Biomonitoring and assessment of monomethylmercury exposure in aqueous systems using the DGT technique.

A series of laboratory experiments was conducted under realistic environmental conditions to test the ability of the Diffusive Gradient in Thin film (DGT) technique to mimic monomethylmercury (MMHg) bioaccumulation by a clam (Macoma balthica, Baltic clam). Using isotope enriched MMHg as tracers, bioavailability was determined by comparing the rate of MMHg uptake by novel DGT devices and sentinel organism over time. Experiments were conducted under varying conditions of salinity and MMHg speciation. Depending on MMHg level and speciation in the dissolved phase, MMHg uptake rates by the sentinel organism varied greatly from 0.4 to 2.4Lg(-1)d(-1). Reproducibilities of MMHg uptakes by DGT and clams were estimated at 7 and 38%, respectively. A significant linear relationship (log basis) between MMHg accumulation by DGT and clams was observed (r(2)=0.89). The study demonstrates that DGT results reasonably predict MMHg uptake by clams from the aqueous phase and provide the basis for application of the DGT device as a surrogate for sentinel organism for monitoring bioavailable MMHg.

Effects, transfer, and fate of RDX from aged soil in plants and worms.

The objectives of this study were to provide data that can be used to predict exposure-based effects of RDX in aged soil on multiple endpoint organisms representing two trophic levels. These data can be used for defining criteria or reference values for environmental management and conducting specific risk assessment. Dose-response experiments formed the basis for the evaluation of toxic effects and transfer of contaminants from soil into two trophic levels. Long-term exposure tests were conducted to evaluate chronic, sublethal, toxicity and transfer of aged soil-based explosives, with RDX as main contaminant. In these tests, plants were exposed for 55 days in the greenhouse, biomass was determined and residues of explosives parent compounds and RDX metabolites were analyzed using HPLC techniques. Worms were exposed for 28 days (Eisenia fetida) and 42 days (Enchytraeus crypticus) in the laboratory, biomass and number were determined, and tissues were analyzed for explosives compounds. The plants tolerated concentrations up to 1,540 mg RDX kg(-1) soil-DW. Biomass of Lolium perenne was not significantly related to soil-RDX concentration, while biomass of Medicago sativa significantly increased. No screening benchmark for RDX in soil for plants was calculated, since concentrations up to 1,540 mg kg(-1) soil failed to reduce biomass by 20% as required for a LOEC. RDX, RDX-metabolite MNX, and accompanying HMX concentrations in plants were significantly related to concentrations in soil after 55 days of exposure (RDX: R(2) = 0.77-0.89; MNX R(2) = 0.53-0.77; HMX: R(2) = 0.67-0.71). The average bioconcentration factors (BCF) were for RDX 17 in L. perenne and 37 in M. sativa, and for HMX 2 in L. perenne and 44 in M. sativa. The worms also tolerated concentrations up to 1,540 mg RDX kg(-1) soil-DW. Biomass of E. fetida adults decreased with soil-RDX concentration, and a LOEC of 1,253 mg kg(-1) soil-DW was estimated. RDX concentrations in E. fetida were significantly related to concentrations in soil after 28-day exposure (R(2) = 0.88). The average BCF in E. fetida for RDX was 1. Because in response to exposure to RDX-contaminated soil the RDX concentrations in plants increased initially and decreased subsequently, while those in worms increased continuously, RDX in worm tissues may accumulate to higher concentrations than in plant tissues, regardless of the low average BCF for worms.

Tolerance towards explosives, and explosives removal from groundwater in treatment wetland mesocosms.

A short-term study was performed to determine the feasibility of using constructed wetlands to remove explosives from groundwater, and to assess accumulation of parent explosives compounds and their known degradation compounds in wetland plants. Tolerance towards explosives in submersed and emergent plants was screened over a range of 0 to 40 mg L(-1). Tolerance varied per compound, with TNT evoking the highest, 2NT the lowest, and 24DNT, 26DNT, and RDX an intermediate growth reducing effect. Submersed plants were more sensitive to TNT than emergent ones. A small-scale 4-month field study was carried out at the Volunteer Army Ammunition Plant, Chattanooga, TN. In this surface-flow, modular system, the influent contained high levels (>2.1 mg L(-1)) of TNT, 2,4DNT, 2,6DNT, 2NT, 3NT, and 4NT, and the HRT was 7 days. The performance criteria of US EPA treatment goals for local discharge of 2,4DNT concentration <0.32 mg L(-1), and 26DNT concentration <0.55 mg L(-1) were not met at the end of the experiment, although explosives levels were greatly reduced. Low levels of 2ADNT and 4ADNT were transiently observed in the plant biomass. Results of two other, older, constructed wetlands, however, indicated that in these systems treatment goals were met most of the time, residues of explosives parent compounds and known degradation compounds in plant tissues were low and/or transient, and in substrates were low.

Environmental behavior of explosives in groundwater from the Milan Army Ammunition Plant in aquatic and wetland plant treatments. Uptake and fate of TNT and RDX in plants.

Uptake and fate of TNT and RDX by three aquatic and four wetland plants were studied using hydroponic, batch, incubations in explosives-contaminated groundwater amended with [U-14C]-TNT or [U-14C]-RDX in the laboratory. Substrates in which the plants were rooted were also tested. Plants and substrates were collected from a small-scale wetland constructed for explosives removal, and groundwater originated from a local aquifer at the Milan Army Ammunition Plant. This study demonstrated rapid uptake of [U-14C]-TNT derived 14C, concentration at the uptake sites and limited transport in all plants. Per unit of mass, uptake was higher in submersed than in emergent species. Biotransformation of TNT had occurred in all plant treatments after 7-day incubation in 1.6 to 3.4 mg TNT L-i, with labeled amino-dinitrotoluenes (ADNTs), three unidentified compounds unique for plants, and mostly polar products as results. Biotransformation occurred also in the substrates, yielding labeled ADNT, one unidentified compound unique for substrates, and polar products. TNT was not recovered by HPLC in plants and substrates after incubation. Uptake of [U-14C]-RDX derived 14C in plants was slower than that of TNT, transport was substantial, and concentration occurred at sites where new plant material was synthesized. As for TNT, uptake per unit of mass was higher in submersed than in emergent species. Biotransformation of RDX had occurred in all plant treatments after 13-day incubation in 1.5 mg RDX L-1, with one unidentified compound unique for plants, and mostly polar products as results. Biotransformation had occurred also in the substrates, but to a far lower extent than in plants. Substrates and plants had one unidentified 14C-RDX metabolite in common. HPLC analysis confirmed the presence of RDX in most plants and in three out of four substrates at the end of the incubation period.

Environmental behavior of explosives in groundwater from the Milan Army Ammunition Plant in aquatic and wetland plant treatments. Removal, mass balances and fate in groundwater of TNT and RDX.

Phytoremediation of 2,4,6-trinitrotoluene (TNT) and hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) in groundwater using constructed wetlands is a potentially economical remediation alternative. To evaluate Explosives removal and fate was evaluated using hydroponic batch incubations of plant and substrate treatments with explosives-contaminated groundwater amended with [U-14C]-TNT or [U-14C]-RDX. Plants and substrates were collected from a small-scale wetland constructed for explosives removal, and groundwater originated from a local aquifer at the Milan Army Ammunition Plant. The study surveyed three aquatic, four wetland plant species and two substrates in independent incubations of 7 days with TNT and 13 days with RDX. Parent compounds and transformation products were followed using 14C and chemical (HPLC) analyses. Mass balance of water, plants, substrates and air was determined. It was demonstrated that TNT disappeared completely from groundwater incubated with plants, although growth of most plants except parrot-feather was low in groundwater amended to contain 1.6 to 3.4 mg TNT L-1. Highest specific removal rates were found in submersed plants in water star-grass and in all emergent plants except wool-grass. TNT declined less with substrates, and least in controls without plants. Radiolabel was present in all plants after incubation. Mineralization to 14CO2 was very low, and evolution into 14C-volatile organics negligible. RDX disappeared less rapidly than TNT from groundwater. Growth of submersed plants was normal, but that of emergent plants reduced in groundwater amended to contain 1.5 mg RDX L-1. Highest specific RDX removal rates were found in submersed plants in elodea, and in emergent plants in reed canary grass. RDX failed to disappear with substrates. Mineralization to 14CO2 was low, but relatively higher than in the TNT experiment. Evolution into 14C-volatile organics was negligible. Important considerations for using certain aquatic and wetland plants in constructed wetlands aimed at removing explosives from water are: (1) plant persistence at the explosives level to which it is exposed, (2) specific plant-mass based explosives removal rates, (3) plant productivity, and (4) fate of parent compounds and transformation products in water, plants, and sediments.

Screening of aquatic and wetland plant species for phytoremediation of explosives-contaminated groundwater from the Iowa Army Ammunition Plant.

The results of this study indicate that the presence of plants did enhance TNT and TNB removal from IAAP groundwater. Most effective at 25 degrees C were reed canary grass, coontail and pondweed. Groundwater and plant tissue analyses indicate that in presence of the plants tested TNT is degraded to reduced by-products and to other metabolites that were not analyzed. TNT removal was best modeled using first order kinetics, with rate constants at 25 degrees C incubations ranging from 0.038 microgram L-1 h-1 for reed canary grass to 0.012 microgram L-1 h-1 for parrot-feather. These kinetics predict hydraulic retention times (HRTs) ranging from 4.9 days to 19.8 days to reach a TNT concentration of 2 micrograms L-1. Decreasing incubation temperature to 10 degrees C affected reed canary grass more than parrot-feather, increasing estimated HRTs by factors of four and two, respectively. The plant species tested showed a far lower potential for RDX removal from the IAAP groundwater. Most effective at 25 degrees C were reed canary grass and fox sedge. Analyses of plant material indicated the presence of RDX in under-water plant portions and in aerial plant portions, and RDX accumulation in the latter. RDX removal was best modeled using zero order kinetics, with rate constants for the 25 degrees C incubation ranging from 13.45 micrograms L-1 h-1 for reed canary grass to no removal in four species. Based on these kinetics, estimated HRTs to reach 2 micrograms L-1 RDX increased from 39 days. Decreasing the temperature to 10 degrees C increased HRT 24-fold for reed canary grass. By using the biomass-normalized K value, submersed plants are identified as having the highest explosives-removing activity (microgram explosive L-1 h-1 g DW-1). However, biomass production of submersed plants is normally five to ten times less than that of emergent plants per unit area, and, thus, in plant selection for wetland construction, both, explosives removal potential and biomass production are important determinants.