JOURNAL OF THE AMERICAN WATER RESOURCES ASSOCIATION Vol. 43, No. 1 AMERICAN WATER RESOURCES ASSOCIATION February 2007 ESTIMATING RELEVANCE OF ORGANIC CARBON, NITROGEN, AND PHOSPHORUS LOADS TO A BLACKWATER RIVER ESTUARY1 John Hendrickson, Nadine Trahan, Emily Gordon, and Ying Ouyang2 ABSTRACT: In blackwater river estuaries, a large portion of external carbon, nitrogen, and phosphorus load are combined in complex organic molecules of varying recalcitrance. Determining their lability is essential to establishing the relationship between anthropogenic loads and eutrophication. A method is proposed in which organic C, N, and P are partitioned into labile and refractory forms, based upon first-order decay estimated by biochemical oxygen demand relative to total organic carbon, and C:N and C:P ratios as a function of organic carbon lability. The technique was applied in developing total maximum daily loads for the lower St. Johns, a blackwater Atlantic coastal plain river estuary in Northeast Florida. Point source organic nutrients were determined to be largely labile. Urban runoff was found to have the highest relative labile organic N and P content, followed by agricultural runoff. Natural forest and silviculture runoff were high in refractory organic N and P. Upstream labile C, N, and P loads were controlled by autochthonous production, with 34-50% of summer total labile carbon imported as algal biomass. Differentiation of labile and refractory organic forms suggests that while anthropogenic nutrient enrichment has tripled the total nitrogen load, it has resulted in a 6.7-fold increase in total labile nitrogen load. (KEY TERMS: bioavailability; blackwater rivers; eutrophication; land use; nutrients; nitrogen and phosphorus loading; organic carbon; organic nutrients; source allocation; watershed development; TMDLs; water quality modeling.) Hendrickson, John, Nadine Trahan, Emily Gordon, and Ying Ouyang, 2007. Estimating Relevance of Organic Carbon, Nitrogen, and Phosphorus Loads to a Blackwater River Estuary. Journal of the American Water Resources Association (JAWRA) 43(1):264-279. DOI: 10.1111 ⁄ j.1752-1688.2007.00021.x INTRODUCTION Accelerated eutrophication arising from nutrient enrichment of estuaries represents one of the most significant water quality problems within near coastal waters world-wide (National Research Council, 2000). Diagnostic and management approaches often rely on linking the sources, magnitude and timing of the external nutrient load to the response of the receiving water body with dynamic water quality process models. In the evaluations of external nutrient loads to estuaries in temperate climates, organic nutrients have typically not been differentiated with regard to lability, and organic carbon is rarely, if ever included (Jaworski et al., 1992; Magnien et al., 1992; Valiela 1 Paper No. J05107 of the Journal of the American Water Resources Association (JAWRA). Received July 26, 2005; accepted March 23, 2006. ª 2007 American Water resources Association. 2 Respectively, (Hendrickson) Environmental Scientist V, St. Johns River Water Management District, P. O. Box 1429, Palatka, Florida 32178-1429; (Trahan) GIS Analyst, Jones, Edmunds & Assoc., Gainesville, Florida 32641, USA; and (Gordon, Ouyang) Environmental Scientist I and Environmental Scientist IV, BCI Engineers and Scientists, Lakeland, Florida 33807-5467 (E-Mail ⁄ Hendrickson: jhendrickson@ sjrwmd.com). JAWRA 264 JOURNAL OF THE AMERICAN WATER RESOURCES ASSOCIATION BLACKWATER ORGANIC CARBON et al., 1992; Boynton et al., 1995; Stepanauskas et al., 1999; Goolsby et al., 2001). For blackwater rivers of the southeast U.S. coastal plain, where a large portion of the nitrogen and phosphorus are contained within the organic fraction (Graves et al., 2004), and where natural organic carbon loads can confound the evaluation of oxygen deficits, the failure to account for differences in organic nutrient and carbon lability in the external load seriously compromises the assessment of anthropogenic eutrophication effects. While inorganic nutrients and some low molecular weight organic compounds are readily assimilated by aquatic primary producers, organic nutrient forms, which must first undergo desorption, hydrolysis, bacterial decomposition or photo-decomposition (Bushaw et al., 1996) for inorganic nutrient regeneration and utilization, are less readily available. Organic nutrient re-mineralization is dependent upon the utilization preference of the parent substrate by general microbial heterotrophs (DeBusk et al., 2001). A general working framework has evolved that partitions organic carbon and nutrients into two pools: a labile pool, that can be utilized in time frames relevant to water quality processes of interest in the receiving water, and a refractory pool, that is decomposed very slowly and essentially inert for relevant time frames (Wetzel, 1990, p. 737). Carbohydrates, proteins, lipids, nucleic acids, and pigments, which are in higher proportion in younger, autochthonous plant material, typically represents the bulk of this labile pool, while humified, allochthonous OM, largely imported to streams as dissolved and highly colored, leeched, degraded terrestrial plant materials (colored dissolved organic matter, or CDOM), typically dominates the refractory pool (Meyer, 1990; Moran and Hodson, 1990; Kaplan and Newbold, 1995; Moran et al., 1999). In their work on piedmont and coastal plain blackwater rivers in the southeast U.S., Sun et al. (1997) demonstrated that the compositional changes that accompany diagenesis relate directly to lability, with blackwater stream CDOM appearing the most refractory per mole carbon, and this is in agreement with work that has shown some forms of soil humus in the allochthonous organic carbon pool to be decades to hundreds of years old (Raymond and Bauer, 2001). Although natural CDOM is generally believed to be resistant to microbial decomposition and largely unavailable for utilization by phytoplankton in typical estuarine residence times, these large, heterogeneous organic molecules contain a substantial amount of nitrogen (N), and to a lesser degree phosphorus (P), in their structures (DeBusk et al., 2001), and hence the sheer volume of this material with respect to other organic matter (OM) pools dictates that its relevance be considered. No clear definition exists on what constitutes labile vs. refractory, and whether or not the range between JOURNAL OF THE AMERICAN WATER RESOURCES ASSOCIATION AND NUTRIENT BIOAVAILABILITY the two extremes exists as a continuum or as discrete states. Labile substrates have been described as those utilized within timeframes of 1-2 weeks (Sondergaard and Middelboe, 1995); as utilization through the exponential growth phase to the stationary phase (approximately 2 days; Stepanauskas et al., 1999); approximately 4 days for dissolved organic nitrogen (DON) of the Delaware River (Seitzinger and Sanders, 1997); or in situ bioreactor residence time (4-18 h; Volk et al., 1997). Moran and Hodson (1989), in their investigation of fresh and salt marsh plant lignocellulose, observed what appeared to be distinct rates of utilization, suggesting distinct, uniform chemical classes driving separate utilization rates. Similarly, Ogura (1975) determined that two distinct pools of dissolved organic compounds existed in most aquatic systems. In order to successfully prescribe pollutant load limits to reduce accelerated eutrophication and oxygen deficits in blackwater river estuaries, relevant, labile organic carbon and nutrients must in some way be distinguished from refractory, unreactive forms. The separation technique must be robust and generally applicable to the variety of OM present in the aquatic environment, and, if possible, reliant upon traditional chemistry so that it can be applied to existing datasets. In this study, a method is proposed to distinguish between labile and refractory organic carbon, nitrogen and phosphorus loads entering a large, blackwater river estuary, the lower St. Johns River in Northeast Florida. Poor water quality in the lower St. Johns River has been identified for over 50 years in reports published by the U.S. NOAA, Florida State Board of Health, and later the Florida Department of Environmental Regulation. Various reaches of the LSJR are listed by the State’s Total Maximum Daily Load (TMDL) criteria as impaired for one or more of the following symptoms of eutrophication: chlorophyll a, turbidity, nitrogen, phosphorus, and dissolved oxygen. The U.S. Army Corps of Engineers water quality process model CE-QUAL-ICM (Cerco and Cole, 1993) has been selected to conduct the diagnostic and scenario modeling investigations necessary to determine these TMDL reductions. A crucial factor in the selection of CE-QUAL-ICM was the model’s capability to perform separate calculations on labile and refractory forms of organic carbon, nitrogen, and phosphorus. The methodology developed here is applied to four different types of loads: (1) small, low-order stream non-point source loads of the immediate contributing basins; (2) domestic waste effluent loads; (3) pulp mill effluent loads; and (4) high-order river loads entering from upstream. Following this partitioning, a labile nutrient budget for the estuary is calculated and compared to the current total nutrient budget, and to the hind-cast, predevelopment labile nutrient budget. 265 JAWRA HENDRICKSON, TRAHAN, GORDON, MATERIALS AND METHODS Study Location The St. Johns River is one of the largest blackwater rivers of the southeast U.S., draining a 24,765 km2 area in northeast Florida. The St. Johns has a mean discharge of 227 m3 ⁄ s (Nazarian et al., 2005), and is slow moving and essentially at sea level for its final 200 km. The lower St. Johns River (hereafter ‘‘LSJR’’) is the estuarine portion of the river, formed at the confluence of the upper St. Johns and AND OUYANG Ocklawaha Rivers, encompassing a 7,123 km2 drainage area (Figure 1). Within this reach, the LSJR is slightly more that 160 km long and has a water surface area, including tributary mouths below head of tide, of 34,400 hectares. The slow velocity and broad lacustrine reaches of the LSJR facilitates phytoplankton production, and spring and summer blooms in this nutrient-rich river often exhibit chlorophyll a concentrations exceeding 100 lg ⁄ l. The northern (downstream) portion of the basin is distinguished by the heavily urbanized cities of Jacksonville, Orange Park and Middleburg. Roughly three quarters (64-82%) of the basin’s highly developed land uses FIGURE 1. The Lower St. Johns River Basin. JAWRA 266 JOURNAL OF THE AMERICAN WATER RESOURCES ASSOCIATION BLACKWATER ORGANIC CARBON rates appeared consistent with the range in apparent decay for aquatic organic matter shown in Figure 2, they were retained in subsequent calculations. Organic Carbon Partitioning The rate of organic carbon consumption in oxygenated surface waters is reflected in biochemical oxygen demand (BOD), with labile substrates consuming more oxygen per mole of carbon in the test period (typically 5 days) than refractory substrates. Consumption of organic carbon by bacterial heterotrophs has generally been found to adhere to first-order exponential decay (Jewell and McCarty, 1971; Chapra, 1997). Chapra (1997) provides a relationship in which the concentration of BOD exerted at time t on the total amount of substrate, or ultimate BOD, is: Ct ¼ C0 ð1 e kt Þ ð1Þ where Ct represents the oxygen consumed at time t, C0 is the maximum oxygen demand exertion (BODultimate), and k is the substrate-specific decomposition coefficient. Measurements of ultimate BOD are rarely performed, although total organic carbon should, in theory, be directly related to ultimate BOD, and can provide a basis for the inter-conversion of organic carbon and oxygen consumption. The molar rate of O2 consumption per organic carbon decomposition of 1:1 (2.67:1 mass ratio) was assumed here, as has been applied elsewhere in computations of community respiration (Wetzel and Likens, 1990; pp. 210-211; as per the respiratory quotient (RQ) of Strickland, 1960) and bacterial carbon utilization (Anderson, 1995; Foreman et al., 1998). Figure 2 compares the theoretical rates of change in substrate organic carbon for BOD exerted over time for effluents or surface waters with differing predominant organic matter types. First order decomposition rates range from 0.094 to 0.002 day)1, with domestic waste and algal organic matter the most labile substrates, and CDOM in runoff of undeveloped-waterwshed blackwater streams largely refractory. This range is similar to that applied by Cifuentes and Eldridge (1998), and blackwater stream organic carbon decomposition rate is similar to that of Moran et al. (1999), who calculated first-order organic matter decay rates for five rivers of the southeast U.S. ranging between 0.004 and 0.001 day)1. Previous applications of the CE-QUAL-ICM water quality model have set the labile and refractory organic carbon decomposition rates at 0.075 and 0.001 day)1. Because these JOURNAL OF THE AMERICAN WATER RESOURCES ASSOCIATION NUTRIENT BIOAVAILABILITY Percent of ulitmate BOD exerted or TOC consumed (medium and high residential, high intensity commercial and industrial) drain to the oligohaline and mesohaline LSJR. In contrast, 62-98% of the basin’s agricultural land uses drain to the fresh tidal reach. AND 100 Algae k = 0.094 day 80 –1 2ndary STP 60 k = 0.0386 day –1 Pulp & Paper Eff. 40 –1 k = 0.0096 day Native DOM 20 k = 0.0022 day –1 0 0 10 20 30 40 50 60 Time, days FIGURE 2. Rates of Exertion of BOD for Effluents and Surface Waters of Predominant Organic Matter Types. Algal rate determined with data from Lake Dora, a hypereutrophic lake in NorthCentral Florida; phytoplankton organic carbon estimated with 50:1 carbon:chlorophyll a. Secondary WWTP effluent values are from a sampling of 23 point sources of the lower St. Johns River basin. Pulp and paper determined from a large mill in the lower St. Johns River basin. Native DOM developed from the mean of BOD and TOC data for blackwater streams draining undeveloped watersheds in northeast Florida. Dashed lines represent rates of 0.075 day)1 (upper line) and 0.001 day)1 (lower). River, tributary and point source effluent water quality monitoring data collected within the LSJR basin from 1993 to 2004 comprised the subject dataset for this study. Tributary sampling programs were designed to characterize water quality for four predominant land uses at a watershed scale: urban, row crop, dairy and forested (i.e., undeveloped). Urban runoff samples were collected from streams in the Jacksonville area, and represented older development, built prior to riparian area protection and stormwater retention ⁄ detention and treatment that have been instituted since 1984. Urban land use included a mix of low to high density residential, commercial and industrial development. Row crop was predominantly seepage-irrigated potatoes and cabbage on ditched and drained coastal plain flatwoods soils. Lands characterized as dairy combined barn, feedlot, and improved pasture areas. Stations were selected so that only one development type (other than the undeveloped condition) occurred within the watershed, facilitating the bivariate analysis of development density on water quality. Point source water quality data for 32 domestic waste facilities and three industrial waste dischargers (all pulp mills) were obtained from monthly operating report compliance files. Most point source effluent is discharged to the oligo- to polyhaline portions of the 267 JAWRA HENDRICKSON, TRAHAN, GORDON, river in the vicinity of the city of Jacksonville. During the time of this sampling, secondary level was the established treatment level, and effluent limits for nutrients did not exist. Constituents of interest included biochemical oxygen demand (BOD), total organic carbon (TOC), particulate organic carbon (POC), total Kjeldahl-N (TKN), ammonia-N (NH4), nitrate + nitrite-N (NO2+3), total phosphorus (TP), orthophosphate (PO4), and water color. The following methods were used in analysis, with numbers in parenthesis referenced from Greenberg et al., 1992. NO2+3 was determined by copper-cadmium reduction and diazitozation colorimetry (4500-NO3-E), NH4 by the alkaline phenol-colorimetric method (4500-NH4-D), TKN by high temperature sulfuric acid digestion on whole water (unfiltered) sample followed by NH4 analysis (4500-Norg-C), PO4 by antimony-phospho-molybdate complex ascorbic acid-colorimetric method (4500-P-F), and TP by high temperature sulfuric acid digestion on whole water sample followed by PO4 analysis. Nutrient analyses were performed on an O-I Analytical Enviro-Flow FS 3000 auto-analyzer (OI Analytical, CMS Field Products Group, College Station, Texas, USA). BOD (total BOD; carbonaceous + nitrogenous) was determined by 5-day dark incubation at 20C (5210-B). TOC was determined by high temperature catalytic combustion to CO2 and detection by infrared detector (5310-B) on a Shimadzu TOC-V organic carbon analyzer, and POC by combustion and coulometric detection, and filtered color determined by the visual comparison method to standard platinum-cobalt solutions (2120-B). Most surface water chemistry was performed by the St. Johns River Water Management District (SJRWMD) laboratory, with some data acquired from the Duval County (Florida) Environmental Quality Division, and POC analyzed by the University of Florida’s Department of Fisheries and Aquatic Sciences. SJRWMD water quality data below the detection limit are not censored, but are instead reported as determined and remarked with the STORET ‘‘T’’ code (value reported is less than the detection limit). This greatly facilitated the ensuing analysis, as many BOD measurements fell below the 2 mg ⁄ l detection limit. In such cases, the usual 99% confidence range for measurement repeatability is not upheld, though analysis precision at these low ranges is still usually acceptable. BOD obtained from point source compliance was typically carbonaceous, while surface water analysis included nitrogenous demand. This was not considered a serious inconsistency, as ammonia concentration was typically low in these samples. Organic nitrogen was computed as TON = TKN – NH3, and total non-orthophosphate phosphorus as TNOP = TPPO4. The fraction of TP not in orthophosphate is referred to as ‘‘total non-orthophosphate-phosphorus,’’ JAWRA AND OUYANG and abbreviated as TNOP, because unlike nitrogen, an undetermined portion of the non-inorganic P may in mineral forms such as calcium or magnesium-complexed polyphosphates. Inorganic nitrogen (DIN) was calculated as NO2+3 + NH4. The final dataset with constituent coverage sufficient to proceed with partitioning calculations yielded 789 samples for 31 tributary sampling stations, 22 domestic waste point sources, and all three pulp mills. Total organic carbon in surface water samples was considered to be the sum of carbon within labile (labile total organic carbon, or LOC) and refractory substrates (total refractory organic carbon, or ROC), and that these respective fractions are decomposed simultaneously, albeit at differing rates. Using the rates of decomposition of the first-order decay model of 0.075 day-1 for labile substrates, and 0.001 day-1 for refractory, a pair of simultaneous equations was set up in the following form: TOCt¼5 ¼ ROC ð1 eð0:001Þ5 Þ þ LOC ð1 eð0:075Þ5 Þ ð2Þ TOCt¼1 ¼ ROC ð1 eð0:001Þ1 Þ þ LOC ð1 eð0:075Þ1 Þ ð3Þ In equation (2), a TOCt=5 was estimated assuming that the moles of organic carbon consumed at t = 5 (CBOD5) conformed to moles of oxygen consumed, consistent with a respiratory quotient = 1, by dividing BOD5, in mg ⁄ l, by 2.67, to get a TOC5, in mg ⁄ l. When all TOC is consumed, at t = ¥ (analogous to ultimate BOD), the exponent term in parenthesis goes to zero, and TOC¥ = ROC + LOC. The above, paired equations were simplified for computation through the following steps: ðBOD5 =2:67Þ ¼ ROC ð0:005Þ þ LOC ð0:3127Þ ð4Þ TOC ¼ ROC ð1Þ þ LOC ð1Þ ð5Þ 200 ½ðBOD5 =2:67Þ ¼ ROC ð0:005Þ þ LOC ð0:3127Þ ð6Þ TOC ¼ ROC ð1Þ þ LOC ð1Þ ð7Þ BOD5 74:906 LOC ð62:54Þ ¼ ROC ð8Þ TOC LOC ¼ ROC ð9Þ Solving these two equations for LOC produces: LOC ¼ ðBOD5 74:906 TOCÞ=61:54 ð10Þ and ROC ¼ TOC LOC 268 JOURNAL OF THE ð11Þ AMERICAN WATER RESOURCES ASSOCIATION BLACKWATER ORGANIC CARBON NUTRIENT BIOAVAILABILITY The tendency for low lability of AHS and high lability of young, macronutrient-rich autotroph biomass results in an inverse relationship between relative LOC content and OC:nutrient ratio that is apparent for surface water and point source effluent samples. Plots of the natural log of the percent of LOC vs. the natural log of sample organic C:organic nutrient ratios exhibited slightly curvilinear relationships (Figures 3a and 3b), and produced R2-values of 0.51 and 0.36 for nitrogen and phosphorus with second-order polynomial equations. One data point from stream runoff draining a large dairy and intensive pasture lands in which the TOC:TNOP was 4225:1 was omitted from this analysis. From these equations, organic C:N and C:P for hypothetical, purely labile (%LOC = 100) or refractory substrates (%LOC = 0) were determined as 4.5 and 37 for nitrogen, and 27 and 617 for phosphorus. This minimum organic C:N value is similar to that reported for bacterial cell composition (Fagerbakke et al., 1996; Kirchman, 2000), while the high C:N ratio corresponds well with values reported for refractory organic matter (Thurman, 1985, pp. 292293). (a) 5 Nitrogen 4 ln (TOC:TON) In calculations, 2 of the 87 point source samples and 6 of the 702 tributary samples had BOD5 values that indicated decay rates less than 0.001 day)1; conversely, three point source samples in the dataset exhibited CBOD5 values that, when converted to TOC, exceeded the TOC at the maximum decomposition rate of 0.075 day)1. These values were omitted from subsequent calculations. Although the tributary organic carbon was considered to be principally allochthonous (of the 265 tributary samples analyzed for chlorophyll a, the median calculated algal OC ⁄ LOC was 4%, and the 90th percentile relative composition was 30%; two tributaries with the highest chlorophyll a concentrations had sampling sites in quiescent, open embayments below the head of tide, where autochthonous production potential was high), a large amount of the upstream inflowing organic C is autochthonous in origin. This results from a number of large lakes, the largest being Lake George, which, at 189 km2, and just 16 km upstream of the LSJR, is the predominant lacustrine feature that determines inflowing organic carbon and nutrient compartmentalization. Within-river TOC was determined by summing measurements of DOC and POC, as organic carbon analyzer measurements were found to underestimate TOC when significant algal biomass was present. Algal biomass (determined from corrected chlorophyll a or biovolume measurements), was considered to be labile organic C, and was separated from non-algal labile organic C assuming a 50:1 ratio of algal C to corrected chlorophyll a. Comparison between POC and corrected chlorophyll a demonstrated very good adherence to the 50:1 ratio at when algal biomass dominated the POC pool. AND C:N = 4.5 3 2 C:N = 37 1 y = –0.0478x 2 – 0.2401x + 3.6156 R 2 = 0.51 0 0 1 2 3 4 Organic Nutrient Partitioning (b) 10 Due to its relatively high content of proteins, amino acids, lipids, and nucleic acids, labile aquatic OM typically exhibits low C:N and C:P ratios, and its decomposition in the aquatic environment tends to lead to the regeneration of inorganic N and P (Goldman et al., 1987; Sun et al., 1997). Conversely, substrates in the aquatic environment with a high C:N and C:P, such as aquatic humic substances (Thurman, 1985; pp. 292-294), will tend to immobilize the macro-nutrients during decomposition (Mann, 1988; Strauss and Lamberti, 2000). Aquatic humic substances (AHS) exhibit low biological availability, exert low oxygen demand even at high concentrations, and regenerate low levels of mineral nutrients for subsequent utilization by autotrophs (Kroer, 1993; Bushaw et al., 1996). JOURNAL OF THE AMERICAN WATER RESOURCES ASSOCIATION Phosphorus ln (TOC:TNOP) 8 C:P = 27 6 4 C:P = 617 2 y = –0.1009x 2 – 0.2109x + 6.4245 R 2 = 0.36 0 0 1 2 3 4 ln (% LOC) FIGURE 3. Organic Carbon:Nutrient Ratios as a Function of Calculated Labile Organic Carbon Content for (a) Nitrogen and (b) Phosphorus. Values in boxes represent regression-calculated OC:Nutrient ratios at 0 and 100% labile organic carbon content. 269 JAWRA HENDRICKSON, TRAHAN, GORDON, To constrain calculated values of labile organic N (LON), refractory organic N (RON), labile non-orthophosphate P (LNOP) and refractory non-orthophosphate P (RNOP) such that the sum of labile and refractory concentrations equaled the laboratory analytical determinations for TKN-NH3 and TP-PO4, total organic N (TON) and total non-orthophosphate P (TNOP) were partitioned, rather than multiplied by, labile and refractory organic C:N and C:P ratios. This proportional compartmentalization calculation was: ( LON ¼ ) LOC 4:5TOC ROC LOC 37TOC þ 4:5TOC TON: ð12Þ Following this calculation, RTON could be calculated by difference with the relationship RON ¼ TON LON ð13Þ or with the complimentary partitioning equation of the form ( RON ¼ ROC 37TOC ROC LOC 37TOC þ 4:5TOC ) TON ð14Þ Similarly, TNOP was partitioned with the relationships ( LNOP ¼ LOC 27TOC ROC LOC 617TOC þ 27TOC ) TNOP ð15Þ TNOP ð16Þ and ( RNOP ¼ ROC 617TOC ROC LOC 617TOC þ 27TOC ) RESULTS Organic Carbon and Nutrient Partitioning Patterns To examine differences in river inflow, tributary runoff, and effluent N, P, and C forms, summary statistics were prepared and are shown in the box and JAWRA AND OUYANG whisker plots of Figure 4. For each of the tributary sampling stations, seasonal mean flow-weighted concentrations of inorganic N and P forms, and organic C, N, and P forms were calculated by summing the product of event concentration and sampling day discharge fraction. Discharge fraction was calculated as the mean daily discharge for the sampled stream (or its nearest proxy gauged stream) divided by the sum of the daily discharges for all sampling dates. Instead of the four Julian calendar seasons, a three-season breakdown was used that conforms more closely to the northeast Florida meteorological conditions: a cool, moderately wet winter from December through March, marked by regular frontal systems; a hot, dry spring-summer from April through July; and a hot, wet summer-fall from August through November, marked by convective thunderstorms and tropical systems. Annual mean concentrations were then calculated for each station from the three seasonal means. Mean concentrations for domestic waste and pulp mill effluents were calculated from the individual facility means. Upstream river mean concentrations were determined from biweekly monitoring from 1995 to 1999. DIN and PO4 were the highest in domestic waste, pulp mill effluent, and runoff from row crop and dairy-dominated watersheds (Figure 4). Concentrations were intermediate in urban runoff, and lowest in samples from the upstream end of the St. Johns River. Domestic waste was also high in LOC, but was the lowest in ROC. Pulp mill effluent exhibited the highest concentrations of both LOC and ROC. In tributary and river samples, river inflow was found to have the highest LOC, but moderate levels of ROC. LOC was also relatively high in urban and dairydominated runoff. LOC levels were moderate in row crop runoff, and lowest in undeveloped watershed runoff. Dairy, row crop and undeveloped watershed runoff exhibited high concentrations of ROC, with the lowest levels seen in urban runoff. Labile organic N and P partitioning followed the general patterns seen in LOC. Pulp mill effluent was found to contain the greatest amount of LON and LNOP. Domestic waste was also high in LON and LNOP, rendering its total composition highly bioavailable, with 98% of TN as TBN (total bioavailable N; calculated as TIN + LON) and 99% of TP as TBP (total bioavailable P; PO4 + LNOP). TBN in pulp mill effluent ranged from 69% to 94% of TN, and TBP ranged from 88 to 98% of TP. These ranges appear consistent with NCASI (2004), which found that in extended decomposition experiments of effluent from 4 mills, between 60% and 84% of TN was TBN, and between 67% to 91% of TP was TBP. Upstream river and urban runoff samples were also found to be moderate to high in LON and LNOP, but relatively low 270 JOURNAL OF THE AMERICAN WATER RESOURCES ASSOCIATION BLACKWATER ORGANIC CARBON AND NUTRIENT BIOAVAILABILITY 100 10 DIN 10 LON 1 1 1 0.1 0.1 0.1 LOC RON 10 10 1 FO UR UP W W PM RC DA FO UR UP W W PM FO UR UP W W PM RC DA FO UR UP W W PM RC DA RC DA 0.01 0.01 0.01 100 PO4 1 LNOP 1 1 0.1 0.1 0.1 0.01 0.01 0.01 ROC RNOP 10 1 FO UR UP W W PM RC DA FO UR UP W W PM FO UR UP W W PM 0.001 RC DA FO UR UP W W PM RC DA 0.001 RC DA 0.001 FIGURE 4. Patterns in Mean Nitrogen, Phosphorus, and Carbon Forms for Stream Runoff and Point Source Samples. Dark line signifies the mean concentration, the light center line the median, box ends the 75th percentile, and whisker ends the 95th percentile values. RC = row crop; DA = dairy; FO = forested or undeveloped; UR = urban; UP = St. Johns River at the basin’s upstream end; WW = domestic waste final effluent; and PM = pulp mill final effluent. Plot vertical axes in log10 scale is concentration in mg ⁄ l. in refractory forms. Conversely, undeveloped watershed runoff was low in LON and LNOP, but high in refractory forms. Row crop and dairy runoff exhibited levels of RON and RNOP roughly similar to that of undeveloped watershed runoff, but were elevated with respect to LON and LNOP. Mean seasonal and annual flow weighted concentrations of DIN, PO4, LON, LNOP and LOC were found to increase with increasing watershed development density. Regressions relating concentration to fraction of watershed developed area (Table 1) exhibited high significance for these nutrient and carbon forms. Slope values indicated the greatest rate of increase for watersheds dominated by dairy land use, while rates of increase for row crop agriculture were intermediate. Rates of increase in these constituents were the lowest for urban land covers (combined residential, commercial, transportation and industrial), but these rates exhibited curvilinear increases with development density. This may be because of the compounding effect of impervious surfaces, which would presumably increase the proportion of urban runoff contribution with land development intensification. In contrast to inorganic and labile organic trends, refractory nutrient and carbon forms tended to remain the same or decrease with increasing development intensity. Slopes for regressions relating RON, RNOP and ROC concentration to dairy or row JOURNAL OF THE AMERICAN WATER RESOURCES ASSOCIATION crop development intensity were either not significant, or exhibited low correlation coefficient values. For urban land, development intensity was strongly negatively correlated with RON and ROC concentration. Seasonal flow-weighted concentrations specific to each land use category were estimated through a regression approach conceptually similar to that applied by McFarland and Hauck (2001). Simple linear regressions were developed in which the dependent variable was the sampling station seasonal flow-weighted mean concentration, and the independent variable the fraction (from 0 to 1) of contributing watershed land area for each predominant land use category. Regressions included undeveloped watershed sampling means, resulting in regressions with y-intercepts that theoretically represented the undeveloped watershed concentration. The specific land use concentrations, shown in Table 1, were determined by solving the regression equations for the condition of 100% land use (i.e., fraction = 1). The most pronounced seasonal patterns were seen in ROC, RON and RNOP, which tended to be the lowest in the April-July season, highest in the AugustNovember season. This pattern is consistent with the annual cycle in rainfall and soil saturation, and the flooding of near-stream source areas that facilitates CDOM export. Maximum orthophosphate 271 JAWRA JAWRA December-March April-July August-November December-March April-July August-November December-March April-July August-November December-March April-July August-November Season 7 7 7 5 5 5 6 6 6 8 8 6 n 0.034* 0.104 0.044* 9.95 (0.92) 1.90 (0.57) 1.38 (0.91) 4.15 (0.83) 4.82 (0.72) 6.41 (0.88) 0.831 (0.66*) 0.447 (0.64*) 0.458 (0.86*) TIN 0.092* 0.161 0.083 1.64 (0.91) 0.969 (0.58) 1.34 (0.75) 2.70 (0.98) 2.63 (0.95) 3.82 (0.92) 1.66 (0.78*) 1.35 (0.78*) 1.69 (0.80*) LON 0.543 0.617 0.719 NS NS NS 1.56 (0.59) NS 2.03 (0.65) 0.145 (0.65) 0.070 (0.78*) 0.059 (0.77) RON 0.041* 0.043* 0.034* 0.914 (0.91) 0.248 (0.30) 0.891 (0.62) 3.70 (0.77) 2.77 (0.79) 4.65 (0.83) 0.130 (0.58) 0.131 (0.44) 0.186 (0.47) PO4 0.009* 0.022 0.014* 0.864 (0.89) 0.309 (0.44) 0.420 (0.88) 0.369 (0.90) 0.221 (0.71) 0.618 (0.90) 0.346 (0.78) 0.177 (0.76*) 0.265 (0.70*) LNOP 0.018 0.024 0.031 0.121 NS NS 0.085 NS 0.128 NS 0.003 NS (0.54*) (0.62) (0.65) (0.61) RNOP 0.33 0.70* 0.39 6.96 (0.95) 1.92 (0.23) 4.92 (0.63) 10.26 (0.91) 13.63 (0.81) 12.94 (0.93) 6.21 (0.86) 5.98 (0.76*) 4.14 (0.90) LOC 21.56 21.42 28.38 NS 3.18 NS NS NS NS 3.96 2.57 1.49 (0.84) (0.82*) (0.86) (0.75*) ROC (Inorganic + labile org.)/total Labile/total Urban = Med. - High density residential, commercial and industrial; dairy = intensive pasture, sprayfield and confined animal; row crop = seepage-irrigated row crop agriculture; undeveloped = native forest, forested wetlands and silviculture. 1 Determined from the extrapolation of regressions relating seasonal flow-weighted mean concentrations and fraction of developed area to the point of 100% watershed development. All concentrations in mg ⁄ l. Correlation coefficients for simple linear regressions between the fraction of watershed categorical land use (independent variable) and mean seasonal flow-weighted concentration (dependent variable) in parentheses. Asterisks in parentheses (*) represent an exponential regression fit. ‘‘NS’’ signifies a nonsignificant regression slope, in which case the concentration is assumed to be the same as that for the undeveloped case. Undeveloped land use category concentrations determined from the mean of the 3 intercepts for row crop, dairy and urban regressions. Asterisks in this case represent instances when at least 1 of the 3 regressions produced a negative intercept, in which case the seasonal mean of the 3 least developed watersheds was use to establish this concentration. Old Urban Dairy Row Crop Undeveloped Major Land Use TABLE 1. Flow-weighted Seasonal Nutrient and Organic Carbon Concentration Values for Aggregated Land Use Categories1. HENDRICKSON, TRAHAN, GORDON, 272 AND OUYANG concentrations are also often observed at this time, and this may be due to the release of iron-bound phosphorus as soil redox potential declines. Also noteworthy is the sharp increase in inorganic nitrogen concentration for the row crop watersheds in the December-April season, coincident with the cropping of winter potatoes. (a) 1 (b) Labile/total 0.8 LNOP 0.6 LON 0.4 0.2 LOC 0 1 Total bioavailable 0.6 0.4 0.2 JOURNAL OF THE TBP 0.8 TBN Forest Dairy Row crop Urban 0 Fraction of watershed area developed FIGURE 5. Changes in (a) Percent Labile Organic C, N, and P and (b) Total Bioavailable N and P With Increases in Watershed Developed Area. As a consequence of the increase in inorganic and labile nutrients and carbon accompanying development, the fractional composition of labile and total bioavailable nutrients and carbon was found to increase as development intensity increased (Figure 5). Despite large absolute differences in concentrations, the relative composition of labile and total bioavailable forms was found to vary similarly regardless of development type. Similar to the exponential increase seen for urban runoff LON, LNOP, and LOC at high development density, the relative LOC content also increased sharply, and can most likely be attributed to the concomitant and pronounced decrease in ROC. The relative content of TBN and TBP increases rapidly with watershed AMERICAN WATER RESOURCES ASSOCIATION BLACKWATER ORGANIC CARBON Partitioning calculations suggest that labile organic matter represents a much greater proportion in upstream river inflow than that of within-basin tributaries, with algal biomass comprising a large portion of this labile organic matter. LOC, LON, and LNOP exhibited annual patterns that are consistent with the seasonal oscillation in autochthonous or allochthonous source dominance (Figure 6), and which were more dynamic than the annual temporal patterns seen in tributary runoff. Algal assimilation in spring and summer resulted in much lower inorganic N and P concentrations than were observed in tributary runoff. By May of most years, increases in TN, driven by increased algal LON resulting from cyanobacterial atmospheric nitrogen fixation are evident (Phlips and Cichra, 2001; Paerl et al., 2003). This internal N loading sharply increases the relative concentration of TBN imported to the LSJR during the months of May-August, increasing from roughly 60% of TN in winter months, to over 80% (Figure 6c). Autochthonous production also increases the proportion of LOC, up from 17% of TOC in winter, to a peak of 39% in July. Between July and September, incoming LOC concentration ranged between 5 and 9 mg ⁄ l, with algal OC representing on average 34-50% of this. At 2.8 mg ⁄ l, the mean annual incoming LOC concentration was found to be similar to the elevated levels for tributary sampling stations of developed watersheds. However, because of prevailing low inorganic nutrients, TBN and TBP concentrations are relatively low in comparison to within-LSJR basin tributary runoff from developed watersheds, at 1.07 mg ⁄ l for TBN and 0.056 mg ⁄ l for TBP. The relationship between the square root of color and mean ROC and TOC for streams draining undeveloped watersheds was found to be linear and very significant, with an R2-value of 0.979 (Figure 7a). Mean concentrations within color brackets have been used to develop this relationship, as color determined by the visual comparison method produces discrete values based on platinum-cobalt standard solutions. The relationship has inherent heteroscedasticity by virtue of the fact that color standard brackets increase in width with higher concentrations. Because undeveloped watershed streams exhibit low concentrations of LOC (calculations performed in (a) 2.5 Nitrogen Concentration, mg/L River Inflow Nutrient and Carbon Partitioning NUTRIENT BIOAVAILABILITY 2 TIN Algal ON Nonalgal LON RON 1.5 1 0.5 0 Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov Dec (b) 0.12 Phosphorus Concentration, mg/L developed area, particularly for agricultural land use, reaching between 60% and 80% relative composition at about 30% of watershed developed area (Figure 5b). AND 0.09 PO4 Algal OP Nonalgal LNOP RNOP 0.06 0.03 0 Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov Dec (c) % Bioavailable 100 Percent 80 Partitioning Verification: Color Comparison 60 40 In blackwater streams draining undeveloped watersheds, the organic carbon pool is predominantly composed of leached, colored humic substances, and a strong correlation between color and TOC has been reported in both boreal and blackwater streams (Rasmussen et al., 1989; Cuthbert and del Giorgio, 1992). In the conceptual dichotomy for organic matter applied here, ROC is analogous to the aged, refractory portion of the total organic matter pool, or CDOM, and theoretically, ROC should exhibit a better correlation to color measurements than TOC. JOURNAL OF THE AMERICAN WATER RESOURCES ASSOCIATION Nitrogen Phosphorus Organic carbon 20 0 Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov Dec Month FIGURE 6. Mean Monthly Nitrogen and Phosphorus Fractionation at the Upstream Inlet to the Lower St. Johns River, 1995-99. (a) Mean monthly nitrogen form concentrations; (b) mean monthly phosphorus form concentrations; (c) mean monthly percent bioavailable (inorganic + labile organic) N and P. Error bars in (a) and (b) are 95% confidence bounds on monthly mean total N and P. 273 JAWRA HENDRICKSON, TRAHAN, GORDON, (a) OC Form, mg/l 30 Undeveloped 40 ROC = 1.8697*(Color0.5) – 6.5585 R 2 = 0.9785 (c) Row crop 40 30 30 20 20 10 10 0 0 0 25 (e) 25 (f) 100 20 Dairy ROC 10 TOC Urban OC Form, mg/l OUYANG (b) 40 (d) AND Pulp mill Upstream river 20 20 90 15 15 80 10 10 70 5 5 60 0 0 50 Color class, (Pt–Co units)0.5 FIGURE 7. Comparison of Color and Color-Derived ROC to ROC and TOC. (a) Linear regression model relating the square root of color to mean TOC and partitioned ROC within color classes for undeveloped LSJR basin watersheds. (b, c, d, e, and f) Comparison of mean TOC and partitioned ROC within color classes to the color versus ROC model for undeveloped tributaries for (b) row crop; (c) dairy; (d) urban; (e) upstream river; and (f) pulp mill effluent samples. Solid line in (b) through (f) is the undeveloped trib color vs. ROC model. Error bars represent 95% confidence intervals for mean concentrations of ROC within classes. this study determined LOC was on average only 4% of un-impacted stream TOC), the relationship between the square root of color and mean ROC and TOC are nearly identical. However, as LOC increases, the TOC verses color relationship should degrade, while partitioned ROC should, in theory, adhere to the color relationship of un-impacted streams. For row crop and dairy runoff samples, calculated ROC compares well to the un-impacted stream relationship (Figures 7b and 7c), though heteroscedasticity is apparent at higher color concentrations. For urban streams (Figure 7d), partitioned ROC appears higher than the undeveloped stream relationship for higher color (and ROC) concentrations, but 95% confidence intervals for ROC still encompass the regression line. For river samples (Figure 7e), partitioning appears to have produced slightly higher ROC concentrations for low color classes. These lower color ranges coincide with longer residence time periods and high phytoplankton biomass. This may indicate a weakness in the partitioning computation when phytoplankton biomass is high, but may also be due to photodecomposition of CDOM chromophores, owing to the longer duration sunlight exposure (Gao and Zepp, 1998; Bertilsson and Tranvik, 2000; Osburn et al., 2001). Weaker relationships between color and urban stream and river JAWRA samples can also be partly attributed to the lower color range observed for these surface water types. Because of the relatively small number of pulp mill effluent samples (only four samples with sufficient data to perform partitioning), the color versus ROC relationship is compared only witho the overall average. The close agreement for calculated pulp mill ROC values with the un-impacted blackwater stream relationship is particularly surprising, as these effluent concentrations represent a large extrapolation beyond measured stream values upon which the color vs. ROC relationship is based. Whole Basin Nutrient and Organic Carbon Loads These specific land use concentrations of Table 1 were added to the existing LSJR watershed model framework (Adamus and Bergman, 1995) to predict LSJR basin total non-point source load. Basin loads above background attributable to each major land-use category were determined by substituting undeveloped land use concentration and runoff parameters in place of the developed land use parameters within the watershed model, and subtracting this model simulation result from the existing condition simulation. Within-basin watershed modeling estimates of 274 JOURNAL OF THE AMERICAN WATER RESOURCES ASSOCIATION BLACKWATER ORGANIC CARBON AND NUTRIENT BIOAVAILABILITY TABLE 2. Mean Annual Source Loads to the Lower St. Johns River, 1995-99. Upstream LSJR Basin Natural Background Agriculture Urban Point Source Atmosph. Wet Dep. Grand Total Total N LON RON DIN 8,415 4,494 3,369 561 1,324 322 513 1,783 222 1,2578 380 104 383 415 883 86 )53 65 5,775 4,350 61 131 183 1,303 222 2,462 Total P LNOP RNOP PO4 LOC ROC 370 206 59 104 17,647 95,216 117 97 146 467 3 1,199 22 27 83 98 16 10 10 5 2,183 197 1,693 2,065 45,706 )208 )3092 2,881 435 101 79 60 53 364 3 663 23,786 140,502 All values in metric tons per year. non-point source loads were combined with point source and upstream river loads to derive a total basin mean C, N, and P budget by source, shown in Table 2. In some cases, most notably for ROC and RON loads from urban and row crop land uses, loads are negative, reflecting a decrease in refractory organic matter export. Overall, it is estimated that within-LSJR basin ROC load has declined from the background load by 7%. Sub-division of nutrient loads into labile and refractory organic forms greatly effects the interpretation of nitrogen loads to the estuary. The exclusion of RON to estimate only TBN load reduces the estimate based on TN by 35%. Conversely, if the relevant, potentially available load to the river is considered to be just the DIN load, the inclusion of LON to this increases the estimate by 234%. Labile and refractory partitioning appears to produce a relatively small effect on the interpretation of phosphorus loads, segregating only 6% of the TP load to RNOP. The greatest TBN load is imported to the LSJR from upstream sources, while the greatest TBP load enters in the downstream, meso-polyhaline reach of the river in the urban Jacksonville area, with most of this coming from wastewater treatment plant discharge. The greatest source of LON, LNOP and LOC to the LSJR is upstream inflow, primarily incorporated into algal biomass. DISCUSSION To diagnose and manage eutrophication of river estuaries stemming from nutrient over-enrichment, the spatially and temporally explicit quantification of the external load represents a fundamental undertaking. Because estuarine eutrophication is more succinctly a problem of organic matter overenrichment (Nixon, 1995), with oxygen depression probably the classic adverse manifestation (Officer et al., 1984), the requirements of the external load JOURNAL OF THE AMERICAN WATER RESOURCES ASSOCIATION quantification apply not only to nitrogen and phosphorus, but also to labile organic carbon that drives microbial metabolism. In blackwater river estuaries, eutrophication assessment is complicated by naturally high organic matter loads, and uncertainty regarding the bioavailability of organic C, N, and P forms. Previous research has convincingly demonstrated that aquatic organic matter can be rendered available over a range of time scales, dictating its relevance to phytoplankton nutrient assimilation and oxygen deficits within estuaries (Seitzinger and Sanders, 1997; Sun et al., 1997; McKnight et al., 2001) and that land development can increase the proportion of labile organic matter in the total aquatic organic matter pool (Seitzinger et al., 2002). Despite this, general methodologies have not been suggested to apply these findings, and labile and refractory carbon and nutrient compartmentalization has generally been ignored in external load budgets. The calculations proposed here, which rely on upon inter-conversion of oxygen demand and organic carbon, and general trends in C:N and C:P ratios along the labile carbon gradient, are an attempt to provide such a methodology. Because incorporated nitrogen exists in aquatic environments affiliated with carbon in organic molecules, organic nitrogen partitioning is well correlated with organic C:N ratio, making this a useful proxy for establishing biodegradability. Separation of LNOP is less definitive, and this may be explained by TNOP incorporated into mineral phases, which is probable in rivers such as the St. Johns that receive large amounts of ground waters containing calcium and bicarbonate (Diaz et al., 1994). This presence of mineral P lowers the apparent OC:TNOP ratio that the method applied here assumes is characteristic of the degradability of an organic substrate, and may be the reason for the poorer correlation between TOC:TNOP and percent LOC. However, given what is known regarding the relatively high P content of fresh, labile organic matter, it appears plausible to accept at least qualitatively that substrates with low OC:TNOP ratios exert higher oxygen demand and 275 JAWRA HENDRICKSON, TRAHAN, GORDON, inferred degradability, that the concentration of LNOP in environments with low LOC is very low, and that the proportion of LNOP increases sharply with land development intensification. Patterns in LOC determined by the methods used here produce results similar to those reported by other investigators in terms of both proportion within TOC and trends with watershed development and source. Volk et al. (1997), in a study of mixed urban ⁄ ag ⁄ forested watersheds in southeast Pennsylvania, found bioavailable DOC to constitute on average 25% of DOC. Sun et al. (1997) reviewed previous studies of OC bioavailability, and found a range in LOC from 0% to 86%. For most rivers dominated by allochthonous OC, the range is closer to between 7% and 25% (Sondergaard and Middelboe, 1995; Volk et al., 1997), with blackwater rivers exhibiting the lowest relative amounts of labile OC (Sun et al., 1997; Moran et al., 1999), and streams draining urban areas the highest reported fractions. In this study, estimated labile organic carbon content ranged from 3% of TOC in waters draining undeveloped, forested streams, to 52% for highly urbanized streams. Urbanized streams exhibited high absolute LOC concentrations, and high relative concentrations in part as a result of simultaneous reductions in ROC. Clinton et al. (2002), in their examination of the changes in DOC in the shallow groundwater flow path in a Pacific Northwest floodplain river, concluded that soil saturation (which controls redox state and subsurface microbial metabolic activity) and organic matter source patchiness largely control the export of labile DOC to the hyporheic zone. Their paradigm may explain why undeveloped, forested watersheds with intact riparian areas export relatively low levels of LDOC. Because of the tendency for labile organic matter to possess higher amounts of N and P relative to C, labile nutrient fractions in runoff from developed watersheds are higher than labile carbon fractions, on average 50% for LON and 75% for LNOP. LON ranged from 20% to 36% of TON for mostly undeveloped watersheds, from 36% to 66% for dairy and row crop-dominated watersheds, and from 38% to 92% for urbanized watersheds. Stepanauskas et al. (2000), in their study of Scandinavian rivers, estimated the percent of labile dissolved organic nitrogen (DON) as between 19% and 55%. Because of the very low levels of TNOP observed in undeveloped watershed runoff, it cannot be said with certainty what percent is composed of LNOP, although it appears that typical concentrations are probably less than 10 lg ⁄ l. For urbanized streams, TNOP was found to range from 66% to 97% of LNOP. Trends identified here for the high relative amounts of LON in urban area runoff are similar to that observed by Seitzinger et al. (2002). Particularly signiJAWRA AND OUYANG ficant was the similar conclusion regarding the relatively high levels of LON in urban ⁄ suburban runoff, compared to agricultural development. However, our analysis suggested that per area developed, urban land use produced lower absolute concentrations of both LON and LNOP than agriculture, and that the high relative concentrations were because of the decline in refractory forms. Tufford et al. (2003) identified a decline in dissolved organic N in urbanized relative to undeveloped streams of coastal plain South Carolina, suggesting a similar lowering of RON, and Graves et al. (2004) observed lower levels of color (assumed a proxy for ROC) in runoff from urban areas relative to pasture and wetland areas in south Florida. Three factors are hypothesized to be largely responsible for this: (1) reduced terrestrial plant organic matter inputs; (2) the expansion of impervious surfaces, which reduces the mingling of shallow ground water with organic matter-rich soil layers; and (3) the disruption of stream-riparian area processes due to wetland destruction and channelization. Owing to these factors, hydrophyllic organic acids that dominate the refractory organic matter pool in the undeveloped watershed setting (Aitkenhead-Peterson et al., 2003) are replaced by labile organic matter favored in surface flow import. Possible sources that might be favored in surface water flow paths include effluent from clogged drainfields and leaking septic tanks, sanitary sewer line leaks, pump station overflows, pet feces, grass clippings, or industrial site waste. At some point in the continuum between roughly third-order stream (typical size of contributing streams within the LSJR basin) and sixth-order river (size of the St. Johns at the upstream end of the LSJR), secondary production dependence appears to shift from allochthonous to autochthonous organic matter sources, adhering to the tenets of the river continuum concept (Vannote et al., 1980). One may presume that the point of this transformation will depend upon stream flow, season, lacustrine characteristics and levels of nutrient enrichment. It is a factor that must be kept in mind in watershed modeling to derive nutrient load budgets, as it determines the extent to which terrestrial characteristics alone can predict stream chemical profile. Beyond this point, instream nutrient and organic matter processing must be linked to watershed modeling, or direct monitoring must be used to characterize incoming load. If the labile and refractory partitioning proposed here can be believed, then these results lead to a dramatically different perspective of the sources and degree of nutrient enrichment in the LSJR basin, and perhaps in other blackwater river systems. Watershed modeling performed on the pre-development scenario within the basin produces a mean annual estimated (1995-99 hydrologic conditions) TN load of 276 JOURNAL OF THE AMERICAN WATER RESOURCES ASSOCIATION BLACKWATER ORGANIC CARBON 1,324 MT, one-third of the present day (1995-99 mean annual) TN load from point and nonpoint sources of 3,940 MT. Arguably more relevant to estuarine eutrophication, however, is the increase TBN load, which has risen from the predevelopment estimated mean annual total of 441 MT ⁄ yr, to the present day level of 2,960 MT ⁄ yr, or a 6.7-fold increase. A bioavailable-P only comparison suggests a smaller increase in relative anthropogenic loading effect, with present day TP load constituting a 7.1-fold increase over the predevelopment scenario (up from 117 MT ⁄ yr to 827 MT ⁄ yr), compared with the TBP increase of 7.8fold (up from 100 MT ⁄ yr to 785 MT ⁄ yr). Thus, it is clear from the compartmentalization performed here that relative increases in potentially bioavailable nutrient load, particularly for nitrogen, are greatly underestimated in blackwater river systems when budgets are based on total nutrient concentrations alone. This finding has important implications for eutrophication modeling, particularly if undeveloped stream conditions are used to hind-cast natural background receiving water productivity levels. There are also important implications in the TMDL process for ascribing assimilative capacity, and, perhaps more importantly, allocation for N and P ( and perhaps LOC, perhaps as BOD), which should be based upon the reactivity of nutrient loads. Historical accounts of ‘‘jubilee,’’ the mass herding of estuarine organisms fleeing hypoxic waters (May, 1973), and the copious supply of natural organic matter characteristic to coastal plain watersheds, has led to the perception that low oxygen episodes are a natural phenomena in southeast U.S. estuaries. While it is plausible that blackwater river estuaries should exhibit net heterotrophy, Sucsy and Hendrickson (2004) concluded through water quality modeling that the refractory organic matter-dominated composition that would have prevailed in the pre-European settlement LSJR would not have been sufficient to sustain the in situ decomposition necessary to drive low dissolved oxygen levels that are now observed. The high relative amounts of LOC calculated at the upstream end of the LSJR arising from algal production, and the large increase in the within-basin load of TBN and TBP leading to phytoplankton production within the LSJR, appears to be a much more likely source of labile organic matter that drives low oxygen episodes. Loworder reaches of blackwater river systems may exhibit naturally low dissolved oxygen as a result of advective volume displacement with waters of low oxygen content from adjacent, net-heterotrophic, stream-side source areas. However, in higher order freshwater reaches at or near the head of tide, within-river volume is typically sufficient to buffer such low oxygen concentration water displacement, and the oxygen regime is dictated more by autochthonous production and respirJOURNAL OF THE AMERICAN WATER RESOURCES ASSOCIATION AND NUTRIENT BIOAVAILABILITY ation cycles (Meyer and Edwards, 1990). 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