Direct application of biota-sediment accumulation factors.

In the early stages of risk assessments for sites with contaminated sediments, predictions of risks are often complicated or limited by sparse or inadequate bioaccumulation data. These limitations often require risk assessors to estimate bioaccumulation relationships in order to complete the assessments of risk. In the present study, the errors are evaluated with the simple (direct) application of field measured biota-sediment accumulation factors (BSAFs) to other species at a specific location, and to the same species and/or other species at other locations within a site and to other sites. The median (90th percentile) differences in directly applying BSAFs to other species at a specific location were < or =2.1x (< or =5.1x) for fish and mussel species groups. The median (90th percentile) differences for applications across locations within a site for a specific species and to other species were < or =3.3x (< or =10x) for fish, mussel, and decapod crustacean groups. For direct application across sites, slightly larger median (90th percentile) differences were observed, i.e., < or =4.0x (< or =12x). The analysis was performed using a data set of 17,848 BSAFs spanning 392 chemicals/chemical combinations and 71 species.

Organic carbon-water concentration quotients (II(SOC)S and pi(poc)S): measuring apparent chemical disequilibria and exploring the impact of black carbon in Lake Michigan.

Chemical concentration quotients measured between water and total organic carbon (TOC) in sediment (II(SOC)) or suspended particulates (pi(poc)) in southern Lake Michigan reveal up to 2 orders of magnitude differences for polychlorinated biphenyl (PCB), dibenzo-p-dioxin (PCDD), dibenzofuran (PCDF), and polycyclic aromatic hydrocarbon (PAH) compounds with similar octanol-water partition coefficients (K(ow)S). Apparent disequilibria for PAHs, PCDDs, and PCDFs, determined as measured II(SOC)S or pi(poc)S divided by their organic carbon equilibrium partitioning values, are significantly greater than disequilibria of PCBs with similar K(ow)S. Apparent disequilibria, when adjusted for black carbon content by using published black carbon nonlinear partition coefficients (K(f,bc)S) and a Freundlich exponent (n(f)) value = 0.7, still exceed equilibrium predictions for the PAHs, PCBs, and PCDDs but with the PCDF disequilibria uniquely below equilibrium. While Monte Carlo analysis of all the variables associated with the black carbon adjusted disequilibria provides wide confidence intervals for individual chemicals, the large class disequilibria differences between PAHs and PCDFs with respect to the PCBs and PCDDs are highly significant. Use of the PCDD K(f,bc)S for calculating both the PCDF and PCDD disequilibria eliminates their extreme divergence. On the basis of the complexity of carbonaceous geosorbent effects and the apparent variable degrees of chemical sequestration in particles, the disequilibria can be adjusted by chemical class to meet expected near equilibrium conditions between suspended particles and water in the hypolimnion. Although these adjustments to the disequilibria calculations produce consistent and plausible values, the complexities of variable carbonaceous geosorbent affinities for these chemicals in Lake Michigan presently favor use of measured, rather than a priori modeled, steady-state total organic carbon-water concentration quotients indexed to TOC as biogenic organic carbon.

Toxicity equivalency values for polychlorinated biphenyl mixtures.

For aquatic, avian, and mammalian species, dioxin equivalency values (TEQs) were computed for Aroclor, Clophen, Kanechlor, Chlorofen, Sovol, Delor, Phenoclor, and Chinese polychlorinated biphenyl (PCB) mixtures by using World Health Organization toxicity equivalency factors (TEFs) and compound-specific compositional data for PCBs, polychlorinated dibenzo-p-dioxins (PCDDs), and polychlorinated dibenzofurans (PCDFs) for the individual mixtures. The TEQs were similar across the different PCB product lines for mixtures of similar chlorine content. Depending on the PCB mixture, the polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs) in the mixture contributed anywhere from 0 to 96% of the total TEQs, and the impact of PCDD/Fs was greatest for the fish TEQs. In comparison to the dioxin-like PCBs, few measurements have been performed for PCDD/Fs in the commercial PCB products.

A hybrid empirical-mechanistic modeling approach for extrapolating biota-sediment accumulation factors and bioaccumulation factors across species, time, and/or ecosystems.

An approach is presented for extrapolating field-measured biota-sediment accumulation factors (BSAFs) and bioaccumulation factors (BAFs) across species, time, and/or ecosystems. This approach, called the hybrid bioaccumulation modeling approach, uses mechanistic bioaccumulation models to extrapolate field-measured bioaccumulation data (i.e., BSAFs and BAFs) to new sets of ecological conditions. The hybrid approach predicts relative differences in bioaccumulation using food web models with two sets of ecological conditions and parameters: One set for the ecosystem where the BSAFs and/or BAFs were measured, and the other set for the ecological conditions and parameters for which the extrapolated BSAFs and/or BAFs are desired. The field-measured BSAF (or BAF) is extrapolated by adjusting the measured BSAF (or BAF) by the predicted relative difference, which is derived from two separate solutions of the food web model. Extrapolations of polychlorinated biphenyl BSAFs and BAFs for lake trout (Salvelinus namaycush) from southern Lake Michigan to Green Bay of Lake Michigan (Green Bay, WI, USA) walleye (Stizostedion vitreum) and brown trout (Salmo trutta), as well as Hudson River largemouth bass (Micropterus salmoides) and yellow perch (Perca flavescens), resulted in generally better agreement between measured and predicted BSAFs and BAFs with the hybrid approach.

Complete elimination of carbonates: a critical step in the accurate measurement of organic and black carbon in sediments.

Accurate measurement of organic carbon (OC) and black carbon (BC) in sediments requires the complete removal of coexisting inorganic carbonates from the sample before instrumental analysis. The removal of carbonates from sediments is achieved with acidification, which causes the dissolution and decomposition of carbonates with accompanying effervescence. This effervescence, or the lack of it, is commonly used as an indicator for the presence or absence of carbonates. We have found that the lack of effervescence endpoint used with the direct acidification method (adding aliquots of acid to samples) is not a reliable indicator for complete removal of carbonates from sediment samples. The ineffectiveness of the lack of effervescence endpoint, we believe, is caused by the presence of carbonates with dissolution rates much slower than those of calcite, resulting in much slower rates of visible effervescence. We propose and demonstrate a method for determining the amount of acid required for complete elimination of all carbonates using Lake Michigan (USA) sediment samples. Based on our experiences with the lack of effervescence endpoint, we recommend that in any scheme for analysis of OC and/or BC, a minimum of two samples be treated with three different levels of acidification, with the lowest level being the same as that planned for all the OC and/or BC analyses. There can be no significant differences among the OC and BC contents measured using the three different levels of acidification.

Comparison of biota-sediment accumulation factors across ecosystems.

Sets of biota-sediment accumulation factors (BSAFs) for fish were compared across ecosystems for nonionic organic chemicals. The sets of BSAFs, when plotted against each other, in log-log space, formed linear relationships and demonstrated that the relative scaling or ranking of the individual BSAFs within a set are consistent, if not the same, across ecosystems. This behavior holds for chemicals that either are, or are not, metabolized by fish. These results demonstrate that sets of BSAF values can differ but with parallel shifts in magnitude between ecosystems (for example, all of the BSAFs in the set are uniformly larger in one ecosystem, while in another they all are uniformly smaller) in response to underlying differences in ecosystem conditions and parameters such as trophic level, diet of the organisms, and distribution of the chemical between the sediment and water column.

Biota--sediment accumulation factors for polychlorinated biphenyls, dibenzo-p-dioxins, and dibenzofurans in southern Lake Michigan lake trout (Salvelinus namaycush).

A set of high-quality, age-specific biota-sediment accumulation factors (BSAFs) for polychlorinated biphenyls (PCBs), dibenzo-p-dioxins (PCDDs), and dibenzofurans (PCDFs) have been determined from concentrations measured with high-resolution gas chromatography/high-resolution mass spectrometry, by use of the 13C isotopic dilution technique, in lake trout and surficial (0-2 cm) sediment samples from southern Lake Michigan. BSAFs ranged from <0.1 to 18 for PCBs and from <0.001 to 0.32 for PCDDs and PCDFs detected in the fish. PCBs with zero or one chlorine in an ortho position had smaller BSAFs than other PCBs. PCDDs and PCDFs with chlorines at the 2,3,7,8-positions had larger BSAFs than most other PCDDs and PCDFs. The fidelity of the relative bioaccumulation potential data between independent lake trout samples, within and among age classes, suggests that differences in slight rates of net metabolism in the food chain are important and contribute to the apparent differences in BSAFs, not only for PCDDs and PCDFs but also possibly for some PCBs. A complicating factor for non-ortho- and mono-ortho-PCBs is the uncertain contribution of enhanced affinity for black carbon (and possibly volatility) acting in concert with metabolism to reduce measured BSAFs for lake trout. On the basis of the association between chemicals with apparent slight rates of metabolism and measured dioxin-like toxicity, several PCDFs with similar measured BSAFs but unknown toxicity may be candidates for toxicity testing.