Jason M. Conder

Evaluation of surrogate measures of cadmium, lead, and zinc bioavailability to Eisenia fetida

We evaluated weak-electrolyte (0.1 M Ca(NO3)2) soil extractions and ion-exchange membranes coated with a metal chelator as measures of Cd, Pb, and Zn bioavailability in spiked artificial soil by comparing their metal availability estimates to acute lethal toxicity in the earthworm Eisenia fetida. Ca(NO3)2 extractions were precisely related to toxicity in all toxicity tests, and enabled the development of time-independent LC50S (incipient lethal-levels, ILLs) calculated using exposure levels based on extraction data. ILLs with 95% CIs for the Cd, Pb, and Zn toxicity tests were 9.8 (9.4-10.3), 1.16 (1.11-1.22), and 6.33 (6.18-6.49) Ca(NO3)2-extractable mmol metal/kg soil, respectively. Mixture toxicity of Cd, Pb, and Zn, assessed using the toxic unit (TU) approach, was 1.35 TU, suggesting additivity. Chelating ion-exchange membrane uptake was variable, and not well related to toxicity. Weak-electrolyte extractions show promise as precise, inexpensive surrogate measures of Cd, Pb, and Zn bioavailability in soil.

Method for determining toxicologically relevant cadmium residues in the earthworm Eisenia fetida

We investigated a method to isolate toxicologically relevant Cd in earthworms (Eisenia fetida) exposed in a 14-d Cd bioaccumulation study. A procedure involving acid insoluble ash (AIA) content was combined with homogenization and centrifugation techniques to divide total earthworm Cd burdens into supernatant (metallothionein-bound), pellet (toxicologically active), and soil-associated Cd fractions. Whereas the supernatant fraction of the earthworm digests increased linearly throughout the exposure period (from approximately 0 to 3.59 mmol/kg), the pellet fraction reached a steady-state concentration (95% CI) of 1.2 (0.9-1.4) mmol/kg, suggesting the ability of the metallothionein detoxification system to sequester incoming Cd. The AIA method was useful for correcting earthworm Cd concentrations for ingested soil-associated Cd and observing soil ingestion, which was suppressed in Cd-spiked artificial soil (1.06 (0.57-1.55)%) compared to controls (17.25 (14.36-20.15)%). These methods may be useful in investigating soil ingestion and Cd uptake and detoxification in earthworms.

Recommendations for the assessment of TNT toxicity in sediment

Previous investigations of the ecotoxicity of TNT in spiked sediments noted the rapid degradation and disappearance of the toxicant, yet little is understood regarding the effects of this process on toxicity and subsequent derivation of toxicity reference values. We conducted environmental fate studies and 28-d sediment toxicity tests with benthic oligochaete worms (Tubifex tubifex) with sediments spiked at three different TNT concentrations (440, 1,409, and 4,403 nmol/g dry wt) aged for 1, 8, and 29 d. Because of rapid degradation of TNT, disappearance of degradation products, and partitioning to overlying water, only 25 to 40% of the added nitroaromatic mass balance was associated with sediment immediately after spiking. Lethal toxicity decreased with aging time and was best described by measured sediment nitroaromatic concentrations (sum of TNT and degradation products) at the beginning of exposure, with a median lethal concentration of nitroaromatic compounds of 184 nmol/g dry weight. To accurately describe the ephemeral exposure doses of TNT and its degradation products during toxicity tests with spiked sediments, we suggest that sediments should be aged at least 8 to 14 d after spiking, exposure should be based on measured sediment concentrations or chemical measures of availability, exchange of overlying water should be avoided or minimized, and short-term toxicity tests should be considered.

Solid-phase microextraction for predicting the bioavailability of 2,4,6-trinitrotoluene and its primary transformation products in sediment and water.

Disposable solid-phase microextraction fibers (SPMEs) were used to measure the availability of 2,4,6-trinitrotoluene (TNT) and its two primary transformation products, 2-amino-4,6-dinitrotoluene (2ADNT) and 4-amino-2,6-dinitrotoluene (4ADNT). The SPMEs (85-microm polyacrylate) and sediment-dwelling oligochaetes (Tubifex tubifex) were exposed to TNT-spiked sediment, to TNT-spiked sediment amended with activated carbon, and to TNT-, 2ADNT-, and 4ADNT-spiked water. Sediment concentration was a poor predictor of bioavailability in unamended and carbon-amended sediments (r2 = 0.14-0.73) The activated carbon amendment reduced the bioavailability of compounds in carbon-amended sediment, causing the relationships between Tubifex concentrations and sediment concentrations to differ significantly between unamended and carbon-amended sediment for all compounds. In contrast, SPME TNT concentrations predicted Tubifex TNT concentrations (r2 = 0.54-0.79). and regression models did not differ significantly among the three TNT-spiked matrices. The SPME 2ADNT and 4ADNT concentrations also were predictive of Tubifex 2ADNT and 4ADNT concentrations (r2 = 0.44-0.90). Relationships between Tubifex concentrations and SPME concentrations were the same between unamended and carbon-amended TNT-spiked sediments for 2ADNT and 4ADNT; however, the relationship in sediment (pooled data) differed from the relationship found in 2ADNT- and 4-ADNT-spiked water. The SPMEs provided carbon amendment-independent measures of ADNT availability in sediment and matrix-independent measures of TNT availability among the three matrices. The SPMEs show promise for predicting bioavailable organic compounds in sediment and water.

Solid phase microextraction fibers for estimating the toxicity of nitroaromatic compounds

Solid phase microextraction fibers are useful for investigating bioavailable organic contaminants in complex environmental matrixes such as aquatic sediments. Solid phase microextraction fibers are polymer-coated silica fibers that sorb dissolved organic compounds from water and sediment. We investigated their concentrations as measures of exposure for 2,4,6-trinitrotoluene and its degradation products in acute sediment and water-only toxicity tests with Tubifex tubifex, Chironomus tentans, and Ceriodaphnia dubia. Results from these exposures allowed us to compare solid phase microextraction fibers concentrations to two conventional measures of toxicant dose: external matrix (water, sediment) and internal (organism) concentrations. Because trinitrotoluene degrades within sediment and organisms, doses based on sediment, water, and organism concentrations were calculated using the molar sum of trinitrotoluene and its nitroaromatic degradation products. Among species and matrixes, median lethal doses based on solid phase microextraction fiber and organism concentrations ranged from 12.6 to 55.3 (μmol nitroaromatic per ml polyacrylate and 83.4 to 172.3 nmol nitroaromatic per gram tissue, wet weight, respectively. In contrast to matrix concentrations, which are specific to sediment or water, both organism and solid phase microextraction fiber concentrations appeared to provide measures of dose independent of exposure scenario (sediment or water). Median lethal doses based on fiber concentrations in whole-sediment and water-only Tubifex tubifex toxicity tests were within a factor of 1.1 (18.7 and 21.3 (μmol nitroaromatic per ml polyacrylate, respectively). Median lethal doses based on organism concentrations were within a factor 1.4 for Chironomus tentans exposed in water-only or whole-sediment scenarios (118.0 and 83.4 nmol nitroaromatic per gram tissue, wet weight, respectively). Solid phase microextraction fibers may provide a powerful chemical estimate of exposure with which to understand bioavailability and toxicity of organic compounds to benthic organisms.

Modeling avian exposures to perfluoroalkyl substances in aquatic habitats impacted by historical aqueous film forming foam releases

Releases of Perfluoroalkyl and Polyfluoroalkyl Substances (PFASs) associated with Aqueous Film Forming Foams (AFFFs) have the potential to impact on-site and downgradient aquatic habitats. Dietary exposures of aquatic-dependent birds were modeled for seven PFASs (PFHxA, PFOA, PFNA, PFDA, PFHxS, PFOS, and PFDS) using five different scenarios based on measurements of PFASs obtained from five investigations of sites historically-impacted by AFFF. Exposure modeling was conducted for four avian receptors representing various avian feeding guilds: lesser scaup (Aythya affinis), spotted sandpiper (Actitis macularia), great blue heron (Ardea herodias), and osprey (Pandion haliaetus). For the receptor predicted to receive the highest PFAS exposure (spotted sandpiper), model-predicted exposure to PFOS exceeded a laboratory-based, No Observed Adverse Effect Level exposure benchmark in three of the five model scenarios, confirming that risks to aquatic-dependent avian wildlife should be considered for investigations of historic AFFF releases. Perfluoroalkyl sulfonic acids (PFHxS, PFOS, and PFDS) represented 94% (on average) of total PFAS exposures due to their prevalence in historical AFFF formulations, and increased bioaccumulation in aquatic prey items and partitioning to aquatic sediment relative to perfluoroalkyl carboxylic acids. Sediment-associated PFASs (rather than water-associated PFASs) were the source of the highest predicted PFAS exposures, and are likely to be very important for understanding and managing AFFF site-specific ecological risks. Additional considerations for research needs and site-specific ecological risk assessments are discussed with the goal of optimizing ecological risk-based decision making at AFFF sites and prioritizing research needs.

Performance of an in situ activated carbon treatment to reduce PCB availability in an active harbor

In situ amendment of surface sediment with activated carbon is a promising technique for reducing the availability of hydrophobic organic compounds in surface sediment. The present study evaluated the performance of a logistically challenging activated carbon placement in a high-energy hydrodynamic environment adjacent to and beneath a pier in an active military harbor. Measurements conducted preamendment and 10, 21, and 33 months (mo) postamendment using in situ exposures of benthic invertebrates and passive samplers indicated that the targeted 4% (by weight) addition of activated carbon (particle diameter ≤74 µm) in the uppermost 10 cm of surface sediment reduced polychlorinated biphenyl availability by an average (± standard deviation) of 81 ± 11% in the first 10 mo after amendment. The final monitoring event (33 mo after amendment) indicated an approximate 90 ± 6% reduction in availability, reflecting a slight increase in performance and showing the stability of the amendment. Benthic invertebrate census and sediment profile imagery did not indicate significant differences in benthic community ecological metrics among the preamendment and 3 postamendment monitoring events, supporting existing scientific literature that this approximate activated carbon dosage level does not significantly impair native benthic invertebrate communities. Recommendations for optimizing typical site-specific assessments of activated carbon performance are also discussed and include quantifying reductions in availability and confirming placement of activated carbon. Environ Toxicol Chem 2018;37:1767-1777. Published 2018 Wiley Periodicals, Inc. on behalf of SETAC. This article is a US government work and, as such, is in the public domain in the United States of America.

Evaluation of PCB Availability in Sediment after the Application of an Activated Carbon Amendment at an Active U.S. Naval Shipyard

The objective of this project was to demonstrate and validate placement, stability and performance of reactive amendments for treatment of contaminated sediments in active Department of Defense (DoD) harbor settings. This project extends pilot-scale testing of the application of activated carbon (AC) to decrease the bioavailability of polychlorinated biphenyls (PCBs) in contaminated sediment to near full-scale demonstration under realistic conditions at an active DoD harbor site. The evaluation was conducted at Pier 7 of the Puget Sound Naval Shipyard and Intermediate Maintenance Facility (PSNS & IMF) in Bremerton, Washington.

Lethal critical body residues as measures of Cd, Pb, and Zn bioavailability and toxicity in the earthwormEisenia fetida

Earthworm heavy metal concentrations (critical body residues, CBRs) may be the most relevant measures of heavy metal bioavailability in soils and may be linkable to toxic effects in order to better assess soil ecotoxicity. However, as earthworms possess physiological mechanisms to secrete and/or sequester absorbed metals as toxicologically inactive forms, total earthworm metal concentrations may not relate well with toxicity. The objectives of this research were to: i) develop LD50s (total earthworm metal concentration associated with 50% mortality) for Cd, Pb, and Zn; ii) evaluate the LD50 for Zn in a lethal Zn-smelter soil; iii) evaluate the lethal mixture toxicity of Cd, Pb, and Zn using earthworm metal concentrations and the toxic unit (TU) approach; and iv) evaluate total and fractionated earthworm concentrations as indicators of sublethal exposure. Earthworms (Eisenia fetida (Savigny)) were exposed to artificial soils spiked with Cd, Pb, Zn, and a Cd−Pb−Zn equitoxic mixture to estimate lethal CBRs and mixture toxicity. To evaluate the CBR developed for Zn, earthworms were also exposed to Zn-contaminated field soils receiving three different remediation treatments. Earthworm metal concentrations were measured using a procedure devised to isolate toxicologically active metal burdens via separation into cytosolic and pellet fractions. Lethal CBRs inducing 50% mortality (LD50, 95% CI) were calculated to be 5.72 (3.54–7.91), 3.33 (2.97–3.69), and 8.19 (4.78–11.6) mmol/kg for Cd, Pb, and Zn, respectively. Zn concentrations of dead earthworms exposed to a lethal remediated Zn-smelter soil were 3-fold above the LD50 for Zn and comparable to earthworm concentrations in lethal Zn-spiked artificial soils, despite a 14-fold difference in total soil Zn concentration between lethal field and artificial soils. An evaluation of the acute mixture toxicity of Cd, Pb, and Zn in artificial soils using the Toxic Unit (TU) approach revealed an LD50 (95% CI) of 0.99 (0.57–1.41) TU, indicating additive toxicity. Total Cd, Pb, and Zn concentrations in earthworms were good indicators of lethal metal exposure, and enabled the calculation of LD50s for lethality. The Zn-LD50 developed in artificial soil was applicable to earthworms exposed to remediated Zn-smelter soil, despite a 14-fold difference in total soil Zn concentrations. Mixture toxicity evaluated using LD50s from each single metal test indicated additive mixture toxicity among Cd, Pb, and Zn. Fractionation of earthworm tissues into cytosolic and pellet digesis yielded mixed results for detecting differences in exposure at the sublethal level. CBRs are useful in describing acute Cd, Pb, and Zn toxicity in earthworms, but linking sublethal exposure to total and/or fractionated residues may be more difficult. More research on detoxification, regulation, and tissue and subcellular partitioning of heavy metals in earthworms and other invertebrates is needed to establish the link between body residue and sublethal exposure and toxicity.