Environmental Toxicology and Chemistry

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Online ISSN: 1552-8618
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Article
Experiments were conducted to determine the ability of citrate to enhance the plant uptake of weathered 2,2-bis(p-chlorophenyl)1,1-dichloroethylene (p,p'-DDE) from soil. Plots containing three rows of clover, mustard, hairy vetch, or rye grass were constructed in soils containing p,p'-DDE. On 11 occasions, the rows of each crop received water or sodium citrate (0.005 or 0.05 M). For each crop, there were significant reductions in p,p'-DDE concentration in the soil fractions (near root and rhizosphere) closely associated with the plant versus bulk soil. The roots of each crop accumulated 2 to 5 times more of the weathered contaminant (dry wt) than present in the bulk soil. Citrate (0.05 M) increased the concentration of p,p'-DDE in the roots of clover, mustard, and hairy vetch by 39% compared with vegetation that received water. In batch desorption studies, the release of weathered p,p'-DDE was significantly greater in the presence of 0.05 M citrate than in water. Citrate increased the extracted aqueous concentrations of five metal ions (Al, Fe, Ca, K, Mn) from soil by five- to 23-fold over distilled water. We hypothesize that citrate physically disrupts the soil through chelation of structural metal ions and release of bound humic material, facilitating p,p'-DDE availability and uptake by plants.
 
Figure .. Schematic diagram showing the flux of water in xylem and phloem between compartments in a plant. The flux is proportional to the thickness of the xylem in black, and the phloem in white. Arrows indicate the direction of flow.
Article
Uptake of organic chemicals into plants depends on the properties of the contaminant and the physiology of the plant. A mass balance model based on fugacity was developed to quantify the uptake and transport in plants of a very hydrophobic chemical, p,p'-dichlorophenyl-1,1-dichloroethylene (DDE). The model included processes for sorption or influx of chemical with water from hydroponic solution to root and sorption or exchange of chemical between the shoot and air. Movement among compartments of the plant was governed by the transfer of water in xylem and phloem. The movement of water was entirely determined by transpiration, growth rate, and weight distribution among tissues. This model was used to predict the kinetics of uptake and movement of DDE from hydroponic solution by seedlings of two species of Cucurbitacea, cucumber and zucchini. These predictions were compared to the results of experiments in a companion paper. These experiments showed that the translocation of DDE in zucchini was much greater than in cucumber. The model correctly predicted the negligible uptake into the shoot of cucumber. The model predicted the greater uptake of DDE by zucchini only if the apparent partitioning of DDE in the xylem was 25-fold higher than that expected in pure water. Predictions using similar parameters were made for uptake and distribution of DDE for plants grown into fruit production in field soil contaminated with DDE. To match the observed concentration of DDE in fruit, the model coefficient for partitioning of DDE into water in phloem had to be increased to 200 times that in pure water.
 
Article
Laboratory experiments were conducted to study the effects of species differences, soil concentration, and contaminant-residence time in soil on the bioaccumulation factor (BAF; dry-weight ratio of contaminant concentration in the tissue to that in the soil) of 2,2-bis (p-chlorophenyl)- 1,1-dichloroethylene (p,p'-DDE) for three species of earthworms. In four field-weathered soils, the BAF for Eisenia foetida, an epigeic species (surface habitat), was approximately 10-fold higher than those for Lumbricus terrestris, an anecic species (deep habitat) and Aporrectodea caliginosa, an endogeic species (habitat within the soil profile). Preliminary analysis indicates that BAF may decline with increasing pollutant concentration in soil. With regard to contaminant-residence time, the BAF for E. foetida was lower in weathered soils relative to that in freshly amended soils, but age of p,p'-DDE did not significantly alter the BAF for A. caliginosa. These data suggest total chemical concentration alone is not a reliable indicator of the toxicological significance of a contaminated soil and that species-specific differences and environmental factors significantly impact overall exposure and risk.
 
Article
Orchard soils can contain elevated concentrations of 1,1-dichloro-2,2-bis(p-chlorophenyl)ethylene (p,p'-DDE), 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane (p,p'-DDT), and heavy metals as a result of historical agrichemical applications. The bioavailability of p,p'-DDE, p,p'-DDT, As, Cd, Cu, and Pb from five field-aged New Zealand orchards and three grazing soils was assessed by using a 28-d bioassay with Aporrectodea caliginosa and chemical assays. Significant relationships were found between total soil and earthworm tissue concentrations for p,p'-DDE (p < 0.001), p,p'-DDT (p < 0.001), Cu (p < 0.001), and Pb (p < 0.01). Two neutral salt solutions, 0.01 M CaCl(2) and 1 M NH(4)NO(3), were used as surrogate measures of the bioavailability of heavy metals. Copper was the only heavy metal for which significant correlations were found between neutral-salt-extractable and earthworm tissue concentrations (p < 0.001). Up to 28% of the aged DDT residues were released from the soils by Tenax over a 24-h extraction period. Significant relationships (p < 0.01) between the Tenax-extractable and earthworm tissue concentrations for p,p'-DDE and p,p'-DDT showed that Tenax provides a good surrogate measure of the bioavailability of these compounds to A. caliginosa. Surprisingly, there was a similarly significant relationship (p < 0.001) between the total soil and earthworm tissue concentrations for p,p'-DDE and p,p'-DDT, suggesting that total soil concentrations alone were sufficient to predict uptake by A. caliginosa. These results demonstrate that the aged agrichemical residues in orchard soils, and particularly p,p'-DDE and p,p'-DDT, remain highly bioavailable to A. caliginosa despite decades of weathering and continue to present an environmental risk.
 
Article
The present study investigated the effects of 1,1-dichloro-2,2-bis(p-chlorophenyl)ethylene (DDE) on the thyroid and steroid-metabolizing system in Atlantic salmon (Salmo salar) parr. Fish were exposed to waterborne DDE and thyroxine (T4), both singly and in combination, for 5 d. Thyroid-stimulating hormone (TSHbeta), T4 deiodinase (T4ORD), thyroid receptors (TRalpha and TRbeta), and insulin-like growth factor type 1 receptor (IGF-1R) were analyzed using quantitative (real-time) polymerase chain reaction in liver, brain, and kidney, whereas cytochrome P4503A (CYP3A) and pregnane X receptor (PXR) mRNA levels were analyzed only in the liver. Exposure to DDE and T4, both singly and in combination, inhibited TSHbeta expression in the brain. The DDE induced TSHbeta in the liver, and T4 inhibited TSHbeta in the liver and kidney, both singly and in combination with DDE. The DDT-metabolite DDE induced T4ORD expression in the kidney and liver, and combined exposure with T4 inhibited T4ORD expression in the brain, kidney, and liver. The IGF-1R and TRalpha expressions were induced by DDE and T4 singly in the brain, whereas combined exposure with both compounds did not affect IGF-1R and TRd transcript levels. Whereas T4 inhibited TRbeta expression in the liver, exposure to DDE, both singly and in combination with T4, induced TRbeta transcript levels in the liver. Exposure to T4 and DDE, both singly and in combination, resulted in a parallel pattern of CYP3A and PXR mRNA induction in the liver. These results indicate that DDE alters thyroid hormone-dependent genes and hepatic CYP3A and PXR levels. The hepatic modulation of CYP3A and PXR transcript levels by DDE represents a novel aspect of DDE toxicity that, to our knowledge, has not been demonstrated previously in fish. Therefore, the present study demonstrates some possible physiological and endocrine consequences from exposure to endocrine-disrupting chemicals for salmon parr during smoltification.
 
Article
Field experiments were conducted to determine the impact of nutrient amendments on the phytoextraction of weathered 2,2-bis(p-chlorophenyl)-1,1-dichloroethylene (p,p '-DDE) by eight cultivars of cucurbits over a single growing season. Four cultivars of Cucurbita pepo ssp pepo are accumulators and extract percent level quantities of persistent organic pollutants (POPs), whereas C. pepo ssp ovifera and Cucumis sativus are nonaccumulators. The nonamended accumulators phytoextracted 1.0% of the p,p'-DDE and had a translocation factor of 0.44; however, the nonaccumulators removed 0.16% of the contaminant and had a translocation factor value of 0.09. The accumulators also had 3.8 times greater inorganic element content than the nonaccumulators. Duplicate mounds of each cultivar also received weekly nutrient amendments of phosphorus (400 mg/L K2HPO4), nitrogen (200 mg/L KNO3), or nitrogen/phosphorus (400 mg/L K2HPO4, 200 mg/L KNO3); a minus phosphorus treatment involved a 1-L addition of 1 g/L AlSO4 to the soil before planting. When normalized to respective control values (unamended vegetation), the root and stem p,p'-DDE bioconcentration factors (BCF) of the accumulator cultivars were significantly greater than those of the nonaccumulator cultivars under most nutrient regimes. The biomass of accumulator cultivars decreased by up to 61% under certain nutrient regimes, resulting in mixed effects on the amount of p,p'-DDE extracted. Treatment with N and P increased nonaccumulator biomass by 40 to 100%, and increased p,p'-DDE extraction from soil by 75%. Although generally assumed that fertilizer amendments will enhance phytoremediation, as evidenced here by the nonaccumulators, additions of macronutrients may reduce the phytoextraction of weathered POPs by C. pepo ssp pepo. These findings support our hypothesis that the ability of C. pepo ssp pepo to remove sequestered organic contaminants is governed by unique nutrient-acquisition mechanisms.
 
Article
Field experiments were conducted to determine the uptake and translocation of highly weathered 2,2-bis(p-chlorophenyl)1,1-dichloroethylene (p,p'-DDE) from an agricultural soil. In soil containing known amounts of p,p'-DDE, experimental plots containing zucchini, pumpkin, or spinach were constructed. At destructive harvest, three soil fractions were collected that differed in the degree of influence exerted by the plant roots. The bulk soil was vegetation-free, the near-root zone was within the area encompassed by the roots, and the rhizosphere remained physically attached to the roots at harvest. For each crop, statistically significant decreases were found in the concentration of p,p'-DDE in either the near-root zone or the rhizosphere relative to the bulk soil, suggesting plant-facilitated mobilization and/or degradation of the residue. Plant tissues were analyzed to determine the extent of contaminant removal from the soil and the magnitude of translocation through the shoot system. The concentration of p,p'-DDE in the roots of both zucchini and pumpkin was more than an order of magnitude larger than the bulk soil concentration, followed by significant translocation through the plant tissues to the fruit. The data indicate that certain plants may effectively accumulate residues of persistent organic pollutants in their tissues, suggesting phytoremediation as a possible treatment strategy.
 
Article
Reduction of structural Fe(III) in smectite clay minerals has been identified as a means to promote dechlorination of polychlorinated ethanes, but its environmental significance has yet to be fully assessed because Fe reduction has normally been achieved by agents uncommon in the environment (e.g., dithionite). This study reports the dehydrochlorination of pentachloroethane and 1,1,1-trichloroethane in the presence of ferruginous smectite reduced by two cultures of microorganisms, Shewanella oneidensis strain MR-1 (MR-R) and an enrichment culture from rice paddy soils (PS-R), in aqueous suspension under anoxic conditions. Microbially reduced ferruginous smectite facilitated dehydrochlorination of 1,1,1-trichloroethane to 1,1-dichloroethene with up to 60% conversion within 3 h of incubation time. In contrast, no formation of 1,1-dichloroethene was observed after incubation of 1,1,1-trichloroethane with chemically reduced ferruginous smectite for 24 h. Microbially reduced ferruginous smectite by MR-R and PS-R promoted the dehydrochlorination of pentachloroethane to tetrachloroethene by 80 and 15%, respectively, after 3 h of incubation time. The conversion of pentachloroethane to tetrachloroethene in the presence of chemically reduced ferruginous smectite after 24 h was 65%. These results indicate that structural Fe(II) in clay minerals has the potential to be an important reductant controlling the fate of organic chemicals in contaminated sediments.
 
Article
Brominated flame retardants (BFRs) including polybrominated diphenyl ethers (PBDEs), decabromodiphenyl ethane (DBDPE), and 1,2-bis(2,4,6-tribromophenoxy) ethane (BTBPE), were investigated in common kingfishers (Alcedo atthis) and their prey fish from an electronic waste-recycling site in south China. Elevated BFR residues were detected in the kingfishers, with median concentrations of 8,760, 12, and 7.7 ng/g lipid weight for total PBDEs, DBDPE, and BTBPE, respectively. The calculated predator/prey biomagnification factors (BMFs) were greater than unity for most of the investigated PBDE congeners, with relatively higher values for some hexa-, hepta-, and octa-BDEs (e.g., BDEs 153, 183, 196, 197, 202, and 203). The average BMFs ranged 0.10 to 0.77 and 1.90 to 3.60 for DBDPE and BTBPE, respectively. The BMFs for BTBPE were comparable to or even greater than those for some tri- to penta-BDEs in certain predator/prey pairs, indicating potentially high environmental risks of this compound. Significantly higher concentration ratios of BDEs 202 and 207 to BDE 209 were observed in the kingfishers compared with their prey fish, and these ratios were negatively correlated with the logarithm of BDE 209 concentrations in the kingfishers. This may indicate biotransformation of BDE 209 to BDEs 202 and 207 in these birds. This is the first assessment of the biomagnification potentials of DBDPE and BTBPE in a wild piscivorous bird.
 
Article
Metals and polycyclic aromatic hydrocarbons (PAHs) are known to be toxic to plants. Because metals and PAHs often are cocontaminants in the environment, plants can be subjected to damage caused by their combined effects. We recently found that copper and an oxygenated PAH (1,2-dihydroxyanthraquinone [1,2-dhATQ]) synergistically are toxic to plants. This synergistic toxicity was linked indirectly to production of reactive oxygen species (ROS). In this study, plant growth, chlorophyll pigments, protein accumulation, and ROS production were chosen as endpoints to assess the mechanism of toxicity of copper and 1,2-dhATQ to Lemna gibba in more detail. Because copper and PAHs can generate ROS, we assayed for specific antioxidant enzymes: Superoxide dismutase (SOD), glutathione reductase (GR), and ascorbate peroxidase (APX). Copper treatment at a concentration that did not cause growth inhibition resulted in upregulation of Mn SOD, Cu-Zn SOD, and APX. At a level that moderately was toxic to plants, 1,2-dhATQ did not alter significantly the levels of these antioxidant enzymes. However, a synergistically toxic mixture of copper plus 1,2-dhATQ upregulated Cu-Zn SOD, Mn SOD, and GR, although APX activity was downregulated. When plants were treated with the ROS scavenger dimethyl thiourea (DMTU), enhanced toxicity and formation of ROS caused by the mixture both were diminished substantially. However, 1,2-dhATQ toxicity was not affected significantly by DMTU. Based on this study, the toxicity caused by the mixture of copper plus 1,2-dhATQ directly can be connected to elevated levels of ROS.
 
Article
Halogenated coamendments enhanced dechlorination of 31 microM of spiked 1,2,3,4-tetrachlorodibenzo-p-dioxin (TeCDD) and 49 microM of spiked 1,2,3,4-tetrachlorodibenzofuran (TeCDF) in sediments from San Diego Bay (CA, USA) and Tuckerton (NJ, USA). Dechlorination of 1,2,3,4-TeCDD occurred to a greater extent under methanogenic than under sulfate-reducing conditions. The most effective stimulation of 1,2,3,4-TeCDD dechlorination occurred with coamendment of 25 microM of 1,2,3,4-tetrachlorobenzene (TeCB), 2,3,4,5-tetrachloroanisole (TeCA), 2,3,4,5-tetrachlorophenol, or 2',3',4'-trichloroacetophenone plus 500 microM lactate and 500 microM propionate as electron donors. The 1,2,3,4-TeCDD dechlorination was evident after three months and sequentially produced mainly 1,2,4-trichlorodibenzo-p-dioxin, 1,3-dichlorodibenzo-p-dioxin, and 2-monochlorodibenzo-p-dioxin (MCDD). Monobromophenols (2-bromo-, 3-bromo-, and 4-bromophenol), monochlorophenols (2-chloro-, 3-chloro-, and 4-chlorophenol), 2,3,5,6-tetrachlorobenzoate, or electron donors alone stimulated less 1,2,3,4-TeCDD dechlorination, with activity apparent only after six months. The 1,2,3,4-TeCDD dechlorination produced 50 mol % 2-MCDD after six months in sediments from the more contaminated Graving Dock and Paleta Creek sites in San Diego Bay. The 1,2,3,4-TeCDD dechlorination by sediments from the less contaminated Shelter Island site in San Diego Bay and in pristine Tuckerton sediments did not produce 2-MCDD. Dechlorination of 1,2,3,4-TeCDF to tri- and dichlorinated daughter products was significantly enhanced by TeCB and TeCA. These results suggest that halogenated aromatic compounds with structural similarity to 1,2,3,4-TeCDD/F stimulate bacteria with the ability to dechlorinate chlorinated dibenzo-p-dioxin and furans.
 
Article
The use of internal concentrations as a dose parameter for baseline toxicity requires an understanding of the relationship between accumulation level and toxic effects, not only for acute but also for chronic exposure. In this study of chronic toxicity of the nonpolar narcotic 1,2,3,4-tetrachlorobenzene (TeCB) to Chironomus riparius, the chronic median lethal concentration (LC50) was determined to be 0.99 (0.54-1.82) microM, the median sublethal effect concentration (EC50) for growth was 0.76 (0.73-0.97) microM, and the chronic (sublethal) no-observed-effect concentration (NOEC) was 0.24 +/- 0.01 microM. An acute-to-chronic ratio of 9.8 was calculated from a previously determined acute LC50 value and this NOEC. The chronic critical body residue (CBR), 136 mmol/kg lipid, was the same as the acute CBR, previously determined. The similarity of the chronic and acute CBRs lends support to the exposure time independent aspect of baseline toxicity theory. An implication of this is that internal concentrations estimated by biomimetic sampling devices may be compared to acute CBR data to determine chronic baseline toxicity risk. Such sampling devices, solid-phase microextraction (SPME) fibers, were simultaneously exposed during the toxicity test. The results of this study suggest that body residues estimated with SPME may be used to predict baseline toxicity for various exposure durations.
 
Article
Concentrations of selected persistent organic pollutants (POPs) in air and water were measured from four lakes that transect the Canadian Rocky Mountains. These data were used in combination with wind velocity and temperature-adjusted Henry's law constants to estimate the direction and magnitude of chemical exchange across the air-water interface of these lakes. Bow Lake (1,975 m above sea level [masl]) was studied during the summers of 1998 through 2000; Donald (770 masl) was studied during the summer of 1999; Dixon Dam Lake (946 masl) and Kananaskis Lake (1,667 masl) were studied during the summer of 2000. Hexachlorobenzene (HCB) and dieldrin volatilized from Bow Lake in spring and summer of 1998 to 2000 at a rate of 0.92 +/-1.1 and 0.55+/-0.37 ng m(-2) d(-1), respectively. The alpha-endosulfan deposited to Bow Lake at a rate of 3.4+/-2.2 ng m(-2) d(-1). Direction of gas exchange for gamma-hexachlorocyclohexane (gamma-HCH) changed from net deposition in 1998 to net volatilization in 1999, partly because of a surge in y-HCH concentrations in the water at Bow Lake in 1999. Average gamma-HCH concentrations in air declined steadily over the three-year period, from 0.021 ng m(-3) in 1998, to 0.0023 ng m(-3) in 2000, and to volatilization in 1999 and 2000. Neither the concentrations of organochlorine compounds (OCs) in air and water, nor the direction and rate of air-water gas exchange correlate with temperature or elevation. In general, losses of pesticides by outflow were greater than the amount exchanged across the air-water interface in these lakes.
 
Article
Shrews are abundant in most areas of toxic chemical contamination and bioaccumulate pollutants at much higher rates than sympatric rodent species. As a part of studies to provide information concerning the toxicity of 1,3-dinitrobenzene (DNB) in least shrews (Cryptotis parva), groups of 10 females and 10 males received DNB at 0 (control), 0.7, 2.9, 11.6, and 46.3 microl/L (equivalent mean daily dosage of 0, 0.26, 1.06, 4.26, and 17.0 mg/kg body wt in each sex) in their diet for 14 d. Leukocytosis present at the 0.26 mg/kg body weight/d dosage established the lowest-observed-adverse effect level (LOAEL). Adrenal enlargement was noted at the 1.06 mg/kg body weight/d level. Splenic enlargement and reductions in hematocrit and hemoglobin values occurred at the 4.26 mg/kg body weight/d treatment. Enlargements in the liver and heart and reductions in brown fat weight, granulocyte numbers, and alanine aminotransferase levels were present at high dose levels. Histopathologic examinations showed Kupffer's cell hemosiderosis and suggested testicular damage at the two highest tested doses but failed to confirm brain lesions. Least shrews do not follow standard scaling estimates for lifespan or metabolic rates. The LOAEL calculated from the standard terrestrial screening benchmark equation was higher than our findings, suggesting that these estimates must be viewed with caution.
 
Article
The fumigant 1,3-dichloropropene (1,3-D) is one of the most heavily used pesticides but also a suspected carcinogen. Previous research has shown that 1,3-D was rapidly transformed and detoxified by ammonium thiosulfate (ATS), a sulfur and nitrogen fertilizer. As common formulations contain cis and trans isomers at roughly equivalent ratios, this study was conducted to understand isomeric differences in thiosulfate transformation and detoxification of 1,3-D. Under the same conditions, reaction of cis-1,3-D with thiosulfate was more than three times faster than trans-1,3-D, which was correlated with a lower reaction activation energy for the cis isomer. The trans isomer was considerably more toxic to the luminescent bacteria Vibrio fisheri than the cis isomer, but the toxicity was reduced by 14 times after thiosulfate transformation. Mutagenic activity to strains of Salmonella typhimurium was observed for trans-1,3-D but was not detected after thiosulfate transformation. These results suggest that thiosulfate transformation detoxifies 1,3-D primarily by deactivating the trans isomer, and the reaction is toxicologically beneficial, as it negates the potential harmful effects of 1,3-D to the environment and human health.
 
Article
Halogenated fumigants have been used extensively in production agriculture to control soilborne pests. These types of pesticides are highly volatile and are prone to affect air quality and imperil public health. In the present study, a chemical tarp approach, termed a reactive surface barrier (RSB), was developed to reduce the emission of fumigant 1,3-dichloropropene (1,3-D) from the soil surface. The agrochemicals thiourea and allylthiourea were tested as active reagents for the construction of a RSB, where these soil amendments react with 1,3-D to form nonvolatile isothiuronium ions at the soil surface and, thereby, impede fumigant emission into the atmosphere. The feasibility of the method largely depends on the reactivity of 1,3-D and the RSB agrochemicals in soil as well as on the mobility, persistence, and toxicity of the transformation products. Therefore, the reaction kinetics and transformation mechanism of 1,3-D by thiourea and allylthiourea were studied comprehensively in aqueous solution and soil. A catalytic process occurring at the surface of soil colloids facilitated the reaction between 1,3-D and thiourea in amended soils. The rate of 1,3-D transformation in thiourea-amended soil increased with decreasing soil moisture or increasing thiourea amendment level. In a field trial, a thiourea RSB reduced cumulative 1,3-D emissions by more than 80% relative to that in bare soil surface. The present results clearly indicate that this chemical remediation technology has great potential to control the emissions of volatile halogenated organic contaminants and to mitigate atmospheric pollution.
 
Article
Reductive (pre)treatment with elemental iron is a potentially useful method for degrading nitramine explosives in water and soil. In the present study, we examined the kinetics, products, and mechanisms of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) degradation with elemental iron. Both RDX and HMX were transformed with iron to formaldehyde, NH4+, N2O, and soluble products. The yields of formaldehyde were relatively constant (71% +/- 5%), whereas the yields of NH4+ and N2O varied, depending on the nitramine and the mechanism. The reactions most likely were controlled by a surface process rather than by external mass transfer. Methylenedinitramine (MDNA) was an intermediate of both RDX and HMX and was transformed quantitatively to formaldehyde with iron. However, product distributions and kinetic modeling results suggest that MDNA represented a minor reaction path and accounted for only 30% of the RDX reacted and 14% of the formaldehyde produced. Additional experiments showed that RDX reduction with elemental iron could be mediated by graphite and Fe2+ sorbed to magnetite, as demonstrated previously for nitroaromatics and nitrate esters. Methylenedinitramine was degraded primarily through reduction in the presence of elemental iron, because its hydrolysis was slow compared to its reactions with elemental iron and surface-bound Fe2+. Our results show that in a cast iron-water system, RDX may be transformed via multiple mechanisms involving different reaction paths and reaction sites.
 
Article
The heterocyclic polynitramine hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) is a highly energetic compound found as a soil contaminant at some defense installations. Although RDX is not lethal to soil invertebrates at concentrations up to 10,000 mg/kg, it decreases earthworm cocoon formation and juvenile production at environmentally relevant concentrations found at contaminated sites. Very little is known about the uptake of RDX in earthworms and the potential risks for food-chain transfer of RDX in the environment. Toxicokinetic studies were conducted to quantify the bioaccumulation factors (BAFs) using adult earthworms (Eisenia andrei) exposed for up to 14 d to sublethal concentrations of nonlabeled RDX or [14C]RDX in a Sassafras sandy loam soil. High-performance liquid chromatography of acetonitrile extracts of tissue and soil samples indicated that nonlabeled RDX can be accumulated by the earthworm in a concentration- and time-dependent manner. The BAF, expressed as the earthworm tissue to soil concentration ratio, decreased from 6.7 to 0.1 when the nominal soil RDX concentrations were increased from 1 to 10,000 mg/kg. Tissue concentrations were comparable in earthworms exposed to nonlabeled RDX or [14C]RDX. The RDX bioaccumulation also was estimated using the kinetically derived model (BAFK), based on the ratio of the uptake to elimination rate constants. The established BAFK of 3.6 for [14C]RDX uptake was consistent with the results for nonlabeled RDX. Radioactivity also was present in the tissue residues of [14C]RDX-exposed earthworms following acetonitrile extraction, suggesting the formation of nonextractable [14C]RDX metabolites associated with tissue macromolecules. These findings demonstrated a net accumulation of RDX in the earthworm and the potential for food-chain transfer of RDX to higher-trophic-level receptors.
 
Article
The metabolic fate of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) in a mixed culture incubated under methanogenic conditions was studied. Analysis by high-performance liquid chromatography (HPLC) confirmed the loss of RDX and the formation of mono-, di-, and trinitroso-RDX as transient biodegradation intermediates. An additional peak observed in the HPLC chromatograms was identified by liquid chromatography-mass spectrometry as hydroxylamino-dinitroso-1,3,5-triazine. This is the first report identifying hydroxylamino-dinitroso-1,3,5-triazine as a transient intermediate produced during the anaerobic biodegradation of RDX.
 
Article
The potential risk to wildlife from exposure to explosives, including 1,3,5-trinitro-1,3,5-triazine (RDX), has been an issue at numerous U.S. military installations where these substances are found in soil and water. Presently, no data describing the effects of RDX exposure in avian species exist. Therefore, an acute lethal dose (ALD) and 14- and 90-d subchronic dietary exposures to RDX were evaluated in a species potentially present at many contaminated sites, i.e., the northern bobwhite (Colinus virginianus). The ALDs for females and males were 187 and 280 mg/kg, respectively. Data from the 14-d dietary trial suggested that RDX exposure inhibited food consumption, weight gain, and egg production. Dietary RDX exposure for 90-d produced a dose-dependant decreasing trend in total feed consumption, total egg production, and hen-housed production parameters. These collective data suggest that quail may respond differently to oral RDX exposure compared with mammals.
 
Article
Absorption, distribution, and biotransformation are three critical aspects affecting toxicant action in animals. In this study, B6C3F1 mice (Mus musculus) were exposed for 28 days to contaminated feed that contained one of five different RDX concentrations: 0, 0.5, 5, 50, 500 mg/kg. RDX (Hexahydro-1,3,5-trinitro-1,3,5-triazine) and its reductive transformation products: MNX (hexahydro-1-nitroso-3,5-dinitro-1,3,5-triazine), DNX (hexahydro-1,3-dinitroso-5-nitro-1,3,5-triazine), and TNX (hexahydro-1,3,5-trinitroso-1,3,5-triazine) were quantified in stomach, intestine, plasma, liver, and brain of these mice. Average RDX concentrations followed a dose-dependent pattern for all matrices tested. No controls had concentrations above limits of detection. Average RDX concentrations in tissues of exposed mice ranged from 11.1 to 182 ng/mL, 25.6 to 3319 ng/g, 123 to 233 ng/g, 144 to 35900 ng/g, and 51.1 to 2697 ng/g in plasma, brain, liver, stomach, and intestine, respectively. A considerable amount of RDX was present in brain, especially in the highest exposure group. This is consistent with the widely observed central nervous system effects caused by GABA inhibition associated with RDX exposure. N-nitroso metabolites of RDX were also present in tested tissues in a dose-dependent pattern. Average MNX concentrations in the stomachs of mice exposed to RDX ranged from ND in control exposures to 490 ng/g in the highest exposure groups. MNX accumulated in brain at a maximum average concentration of 165.1 ng/g, suggesting the potential formation of MNX from RDX within the brain. DNX and TNX were present in stomach, plasma, and brain of mice at higher exposures. The presence of RDX metabolites at notable amounts in different tissues suggests RDX can transform into its N-nitroso metabolites in vivo by an undefined mechanism. Environ. Toxicol. Chem. © 2013 SETAC.
 
Article
Contamination with hexahydro-1,3,5-trinitro-1,3,5-triazine (Royal Demolition Explosive [RDX]) has been identified at areas of explosive manufacturing, processing, storage, and usage. Thus, the potential exists for exposure to N-nitroso compounds, hexahydro-1-nitroso-3,5-dinitro-1,3,5-triazine, hexahydro-1,3-dinitroso-5-nitro-1,3,5-triazine, and hexahydro-1,3,5-trinitroso-1,3,5-triazine (TNX), formed via anaerobic transformation of RDX. Following exposure, reproductive toxicity of TNX was evaluated in three consecutive litters of deer mice (Peromyscus maniculatus). Hexahydro-1,3,5-trinitroso-1,3,5-triazine was administered ad libitum via drinking water at four doses: 0 (control), 1, 10, and 100 microg/L. Endpoints investigated included reproductive success, offspring survival, offspring weight gain, offspring organ weights, and liver TNX residues. Data from the present study indicate that TNX bioaccumulates in the liver and is associated with postpartum mortality, dose-dependent decrease in body weight from birth to weaning, and decrease in kidney weight of deer mice offspring.
 
Article
Military activities associated with training have resulted in soil residues of munition compounds and their breakdown products. Often, these areas are valuable habitats used by birds. To evaluate the possibility of adverse effects in birds, the effects from oral exposures of 2,6-dinitrotoluene (2,6-DNT) and 1,3,5-trinitro-1,3,5-triazine (RDX) were tested using a controlled dosing regime in northern bobwhite (Colinus virginianus). Nine groups of birds of mixed sex received either corn oil or 50, 100, 190, or 350 mg 2,6-DNT/kg body weight/d or 20, 80, 125, or 180 mg RDX/kg body weight/d mixed in corn oil via gavage for 14 d. Etiology of disease was markedly different between compounds. Increased RDX exposure caused an inverse relationship to time of death, symptoms including clonic followed by tonic convulsions, and death shortly thereafter. Brain concentrations of RDX postmortem, however, were relatively consistent (mean +/- standard error, 20.5 +/- 2.9 mg/kg tissue). Observations of 2,6-DNT effects included gastrointestinal distress, dehydration, and a reduction in body mass and feed consumption. Together, these data suggest that RDX is more toxic from short, repeated exposures than 2,6-DNT, resulting in central nervous system-related effects, whereas 2,6-DNT causes gastrointestinal disturbances at higher exposures.
 
Article
Although hexahydro-1,3,5-trinitro-1,3,5-triazine (also called RDX or hexogen) is a potentially toxic explosive compound that persists in soil, its ecotoxicological effects on soil organisms have rarely been assessed. In this study, two uncontaminated garden soils were spiked with 10 to 12,500 mg RDX/kg dry soil. Soil microbial activities, i.e., potential nitrification, nitrogen fixation, dehydrogenase, basal respiration, and substrate-induced respiration were chosen as bioindicators and were determined after 1-, 4-, and 12-weeks of exposure. Experimental results indicate that RDX showed significant inhibition (up to 36% of control) on indigenous soil microbial communities over the period of this study. All five bioindicators responded similarly to the RDX challenge. The length of exposure also affected the microbial toxicity of RDX, with 12-week exposure exerting more significant effects than the shorter exposure periods, suggesting that soil microorganisms might become more vulnerable to RDX when exposure is extended. The estimated lowest observable adverse effect concentration of RDX was 1,235 mg/kg. No biodegradation products of RDX were detected at all three sampling times. Compared with 2,4,6-trinitrotoluene (TNT), RDX is less toxic to microbes, probably because of its resistance to biodegradation under aerobic conditions, which precludes metabolic activation of nitro groups.
 
Article
Northern bobwhite (Colinus virginianus) were orally exposed via gavage to 0, 0.5, 3, 8, 12, or 17 mg/kg of RDX (1,3,5-trinitro-1,3,5-triazine) in corn oil daily for 14 d to evaluate sublethal effects of this explosive in birds. Mortality occurred at a rates of 100, 67, and 25% for the 17, 12, and 8 mg/kg/d dose groups, respectively. Death was preceded by clonic and tonic convulsions and weight loss caused by gastrointestinal effects. Increases in serum globulin and total leukocytes were observed in the two highest-dose groups. Degeneration of testicular and splenic tissue also was observed. The no-observed-adverse-effects and lowest-observed-adverse-effects levels were determined as 3.0 and 8.0 mg/kg/d, respectively.
 
Article
The toxicity of the explosives 2,4,6-trinitrotoluene (TNT); hexahydro-1,3,5-trinitro-1,3,5-triazine (royal demolition explosive [RDX]); and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (high-melting explosive [HMX]), was evaluated in spiked sediment with two freshwater invertebrates. The midge Chironomus tentans and the amphipod Hyalella azteca demonstrated significant toxic effects after exposure to TNT and its degradation products, 1,3,5-trinitrobenzene (TNB) and 2,4-diamino-6-nitrotoluene (2,4-DANT). Significant reductions in survival of C. tentans exposed to TNT, TNB, and 2,4-DANT were observed at nominal sediment concentrations as low as 200 mg/kg. Hyalella azteca was more sensitive to TNT, TNB, and 2,4-DANT than the midge, where significant reductions in survival were observed at nominal concentrations of 50, 100, and 200 mg/kg, respectively. Survival of the midge and the amphipod was unaffected after exposure to RDX or HMX at the highest concentrations of 1,000 and 400 mg/kg, respectively. Growth of the midge, measured as total weight, was significantly reduced by 2,4-DANT. However, significantly increased growth was observed after exposure to sublethal concentrations of RDX and HMX. Although significant reductions in amphipod survival were observed at high concentrations of TNB, growth was significantly increased at sublethal concentrations. The results of the current investigation suggest that organisms exposed to explosives at contaminated sites may be affected at concentrations less than 25 mg/kg through hormetic growth enhancement and at higher concentrations through increased mortality.
 
Article
Hexanitrohexaazaisowurtzitane (CL-20) and hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), both energetic compounds, share some degree of structural similarity. A noninvasive electrophysiological technique was employed to assess the impacts of acute sublethal exposures on impulse conduction in medial (MGF) and lateral (LGF) giant nerve fiber pathways of the earthworm Eisenia fetida and to evaluate the reversibility of neurotoxic effects. Earthworms were exposed to either 0.02 to 2.15 microg/cm2 of CL-20 or 0.04 to 5.35 microg/cm2 of RDX, for 1 to 14 d, on moistened filter paper. Conduction velocities of MGF and LGF were recorded on a digital oscilloscope before and after exposure. Results indicate that at exposure levels as low as 0.02 microg/cm2 of CL-20 or 0.21 microg/cm2 of RDX, worms exhibited physiological impacts such as retardation, stiffness, and body shrink. Both MGF and LGF conduction velocities were negatively correlated with increasing doses of CL-20 or RDX. However, such neurotoxic effects were alleviated or even eliminated within a few days after exposed worms were transferred to an uncontaminated environment, indicating that the neurotoxicity is reversible even after 6-d exposure. The CL-20 is more potent than RDX, which is consistent with previous studies on lethality, growth, and reproduction endpoints in soil oligochaetes.
 
Article
Hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) has been widely used as an explosive in munition formulations, resulting in contamination of wildlife habitat on military installations. To estimate health effects for reptilian species, acute, subacute, and subchronic oral toxicity studies were conducted using the Western fence lizard (Sceloporus occidentalis). Estimated oral median lethal doses were 72 (95% confidence interval [CI], 49-106) mg/kg body weight (slope, 3.754) for males and 88 (95% CI, 65-119) mg/kg (slope, 4.525) for females. Toxicity from RDX suggested the neurological system as the critical target tissue. A 14-d subacute study followed with males dosed orally with RDX (corn oil) at 0, 10, 20, 25, 30, 45, and 60 mg/kg/d. Signs of toxicity frequently included a characteristic body posture. A significant dose-survival relationship was seen over the range of doses, with a significant decrease in survival at 20 mg/kg/d. Males in the 60-d subchronic study were dosed at 0, 1, 2.5, 5, 8, and 11 mg/kg/d, and signs of toxicity included lethargy, cachexia, and anorexia. Survival was decreased at 8 and 11 mg/kg/d. Reduced growth rate and food consumption occurred at 5 mg/kg/d. Brain tissue was assayed for RDX when seizures were observed at a residue concentration of at least 18 microg/g. No abnormalities were observed in the hematologic indices, whereas plasma proteins were reduced. Hepatic enlargement and decreased testes mass occurred at 8 and 11 mg/kg/d. Plasma testosterone concentrations, sperm counts, and motility measures were variable for all treatment levels. Based on survival, growth rate, food intake, and testes to brain weight ratios, these data suggest a lowest-observed-adverse effect level of 5 mg/kg/d and a no-observed-adverse effect level of 2.5 mg/kg/d.
 
Article
Concerns have been raised over potential bioavailability and biotransfer of energetic materials such as hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX). The present study assessed plant-incorporated [14C]RDX and plant-derived [14C]RDX-metabolite ingestion by the prairie vole (Microtus ochrogaster). The animals were fed labeled chow (maximum, < or =10 g/d) for 5 or 7 d, followed by a 6- or 4-d chase period. More than 95% of all label presented was recovered in the summed excreta, with 74% of this in the fecal nonabsorbed bulk. Greater than 20% of the presented [14C]RDX and plant-derived [14C]RDX metabolites were absorbed by the animals' digestive tracts. These materials were either metabolized to (14)CO2 (8-10% of the total label) or removed as nitrogenous waste through the kidneys (10-14%). Both 14C-urine and (14)CO2 excretion continued after the feces cleared, indicating ongoing metabolism of the labeled material. Approximately 4% was retained within the tissues at death, with the highest total activity in the liver and the highest specific activity in the testes. Other labeled tissues included the lung, heart, brain, spleen, skeletal muscle, bone, and pancreas. All these tissues containing [14C]RDX-derived materials are available to subsequent predators, indicating a potential for transfer to a higher trophic level.
 
Article
The effect of adsorption to elemental iron on the reductive transformation of 2,4,6-trinitrotoluene (TNT) and hexahydro-1,3,5-trinitro-1,3,5-triazine (royal demolition explosive [RDX]) in aqueous solution was studied with scrap iron and high-purity iron. In batch experiments with the same total iron surface area and a mixing rate of 100 rpm, TNT and RDX were removed from the solution within 30 min. With high-purity iron, adsorbed TNT was reduced to 2,4,6-triaminotoluene (TAT) rapidly, with little accumulation of intermediates at the surface. With scrap iron, the extent of adsorption of TNT and its daughter products was more significant and reduction of these adsorbed molecules to TAT was slower. Distribution of the intermediates indicated that the reaction with scrap iron occurred primarily through reduction of the ortho nitro group. Kinetic analysis suggests that mass transfer or adsorption of TNT controlled the overall rate of TNT reduction to TAT with pure iron, whereas with scrap iron, the rate of TAT formation was probably limited by other processes. Compared to TNT, transformation of adsorbed RDX was more rapid and less affected by iron type. The RDX was reduced to an unidentified, water-soluble intermediate and NH4+, which accounted for approximately 50% of the RDX nitrogen. No total organic carbon reduction was observed before and after RDX transformation with scrap iron.
 
Article
The uptake of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) from soil by the earthworm Eisenia andrei was examined by using the equilibrium partitioning (EqP) theory and a three-compartment model including soil (S), interstitial water (IW), and earthworms (E). The RDX concentrations were measured using U.S. Environmental Protection Agency (U.S. EPA) Method 8330A and high-performance liquid chromatography (HPLC). The S-IW studies were conducted using four natural soils with contrasting physicochemical properties that were hypothesized to affect the bioavailability of RDX. Each soil was amended with nominal RDX concentrations ranging from 1 to 10,000 mg/kg. The HPLC analysis showed that the IW extracted from soil was saturated with RDX at 80 mg/kg or greater soil concentrations. The calculated S-IW coefficient (K(p)) values for RDX ranged from 0.4 to 1.8 ml/g soil, depending on the soil type, and were influenced by the organic matter content. In the IW-E studies, earthworms were exposed to nonlethal RDX concentrations in aqueous media. The uptake of RDX by the earthworms correlated well (r(2) = 0.99) with the dissolved RDX concentrations. For the E-S studies, earthworms were exposed to RDX-amended soils used in the S-IW studies. The bioconcentration factors (BCF; ratios of E-to-IW RDX concentrations) were relatively constant ( approximately 5) up to 80 mg/kg soil RDX concentrations, which encompass the RDX saturation limit in the interstitial water of the tested soils. At this concentration range, the RDX uptake from interstitial water was likely dominated by passive diffusion and could be used as an indicator of bioavailability. Other mechanisms may be involved at greater RDX soil concentrations.
 
Article
Few studies have examined the potential long-term effects of high concentrations of hexahydro-1,3,5-trinitro-1,3,5-triaxine (RDX) on bacterial communities in soil. In the present study, a sandy loam soil and a silt loam soil (high and low bioavailability, respectively) were artificially contaminated with RDX (0, 50, 500, 1,500, 5,000, 10,000, and 15,000 mg/kg soil). Bacterial communities from each treatment were monitored over 63 d to characterize the effects of RDX exposure on bacterial activity, biomass, functional diversity (Biolog microtiter plates), and structural diversity (denaturing gradient gel electrophoresis of 16S rDNA). Bacterial communities native to the high bioavailability soil were inherently different than bacterial communities native to the silt loam soil, not only in terms of bacterial activity and biomass, but also in terms of bacterial community functional and structural diversity. Soil RDX contamination was correlated with decreased bacterial biomass in the silt loam soil treatments and with decreased bacterial activity in the sandy loam soil treatments on day 7. Soil RDX contamination did not cause a significant shift in the functional diversity of the bacterial communities native to the silt loam soil, but was correlated with a shift in identities of substrates used by bacterial communities native to the sandy loam soil on day 7. Bacterial community structure was insensitive to the gradient of RDX concentrations at the beginning of the incubation. However, the identities of carbon substrates used by bacterial communities in both soil types were affected by long-term incubation with RDX.
 
Article
Laboratory studies were conducted to investigate the biologically mediated, aerobic mineralization of both freshly added and artificially aged, desorption-resistant 1,4-dichlorobenzene (1,4-DCB). The adsorption and desorption of 1,4-DCB isotherms were established in three wetland soils using decant-refill batch techniques. Significant nonlinearity and hysteresis were observed in the isotherms with a hysteresis index ranging from 0.11 (relatively low hysteresis) in a marsh soil to 2.26 (relatively high hysteresis) in a bottomland hardwood soil from the Petro Processor (PPI) Superfund site. Mineralization of freshly added 1,4-DCB was observed in all three soils without lag after the addition of a 1,4-DCB degrading culture. Mineralization curves were plotted above theoretical lines predicted from a first-order model assuming instantaneous desorption, indicating that the microbial population had access to sorbed 1,4-DCB. In separate experiments, mineralization of artificially aged, desorption-resistant 1,4-DCB was also observed. Mineralization curves in these studies also indicated that the microbial population could directly access sorbed 1,4-DCB. The extent and rate of mineralization of desorption-resistant 1,4-DCB decreased significantly, including rate constants decreasing from approximately 0.01 d-1 in the freshly added treatments to approximately 0.002 d-1 in the desorption-resistant treatments. Although sorption/desorption partitioning helped explain mineralization patterns in the treatments with freshly added 1,4-DCB, no differences were observed in mineralization curves in the desorption-resistant treatments between soils with widely varying sorption/desorption properties.
 
Article
Hysteresis, a frequently observed phenomenon in sorption studies, is inconsistent with the key assumption of sorption reversibility in most fate and bioavailability models. Therefore, a study of the underlying causes of hysteresis is essential. Carbon-radiolabeled 1,4-dichlorobenzene (DCB) isotope tracer exchange was carried out at select points along the isotherms of DCB in a brown coal and a peat soil, holding total DCB concentration constant. Tracer exchange was performed both in the forward (sorption) and reverse (desorption) directions at the bulk sorption points and in the desorption direction at the corresponding bulk desorption points. Bulk DCB isotherms showed concentration-dependent hysteresis. However, tracer reequilibration in all cases was consistent with free exchange between sorbed and aqueous-phase molecules. These results rule out common experimental artifacts and demonstrate that sorption of bulk DCB is truly hysteretic (i.e., irreversible). The differences in rates between bulk and tracer sorption and desorption are consistent with the coupling of bulk DCB diffusion to other processes that retard equilibration, which we assign to matrix swelling or shrinking. Hysteresis is attributed to matrix deformation--specifically, to inelastic expansion and creation of voids accommodating sorbate molecules in the matrix, which leads to enhanced affinity in the desorption step. Comparing the results to previous results for naphthalene in the coal, we find that irreversible effects are similar for DCB and naphthalene in the coal but differ for DCB between the two sorbents. An explanation based on the different physical properties of these sorbents is provided. Solid-phase extraction of equilibrated DCB with Tenax revealed a highly desorption-resistant fraction. While too small to account for the observed hysteresis, this fraction may represent molecules that become trapped as the matrix collapses and simultaneously stiffens during abrupt desorption.
 
Article
Strong positive correlations between selenium (Se) and total mercury (HgT) contents in the liver of marine mammals and mercury mine workers in modern times have been documented in numerous investigations. Herein, we report a positive correlation between Se and HgT concentrations over the past 1,500 years in the seal hairs and in the lake sediments amended by seal or penguin excrements on King George Island (63 degrees 23' S, 57 degrees 00' W), West Antarctica. Because the changes in the input of Se and Hg into the marine environments of the studied sites do not seem to be synchronous, this striking correlation indicates a self-protection mechanism in Antarctic seals and penguins: Every time there is heavier Hg burden, more Se is accumulated to reduce the toxicity of Hg. This positive correlation between Hg and Se contents in the seal hairs and excrement sediments, however, becomes insignificant in the recent 50 years for unknown reasons.
 
Article
Daphnia magna is widespread in many freshwater systems of temperate regions and frequently is used to test metal toxicity. Recently, studies have been performed to determine metal biokinetics and development of tolerance in this important zooplankton species. In the present paper, we review the recent progress in these areas and suggest possible directions for future studies. Substantial differences exist in aqueous uptake, dietary assimilation, and elimination of several metals (Cd, Se, Zn, Ag, Hg, and MeHg) by D. magna. The routes of uptake are metal-specific, with Se and MeHg being accumulated predominantly through diet. All metals except Ag can be biomagnified from algae to D. magna, providing that metal concentrations in algae and algal food density are relatively low. Methylmercury is biomagnified in all situations. As a route for metal elimination in D. magna, maternal transfer is especially important for Se, Zn, and MeHg. On the other hand, the effect of single-generation exposure to metals on D. magna is very different from multigeneration exposure, which often results in a significantly higher metal tolerance. Moreover, D. magna easily loses metal tolerance developed through long-term exposure. Recovery from metal stress can temporarily increase the sensitivity of D. magna to metal toxicity. Finally, metallothionein-like protein is responsible for minimizing metal toxicity in D. magna. The results inferred from these studies can be extrapolated to other aquatic invertebrates as well as to other pollutants in the aquatic environment.
 
Article
Sodium fluoroacetate (compound 1080) is applied as a vertebrate pesticide in New Zealand for control of introduced mammalian pests. Despite its widespread use, little is known about the soil ecotoxicity of 1080. Therefore, the hazard of 1080 to soil invertebrates, plants, and soil microorganisms was evaluated in a series of controlled laboratory tests. No earthworm (Eisenia fetida) mortality was reported with 1080 exposures up to 865 mg/kg soil. The lowest-observable-effect concentration and the median effect level for earthworm reproduction were 100 and 90 mg/kg soil, respectively, for cocoon production and 100 and 160 mg/kg soil, respectively, for juvenile production. Lettuce (Lactuca sativa) was more sensitive than oats (Avena sativa) to 1080. Lettuce seedling emergence and seedling shoot growth were adversely affected at a soil concentration of 7 mg/kg. The presence of 1080 in soil at concentrations up to 1 g/kg soil did not affect the ability of soil microorganisms to mineralize nitrogen. Furthermore, nitrate mineralization was not inhibited in soil treated with the urine of 1080-poisoned possums (Trichosurus vulpecula). The data collectively indicate that 1080-related effects on soil organisms occur at levels well above those that have been measured in soil (<0.1 mg/kg) following application of 1080 in baits for vertebrate pest control in New Zealand.
 
Article
A ring test was carried out within the standardization process of ISO 10872 to evaluate the precision of the toxicity test for the nematode Caenorhabditis elegans. Eight different laboratories tested aqueous solutions of the reference substance benzylcetyldimethylammonium chloride as well as native sediments and soils for toxic effects on the growth and reproduction of C. elegans. Validity criteria were met in all laboratories. Average median- and low-effect concentrations were determined to be 15.1 mg L(-1) (EC50) and 8.7 mg L(-1) (EC10) for growth and 7.5 mg L(-1) (EC50) and 3.8 mg L(-1) (EC10) for reproduction of C. elegans, with ECx values showing a high degree of reproducibility (CV(R) : <21% and <11% for EC10 and EC50, respectively) and repeatability (CV(r) : <20% and <7% for EC10 and EC50, respectively). The toxic effects of the sediments and soils revealed by the different laboratories were well related to each samples' degree of chemical contamination. Moreover, the effects showed an acceptable reproducibility (CV(R) : 5-33% and 0-28% for growth and reproduction, respectively) and repeatability (CV(r) : 3-13% and 0-12% for growth and reproduction, respectively). The present study confirms that the toxicity test with C. elegans according to ISO 10872 is a reliable and precise tool to assess the toxicity of aqueous media, freshwater sediments, and soils.
 
Article
An often overlooked problem in the use of radiotracers is the possibility of isotopic contamination. Commercially available silver 110mAg was used to study silver uptake and depuration in rainbow trout and European eel. Quality control by means of comparative gamma and beta counting brought our attention to a contamination of the 110mAg stock with 109Cd, which could be seen only because the 109Cd was markedly bioconcentrated by trout gills. The contamination could not be detected in eel gills or in other tissues of both species. The difference between trout and eel gill structure and function is the probable explanation for the marked difference in 109Cd accumulation. This contamination was identified as 109Cd by gamma spectroscopy and its origin by transmutation of natural silver as a result of neutron activation is described. Failure to recognize this contamination problem would have resulted in serious misinterpretation of the data set. Guidance for avoiding this problem is given.
 
Article
Endocrine-disrupting chemicals (EDCs) are exogenous substances that can impact the reproduction of fish, potentially by altering circulating concentrations of 17β-estradiol (E2 ), testosterone (T) and 11-ketotestosterone (11-KT). Common methods to measure steroids in plasma samples include radioimmunoassays (RIAs) and enzyme-linked immunosorbant assays (ELISAs). This paper examines variability in E2 , T and 11-KT across eight laboratories measuring reference and pulp mill effluent-exposed white sucker (Catostomus commersoni) plasma. We examine the contribution of assay type (RIA vs ELISA), standardized hormone extraction, location of values on the standard curve (upper and lower limits), and other variables on the ability to distinguish hormone levels between reference and exposed fish, and the impact of these variables on quantitation of hormones in different laboratories. Of the eight participating laboratories, seven out of eight and seven out of seven identified differences between sites for female E2 and female T, respectively, and seven out of seven and four out of five identified no differences between male T and male 11-KT, although the ng/ml concentration of steroids measured across laboratories varied by a factor of 10-, 6-, 14- and 10-fold, respectively. Within laboratory intra-assay variability was generally acceptable and below 15%. Factors contributing to inter-laboratory variability included calculation errors, assay type, and methodology. Based on the inter-laboratory variability detected, we provide guidelines and recommendations to improve accuracy and precision of steroid measurements in fish ecotoxicology studies. Environ Toxicol Chem © 2013 SETAC.
 
Article
The potential for temperature to influence estrogen-mediated responses in poikilothermicanimals suggested that temperature may be an important variable to consider when using an estrogen-responsive reporter gene in a rainbow trout cell line to test chemicals for estrogenic activity. Rainbow trout hepatoma cells (RTH 149) incubated at 11 or 18°C were cotransfected with an estrogen-responsive luciferase reporter plasmid and a plasmid containing a constitutively expressed rainbow trout estrogen receptor. The RTH-149 cells were then exposed to estradiol, with samples collected at 24-h intervals. The 72-h effective concentration for 50% maximal response (EC50) for estrogen-responsive luciferase activity at 11°C was 3.8 × 10−9 M and 7.4 × 10−10 M at 18°C. The efficacy of estradiol was lower at 11°C. The maximal response to estradiol in cells at 11°C was generally two- to threefold greater than controls (mean = 2.6-fold), whereas the maximal response at 18°C was three- to fourfold greater than controls (mean = 3.2-fold). Ethinylestradiol, a strong estrogen receptor agonist, was similar to estradiol in potency (relative potency = 0.8) and efficacy at the two temperatures. The EC50 of the weak estrogen receptor agonist 4-tert-pentylphenol was 7.6 × 10−7 M at 11°C and 6.9 × 10−7 M at 18°C; its potency relative to 17β-estradiol was not significantly different at the two temperatures, 0.00036 and 0.00054 at 11°C and 18°C, respectively. The estrogen-responsive reporter gene activity produced by 10−8 M estradiol was completely inhibited by the two estrogen hormone receptor antagonists, ZM 189,154 and ICI 182,780, at 10−6 M concentration of either antagonist. Although there may be slight differences in responses between the two temperatures tested here, this assay can be used to effectively determine the relative estrogenic activity of chemicals within the physiological temperature range of rainbow trout.
 
Article
11-Oxoetiocholanolone and related substances are important metabolites of cortisol and are excreted via feces in ruminants. To investigate whether 11-ketotestosterone (11-KT) or its immunoreactive metabolites are formed and excreted in ruminant feces, an enzyme immunoassay (EIA) was developed and validated. The antibody was raised in rabbits against 11-KT-3-CMO:BSA with biotinylated 11-KT as a label. The assay showed a sensitivity of 0.3 pg/well. To validate the assay biologically, six rams were injected with a synthetic analogue of the adrenocorticotropic hormone (Synacthen, 2 µg/kg body weight). An aliquot was collected of each fecal portion spontaneously defecated 8 h before Synacthen injection to 24 h after injection and stored at -20°C until analysis. Samples (0.5 g) were extracted using 80% methanol and immunoreactive metabolites measured using the 11-KT EIA and an already established 11,17-dioxoandrostane (11,17-DOA) EIA. HPLC separation revealed no peak in the same elution position as authentic 11-KT; therefore, reacting substances were referred to as 11-KT equivalents. In the case of 11-KT immunoreactive substances, the values increased from baseline (median: 136 ng/g feces) to a peak concentration (median: 424 ng/g) 10 to 14 hours after Synacthen injection and declined afterwards. Concentrations of 11,17-DOA showed the same pattern, but the values were 2-4 times higher. From this data we conclude that 11-KT-like substances, specifically C(19) O(3) -androgens with a 17ß-hydroxy group, were present in the feces. These substances originate from the adrenals, and are most likely cortisol metabolites. Environ. Toxicol. Chem. © 2013 SETAC.
 
Article
We measured two nitro musk fragrances (musk xylene) and musk ketone) and five polycyclic musk fragrances (galaxolide [HHCB], tonalide [AHTN], celestolide [ADBI], traseolide [ATII], and phantolide [AHMI]) in human blood samples from 11 cities of China (n = 204). Possible temporal trends in musk concentrations and associations with personal factors, such as gender, age, and others, were studied. Galaxolide (HHCB) showed the highest median concentration (0.85 ng/g) followed by AHTN (0.53 ng/g) with high detection frequency (91 and 77%, respectively). Concentrations of the other synthetic musk fragrances, including musk ketone and musk xylene, were all below the quantification limits. The results suggested that musk concentrations were not significantly relative to gender and body weight but positively correlated with age groups and locations. Apparent differences were also observed in the ratios of HHCB to AHTN concentrations among different cities.
 
Article
The disposition and depuration of lindane (gamma-hexachlorocyclohexane [HCH]) and polychlorinated biphenyl (PCB)-110 (2,3,3',4',6-pentachlorobiphenyl), orally administered to cod (Gadus morhua) and bullrout (Myoxocephalus scorpius), were investigated using whole-body autoradiography, liquid scintillation counting, and gas chromatography with electron-capture detection. Both gamma-HCH and PCB-110 were distributed mainly to lipid-rich organs after absorption from the gastrointestinal tract of cod and bullrout. Compared to bullrout liver, the cod liver contained higher concentrations of both compounds, reflecting the distribution of fat in the two species. In both species, the depuration time for gamma-HCH was shorter than for PCB-110. Both substances were excreted via bile and urine, largely as water-soluble metabolites. The water-soluble bile metabolites, together with PCB-110 metabolites associated to endogenous macromolecules, strongly indicate that this compound is metabolized in both species.
 
Article
Field and laboratory experiments were carried out to assess the influence of Cd and Zn on the contamination levels of 110Ag, 57Co, and 134Cs in rainbow trout. During a four-week prior exposure phase, two fish groups were held in tanks in the Lot River (France) at a reference (<0.05 microg Cd/L and 68 microg Zn/L) and at a polluted site (1.5 microg Cd/L and 152 microg Zn/L). During a subsequent phase, organisms were brought back to the laboratory, where the radionuclide accumulation and depuration were studied for 14 and 7 d, respectively. During this second phase, the water used in the experiments was brought back from the two sites on the Lot River in order to work under the same chemical conditions. The potential effect of chronic exposure to stable metals on several biomarkers has been explored: Plasma analysis indicated the disruption of certain variables linked to the energetic metabolism and to the maintenance of the ionic balance. In contrast, no significant disruption of the measured enzyme activities was observed. With regard to the bioaccumulation of radionuclides, concentrations in fish exposed to metals are much lower than those in fish from the control group. Various hypotheses are proposed to link fish metabolic profiles due to metal exposure to the radiocontamination of organisms.
 
Article
Polycyclic aromatic hydrocarbon (PAH) desorption partition coefficients between black carbon and water (K(BC)) were determined using 114 historically contaminated and background sediments from eight different rural and urban waterways. Black carbon was measured after oxidation at 375 degrees C for 24 h. Organic carbon-water partition coefficients (K(OC)) required for the calculation of K(BC) values were determined for two- to six-ring parent and C1- to C4-alkyl PAHs based on the lower range of measured K(OC) values from the same sediments and comparisons to literature K(OC) values. Approximately 2,050 log K(BC) values were determined on sediments having a range of total organic carbon from 0.3 to 42% by weight, black carbon from 0.1 to 40% by weight, and total PAH concentrations (U.S. Environmental Protection Agency 16 parent PAHs) from 0.2 to 8,600 microg/g. Contrary to expectations, PAH partitioning was not better explained using the combined K(OC) and K(BC) models rather than the simple K(OC) model (i.e., K(BC) values for each individual PAH ranged nearly three orders of magnitude). No effect of PAH concentration on measured K(BC) values was apparent. Values of K(BC) also showed no trends with total organic carbon, black carbon, or the presence or absence of a non- aqueous phase liquid. Multiple linear regression analysis with K(OC) and K(BC) as fitted values also failed to explain the variance of the experimental data (r(2) values typically less than 0.20, and standard errors greater than two orders of magnitude). These results demonstrate that models of PAH partitioning that account for different carbon types, although useful for understanding partitioning mechanisms, cannot yet be used to accurately predict PAH partitioning from historically contaminated sediments.
 
Article
Polycyclic aromatic hydrocarbon (PAH) partitioning coefficients between sediment organic carbon and water (K(OC)) values were determined using 114 historically contaminated and background sediments collected from eight different rural and urban waterways in the northeastern United States. More than 2100 individual K(OC) values were measured in quadruplicate for PAHs ranging from two to six rings, along with the first reported K(OC) values for alkyl PAHs included in the U.S. Environmental Protection Agency's (U.S. EPA) sediment narcosis model for the prediction of PAH toxicity to benthic organisms. Sediment PAH concentrations ranged from 0.2 to 8600 microg/g (U.S. EPA 16 parent PAHs), but no observable trends in K(OC) values with concentration were observed for any of the individual PAHs. Literature K(OC) values that are commonly used for environmental modeling are similar to the lowest measured values for a particular PAH, with actual measured values typically ranging up to two orders of magnitude higher for both background and contaminated sediments. For example, the median log K(OC) values we determined for naphthalene, pyrene, and benzo[a]pyrene were 4.3, 5.8, and 6.7, respectively, compared to typical literature K(OC) values for the same PAHs of 2.9, 4.8, and 5.8, respectively. Our results clearly demonstrate that the common practice of using PAH K(OC) values derived from spiked sediments and modeled values based on n-octanol-water coefficients can greatly overestimate the actual partitioning of PAHs into water from field sediments.
 
Article
A next-generation mobile automobile air-conditioning (MAC) refrigerant, HFO-1234yf (CF(3) CF = CH(2)), is being developed with improved environmental characteristics. In the atmosphere, it ultimately forms trifluoroacetic acid (TFA(A); CF(3)COOH), which is subsequently scavenged by precipitation and deposited on land and water as trifluoroacetate (TFA; CF(3)COO(-)). Trifluoroacetate is environmentally stable and has the potential to accumulate in terminal water bodies, that is, aquatic systems receiving inflow but with little or no outflow and with high rates of evaporation. Previous studies have estimated the emission rates of HFO-1234yf and have modeled the deposition concentrations and rates of TFA across North America. The present study uses multimedia modeling and geographic information system (GIS)-based modeling to assess the potential concentrations of TFA in terminal water bodies over extended periods. After 10 years of emissions, predicted concentrations of TFA in terminal water bodies across North America are estimated to range between current background levels (i.e., 0.01-0.22 µg/L) and 1 to 6 µg/L. After 50 years of continuous emissions, aquatic concentrations of 1 to 15 µg/L are predicted, with extreme concentrations of up to 50 to 200 µg/L in settings such as the Sonoran Desert along the California/Arizona (USA) border. Based on the relative insensitivity of aquatic organisms to TFA, predicted concentrations of TFA in terminal water bodies are not expected to impair aquatic systems, even considering potential emissions over extended periods.
 
Article
The purpose of this experiment was to determine the effects of Aroclor 1242, a mixture of polychlorinated biphenyls (PCBs), on plumage characteristics and molt in the American kestrel, Falco sparverius. Several characteristics of plumage, including color and molt schedule, are modulated by hormonal signals and hence may be modified by endocrine-active contaminants. If so, the functions of plumage (e.g., communication for mating or territorial defense) may be compromised by exposure to such compounds. Captive American kestrels were fed Aroclor 1242 at 0, 6.0, and 60.0 ppm (n = 6 males and 6 females per treatment) mixed in their normal diet. Concentrations of plasma estradiol and thyroxine were measured weekly from the beginning of treatment. Measured plumage characteristics included width of the black subterminal band on the tail, color (a composite index of hue and saturation), reflectance from 230 to 800 nm. pattern of feather loss and regrowth on the tail and wing, and timing of onset and duration of molt. Aroclor 1242 depressed plasma thyroxine. Plasma estradiol levels remained low due to the phase of the breeding cycle. Treatments did not disrupt the measured plumage characteristics. This may be due to timing or dose of exposure or to genetic factors.
 
Top-cited authors
Gerald T Ankley
  • United States Environmental Protection Agency
John Sumpter
  • Brunel University London
Stephen J Klaine
  • Clemson University
Peter Matthiessen
Walter J Berry
  • United States Environmental Protection Agency