Degradability of Sediments from the St. Lucie Estuary Florida A Pilot Study Mark Thompson, Thomas White and Greg Graves Florida Department of Environmental Protection Water Quality Program Port St. Lucie February 2001 Introduction The St. Lucie Estuary (SLE) is an important ecological feature of east central Florida. The Estuary also serves as a recreational and commercial resource for the area. Sea level rise since the end of the Wisconsin Glaciation 15,000 years ago flooded a portion of the St. Lucie River Valley forming the estuary (Graves and Strom, 1992). The average tidal range is 3 feet near the ocean and 2 feet in the inner estuary. Tidal currents are nominal throughout and the SLE may be classified as a low energy, microtidal estuarine system (Haunert, 1988). The chemistry and relative quiescence of the estuary create a depositional environment for sediments transported from upstream. Under normal conditions, the St. Lucie Estuary is moderately stratified with a layer of fresh water flowing over a wedge of tidally pumped saline water. The layers may flow at different velocities and directions resulting in a circulation pattern which enhances deposition of heavier than water particles (Olson and Burgess, 1967). It is a normal condition for estuaries to be turbid and act as sediment traps accumulating deposits at rates which estuarine species have become adapted, but anthropogenic activities may adversely increase sedimentation rates and change sediment characteristics. The modern day St. Lucie Estuary has been impacted by major anthropogenic changes within its watershed. Natural streams and wetlands have been systematically altered and drained with canals and channelization projects. Sediment-laden runoff from rainfall events is rapidly transported downstream into the estuary. The C-23 and C-24 Canals discharge into the North Fork of the estuary and drain coastal watersheds which are being converted to predominantly urban and intense agricultural land uses (Figure 1). Figure 1. The St. Lucie Estuary with Significant Features. Sample Site 1 The Okeechobee Waterway (C-44 Canal) empties into the South Fork of the estuary and serves as a source for large influxes of freshwater and sediments from Lake Okeechobee. These activities have resulted in a rapid increase in sedimentation rates. Fine particle sediments are accumulating at a rate of 1 to 2 cm/yr. (Davis and Schrader, 1984; Schrader, 1984). Turbidity and sediment smothering may adversely affect benthic and plankton communities, which are the base of the estuarine ecosystem. Historical accounts of SLE indicate aquatic species diversity was high, water clarity good and submerged aquatic vegetation (SAV) and oysters were an important feature of the estuary (Chamberlain and Hayward, 1996). Currently the SLE is devoid of significant populations of oysters or SAV. Additionally, pesticides and heavy metals associated with agriculture and urban activities adsorb onto sediment particles and accumulate in low energy areas. These toxic substances accrue in benthic organisms and bioaccumulate at higher trophic levels. Monitoring studies have found concentrations of some heavy metals and pesticides in SLE sediments to be above threshold effects levels (TELs) which are used as guidelines for evaluating sediment quality (Table 1) (MacDonald et al. 1996; Haunert, 1988; Florida Department of Environmental Protection, 2001). Table 1. SLE Sediment monitoring data from Florida DEP Southeast District. Values exceeding threshold effects level shown in Italics. Values exceeding probable effects level shown in bold. Site Storet TEL PEL NEST 28010037 SEST 28010229 NEST 28010037 SEST 28010229 NEST 28010037 SEST 28010229 NEST 28010037 SEST 28010229 NEST 28010037 SEST 28010229 NEST 28010037 SEST 28010229 NEST 28010037 SEST 28010229 Mean Stdev Min Max Date 9/14/100 9/14/100 7/25/100 7/25/100 4/20/100 4/20/100 11/23/99 11/23/99 8/25/99 8/25/99 6/28/99 6/28/99 9/30/98 9/30/98 Hg As Cd Cr Cu Pb Mn Ni Zn DDE 0.13 7.24 0.68 52.30 18.70 30.20 15.90 124.00 2.07 0.70 41.60 4.21 160.00 108.00 112.00 42.80 271.00 374 0.15 5.90 2.10 32.10 71.60 26.60 244.00 7.30 110.00 4.7 0.20 5.40 2.20 25.60 46.40 25.60 231.00 7.70 85.00 9.5 0.19 5.30 0.78 38.30 70.40 28.00 238.00 8.60 110.00 7.4 0.24 4.80 0.83 36.40 41.10 25.00 222.00 9.70 82.00 12 0.16 6.80 0.60 32.80 93.10 27.00 264.00 9.60 110.00 0.20 5.10 0.49 27.10 44.10 26.00 249.00 9.80 85.00 8.6 0.24 9.40 0.48 40.00 68.30 83.10 197.00 12.50 94.00 6.4 0.17 13.00 0.33 28.00 125.00 103.00 246.00 9.40 130.00 11 0.18 3.71 0.43 27.50 38.40 30.50 223.00 7.12 106.00 7.6 0.26 2.65 0.44 23.30 20.70 26.70 196.00 6.01 76.10 10 3.00 0.35 39.30 23.60 28.50 234.00 9.08 63.00 0.25 2.10 0.45 37.40 15.20 28.20 195.00 7.43 35.80 7.4 5.00 87.80 4.8 4.00 34.20 4.9 0.20 5.44 0.04 2.85 0.15 2.10 0.26 13.00 0.79 0.65 0.33 2.20 32.32 55.71 38.18 228.25 8.69 90.57 7.86 5.89 31.56 26.02 22.56 1.72 25.30 2.44 23.30 15.20 25.00 195.00 6.01 35.80 4.70 40.00 125.00 103.00 264.00 12.50 130.00 12.00 2 Sediment oxygen demand has been shown to be a significant component of the total oxygen demand on a water column (Davis and Davis, 1958) and may produce anoxic conditions near the bottom during times of high respiration rates and high water temperatures and salinity. Monitoring of water quality in the SLE has shown anoxia to be a major concern (Chamberlain and Hayward, 1996; Florida Department of Environmental Protection, 2001). Pursuant to the directive of the Florida Surface Water Improvement and Management Plan, goals have been established to maintain a salinity and flow regime within the SLE which is conducive to restoring vital ecosystem components, and to maintain water quality to ensure bottom dissolved oxygen (DO) concentrations of at least 4 mg/l (state standards). Turbidity and accumulation of sediments and pollutants within the modern day SLE will necessitate significant action to achieve these goals. The impacts of increased sedimentation rates, surges of freshwater inputs and the pollutants large pulses of water carry have become a major concern to all St. Lucie Estuary stakeholders. Federal, state and local governments are currently evaluating alternatives, under the auspices of the Comprehensive Everglades Restoration Plan (CERP), to improve water quality conditions in the estuary. These improvements aim to help reestablish a viable estuarine ecosystem, including successful populations of oysters and expansion of SAV communities into areas where they are currently absent. However, deposits of unconsolidated sediment may restrict, and in some areas prevent oyster and SAV recovery. This analysis seeks to answer questions regarding the rate at which widespread deposits of unconsolidated sediment may be expected to degrade. If the current rate of sediment input is reduced via CERP or Best Management Practices (BMPs) implementation, how long will it take for the existing deposits to be transformed through in-situ biological processes into a substrate suitable for establishment of a viable ecosystem? Will natural processes be capable of transforming these sediments into a usable substrate or will more invasive management options such as dredging be required? This study will attempt to give some insight into the degradability of SLE bottom sediments and the feasibility of allowing natural processes to convert these to viable substrates. Samples of SLE sediments were subjected to extended Biochemical Oxygen Demand (BOD) analyses at differing sample concentrations and larger samples of sediment submerged in ambient SLE water were subjected to extended aeration within open containers (a bucket and beaker). The BOD and Chemical Oxygen Demand (COD) results were analyzed and compared to estimate degradability and toxicity. COD results for sediment samples taken before the extended aeration trials were compared to results for samples taken after the trials to further establish the extent of sediment degradability. Percent volatiles for samples before and after extended aeration were established and related to the degradability study. Alternate hypotheses for these experiments include: 1. The sediment BOD after an extended test (83 days) will approach the sediment COD value; 2. The COD before the extended aeration experiment will be significantly greater than the COD after treatment; 3. The sediment volatile solids component before the extended aeration treatment will be significantly greater than the sediment volatile solids after treatment; 4. There will be a significant correlation of sediment sample size with BOD value. The results of these limited studies will be disseminated to become a component of a weight-of-evidence case for establishing a proper sediment management alternative. 3 Methods In August 2000, sediment samples were collected in a water depth of about 2.5 meters, using an Eckman sediment sampler. The sample site was approximately 100 meters offshore in the South Fork of the SLE between the Roosevelt Bridge and Palm City Bridge in Stuart Florida (Figure 1). Surface water samples were collected from the same site for use as dilution water in the BOD analyses and as a medium for the extended aeration experiment. For the extended aeration experiment, two separate units were assembled to assure a sufficient volume of sediment would be recoverable after the aeration process. One unit consisted of a 4000 ml beaker filled with 100 grams of wet sediment and about 3500 ml of site water and fitted with a 2000 cc/min aquarium aerator. The second unit consisted of a 5-gallon plastic bucket filled with about 1 kg of sediment and 4 gallons of site water and fitted with a 9000 cc/min aerator. The mixtures were then aerated continuously for 82 days and samples were collected after the treatment by allowing the sediments to settle and decanting supernatant. COD analyses were performed in replicate on sediment subsamples before treatment and subsamples taken after treatment using Standard Methods 5220B – Open Reflux Method (Standard Methods, 1992). A sample size of 0.5 gram was found to give acceptable results when diluted to 50 ml with deionized water. Before and after treatment sediment subsamples were also analyzed in replicate for total solids and volatile solids per Standard Methods 2540G (Standard Methods, 1992). BOD analyses followed a modified version of Standard Methods 5210. Water from the sample site was filtered and used as the dilution water for initial runs. It was found that the oxygen demand of this water was too great to be used as dilution water. Seawater was then collected immediately north of the St. Lucie Estuary confluence with the Atlantic Ocean then filtered and diluted with demand-free water to obtain a salinity concentration similar to that of the sample ambient conditions. The solution was aerated while covered with a dark trash bag (to discourage algal growth) for a week to further lower its oxygen demand and revitalize microorganism vitality. This mixture exhibited an acceptable level of oxygen demand and was used as dilution water. A random subsample of sediment was stirred to a uniform consistency and re-stirred prior to weighing and introduction into the BOD bottles. Three sample aliquots of the same wet weight (weight set = 3 samples) were transferred to individual 300 ml BOD bottles with a dilution water rinse of the weigh boat. The weight sets were 0.1 – 0.5g in 0.1g increments. Bottles were diluted to volume, stoppered and capped. Blanks accompanied the setup for subtraction of dilution water demand from the oxygen depletion of the sample bottles. Oxygen concentrations of sample solutions and blanks were read by probe about every four days and recorded. As the DO concentration approached 1 mg/l, dilution water was decanted from each sample’s flock, re-aerated and returned. Sample aliquots larger than 0.3g per bottle depleted oxygen at a rate too great for the bottle size. These sample dilutions were omitted from the study to keep re-aeration demand uniform. Samples were re-aerated two times during the study. Total oxygen consumed over the test period was recorded and summed at the test’s end. The BOD test was performed over an 83-day period. Plots of BOD vs. time showed the curves approaching an asymptotic value. The pooled BOD83 (mean values) data was used as an estimate of the ultimate BOD (asymptotic value). Mean sediment COD before aeration treatment was compared to mean BOD83 for significant difference using a t-test on Box-Box transformed data (α= 0.05). The difference in sediment COD before and after 4 aeration was tested for statistically significant difference using a t-test (n= 4, α= 0.05). The difference in volatile solids before and after the aeration treatment was tested for significant difference using a t-test (n=6, α= 0.05). BOD verses sample concentration (weight) was analyzed for significant correlation using Pearson’s test on Box-Cox transformed data. All data was tested for normality using the Ryan-Joiner test. BOD data (individual and pooled) was plotted vs. time to estimate ultimate BOD graphically. Results Plots of BOD vs. time show BOD values approaching an asymptotic value (Figure 2). The mean BOD83 value for the pooled data was 67879 mg/kg (Table 2). The mean COD/mean BOD5 ratio was 26.6/1 while the COD/BOD83 ratio was 4.95/1. Mean sediment COD before the extended aeration treatment (335908 mg/kg) was significantly greater than the mean BOD83 (67870mg/kg) (t-test, t = 25.59, p = 0.0000). The average sediment COD before the extended aeration treatment was not significantly different than COD after treatment (t-test, t = 2.99, p = 0.0058). Sediment volatile solids composition before aeration was not significantly different than sediment volatile solids after treatment (t-test, t = 1.00, p = 0.362). The average change in sediment COD during the 82 day aeration experiment was significantly less than the average BOD83 (t-test, t = -4.89, p = 0.009). A significant correlation was found between increasing sample size and decreasing BOD5, BOD26, and BOD45. No significant correlation was found between increasing sample size and decreasing BODs after day 45 (Pearson’s, p > 0.1). Table 2. COD and Volatile Solids Analyses Results for SLE Sediment Samples (Before and After Extended Aeration Experiment). Initial COD (mg/kg) 321554 323181 349365 349531 Mean 335908 St. Dev. 15649 Final COD (mg/kg) 317042 309657 316431 319336 315617 4165 Mean St Dev Initial % Volatiles 36.9 38.4 23.7 35.3 25.31 23.47 30.51 7.06 5 Delta COD (mg/kg) 4512 13524 32934 30195 20291 13573 After % Volatiles 27.04 26.34 24.66 26.41 30.8 28.37 27.27 2.10 Bod vs. Time for SLE Sediment 140000 Series1 2 120000 3 4 100000 BOD (mg/kg) 5 80000 6 7 60000 8 9 40000 10 11 20000 12 Mean 0 0 5 10 14 19 26 29 33 36 39 45 48 52 55 62 66 69 76 83 Days Discussion General findings of these experiments suggest that the SLE sediments are composed of a high proportion of organic matter which is very resistant to degradation. BOD results show that the sediments exert a BOD which approaches an asymptotic value. After 83 days of testing, the BOD values were on the asymptotic segment of the curve, yet these values were significantly lower than the sediment COD. COD values are often used as an estimate of the ultimate BOD (the asymptotic value). COD/BOD5 ratios normally range from 2 to 5 in domestic wastewater with increasing ratios corresponding to less degradable influent (industrial components) (WPCF, 1975). The COD/BOD5 ratio for the SLE sediments was 26.6/ 1 suggesting the sediments are very resistant to degradation. The significant correlation between increasing sample size and decreasing BOD for the first 45 days also suggests the sediments were exerting a toxic affect on the decomposer community. After 45 days, any toxic affect on the decomposers seemed to have dissipated or it was consistent with regards to sample concentration. The change in sediment COD over the duration of the 82 day extended aeration experiment would be expected to approximate the BOD exerted over a similar period. The fact that mean BOD83 was significantly greater than the change in COD over the 82 day duration of the extended aeration experiment may be explained by the difference in proportion of sample size to volume of dilution water. The range in the proportion of sample size to dilution volume in the BOD test was 0.36 to 1.07 g/l. The range of proportions in the extended aeration experiment was 29 to 66 g/l. Because of the other confounding factors (aeration variability, dilution water and seed differences, etc.), toxicity can only be recognized as one of the possibilities for the great difference between expected change in COD and actual change in COD over this period. 6 Sediment monitoring within the SLE has revealed threshold effects-level (exceed TEL’s) concentrations of metals and pesticides exist in these sediments (Table 1) (MacDonald et al., 1996). Sampling has also revealed that probable effects level (PEL’s) concentrations of Copper may exist in SLE sediments. At least six different parameters exceeded PEL’s during seven sampling events at two DEP sites within the SLE since 1998. The additive effects of several pollutants at concentrations above effects-levels may contribute to overall sediment toxicity. Combined with the negative correlation of sample volume and BOD, sediment monitoring results suggest SLE sediments exert toxic effects on the SLE benthic microbial environment. However, toxicity may not be exclusively related to contaminants associated with the sediments. Under anaerobic conditions, ammonia produced by microbial activity can accumulate to toxic levels in the benthic region (Beaton, 2001). In our study, all samples were well aerated and toxicity affects were probably not related to ammonia buildup. Volatile solids analyses offer a rough estimate of the amount of organic matter present in the solid fraction of sediments (Standard Methods, 1999). Though the availability of volatile solids data for estuarine sediments in the southeastern United States is limited, the results of analyses on SLE sediments at our sample site is high (Table 2) compared to the existing data (McCabe and Hinson, 1996). Previous studies have found the volatile solids component of St. Lucie Estuary sediments to vary spatially according to hydrographic characteristics (Schrader, 1984). Volatile solids ranged from less than 10% in higher energy areas to near 30% in low energy regions with smaller sediment sizes. Our sample site fell within a low energy area of the SLE. The high volatile solids component of the sediments suggests there is a large amount of potentially degradable material available in the sediments. Degradation of this material would change the physical and chemical characteristics of the sediments and perhaps produce a substrate more amenable to ecosystem development. However, degradation of so much material would cause sediment oxygen demands detrimental to normal ecosystem function. Our study suggests that even though there is a large proportion of organics in the sediments much of it is not readily available to degradation. Organic material originating from plant cell walls has been shown to be highly resistant to degradation (Richard, 1996). Lignin, a major component of cell walls has been shown to be particularly resistant with typically only 20% available to aerobic decomposition and even less under the anaerobic conditions possible in the SLE benthos (Richard, 1996). Releases of sediment-laden fresh water from Lake Okeechobee may be a major source of the nondegradable organic material found in the SLE sediments. The organic component of sediments released from the lake bottom may have already been oxidized as much as possible in a benthic environment. The released material may be primarily lignin and cellulose based materials which degrade little with continued biological activity. The low energy St. Lucie Estuary provides an ideal settling area for these already degraded organics. Land clearing and burning of large tracts of woodlands associated with the conversion of natural landscapes within the SLE watershed, may contribute additional masses of non-degradable organics to the SLE sediment load. Anecdotal material supports these ideas. Letters to the editors of local newspapers and recollections by long time area residents, describe the SLE as very productive with good water clarity and a sandy bottom throughout much of its extent in the 1930’s and 1940’s. Some suggest catastrophic releases of sediments from Lake Okeechobee into the estuary during hurricanes of that era coated the estuary with thick deposits and changed its productivity rapidly (Stuart News, 1992). 7 Conclusions Sediments from one sample site in the SLE show they contain a high proportion of non-biodegradable organics. The origin of the organic portion is unknown, but may be associated with plant cell wall material found in bottom sediments from Lake Okeechobee and from the effects of natural landscape conversion to agricultural and urban land uses within the watershed. Even though a large portion of the sediment is non-degradable, the BOD exerted by microorganisms in the sediments may be significant enough to promote anoxic conditions in the benthic environment. Additionally a significant toxic effect on decomposer microorganisms was found at early stages of decomposition. These findings suggest SLE sediment characteristics will not change significantly due to biodegradation if allowed to remain without remediation. An active management scheme may be required if we wish to improve the present quality of this once viable ecosystem. Our study was performed using only two samples taken from one sampling site in the SLE. Statistically valid conclusions relating to sediment characteristics for the entire SLE cannot be drawn from our results. These experiments were intended only to provide a basis for further study and a bit of additional insight into selection of the most viable management options. 8 References Beaton, L. 2001. Toxicity of Sediments. http://www.science.mcmaster.ca/Biology/4S03/LB6.HTM. Accessed February 2001. Chamberlain, R. and D. Hayward, 1996. Evaluation of Water Quality Monitoring in the St. Lucie Estuary, Florida. Water Resources Bulletin. Vol 32, No. 4. Davis, W. and J. Lathrop-Davis, 1958. Brief History of Sediment Oxygen Demand Investigations. Florida Department of Environmental Protection, 2001. Unpublished Data. Water Quality Section. Port St. Lucie, Florida. Graves, G. and D. Strom, 1992. Bessey Creek and the Greater St. Lucie Estuary. Florida Department of Environmental Protection. Water Quality Section, Port St. Lucie, FL. Haunert, D. and J. Startzman, 1985. Short Term Effects of a Freshwater Discharge on the Biota of St. Lucie Estuary, Florida. South Florida Water Management District. Technical Publication 85-1. Haunert, D. 1988. Sediment Characteristics and Toxic Substances in the St. Lucie Estuary, Florida. Technical Publication 88-10. South Florida Water Management District. MacDonald, D., R. Carr, F. Calder, E. .Long, and C. Ingersoll, 1996. Development and Evaluation of Sediment Quality Guidelines for Florida Coastal Waters. Ecotoxicology 5, 253-278. McCabe, G and S. Hinton, 1996. Benthic Invertebrates and Sediment Characteristics in Freshwater, Beach Habitats of the Lower Columbia River, 1994-95. National Marine Fisheries Center. NOAA. Seattle, WA. Richard, T. 1996. Cornell University Waste Management Institute. The Effect of Lignin on Biodegradability. http://www.cfe.cornell.edu/compost/calc/lignin.html Scrader, D. 1984. Holocene Sedimentation in a Low Energy Microtidal Estuary, St. Lucie River, Florida. A Master’s Thesis submitted to the University of South Florida Department of Geology. Standard Methods, 1992. Standard Methods for the Examination of Waters and Wastewater. 18th Edition. American Public Health Association. American Water Works Association. Water Environment Foundation. Washington, DC. Stuart News, 1992. Letter to the Editor from Richard Hupfel. Staurt News. Stuart, Florida. WPCF, 1975. Operation of Wastewater Treatment Plants. MOP # 11. Water Pollution Control Federation. 9
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