elevated topographic condition of pocosins re- stricts surface water influx from surrounding terrestrial ecosystems. Thus nutrient input to pocosins is limited to precipitation and atm^ospheric depositions. Peat thickness isolates the water held within the peat from contact with underlying mineral soils and the regional groundwater system. As a result the nutrient levels in pocosin drainage water are low. Finally, precipitation may have a major influence on streamwater chemistry. Precipitation is a major water input pathway in most streams, however indirectly, and therefore the chemical composition of rainfall is an important factor to consider in analysis of stream water chemistry. V7hen precipitation reaches terrestrial ecosystems its chemical composition becomes modified as it passes over vegetation and dissolves nutrient-rich exudates from the leaves. When P throughfall and stemflow reach the ground surface, inter- actions with the surface litterfall and soil humus layer occur before infiltration into the soil further alters precipitation chemistry. Cations and anions dissolved in rainfall originate from, diverse sources including oceanic spray, terrestrial dust, gaseous pollutants, and volcanic emissions (Likens et al. 1977). Strong acids such as nitric and sulfuric acid contribute to the acidity of rainfall. Hall et al. (1980) experimentally demonstrated that concentrations of Ca, Mg, K, and Fe increased as a result of stream acidifications in the Hubbard Brook Experimental Forest; however, there was no change in DOC, Na, NO^-N, or NH^-N levels at the lowered pH. The strong coupling between streams and the surrounding terrestrial watershed has been demonstrated in various studies. Fisher and Likens (1973) prepared an annual energy budget for Bear Brook in a forested area of northern Nev; Hampshire. This study revealed that over 99% of the energy input comes from the surrounding forested watershed or upstream areas. In Bear Brook 66% of the organic input was exported downstream, leaving 34% to be utilized locally. Once this material enters the stream system it undergoes biochemical and mechanical degradation m.ediated by the biotic community within the stream (Kaushik and Hynes 1968, Cummins 1974). In an unpolluted Georgia stream. Nelson and Scott (1962) discovered that primary consumers derive 66% of their energy from allochthonous leaf material. Mann (1969) Q estimated that the Thames River depends on allochthonous input for approximately half of its energy flow. Fisher and Likens (1973) concluded that small, headwater streams in forested areas are almost totally dependent on input of course particulate organic matter as an energy source, such as leaf litter, from the terrestrial ecosystem. These studies illustrate the importance of a land-water inter- change in providing lotie ecosystem, energy requirements. The orientation and branching pattern of streamiS reflect topographic and geological variations in the water- shed. The nature of the underlying geologic formations and surface soils in the drainage basin are important factors affecting stream water chemistry. Due to the diversity in lithology and solubility of rocks underlying North Carolina, differences in regional geology will cause base flow to contain variable amounts of dissolved constituents in the water (Sirronons and Heath 1979). Because surface soils interact with precipitation to produce base flow, soil is an important component of watersheds that strongly influences the hydrology and water chemistry of streams. The effect of base flow influx on stream water chemistry is most pro- nounced during low flow periods (Wharton et al. 1982). Lotie ecosystems, and their adjacent floodplains, are fluctuating water level ecosystems (Wharton and Brinson 1979). Low flows during summer and fall are a result of high évapotranspiration rates whereas high flows typically 10 occur during winter and spring, when precipitation exceeds évapotranspiration (Brinson et al. 1981b). Nutrient cycling and sedimentation in seasonally flooded bottomlands influence the water quality in Coastal Plain streams and rivers. Sedimentation represents a sink of nutrients for streams that would be carried downstream, if the floodplain ecosystem did not provide depositional space. Southeastern floodplain swamp forests exhibit a rapid nutrient cycling rate which serves as a mechanism of nutri- ent conservation. This efficient recycling component reduces the probability that allochthonous input of nutri- ents will be removed from the system by leaching from the soil and export in drainage waters (Brinson et al. 1981b). Chemical and biological interactions between streams and their floodplains affect the quality of water exported to estuaries (Kuenzler et al. 1977). Nutrient inflow from upstream lotie ecosystems is essential to estuarine produc- tivity (Odum 1971). However, excessive amounts of nitrogen and phosphorus in drainage water can result in eutrophica- tion in estuarine waters (Robbie 1974, Kuenzler et al. 1979). The water quality of streams and rivers, which drain into estuaries, potentially influences the chemical, physi- cal, and biological structure of these estuarine ecosystems. Examination of water quality characteristics of these Coastal Plain streams should provide a basis for the eval- uation, management, and protection of North Carolina coastal aquatic ecosystems. 11 Today, perhaps the most active biotic component affect- ing the water quality of streams and rivers is man. Human activities in the watershed significantly affect the water chemistry of streams. Streams receive anthropogenic inputs of domestic and industrial wastewater, agricultural runoff loaded with fertilizer nutrients, and wastes resulting from animal husbandry activities which increase nutrient concentrations in streamflow and contribute to degradation of water quality (Kuenzler et al. 1977). One of the most recent alterations of natural lotie ecosystems is the process of channelizetion--the widening, deepening, and straightening of a stream channel to provide better drainage, thereby reducing flooding of adjacent terrestrial ecosystems. Channelization results in drastic changes in lotie ecosystem structure and function which alter the biology and hydrology of the natural stream. Kuenzler et al. (1977) has demonstrated that channelized streams differ in water quality characteristics from natural streams. Their study showed that channelized streams are characterized by lower color, yet higher levels of pH, conductivity, turbidity, and also higher concentrations of nitrate and total phosphorus, than observed in the natural streams studied. Other studies have shown that biotic productivity is decreased as a result of channelization due to the destruction of habitat (Maki et al. 1980). 12 Features of this Study The purpose of this study is to demonstrate simi- larities and differences in water chemistry of streams in the central Coastal Plain of North Carolina. Study sites were chosen to reflect the diversity of stream types in the Coastal Plain. This study examines water chemistry in a Piedmont-draining alluvial river (and the associated flood- plain) and in ten Coastal Plain-draining streams, which are further subdivided into two general categories based on their geologic origin (Table 1). These categories are mineral soil-draining streams and peat-draining streams. The designation mineral soil-draining streams refers to streams primarily associated with sands, silts, and clays, in varying amounts, throughout the watershed. The peat-draining streams category refers to streams with headwaters draining pocosin peat deposits; however, further downstream, these streams drain predominately mineral soils. This study investigates the differences in streamwater chemistry which result from the lithological variations in the drainage basins. Organic soils have a number of characteristics which distinguish them from mineral soils such as: lower bulk density (Dolman and Buol 1967, Ingram and Otte 1981), high water-retention capacity (Dolman and Buol 1967, Bannister 1976, Ingram and Otte 1981), low hydraulic conductivity (Boelter 1970), high organic content (Dolman and Buol 1967, Ingram and Otte 13 Table 1. Stream categories with representative sampling sites and v/atershed areas. Stream, abbreviations are in parentheses. Watershed Stream categories area (km^) I, Coastal Plain-draining blackwater streams A. Peat origin 1. Natural drainage East Brice Creek (EB) 32 West Brice Creek (WB) 28 Black Swamp (BL) 78 Mill Creek (MI) 82 2. Artificial drainage Catfish Lake drainage canal (CL) 5 B. Mineral soil origin 1. Natural Island Creek (IS) 18 Creeping Swamp (CS) 80 Palmietto Swamp (PA) 54 Chicod Creek (CH) 132 2. Channelized Grindle Creek (GR) 183 II. Piedmont-draining alluvial river Tar River (TR) 7097 Tar Swamp (TS) 14 1981), a high cation exchange capacity (Puustjarvi 1956), poor thermal conductivity (VJilliams 1970), and low ash (mineral) content (Ingram and Otte 1981). With these edaphic differences in mind, one might expect differences in water chemistry of streams draining peat deposits from streams which drain predomiinately mineral soils. An objec- tive of this research is to determine if Coastal Plain- draining streams can be distinguished and categorized on the basis of the chemical composition of their waters. Although categories are useful for data interpretation, it should be realized that differences in biology, geology, water chemistry, and hydrology make each stream unique. This study attempts to elucidate relationships between water chemistry, regional geology, and watershed land use prac- tices in each study area. Kuenzler et al. (1977) conducted a study to examine water quality in Coastal Plain streams, with emphasis on comparing water quality between natural and channelized streams. Four sampling sites in this study were located on the same streams used by Kuenzler and his co-workers. The sampling sites were at the same location on Creeping Swamp (CP-10), Palmetto Swamp (PM-10), and Chicod Creek (CH-20), but my collection site on Grindle Creek was approximately 10 km downstream from the sampling site location used in the Kuenzler et al. (1977) study. The purpose of choosing the same collection sites, in some cases, was to compare data and to expand the data file 15 of water quality characteristics and changes v/ithin these streams. Historical reviews of water chemistry and stream conditions are a valuable basis for detecting water quality changes resulting from the alteration of land use patterns in the watershed. In addition to examining water quality differences between natural, mineral soil-draining streams (Creeping Swamp and Palmetto Swamp) and a channelized stream (Grindle Creek), this study investigates water quality characteris- tics of: a Piedmont-draining alluvial river (Tar River), and the waters in the bordering floodplain (Tar Swamp); streams which originate in and drain peat deposits (Brice Creek, Mill Creek, Black Swamp); a stream in contact with Tertiary limestone deposits (Island Creek) and the influence of this deposit on two other streams; an artificially con- structed drainage canal associated with an experimental waterfowl impoundment underlain by peat (Catfish Lake canal); and a stream undergoing transition from natural to channelized (Chicod Creek). Many different physical, chemical, and biological param.eters are of significance in determining water quality in lotie ecosystem.s. However, due to time and cost limita- tions, it is not feasible for most water quality studies to measure all of these parameters, so general or special purpose parameters are chosen on the basis of research goals. The water quality parameters chosen for my research are examined to detect similarities and differences that might occur in water quality of Coastal Plain-draining streams. These include major nutrients (form.s of carbon nitrogen, and phosphorus) and several cations, as well a dissolved oxygen, biochemical oxygen demand, pH, total alkalinity, and conductivity. ÍTTUDY I^PEA The study area for this project is located in the central portion of the North Carolina Coastal Plain. In addition to the Tar River, streams associated with the Tar-Pamlico, White Oak, and Trent-Neuse River drainage basins are included in this study. The watersheds of the streams examined encompass portions of Pitt, Craven, Jones, and Beaufort counties (Figure 1). North Carolina has a warm and humid clim^ate and is located in the temperate zone. The Piedmiont Plateau is located in the central region of the state and is charac- terized by clayey soils and intermediate elevations and slopes. The central portion of the Coastal Plain has clayey to sandy soils, low elevations, and gentle slopes (Kuenzler et al. 1977). Sediments underlying this region are composed of sands, clays, shell beds, limestones (Heath 1980) , and peat (Ingram and Otte 1981) . Many elements (such as m.ajor cations) exhibit low concentrations in the soils of the Atlantic Coastal Plain when compared to other regions of the United States (Shacklette and Boerngen 1984). The climate is seasonal with cool winters and warm summers. July and August are the warmest months with 30-year average temperatures of 26.0 and 25.5°C, respective- ly; December and January are the coldest months with mean temperatures of 7.1 and 6.5°C, respectively (NCAA 1973). The mean annual temperature of the area (averaged from 18 Figure 1. Map of North Carolina showing the location of the study areas. The streams examined in this study and their watershed areas are shaded. The Catfish Lake station is not illustrated. 19 1941-1970) is 16°C (NOAA 1973). This region receives abundant rainfall, which has approximately even distribution throughout the year (Sumsion 1970, Kuenzler et al. 1977). The mean annual precipitation for the central Coastal Plain, averaged for 30 years, is 129 cm (NOAA 1973). The study area is a region of flat to gently undulating topography which is characterized by low gradient, slow flowing streams bordered by seasonally flooded bottomlands. Sediments in the stream bottoms consist of varying amounts of sand, silt, and clay. These sediments are sometimes overlain by organic matter, especially in the summer months when discharge rates are low and no flow periods occur (Maki et al. 1980). Coastal Plain-draining streams are closely associated with wetlands. Peat-draining streams originate in pocosin wetlands and, as they increase in size downstream, pass through floodplain wetlands similar to those bordering mineral soil-draining streams. Pocosin wetlands may have peat deposits up to 3 m in thickness. The low nutrient status in pocosins is due to isolation of the vegetation from mineral soils by peat. Pinus serótina (pond pine), the only tree species found in low pocosin vegetational systems, exhibits a deformed and stunted growth form. These structural characteristics may be due to a combination of environmental stresses including long hydroperiods, acidic soils, low nutrient availability, and periodic fires (Christensen et al. 1981, Otte 1981). 20 The density and height of serótina and shrub species decreases from the outer margins, where pond pine woodland and high pocosin occur, to the center of the pocosin, which is underlain by the thickest peats and dominated by low pocosin vegetation (Otte 1981) . Ingram and Otte (1981) reported the following species were observed at almost every one of their sampling lo- cations in the Croatan National Forest pocosins: Pinus serótina, Lyonia lucida, Zenobia pulverulenta, Gordonia lasianthus, Persea borbonia, Smilax spp., Woodwardia virginica, Cyrilla racemiflora, and Ilex glabra. Other frequently encountered species were Magnolia virginiana, Kalmia augustifolia, Cassandra calyculata, Sorbus arbu- tifolia, and Vaccinium spp. (Ingram and Otte 1981). An extensive moss network forms a spongy ground cover through- out the pocosin; the most comm.on moss encountered is Sphag- num (Christensen et al. 1981). For a more detailed descrip- tion of the vegetational composition of the Croatan National Forest pocosins, see Snyder (1977) and Otte (1981). Along mineral soil-draining streams, Nyssa aquatica and Taxodium distichum are common riparian species found in the wettest habitats in floodplains. Species diversity is higher in more elevated portions of floodplains and in upland plant communities within these watersheds (Kuens^ler et al. 1977). Common floodplain species are Acer rubrum, N. sylvatica var. biflora, Liquidambar styraciflua, and Quercus michauxii. These species also occur in the upland regions 21 of the watershed but are much less prevalent. Other riparian vegetation commonly encountered in the central region of the North Carolina Coastal Plain are Betula nigra, Fraxinus caroliniana, Q. nigra, Carya aquatica, Populus heterophylla, Ulmus americana, Carpinus caroliniana, Ilex opaca, and Persea borbonia. For a more detailed description of southern riparian vegetation, see Brinson et al. (1981b) and Wharton et al. (1982). The Coastal Plain-draining streams in this study are located in Geochemical Zone V, and are described below according to information in Simmons and Heath (1979). The Coastal Plain region is underlain by sedimentary rocks that create a complex series of geologically distinct formations. Five geological units are found in the upper sediments of the Coastal Plain (arranged from youngest to oldest) are: (1) Quaternary deposits--dominate in the exposed sediment and comiposed of stream-deposited beds of yellow (or tan) sandy silt and clay; (2) Yorktown Formation--of Pliocene Age composed of marine-deposited clay, silt, and sand inter- spersed with a few, thin shell beds; (3) Pungo River Forma- tion--of Miocene age, which consists of phosphatic sand interbedded with silt and calcareous clay; (4) Castle Ilayne Limestone--of Eocene age which is composed of fossiliforous limestone, containing a few calcareous sand bed layers (Simmons and Heath 1979, Winner and Simmons 1977, Heath 1980); and (5) Cretaceous sediments--composed of a complex miixture of fluvial estuarine and m^arine sand and mud (L. 22 Otte, personal communication, 1984). These formations intersect with groundwater in a discontinuous manner over Geochemical Zone V, which results in variation in the water chemistry (especially dissolved solids) of streams in this region (Simmons and Heath 1979). These surficial aquifers provide base runoff to streams in this study. The upper 30 m of these sediments are hydrologically important to lotie ecosystem dynamics, since most of the groundwater circu- lation is restricted to this depth (Simmons and Aldridge 1980). The limestone and shell beds, associated with these formations, are water soluble and thereby contribute dis- solved solids to streams in the area (Simmons and Heath 1979). The amount of dissolved minerals in streamwater is a function of their relative abundance in the watershed and their solubility. Ten streams, a drainage canal, and a seasonally flooded bottomland were studied, with all but one (Tar River) confined to the central portion of the North Carolina Coastal Plain (Figure 1) . The stream.s and their watershed areas are listed in Table 1. Coastal Plain-draining Streams The streams examined in this study are collectively categorized as Coastal Plain-draining streams and are blackwater streams originating in the central region of the North Carolina Coastal Plain. The name "blackwater stream" 23 originates from the characteristically dark brown-colored v/ater found in these streams. Prolonged contact with organic matter in swamp forests adjacent to these streams results in leaching of humic and fulvic compounds which darkly stain the drainage water (Beck et al. 1974, Gjessing 1976). These streams are precipitation-dominated (sensu Wharton et al. 1982); however, base flow is the primary source of water to these streams during summer and fall. Surface runoff, along with base flow, becom.es hydrologically important to stream water chemistry during the winter and spring when low évapotranspiration rates result in soil saturation and hence, increased overland runoff of local precipitation (Brinson et al. 1981a). Although both base flow and overland runoff originate from precipitation, base flow typically has a higher mineral content than surface runoff waters due to longer contact with mineral soils (Simmons and Heath 1979). When compared to alluvial rivers, undisturbed blackwater streams usually have narrower flood- plains and transport louver sedim.ent loads (Wharton and Brinson 1979). Peat-draining streams The peat-draining streams in this study have headwaters originating in the peat deposits of the Croatan National Forest which is located south of New Bern, North Carolina (Figure 1). The Croatan National Forest contains the third 24 largest peat deposit in North Carolina (Ingram and Otte, 1981). A large portion of the Croatan is covered by pocosin peat, although mineral soil is exposed in many areas. Peat is defined as any partially decomposed plant material that has accumulated, over time, in water-saturated soil where plant growth and deposition have exceeded the rate of decomposition. The designation, peat-draining stream, refers to the fact that pocosin peats exist in the stream drainage basin; however, it does not imply that peat is the only substrate in contact with the stream. The stream water passes through a gradient of edaphic conditions ranging from predominately peat, to mixed organic-mineral soils, and gradually to mineral-rich soils as it travels from the stream, headwaters to my collection sites. Two sampling sites were chosen on Brice Creek (Figure 1), a natural, peat-draining stream whose headwaters drain areas containing a maximum of 1.8 m of peat thickness (Ingram and Otte 1981). Brice Creek is located in the northern portion of the Croatan National Forest and drains northv/ard into the Trent River, which flows into the Neuse River estuary. The sampling site on East Brice Creek (EB) is located on Catfish Lake Road (SSR 1100) and has a watershed area of 32 km2. The sampling site at West Brice Creek (WB) is located on Little Road (FSR 121-2) and has a watershed area of 28 km^. Disturbances resulting from forestry practices 25 (i.e., clearcutting, controlled burns, pine monoculture) were observed in the watershed in close proximity to the WB sampling station. The vegetation surrounding the collection site is predominately pond pine forest or pond pine wood- land. For a description of these plant communities, the reader is referred to Otte (1981). The sampling stations at Mill Creek (MI) and Black Swamp (BL) are located on the western border of the Croatan National Forest. The headwaters of Mill Creek and Black Swamp contact regions underlain by 0.6 m of peat (Ingram^ and Otte 1981). The water chem.istry of these streams is also influenced by an underlying Tertiary limestone deposit. The Mill Creek station is located on SSR 1004, on the edge of Pollocksville's city limit. Mill Creek drains into the Trent River and has a watershed area of 82 km^. in addition to agricultural runoff, this stream receives pollution from a hog farm a short distance upstream from the sampling site. The sampling station at Black Swamp is located on State Highway 58, south of Maysville. Black Swamp has a watershed area of 78 km^ and drains into the White Oak River, which flows into the Bogue Sound estuary. The Catfish Lake (CL) sampling station is located in the northwestern part of the Croatan National Forest, just northwest of Catfish Lake. The sampling site is an artifi- cial drainage canal, associated with a waterfowl impound- ment, underlain by 1.2 m of peat (Ingram and Otte 1981). The watershed area is 5 km^, which is much smaller than any of the other study areas. Water level in the impoundment is controlled by a floodgate constructed in the drainage canal. This device allows artificial manipulation of the water level in the imipoundment. When closed, the floodgate acts as a barrier obstructing water outflow. Opening the floodgate would result in slow drainage of the impoundment area. Water samples were collected at a location in the drainage canal approximately 10 m upstream from the flood- gate. Because discharge in this canal is artificially con- trolled by the floodgate, no flow data was collected for this sampling site. During most of the study year, the floodgate remained closed; therefore, the water in the drainage canal was usually in a stagnant condition. The pre-impoundment vegetation of the Catfish Lake watershed was typical low pocosin growing on waterlogged, deep peats (L. Otte, personal communication, 1983). Approximately 20 years ago, the area was cleared of its pocosin vegetation and burned in an attempt to put the land into experimental agricultural production. Later, the farming attempt was abandoned and, at least 10 years ago, the area was planted with vegetation suitable for v;aterfowl consumption and flooded to provide an experimental waterfowl impoundment area. The aquatics v/hich were planted have not prospered in the acidic impoundment water. The im.poundment 27 area has remained inundated for several years, yet has not been a successful waterfowl habitat. Mineral soil-draining streams Island Creek (IS) is a mdneral-soil draining stream located in Jones County, east of Pollocksvilie. The samp- ling site is located on SSR 1004. The watershed is only 18 km^ and is relatively undisturbed above the sampling site. The stream, flows northward into the Trent River, which flows into the Neuse River. Island Creek differs from the other streams in this study because the stream channel dissects a Tertiary lime- stone formation of Eocene or Oligocčne age (L. Otte, person- al communication, 1984). Limestone outcrops (often covered with liverworts and other bryophytes) are exposed along the stream banks. These outcrops are visible during low flow periods, but are sometimes obscured during high flov; stages. Rare calciphytes occur on the calcareous outcrops (Sears 1966) . The erosive action of flowing water along the stream, banks results in gradual disintegration of minerals in the limestone outcrop. Creeping Swamp (CS) and Palmetto Swamp (PA) represent natural, mineral soil-draining streams, which are bordered by seasonally flooded bottomland forests. The two streams flow southwesterly into Swift Creek, which flows southward into the Neuse River drainage basin. The sampling stations 28 are located on State Highway 43, southeast of Calico. Both streams are gauged by the U.S. Geological Survey. The watershed areas are similar in size, with that of Creeping Sv/amp (80 km^) being slightly larger than that of Palmetto Swamp (54 km^) (Kuenzler et al. 1977). Creeping Swamp and Palmetto Swamp drain watersheds that are over 60% wooded (Kuenzler et al. 1977). Pine plan- tations in various stages of development, and mixed hard- woods in the uplands and floodplain, comprise the woodlands in the watershed (Kuenzler et al. 1977). For a detailed description of the vegetation in the Creeping Swamp and Palmetto Swamp watersheds, see Kuenzler et al. (1977). The watersheds contain no point sources of pollution, with the exception of a small tributary entering Creeping Swamp less than 2 km upstream from my collection site, which receives effluent from a hog farm (Kuenzler et al. 1977). Winner and Simmons (1977) prepared an annual water budget for the Creeping Swamp watershed. In this model, precipitation provides 100% of the water inflov/. Base runoff (20%), overland runoff (17%), and groundwater outflow through deep aquifers (2%) together constitute less than half of the total water outflow pathway, while evapotrans- piration is responsible for 61% of the water output. Chicod Creek (CH) is a mineral soil-draining stream which flov/s northward into the Tar River. The sampling station on Chicod Creek was located on Secondary Road 1760. The watershed area above the sampling site is 132 km^ (Kuenzler et al. 1977). Chicod Creek is a U.S. Geological Survey gauged stream, which is equipped with a continuous stage recorder, a continuous conductance and temperature recorder, and an automatic sediment sampler. Base flow is the primary source of stream water during dry conditions (Simmons and Aldridge 1980). The Chicod Creek watershed is sparsely populated and 50% of the region is forested by mixed pine-hardwood commu- nities. Approximately 43% of the watershed is used for cropland and pastures, and the remaining 5% of land use is occupied by residential areas, roadways, and waterways. A reconnaissance of the watershed, conducted in 1978, revealed that poultry and swine farms are the most prevalent animal husbandry activities in the watershed. Sources of stream pollution are from several large poultry farms (each with approximately 80,000 chickens) which are located near the stream, and from direct outlets to the stream from holding ponds adjacent to animal shelters. Buffer zones of forest separate the stream* and farmland in most parts of the watershed. In addition to the above information, Simmons and Aldridge (1980) provide a geologic overview of Chicod Creek. The sampling site at Chicod Creek provided an oppor- tunity to study a stream in transition from a semi-natural system to one undergoing channelization. Local farmers 30 requested help from the U.S, Department of Agriculture in 1963 to solve flooding and drainage problems (Coffey 1982). Channelization of Chicod Creek was proposed by the Soil Conservation Service (SCS) to provide better drainage and thereby reduce flooding of cropland, and roads, in the watershed. Phase I of the project began in November 1978, and consisted of obstruction removal (clearing and snagging) in the downstream reaches of Chicod Creek (Coffey, 1982). This phase of the project was completed in January 1979. Because my sampling site was located upstream from the obstruction removal project, the disturbance probably did not affect the water quality of my samples. From February 1979 through June 1979 all drainage improvement efforts ceased in an attempt to avoid interference with fish spawning patterns (A. Coffey, personal communication). Phase II of the channelization project began in July 1979, and involved channel excavation using draglines and hydraulic hoes (A. Coffey, personal communication, 1984). This phase of the project was conducted approximately 4 km upstream from my sampling site. Therefore, this disturbance in the v/atershed and stream channel potentially could affect the water quality characteristics of the stream water at my collection site from July through August 1979. Grindle Creek (GR) is a mineral soil-draining stream which was channelized in 1966. The watershed area is 183 km2. The sampling site is on U.S. Highway 264, near the 31 small town of Pactolus. Grindle Creek flows southward into the Tar River. Base flow results in a continuous discharge throughout the year (Kuenzler et al. 1977). High banks, a clean, sandy bottom, and relatively fast flowing waters distinguish Grindle Creek from natural Coastal Plain- draining streams. Since channelization nearly 20 years ago, woody vege- tation has become re-established along the stream banks. Approximately 59% of the watershed is wooded, while the remaining 41% is cleared (Kuenzler et al. 1977). Agricul- ture and animal husbandry activities are prevalent in the watershed. The town of Bethel, located in the headwaters of Grindle Creek, is a point source of sewage effluent. Alluvial river and swamp Tar River, a Piedmont-draining alluvial river, is the only stream in this study that does not originate in the Coastal Plain. The inorganic chemical composition of alluvial rivers is affected by weathering and leaching of parent rocks and soil in the Piedmont (Wharton et al. 1982). Alluvial rivers typically have periods of sustained high flow, following heavy precipitation, which results from the cumulative effect of contributing tributaries (Wharton et al. 1982). In the low elevation of the Coastal Plain, alluvial rivers tend to form large floodplains which are seasonally inundated (Wharton et al. 1982). A prolonged 32 hydroperiod occurs during the winter, which results more from reduced évapotranspiration rates than higher precipita- tion (Wharton and Brinson 1979, Brinson et al, 1981a). Tar River is affected by Geochemical Zones I and II described by Simmons and Heath (1979). Zone I, at the headwaters of Tar River, is underlain by a large, complex series of granite rocks and a smaller area of rocks in the diorite group. Zone II is underlain by metamorphosed volcanic and sedimentary rocks and by a combination of cemented conglomerates, sandstones, siltstones, and shales. This zone is characterized by relatively im.permeable clayey surface soil which restricts percolation of rainfall through the soil, thereby inhibiting aquifer recharge. The presence of clayey soils results in a large amount of overland runoff, and the easily eroded soils contribute to the high concentrations of suspended sediments in the Tar River. The area of the Tar River watershed above the sampling site on SSR 1565 is 7097 km^. Samples were collected in the middle of the channel which was accessible from a catwalk extending from the main bridge crossing the river. Chicod Creek and Grindle Creek are tributaries of the Tar River that join it less than 2 km upstream from the samipling site. Tar River flows eastward into the Pamlico River estuary, which is located approximately 15 km downstream from my sampling site. Tar Swamp is an alluvial, tupelo-cypress swamp forest that is part of the Tar River floodplain. It was sampled 33 when standing water was present in order to gain information on possible consequences of floodplain-stream exchanges on water chemistry. The sampling site in Tar Swam.p is located 150 m from the north bank of Tar River where the river was sampled. The dominant canopy trees of Tar Swamp are Nyssa aquatica. Scattered Taxodium distichum occur throughout the upper canopy and Fraxinus caroliniana dominates the under- story. Trees are relatively uniform in size as a result of clearcutting approximately 30 years ago. This area has been described in more detail by Brinson (1977). Tar Swamp has an aquic moisture regime; however, water levels in the swamp vary seasonally. During the winter and spring, water levels above the sediment surface may reach as high as 1.3 m when Tar River rises above its natural levee during flood stages, causing water to flow onto the flood- plain. During summer and early fall, water levels m.ay drop to 10 cm or more below ground surface (Brinson et al. 1981a). During this annual drydown phase, a few centimeters of standing water may occur in the swamp for short periods following heavy, local rainfall, but it is usually removed within a few days as a result of high évapotranspiration rates. Sources of Tar Swamp water include: (1) precipitation, (2) overbank flooding from the Tar River, (3) groundwater seepage, and (4) surface runoff from terrestrial ecosystems. Overbank flooding of the Tar River results in sustained hydroperiods in Tar Swamp during winter and spring when 34 évapotranspiration rates are low. Below the leaf litter layer, the principal components of the surface sediments in Tar Swamp are silts and clays v/hich have settled out from the floodwaters of Tar River. Because of the low elevation, wind tides in the Pamlico River may also affect inundation and floodplain dynam.ics. METHODS Field Measurements, Collections, and Sample Preparations Eleven streams were chosen to represent the diversity of stream water quality in the North Carolina Coastal Plain. The collection of field data and water samples for chemical analyses was designed to elucidate differences and simi- larities in water chemistry among streams and to determ.ine if seasonal patterns exist. One site was chosen for each stream for biweekly collections of water samples. Data were collected for 1 year (September 1978 through August 1979). All of the sampling sites were located near bridges for accessibility. Sampling site, date, time, weather con- ditions, sample bottle numbers, field measurements, and notes concerning stream and watershed conditions were recorded. Field measurements included water temperature, water level (stage height), and flow velocity. Originally, pH measurements were to be taken in the field; however, due to the questionable accuracy of the field pH meter, laboratory pH readings were made instead, promptly after returning from the field. Water temperatures were determined by submerging a thermometer into a water sample. Water levels (stage heights) were measured by direct reading of U.S.Geological Survey staff gauges where present. Water levels for the 36 ungauged streams were determined by measuring the vertical distance, from a reference point on the bridge, to the water surface, using a field meter tape with a metal v/eight at- tached to the end. On each collection date, instantaneous discharge for the gauged streams was estimated by applying stage height data to U.S. Geological Survey rating curves. Tar River was gauged at Tarboro, which is upstream from the sampling site chosen for this study. The average daily discharge for Tar River on the sample dates had to be corrected for the additional watershed area involved. This was accomplished by dividing the total drainage area of Tar River above Grimesland (7,097 km^) by the drainage area above Tarboro (5,540 km2) to produce a ratio (1.28). This value can be used to calculate Tar River discharge at Grimesland by multiplying it by the discharge at Tarboro (Barry Adam.s, personal communication, 1979). This method assumées that the area between the sites v/ill yield the same amount of water as the area above Tarboro. Instantaneous discharge for the ungauged streams was calculated from the stream cross-sectional area and flow velocity measurements made during each sampling interval. A stream profile was constructed for each ungauged streami by measuring the depth, at set intervals, across the width of the stream and by measuring the stage height to determine the cross-sectional area. Stream velocity was measured by using a stopwatch to time the passage of dye (sodium fluorescein) across a standardized distance (5 m or the width of the bridge) in relatively uniform reaches, either upstream, downstream, or underneath the bridge. Stream velocity measuremcents were duplicated in the center, and the right and left sides of the stream. These velocities were averaged and then used to calculate the discharge rate. The difference in stage height, multiplied by the stream width, was appropriately added to, or subtracted from, the original cross-sectional area. Discharge (Q) was then calculated by the formula: Q = A X V where Q is the instantaneous discharge on a given sampling date (m^/s) , A is the total cross-sectional area (m.^) , and V is the mean velocity of streamwater (m/s). Discharge rates were used to calculate the weighted mean concentrations of organic and inorganic nutrients, as well as other aqueous parameters. Samples were collected for dissolved oxygen analyses with a van Dorn sampler and transferred to 300 ml BOD bottles. These samples were fixed in the field, returned to the lab, and analyzed by the azide modification of the Winkler method (Golterman and Clymo 1969) within 24 h. In the field, duplicate samples were collected in the van Dorn sampler and stored in 300 ml BOD bottles to determine biochemical oxygen dem.and (BOD^). Samples were aerated to saturation level using the laboratory air terminals. The oxygen concentration was measured with a YSI Model 51B 38 dissolved oxygen meter with a YSI Model 5720 bottle probe prior to incubation. The BOD bottles were capped and placed in a Fisher Model 300 low temperature incubator at 20°C for 5 days (APHA 1975). After the incubation period, the oxygen concentration was measured to determine oxygen uptake by microbial activity within the 5-day period. Water samples for laboratory analyses were collected in 4-liter polyethylene bottles that were prepared for use by acid-washing in a 50% HCl solution and then thoroughly rinsing them in distilled water. In the field, each sample bottle V7as rinsed with stream water prior to collecting the sample. Samples were immediately placed in an ice-packed cooler for transport back to the lab that day. The samples were transferred from the ice chest to a refrigerator set at 4-5°C upon returning to the lab. The water samples were prepared for chemical analyses within 12-48 h of collection time (Figure 2). All polyethy- lene bottles used for storage of subsamples were acid-washed in 50% HCl solution and then thoroughly rinsed with dis- tilled water. Bottles for use in cation analyses were soaked in a 2% HNO^ wash for 24 h, followed by a thorough rinsing with deionized water (APHA 1975). Samples v/ere stored in labeled bottles to await chem.i- cal analyses. Each sample v/as shaken before pouring, to insure homogeneity. For filtering water samples, Gelman magnetic filter funnels were used and rinsed thoroughly with distilled water after each use. Gelman glass fiber filters 39 Field sample (4 liters) Total alkalinity and pH (100 ml) Conductivity (250 ml) FILTERED UNFILTERED K jeldahl- Nitrogen and Total phosphorus Total organic nitrogen phosphorus I carbon I 1. NH -N (250 ml) (500 ml) 2. NO^-N refrigerate (50 ml) freeze 3. NO^-N acidify with I 2 drops HCl- Particulate 4. FPP refrigerate organic 5. FTP nitrogen I (250 ml) (filters) refrigerate freeze Dissolved Cations organic carbon 1. Ca I 2. Mg (50 ml) 3 . K acidify with 4. Na 2 drops HCl- 5 . Fe re frigerate 1 (50 ml) Acidify to 1% HNO- and 2.5% HCl (v/v)^- freeze Figure 2. Preparation of field samples for chemical analyses. 40 (type A/E, 47 nun, nominal pore size 0.3 urn) were used for particulate organic nitrogen analyses. They were prepared for use by placing the filter on the funnel and rinsing with 5 ml of 5% HCl, followed by addition of 150 ml deionized water to the filtering apparatus (to thoroughly rinse the filter). After the filters were prepared by this procedure, 500 ml of the sample were filtered. The filter was removed with forceps, placed in a plastic container, and frozen until analysis. Total alkalinity and pH were measured with a Corning Model 101 Digital Electrometer equipped with pH and refer- ence electrodes (APHA 1971) . Conductivity v/as measured by a Beckman RC-16C Conductivity Bridge, with a 0.1 constant cell, at 25°C. These measurements were made within 4-18 h after returning to the lab. Two rain gauge stations were constructed to collect and measure bulk precipitation over the study year. One rain gauge station v/as located in Tar Swam.p and the other one in the Croatan National Forest. Both gauges were placed in clearings where no tree canopy interfered with rainfall R R collection. A Taylor Clear-Vu rain gauge, with a Tenite butyrate calibrated cylinder for measuring rainfall volum.e, was attached to a post. A large plastic trash can was hung on the opposite side of the post to collect a rainfall sample for chemical analyses. The trash can was lined with a polyethylene bag, with several drops of saturated HgCl^ solution added to inhibit microbial growth. The lid of the 41 trash can was placed upside down and secured by handles to the can. To collect rainfall, a hole was cut through the center of the lid and stuffed with Pyrex wool (which was acid-washed in 50% HCl solution then rinsed with deionized water) which served as a filter to prevent leaf litter and other debris from entering the rainfall sample. Bulk precipitation was collected and rainfall volume was measured at biweekly intervals which corresponded with the stream sampling schedule. The rainfall sample was transferred from the collection bag to a clean sample bottle. The collection bag and glass wool were replaced each sampling time. Rainfall samples were treated in the same manner as the stream samples (i.e., packed in ice for transport back to the lab) and selected chemical analyses followed the same procedures as used for the stream waters. Chemical Analyses Chemical analyses were performed in the Central En- vironmental Laboratory of the Department of Biology at East Carolina University. The nutrient analyses consisted of nitrate-nitrogen, ammonium-nitrogen, nitrite-nitrogen, dissolved Kjeldahl-nitrogen, dissolved organic nitrogen, particulate organic nitrogen, total phosphorus, filterable total phosphorus, filterable reactive phosphorus, particu- late phosphorus, total organic carbon, dissolved organic carbon and particulate organic carbon. The cation analyses 42 consisted of calcium, magnesium, sodium, potassium, and iron. Dissolved organic nitrogen concentrations were calculated by subtracting ammonium from dissolved Kjel- dahl-N. Particulate phosphorus levels were calculated by subtracting filterable total phosphorus from total phosphor- us. Total (TOC) and dissolved organic carbon (DOC) analyses v/ere performed by combustion and infra-red analyses using a Beckman Model 915 Total Organic Carbon Analyzer (Beckman Instruments, Inc. 1977). Due to the inaccuracy associated with derivation of particulate organic carbon (POC) by subtraction of DOC from TOC, POC values were determined on a group of samples (collected in November 1979) by dichromate oxidation. For this collection, analysis of POC from 1-liter samples, from representative streams, was used to determine POC concentrations for other collection dates by extrapolation from PON-POC relationships (Banse 1974). Strickland and Parsons (1979) served as a reference for reagent and filter preparations and for glassware cleaning procedures. Sample treatment followed the method outlined by Wetzel and Likens (1979). POC was determined by "wet ashing" particulate matter filtered onto a glass filter with a mixture of potassium dichromate and concentrated sulfuric acid, and measuring spectrophotometrically the decrease in the extinction of the yellow dichromate solution after it had been reduced by organic m.atter. The empirical relation- ship between POC and PON from replicate subsamples, for all 43 stations except Tar River, was described by the equation POC = 12.117 PON - 0.075 (r=0.82). POC concentrations from Tar River were estimated independently because phytoplankton may have contributed significant amounts of particulate matter to the POC pool, since the Tar River channel is wider and more illuminated than the other streams. The empirical POC/PON ratio of the TR sample was 7.2. Ammonium was measured by the indophenol spectrophoto- metric method (Scheiner 1976) with a Bausch and Lomb Spec- tronic 88 Spectrophotometer. Dissolved Kjeldahl-nitrogen and particulate organic nitrogen were determined by mercuric sulfate digestion-distillation (APHA 1971) using a Labconco 12 unit digestion-distillation apparatus followed by indo- phenol spectrophotometric analysis, using a Turner Model 350 spectrophotometer. Nitrate-nitrogen determination was m.ade by ultraviolet light absorption (Brown and Bellinger 1977) using a Coleman-Hitachi Model 124 Spectrophotometer. Nitrite-nitrogen was measured by a diazotization spectropho- tom.etric method (EPA 1976) using a Bausch and Lomb Spec- tronic 88 Spectrophotometer. This instrument was also used for molybdate spectrophotometer analysis of phosphorus (EPA 1976). Total phosphorus and total dissolved phosphorus received persulfate digestion prior to analysis. Unfiltered samples for cation analyses were acidified to 1% HNO^ and 2.5% HCl (to facilitate solution of cations and serve as a preservative) and then frozen until time of analysis. Samples were autoclaved before determining cation 44 concentrations by atomic absorption spectrophotometry (Perkin-Elmer Corporation 1976) , using a Perkin-Elmer Model 305B Atomic Absorption Spectrophotometer. Data Processing and Analysis Annual weighted mean concentrations for organic and inorganic nutrients were calculated for all stations where discharge measurements were available. For a given year and sampling station, the annual weighted mean concentration of a given species was weighted on the basis of discharge in the following manner: Wt. Cone. = Y, [Cone. (Date X) x Discharge (Date X) ] E Discharge where Wt. Cone, represents the weighted concentration of the constituent during the sampling period. Cone. (Date X) is the measured concentration of the constituent on a given sampling date (Date X), Discharge (Date X) is the instanta- neous discharge on a given sampling date (Date X), and E Discharge is the sum of all the discharge values on all sampling dates for the given year and station. Annual inputs of chemicals in rainfall were calculated using weighted mean average of precipitation. Annual rainfall volumes for 1978 and 1979 were obtained from. NOAA (1978, 1979) and were averages of values measured at Greenville and Viashington, North Carolina, for sampling stations close to these cities, and averages at New Bern and Maysville, North Carolina, for sampling stations near these cities. Annual 45 volume of precipitation per square kilometer was multiplied by concentrations to obtain the annual area based inputs of chemicals delivered by bulk precipitation. Linear correlations (r) between all of the physical and chemical factors, measured at each station between 7 Septem- ber 1978 and 22 August 1979 were calculated by means of a SAS program using the CORR procedure (Barr and Goodnight 1972). This produces product-moment correlation coeffi- cients which were used to elucidate interrelationships among stream constituents representing random, bivariate normal distributions. Computation of correlation coefficients by the CORR procedure of a SAS program produces the product- moment correlation coefficient, its significance probabil- ity, and the number of observations contributing to the correlation coefficient (Barr and Goodnight 1972). Corre- lation coefficients are reported in this paper only if the significance probability is less than or equal to 0.002 (Kuenzler et al. 1977). Discharge measurements were not taken frequently enough to accurately estimate annual runoff. Therefore, runoff at each of the sampling sites was determined from U.S. Geolo- gical Survey (1979, 1980) for the gauged streams, estimated from U.S.Geological Survey gauging stations in proximal streams, or extrapolated from monthly relationships between precipitation and runoff. Creeping Swamp and Chicod Creek had gauging stations at the sampling site. Because the watershed of Palmetto Swamp is adjacent to that of Creeping 46 Swamp, equivalent runoff was assumed. However, because I used the Kuenzler et al. (1977) estimate of watershed size of 80 km^ rather than the 70 km^ assumed by U.S. Geological Survey, the annual runoff from U.S. Geological Survey was multiplied by a factor of 0.875 (70/80). Winner and Simjnons (1977) reported that annual runoff is not altered by chan- nelization--therefore, runoff for Grindle Creek (chan- nelized) and Chicod Creek (natural) was assumed to be equal since they were in relatively close proximity to each other. Runoff for peat-draining streams was estimated on a monthly basis as a percentage of precipitation that occurred at weather stations closest to the study sites. The per- centages were calculated from precipitation-runoff relation- ships derived from the average of Greenville and Washington, North Carolina precipitation data (NOAA 1978, 1979) and from U.S. Geological Survey mean runoff values for Creeping Swamp and two tributaries of Chicod Creek. These monthly runoff percentages of precipitation were applied to the monthly precipitation averaged for New Bern and Maysville, North Carolina to calculate runoff for peat-draining streams. Annual export of selected chemical constituents of streamwater was calculated by the formula; E = R X W where: E is the annual export of a specific chemical parameter (g/m^’yr), R is the annual runoff rate for the watershed (m/yr), and W (g/m^) is the discharge weighted mean of the specified chemical parameter. RESULTS The figures in this section are histograms that show both the annual arithmetic mean and the weighted mean of water chemistry analyses for the study year (Figures 3-11). Comparison of arithmetic and weighted means is used as an interpretive tool in this section to elucidate the relation- ship between elemental concentrations and flow regime. For example, when the weighted mean exceeds the arithmetic mean, this is interpreted to suggest higher concentrations during high flows. The limitations of this approach must be realized, especially when the differences between the two means is small. When differences are small, a relationship between elemental concentration and flow pattern may or may not actually exist. Correlation coefficients are used to further determine the reliability of this relationship. However, many other factors beside flow may be involved in concentration regulation. Unless otherwise indicated, arithmetic means will be used for comparing stream categories. The arithmetic m.ean is preferred because it represents the average of the actual biweekly m.easurements at the sampling site and because its standard error can be used as an index of variation. The weighted mean is used later to estimate exports from, the watershed. Concentrations are referred to as "intermediate" when they tend to fall between the highest and lowest group of concentrations on the figures. 48 Stream abbreviations used in this section are listed in Table 1. The streams are arranged vertically on the histo- gram following the categories outlined in Table 1. Peat- draining streams appear first, following by mineral soil- draining streams, and lastly the Piedmont-draining alluvial river and swamp. Dissolved Oxygen and Biochemical Oxygen Demand Mean dissolved oxygen (0^) levels for the streams were very similar, with no distinguishing pattern evident betv/een peat-draining streams and mineral soil-draining streams (Figure 3a, Appendix Table 2). Peat-draining CL, WB, and EB had low 0^ concentrations ranging between 5.6 and 6.7 mg/1. MI and BL, in the peat-draining category, had intermediate 0^ concentrations of 7.1 and 7.3 mg/1, respectively. Mineral soil-draining CS, PA, and CH had low 0^ concen- trations between 5.6 and 6.3 mg/1. However, mineral soil- draining IS and GR (channelized) exhibited the highest concentrations of any of the Coastal Plain-draining streams studied, with 8.4 and 9.0 mg/1, respectively. Piedmont- draining TR also had a high concentration of 8.5 mg/1 which sharply contrasted with the extremely low 0^ level observed in TS (3.5 mg/1). TS had a lower average annual 0^ content than any of the streams examined. Weighted mean 0^ levels were generally higher than the arithmetic means for most of the streams sampled (Figure 3a, O2 (mg/liter) BOD5 (mg/liter) o 2 4 6 8 10 Figure 3. Annual arithmetic means (shaded) and weighted means (solid) for (a) dissolved oxygen (0„) and (b) biochemical oxygen demand (BODj.) from September 1978 through August 1979. 50 Appendix Table 2). This would suggest that 0^ concen- trations in natural Coastal Plain-draining streams tend to be highest during high flows. However, positive corre- lations between discharge (Q) and 0^ concentrations were not significant in any of the streams. Channelized GR had a higher arithmetic mean than weighted mean and a negative correlation between Q and O2 concentrations. The 0^ content of streamwater is negatively correlated with temperature in most of the Coastal Plain-draining streams examined in this study (Appendix Tables 5-12). However, temperature has only an indirect influence on the oxygen content of streamwater. Reid and Wood (1976) identi- fy other factors contributing to the status of stream- water as: (1) the amount of physical aeration created by turbulent flow, (2) the photosynthesis-respiration balance of the stream biotic community, and (3) oxygen-consuming chemical reactions within the stream. Peat-draining EB, WB, BL, and MI exhibited the lowest biochemical oxygen demand (BOD^) along with mineral soil- draining IS (Figure 3b, Appendix Table 2). The BOD^ in these streams ranged between 0.60 and 1.1 mg/1. CL, the pocosin drainage canal, had a high to intermediate average BOD^ of 1.8 mg/1. Two of the mineral soil-draining streams, GR (channelized) and PA, also had intermediately ranged body's of 1.4 and 1.7 mg/1, respectively. Highest BOD^ levels were observed in mineral soil-draining CS (2.3 mg/1) and CH (2.3 mg/1). These concentrations were exceeded by 51 the BOD^ for TS, which was 4.1 mg/1. The TS level was almost three times greater than the intermediate BOD^ recorded for Piedmont-draining TR (1.6 mg/1). Arithmetic mean BOD^ levels exceeded the weighted means in peat-draining EB and VTB, in Piedmont-draining TR, and in most of the mineral soil-draining streams, with IS and GR the exceptions (Figure 3b, Appendix Table 2). However, none of the streams had significant correlations between dis- charge and BOD^ which indicates that other factors m.ay control BOD^ levels. positively correlated with POC in CS (r = +0.85), PA (r = +0.65), and CH (r = +0.64) (Appendix Tables 10, 11, and 12). pH, Total Alkalinity, and Conductivity A clear difference existed between pH levels of the peat-draining and the mineral soil-draining streams; how- ever, two of the streams categorized as peat-draining (MI and BL) did not have the characteristic low pH of the other streams in the peat-draining category (Figure 4a, Appendix Table 2). This deviation is attributed to the influence of Tertiary limestone in their drainage basins. The solution of limestone deposits is responsible for the high pH levels exhibited in mineral soil-draining IS (7.3), as well as in peat-draining MI (6.8) and BL (5.9). Peat-draining EB, WB, and CL exhibited low mean pH's ranging from 3.7 to 4.5. Mineral soil-draining CS, PA, CH, and GR had interm.ediate pH TA (meq/liter) gure 4 Annual arithmetic means (shaded) and weighted means (solid) for (a) pH and (b) total alkalinity (TA) from September 1978 through August 1979. 53 mean pH levels between 5.8 and 6.5. Intermediate mean pH levels were also observed in Piedmont-draining TR (6.6) and TS (6.3). Although the arithmetic and weighted means for pH were similar in most cases, the arithmetic means surpassed weighted means (Figure 4a, Appendix Table 2). This trend indicates that pH levels are highest during low flows. However, a negative correlation between pH and discharge was found only in IS (r = -0.62, Appendix Table 9). The mean pH of precipitation over the study year was 4.1 for the Croatan rain gauge, and 4.8 for the Tar Sv/amp rain gauge station (Table 2). These data suggest that rainfall contributes to the acidity of Coastal Plain- draining streams. Peat-draining EB, WB, and CL exhibited the lowest total alkalinity (TA) of all the streams sampled (Figure 4b, Appendix Table 2). Mean TA for these streams were practi- cally nil, with only 0.01 meq/1 recorded for CL, 0.02 meq/1 for EB, and 0.04 meq/1 for WB. The other streams in the peat-draining category (MI and BL) did not have the same trend as the other peat-draining streams due the influence of Tertiary limestone within their watersheds. Mineral soil-draining IS had the highest TA of 1.7 meq/1, followed by peat-draining MI with 0.88 meq/1, and BL with 0.58 m.eq/1. The high buffering capacity of these streams results from solution of limestone deposits in their drainage basins. Mineral soil-draining CS, PA, CH, and GR displayed 54 Table 2. Annual arithmetic means (A), with standard errors, and annual weighted mean (W) of concentrations of rainfall constituents in the Croatan (RGC) and Tar Swamp (RGT) rain gauge collections. Measurements are expressed in mg/1 for all constituents, except pH and total alkalinity (which is in meq/1). Constituent Mean RGC RGT pH A 4.08±0.17 4.8210.26 W 3.60 3.90 TA A 0.01±0.004 0.0410.02 W 0.004 0.02 Ca A 1.26+0.26 0.8010.23 W 0.95 0.58 Mg A 0.30±0.07 0.2010.04 W 0.21 0.15 Na A 2.21±0.45 1.2010.28 W 1.68 0.90 K A 0.52±0.12 0.4710.09 W 0.37 0.40 NO.-N A 0.72+0.16 0.4210.08 W 0.56 0.58 NH, -N A 0.15±0.02 0.1010.024 W 0.13 0.10 TON A 0.23±0.04 0.3310.05 W 0.19 0.28 TP A 0.04±0.01 0.0610.02 W 0.03 0.05 TOC A 4.7510.75 4.03 10.51 W 4.03 3.70 55 intermediate mean TA ranging between 0.24 and 0.39 meq/1. Piedmont-draining TR also had an intermediate mean TA of 0.36 meq/1, which was lower than the TA observed for TS (0.45 meq/1). Total alkalinity was highest at low flow periods for all of the streams sampled (Figure 4b, Appendix Table 2). * In most cases the arithmetic mean was more than double the weighted mean. The relationship between high TA and low flow periods can be attributed to the mineral contributions of base flow, v/hich becomes the primary source of stream- water during dry conditions. A hydrologic shift to surface runoff as the main source of streamwater, during winter and spring, resulted in base flow dilution since rainfall typically contains low concentrations of dissolved minerals (Kuenzler et al. 1977). The result of this shift would be an inverse relationship between TA and discharge rates. However, negative correlations between TA and discharge were significant only for IS (r = -0.67) and TR (r = -O.^p.) (Appendix Tables 9 and 14, respectively). Total alkalinity was low in the rainfall samples. Precipitation from the Croatan rain gauge station had a mean TA of 0.01 meq/1, and the Tar Swamp rain gauge sample had a mean TA of 0.04 meq/1 (Table 2). The peat-draining streams, geographically removed from the influence of limestone, had lower conductivities than the mineral soil-draining streams (Figure 5a, Appendix Table 2). Peat-draining EB and WB had the lowest conductivities. COND (jjmho/cm) Ca (mg/liter) Figure 5 Annual arithmetic means (shaded) and weighted means (solid) for (a) conductivity (COND) and (b) calcium (Ca) from September 1978 through August Ul 1979. 57 with 51 and 47 umho/cm, respectively. Peat-draining CL (83 umho/cm) and BL (86 umho/cm) ranked in the intermediate range of mean conductivity measurements. MI, of the peat- draining category, had a high mean conductivity of 131 umho/cm, which reflects the influence of limestone deposits on streamwater chemistry. This high value for MI is more than twice the mean conductivities recorded for EB and WB. Conductivity levels for the mineral soil-draining streams showed a large degree of variation among streams. CS had the lowest conductivity of the mineral soil-draining streams, with 69 umho/cm. PA had an intermediate ranged conductivity of 88 umho/cm. The mineral soil-draining streams, IS, CH, and GR, had high conductivities between 116 and 188 umho/cm. The highest conductivity for all of the streams sampled was observed in IS (188 umho/cm) and result- ed from solution of limestone formations along the stream channel. Piedmont-draining TR had an intermediate average conductivity of 90 umho/cm. TS, however, exhibited a much higher mean conductivity than TR, with 164 umho/cm. Conductivity was generally lower at high flow periods in most of the streams investigated, since the arithmetic mean consistently exceeded the weighted mean (Figure 5a, Appendix Table 2). Exceptions to this trend were observed in peat-draining EB and WB, and also in mineral soil- draining CS. Conductivity was positively correlated with major cations in most of the m.ineral soil-draining streams (Appendix Tables 9-13). 58 Cations Lov/ mean calcium (Ca) concentrations were observed in the peat-draining streams EB, WB and CL with levels between 1.0 and 2.1 mg/1 (Figure 5b, Appendix Table 3). The highest Ca concentrations over the study year were observed in mineral soil-draining IS, which dissects a Tertiary lime- stone deposit. The water chemistry of MI and BL were also affected by this deposit, giving them much higher Ca concen- trations than the other streams in the peat-draining catego- ry. Island Creek had a weighted mean Ca concentration of 17 mg/1 and an arithmetic mean of 43 mg/1. The strong negative correlation (r=-0.79) between Ca concentrations and discharge illustrates this relationship. Peat-draining MI had a weighted mean similar to IS with 17 mg/1, but exhibit- ed a lower arithmetic mean value of 26 mg/1. Peat-draining BL had a weighted mean Ca content of 7.5 mg/1, making it intermediate in Ca concentrations. However, the higher arithmetic mean value of 15 mg/1 reflects the small influ- ence of the limestone deposit on BL water chemistry. Base flow probably accounts for the main influx of Ca into BL. Mineral soil-draining CS, PA, CH, and GR displayed interme- diate mean Ca levels ranging between 6.3 and 12 mg/1. Piedmont-draining TR and TS are also within the intermediate range of Ca concentrations, with 6.6 and 11 mg/1, respec- tively. 59 Arithmetic mean Ca concentrations exceeded the weighted mean for all the streams sampled, with two exceptions (V7B and CS) (Figure 5b, Appendix Table 2). Generally, Ca concentrations are highest at low discharge, except in WB and CS where discharge rates did not appear to affect Ca levels, since the means were equal. The dominance of Ca among cations and its high correlation with conductivity suggests that Ca is an important contributor to conductivity levels in Coastal Plain streams. The Ca concentrations measured in the bulk precipita- tion samples were lower than in any of the streams sampled, except for CL. The mean Ca content for both the Croatan rain gauge and Tar Swamp rain gauge samples was less than 1.3 mg/1 (Table 2). The lowest mean magnesium (Mg) levels were found in peat-draining EB (0.69 mg/1) and WB (0.47 mg/1) (Figure 6a, Appendix Table 2). Peat-draining CL, BL, and MI, and mineral soil-draining IS and CS, displayed intermediate mean Mg concentrations between 1.0 and 1.6 mg/1. The highest Mg levels were observed in mineral soil-draining PA, CH, and GR, with means between 1.9 and 2.6 mg/1. Piedmont-draining TR is also ranked in the high mean category, with a Mg concentration of 2.1 mg/1. TS had the highest overall Mg level over the study year with a mean of 4.7 mg/1. This value is double the concentration determined for TR and is almost seven times greater than the average annual Mg Mg (mg/liter) No (mg/liter) Figure 6. Annual arithmetic means (shaded) and weighted means (solid) for (a) magnesium (Mg) and (b) sodium (Na) from September 1978 through August 1979. o 61 concentrations recorded for EB and WB of the peat-draining streams. In most of the stream.s, the arithmetic means for Mg surpassed the weighted means (Figure 6a, Appendix Table 2), indicating that Mg levels generally were highest at low discharge. Negative correlations between Mg and discharge were found in MI (r = -0.71), IS (r = -0.82) and GR (r = -0.74) (Appendix Tables 7, 9, and 13). Exceptions to this trend were found in EB [in which Mg levels were positively correlated with discharge with r = +0.71 (Appendix Table 4)] and WB (where the means were equal and no significant correlations existed, disclosing that flow patterns do not significantly affect Mg concentrations). The Mg content of the precipitation samples was lower than the average amount found in any of the Coastal Plain- draining streams. The rainfall sample at Tar Swamp (0.20 mg/1) had a lower annual mean Mg concentration than the Croatan rain sample (0.30 mg/1) (Table 2). Peat-draining EB, WB, and CL had the lowest mean sodium (Na) concentrations, ranging from 2.8 to 3.3 mg/1 (Figure 6b, Appendix Table 2). BL (4.0 mg/1) and MI (5.0 mg/1) had higher Na levels than reported for the other peat-draining streams. Sodium concentrations were between 4.0 and 4.9 mg/1 in mineral soil-draining IS, CS, and PA, giving them an intermediate ranJcing. The highest mean Na levels were found in mineral soil-draining CH (6.9 mg/1) and channelized GP. (7.5 mg/1). Piedmont-draining TR also had a high mean Na 62 concentration of 7.4 mg/1. TS exhibited the highest overall Na level (20 mg/1); however, the standard error of the m.ean was also high (3.8) indicating a large amount of variation in Na concentrations. The annual mean Na concentration in TS was three times higher than the amount recorded for TR. Weighted mean Na levels were higher than arithmetic means in peat-draining EB and WB, and in mineral soil- draining CS (Figure 6b, Appendix Table 2). This trend suggests that Na concentrations are highest during high discharge. BL and MI, in the peat-draining category, along with the remaining mineral soil-draining streams (IS, PA, CH, and GR) and Piedmont-draining TR, exhibited higher arithmetic means than weighted means indicating that Na levels are highest during low flow stages in most Coastal Plain streams. Rainfall samples were lower in Na than streamwater concentrations. There was a fairly large difference in the Na levels between rain gauge stations (Table 2). The Tar Swamp rainfall sample had a mean Na concentration of 1.2 mg/1 whereas the Croatan rainfall had a mean of 2.2 mg/1. Comparison of potassium (K) concentrations between peat-draining and mineral soil-draining streams reveals that peat-draining streams generally exhibit lower annual K levels (Figure 7a, Appendix Table 2). The lowest K concen- trations are found in peat-draining EB (0.35 mg/1) and V7B (0.27 mg/1). Peat-draining MI, BL, and CL have intermediate mean K, levels from 0.63 to 1.2 mg/1. Mineral soil-draining K (mg/liter) Fe (mg/liter) Figure 7. Annual arithmetic means (shaded) and weighted means (solid) for (a) potassium (K) and (b) iron (Fe) from September 1978 through August 1979. 64 IS, CS, and PA displayed intermediate ranged K concen- trations. IS has an annual mean K content of 0.94 mg/1, and CS and PA have mean K levels of 2.5 mg/1 and 2.4 mg/1, respectively. The highest mean K concentrations were in mineral soil-draining CH (7.2 mg/1) and GR (3.8 mg/1). CH exhibited the highest annual mean K level of all of the streams studied, with a value that was 20 times greater than the average K concentrations reported for peat-draining EB and WB. Piedmont-draining TR exhibited an intermediate K content of 2.7 mg/1. This value was similar to the mean K level reported for TS, which was 2.9 mg/1. The arithmetic means for K exceeded the weighted means in all of the mineral soil-draining streams (except for CS) , in peat-draining BL and MI, and also in Piedmont-draining TR (Figure 7a, Appendix Table 2). This trend indicates that the highest K levels in these streams are associated with low flow stages. In mineral soil-draining CS, and peat- draining EB and WB, the weighted mean was greater than the arithmetic mean, suggesting that high K concentrations occur most frequently during high discharge; however, K and discharge were not significantly correlated in any of the streams examined. Mean annual K levels for the two rain gauge stations were generally lower than the concentrations reported for streamv/ater (except in peat-draining EB and VJB) . The Tar Swamp rainfall sample had a mean K concentration of 0.47 65 iîig/1 and the Croatan rainfall sample had a similar K level of 0.52 mg/1 (Table 2) . The lowest mean iron (Fe) concentrations occurred in the peat-draining EB, WB, BL, MI, and CL with values betv/een 0.41 and 1.2 mg/1 (Figure 7b, Appendix Table 2). IS, from the mineral soil-draining category, also had low Fe levels (0.55 mg/1). Mineral soil-draining PA, CH, and GR exhibited intermediate ranged Fe concentrations between 1.3 and 1.5 mg/1. The highest annual mean Fe level occurred in m.ineral soil-draining CS (3.08 mg/1). Piedmont-draining TR had an intermediate Fe concentration of 1.9 mg/1. TS exhibited a higher mean Fe level (10.0 mg/1) than reported for any of the streams. The m^ean Fe concentration in TS was five times higher than the average Fe content found in TR. The high arithmetic mean for Fe in the waters of TS is associated with a high standard error (2.16), which reflects a large degree of variation among collections. Weighted means and arithmetic means for Fe were similar in most cases, except in EB and CS, where the arithmetic means were significantly greater than the weighted means, and in TR, where the weighted mean also surpassed the arithmetic mean (Figure 7b, Appendix Table 2). In the streams where the arithmetic mean exceeded the weighted m.ean (EB, WB, BL, and CS), Fe levels were highest during low discharge. East Brice Creek exhibited a negative corre- lation (r = -0.59) between Fe and discharge (Appendix Table 4). Identical weighted means and arithmetic means in 66 mineral soil-draining IS and PA, suggest that Fe concen- trations were not affected by flow patterns. This is supported by the lack of significant correlations between Fe and discharge for these streams. The weighted means were higher than the arithmetic means in MI, CH, GR, and TR, indicating that high Fe levels correspond with high dis- charge rates. Nitrogen Inorganic forms The lowest nitrate-nitrogen (NO^-N) levels were found in peat-draining EB, WB, and BL, with mean concentrations between 0.09 and 0.12 mg/1 (Figure 8a, Appendix Table 1). MI and CL had higher NO^-N levels than the other peat- draining streams with intermediate means of 0.25 mg/1 reported for both of these streams. IS had the lowest average NO^-N concentration (0.08 mg/1) in any of the streams sampled. Mineral soil-draining CS and PA had intermediate NO^-N levels of 0.24 and 0.23 mg/1, respective- ly. The highest concentrations of NO^-N were found in mineral soil-draining CH (1.2 mg/1) and in channelized GR (1.5 mg/1). Piedmont-draining TR had an intermediate ranged NO^-N level of 0.59 mg/1. The average NO^-N concentration in TS (0.31 mg/1) was lower than the average annual amount reported for TR. NOj-N (mg/liter) NH^-N (mg/liter) NOj-N (mg/liter) Figure 8. Annual arithmetic means (shaded) and weighted means (solid) for nitrate- nitrogen (NO_-N), (b) ammonium-nitrogen (NH^-N), and (c) nitrite-nitrogen EWPPTOCDOCPOCCaMgNaK FepllTA OOB °C 0ż, HI), !?IWrJ NOj-N 4 N02-*^ DCN 0.77 0.76 0.66 0.92 0.93 0.79 0.77 0.76 0.72 0.62 0.76 -0.82 0.87 PtW 0.69 0.62 0.75 TP 0.77 0.92 0.81 0.81 0.83 0.81 0.90 0.84 0.63 -0.75 0.68 FTP 0.76 0.92 0.92 0.60 0.83 0.77 0.66 -0.67 FRP 0.65 0.81 0.92 0.68 0.72 0.62 PP 0.69 0.81 0.69 0.82 0.84 -0.65 TOC 0.92 0.62 0.83 0.80 0.68 0.98 0.62 0.84 0.84 0.87 0.85 0.68 0.82 -0.79 0.84 DOC 0.93 0.81 0.83 0.72 0.98 0.81 0.82 0.88 0.82 0.81 -0.77 0.84 POC 0.69 0.62 0.75 Ca 0.79 0.84 0.81 0.93 0.77 0.69 0.88 0.77 Mg 0.77 0.84 0.82 0.93 0.84 0.81 0.73 Na 0.76 0.87 0.88 0.77 0.84 0.75 0.86 0.75 K Fe 0.72 0.75 0.90 0.77 0.62 0.82 0.85 0.82 0.75 0.69 0.75 0.72 0.78 -0.68 0.68 pH TA 0.62 0.84 0.66 0.84 0.68 0.72 -0.73 OM) 0.76 0.63 0.82 0.81 0.86 0.88 0.81 0.86 0.78 -0.65 0.80 "C «2 -0.82 -0.75 -0.67 -0.65 -^.79 -0.77 -0.71 -0.68 -0.68 -0.73 -0.65 -0.80 BOD 0.87 0.68 0.84 0.84 0.71 0.77 0.73 0.71 0.68 0.80 -0.80 STifT CaJ