Stephan A. Ryba

Effects of sample preparation on the measurement of organic carbon, hydrogen, nitrogen, sulfur, and oxygen concentrations in marine sediments

The elemental composition of marine sediment provides useful information for the study of environmental processes including biogeochemical cycling and contaminant partitioning. It is common practice to acidify marine sediment samples to remove carbonate before measuring the concentrations of organic carbon (C). To date, however the effects of acidification on the concentrations of hydrogen (H), nitrogen (N), sulfur (S) and oxygen (O) in marine sediments have not been explicitly addressed. Acidification may contaminate or alter the sediment samples and create experimental artifacts affecting the validity of resulting H/C, C/N and O/C ratios. The objective of this study was to quantify how various preparation techniques affect the measured concentrations of C, H, N, S and O in marine sediments. Effects of four different pretreatments: unacidified (whole), acidification by HCl vapor, acidification by direct addition of HCl, and combustion were evaluated using five marine sediments and a standard reference material. The magnitude of carbonate loss between the vapor and direct acidification treatments was evaluated using stable C isotope analysis. Carbonates were most effectively removed by direct addition of HCl; and our results agree with findings of other studies which found direct addition of HCl to be the most accurate method for measuring organic C. However, the acid treatments elevated the apparent concentration of H and O; and in a few cases concentrations of N and S were significantly affected by acidification. In general, combustion significantly reduced all elemental concentrations compared to the whole sample. Based on these results, we recommend analysis of the untreated whole sediment for determining N, H, O, and S.

Using mussel isotope ratios to assess anthropogenic nitrogen inputs to freshwater ecosystems

Stable nitrogen isotope ratios (δ15N) of freshwater mussels from a series of lakes and ponds wererelated to watershed land use characteristics to assess their utility in determining the source ofnitrogen inputs to inland water bodies. Nitrogen isotope ratiosmeasured in freshwater musselsfrom 19 lakes and ponds in Rhode Island, U.S.A., ranged from4.9–12.6‰ and were found tosignificantly correlate with the fraction of residential development in 100 and 200 m bufferzones around the ponds. Mussel δ15N values in 12 of the 19 ponds also showed significantcorrelation with average dissolved nitrate concentrations, which ranged from 23–327 μg L-1.These observations, in light of previous studies which link elevatedδ15N values of nitrogenderived from septic wastewater with those seen in biota, suggest that mussel isotope ratios mayreflect nitrogen source in freshwater ecosystems. We followed aniterative approach usingmultiple regression analysis to assess the relationship between musselδ15N and the land usecategories fraction residential development, fraction feedlotagriculture, fraction row-cropagriculture, and fraction natural vegetation in 100 and 200 m bufferzones and pond watersheds.From this we developed a simple regression model to predict musselδ15N from the fraction ofresidential development in the 200 m buffer zone around the pond.Subsequent testing with datafrom 16 additional sites in the same ecoregion led us to refine themodel by incorporating thefraction of natural vegetation. The overall average absolute differencebetween measured andpredicted δ15N values using the two-parameter model was 1.6‰. Potential sources of error inthe model include differences in the scale and categorization ofland-use data used to generate andtest the model, differences in physical characteristics, such asretention time and range ofresidential development, and exclusion of sources of enrichednitrogen such as runoff from feedlot operations or increased nitrogen loading from inefficient or failed septic systems.

Soil respiration rates in coastal marshes subject to increasing watershed nitrogen loads in southern New England, USA.

Mean soil respiration rates (carbon dioxide efflux from bare soils) among salt marshes in Narragansett Bay, RI ranged from 1.7–7.8 μmol m−2 s−1 inSpartina patens in high marsh zones and 1.7–6.0 μmol m−2 s−1 inS. alterniflora in low marsh zones. The soil respiration rates significantly increased along a gradient of increasing watershed nitrogen (N) loads (S. alterniflora, R2 = 0.95, P = 0.0008;S. patens, R2 = 0.70, P = 0.02). As the soil respiration increased, the percent carbon (C) and N in the soil surface layer decreased in theS. alterniflora, suggesting that in part, the increased soil respiration rates are contributing to the increased turnover of labile organic matter. In contrast, there were no apparent relationships between the soil respiration rates in the high marsh and the soil C and N contents of the surface layer. However, there was a broad-scale pattern and significant inverse relationship between the high marsh soil respiration rates and the landscape belowground biomass ofS. patens. As more and more salt marsh systems are subjected to increasing nutrient loads, decomposition rates of soil organic matter may increase in marsh soils leading to higher turnover rates of C and N.

Spatial variability in Mussels used to assess base level nitrogen isotope ratio in freshwater ecosystems

Freshwater mussels have been used to establish base level nitrogen isotope ratio values (δ15N) used in trophic position and food web studies in freshwater ecosystems. In this study, we assess the variability introduced when using unionid mussels in this manner by investigating the spatial variation in δ15N values in mussels from different locations in shallow freshwater ponds, and also differences in δ15N in different tissue types in the mussels. Results from the analysis of adductor, foot and a section of the mantle tissues from mussels across all ponds showed that adductor tissue was consistently enriched by about 1‰ versus the mantle and foot. The foot showed the least variability which, coupled with ease in obtaining consistent samples, led us to select this tissue type for subsequent analysis. The six ponds included in the study had average mussel δ15N values ranging from 4.9‰ to 11.9‰. Four of the six ponds showed no significant within pond differences between δ15N values from mussels collected at different sampling sites. The range of mussel δ15N values obtained from within ponds showed that using data from a single mussel to assess baseline δ15N values would result in the introduction of a maximum error of 0.56 of a trophic level to subsequent trophic position calculations.

Exploratory Analysis of the Effects of Particulate Characteristics on the Variation in Partitioning of Nonpolar Organic Contaminants to Marine Sediments

The partitioning of nonpolar organic contaminants to marine sediments is considered to be controlled by the amount of organic carbon present. However, several studies propose that other characteristics of sediments may affect the partitioning of contaminants. For this exploratory analysis, we measured 19 sediment characteristics from five marine sediments and 11 characteristics of humic acids extracted from the sediments. These characteristics included elemental composition, grain size, soot carbon, polarity indices and molar ratios. Each individual characteristic and combinations of these characteristics were then used to normalize partition coefficients (Kp) generated for three organic contaminants: lindane, fluoranthene and a tetrachlorinated biphenyl (PCB). A coefficient of variation (CV) was then calculated for each contaminant to determine which normalization characteristic (individually or in combination) resulted in the lowest variability in partitioning between study sediments. For lindane and the PCB. normalization by the amount of sediment organic carbon resulted in the lowest variability in partition coefficients with CVs of 16.2% and 37.7%. respectively. However, normalization of fluoranthene by silt content resulted in lower CVs than those generated by organic carbon normalization: 31.0% vs. 37.6%. Normalization of contaminants Kps by combined values of sediment characteristics resulted in lower CVs but only by a few percent. Using humic acid characteristics, humic organic carbon reduced variability between sediments most effectively. But only the normalized fluoranthene values had a CV (i.e., 25.4%) lower than the one based on normalization by sediment characteristics. When combined, humic acid characteristics resulted in lower CVs than normalization by individual or combinations of sediment characteristics for fluoranthene and the PCB with CVs of 19.3% and 28.7%, respectively. This analysis indicates variability associated with the partitioning of some organic contaminants to marine sediments can be further reduced when normalization by sediment characteristics other than organic carbon are utilized.

Evaluation of the effects of coal fly ash amendments on the toxicity of a contaminated marine sediment.

Approaches for cleaning up contaminated sediments range from dredging to in situ treatment. In this study, we discuss the effects of amending reference and contaminated sediments with coal fly ash to reduce the bioavailability and toxicity of a field sediment contaminated with polycyclic aromatic hydrocarbons (PAHs). Six fly ashes and a coconut charcoal were evaluated in 7-d whole sediment toxicity tests with a marine amphipod (Ampelisca abdita) and mysid (Americamysis bahia). Fly ashes with high carbon content and the coconut charcoal showed proficiency at reducing toxicity. Some of the fly ashes demonstrated toxicity in the reference treatments. It is suspected that some of this toxicity is related to the presence of ammonia associated with fly ashes as a result of postoxidation treatment to reduce nitrous oxide emissions. Relatively simple methods exist to remove ammonia from fly ash before use, and fly ashes with low ammonia content are available. Fly ashes were also shown to effectively reduce overlying water concentrations of several PAHs. No evidence was seen of the release of the metals cadmium, copper, nickel, or lead from the fly ashes. A preliminary 28-d polychaete bioaccumulation study with one of the high-carbon fly ashes and a reference sediment was also performed. Although preliminary, no evidence was seen of adverse effects to worm growth or lipid content or of accumulation of PAHs or mercury from exposure to the fly ash. These data show fly ashes with high carbon content could represent viable remedial materials for reducing the bioavailability of organic contaminants in sediments.

Effects of different forms of organic carbon on the partitioning and bioavailability of nonylphenol

Oxygenated nonpolar organic contaminants (NOCs) are underrepresented in studies of the partitioning and bioavailability of NOCs, including nonylphenol. In this investigation, we evaluated the toxicity, partitioning, and bioavailability of nonylphenol as affected by different forms of organic carbon. Along with organic carbon content, the role of organic carbon polarity was assessed. Toxicity of nonylphenol to a mysid and amphipod was comparable to results reported in the literature for marine organisms with median lethal concentrations (LC50s) of 82.3 and 236 microg/L, respectively. The presence of the different forms of organic carbon in every instance altered, often statistically significantly, the toxicity and bioavailability of the nonylphenol and increased the LC50 by approximately a factor of two. Partition coefficients (KPs) for nonylphenol ranged from 21.3 for cellulose to 9,770 for humic acid; log organic carbon-normalized partition coefficients (KOCs) ranged from 1.71 for cellulose to 4.71 for sediment. An exercise to predict nonylphenol effects using our toxicity data and normalized partition coefficients indicated organic carbon content was most protective and also highlighted the need for further research to better understand nonylphenol bioavailability. These data suggested that with regard to partitioning and bioavailability, the oxygenated NOC nonylphenol behaves like conventional NOCs. The data also suggest that, with refinements, polarity may have some advantages in predicting nonylphenol bioavailability.

Interaction of planar and nonplanar organic contaminants with coal fly ash: Effects of polar and nonpolar solvent solutions

Coal fly ash has a very high sorption capacity for a variety of anthropogenic contaminants and has been used to cleanse wastewater of pollutants for approximately 40 years. Like other black carbons, the planar structure of the residual carbon in fly ash results in elevated affinities for planar organic contaminants, such as polycyclic aromatic hydrocarbons (PAHs) and some polychlorinated biphenyls (PCBs). The present study was performed to understand better the mechanisms affecting the strong interaction between planar contaminants and coal fly ash. The removal of 10 PCBs and 10 PAHs by several fly ashes and other sorbents was evaluated under different experimental conditions to highlight the intermolecular forces influencing adsorption. Varying fly ash concentration and solvent system composition indicated that dispersive interactions were most prevalent. For the PCBs, empirical results also were compared to molecular modeling estimates of the energy necessary for the PCB molecule to assume a planar conformation (PCe). The PCe levels ranged from 8 to 25 kcal/mol, depending on the degree of ortho-substituted chlorination of the PCB. A significant correlation between PCe and PCB removal from solution was observed for the fly ashes and activated carbon, whereas the nonplanar sorbent octadecyl (C18) indicated no relationship. These findings demonstrate the strong interaction between black carbon fly ash and planar organic contaminants. Furthermore, as exemplified by the PCBs, these results show how this interaction is a function of a contaminants ability to assume a planar conformation.

Mercury and stable isotopes of carbon and nitrogen in mink

Total Hg concentrations and values of stable isotopes (delta(15)N, delta(13)C) in tissues of mink (Mustela vison) captured in Rhode Island (USA) during winters of 1999 to 2004 were statistically distinct based on location. Mink captured in salt marsh environments (salt marsh group mink [SMGM]) had significantly lower mean Hg concentrations in liver and muscle tissue, and significantly higher delta(15)N and delta(13)C values in muscle, than those in corresponding samples of mink from upland freshwater locations (upland group mink [UPGM]). Stomach content samples obtained from the mink carcasses showed that fish, frogs, and crayfish were the dominant food items in UPGM, but in SMGM, fish predominated. Significant correlations were found for total Hg concentrations and stable isotope values between stomach contents and tissues. Comparisons of increases in Hg concentrations and delta(15)N values from stomach contents to muscle tissue showed nonsignificant differences between UPGM and SMGM for Hg concentrations (SMGM, factor of 4.2; UPGM, factor of 3.9) and delta(15)N values (SMGM, difference of 3.9 per thousand; UPGM, difference of 3.1 per thousand). These results suggest that the length of the trophic step and the extent of accumulation of Hg were approximately equal in both mink groups despite the differences in dietary composition and possible differences in accumulation of organic and inorganic Hg. The correspondence of stable isotope values and Hg concentrations between mink tissues and their stomach contents indicates that use of stomach content analysis to identify major prey items, followed by collection and analysis of appropriate field prey, may represent an approach for estimating Hg exposure to mink.

Marine sediment toxicity identification evaluation methods for the anionic metals arsenic and chromium

Marine sediments accumulate a variety of contaminants and, in some cases, demonstrate toxicity because of this contamination. Toxicity identification evaluation (TIE) methods provide tools for identifying the toxic chemicals causing sediment toxicity. Currently, whole-sediment TIE methods are not available for anionic metals like arsenic and chromium. In the present paper, we describe two new anion-exchange resins used in the development of whole-sediment TIE methods for arsenic and chromium. Resins were shown to reduce whole-sediment toxicity and overlying water concentrations of the anionic metals. Sediment toxicity, expressed as the median lethal concentration, was reduced by a factor of two to a factor of nearly six between amended sediment treatments containing resin and those without resin. Aqueous concentrations of arsenic and chromium in the toxicity exposures decreased to less than the detection limits or to concentrations much lower than those measured in treatments without resin. Interference studies indicated that the anion-exchange resins had no significant effect on concentrations of the representative pesticide endosulfan and minimal effects on concentrations of ammonia. However, the anion-exchange resins did significantly reduce the concentrations of a selection of cationic metals (Cd, Cu, Ni, Pb, and Zn). These data demonstrate the utility of anion-exchange resins for determining the contribution of arsenic and chromium to whole-sediment toxicity. The present results also indicate the importance of using TIE methods in a formal TIE structure to ensure that results are not misinterpreted. These methods should be useful in the performance of marine whole-sediment TIEs.