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Researchers from Rice University, TX, and Tyndall Air Force Base, FL, demonstrated the degradation of dinitrotoluenes in highly contaminated soils from two ammunition plants in Chattanooga, TN and Baraboo, WI, using an aerobic slurry reactor.

BisphenolA analogues (BPAs) belong to a wide variety of largevolume chemicals with diverse applications yet emerging environmentalconcerns. Limited experimental data have demonstrated that BPAs withdifferent halogenation patterns distinctly affect the agonistic activitiestoward proliferator-activated receptor (PPAR)γ and estrogenreceptors (ER)α. Understanding the modes of action of BPAs towarddifferent receptors is essential, however, the underlying molecularmechanism is still poorly understood. Here we probed the molecularrecognition process of halogenated BPAs including TBBPA, TCBPA, BPAF,BPC, triBBPA, diBBPA, and monoBBPA toward PPARγ and ERαby molecular modeling, especially the impact of different halogenpatterns. Increasing bromination at phenolic rings of BPAs was foundhighly correlated with electrostatic interactions (R2= 0.978 and 0.865 toward PPARγ and ERα,respectively) and van der Waals interactions (R2= 0.995 and 0.994 toward PPARγ and ERα, respectively).More halogenated phenolic rings at 3,5-positions of BPAs increasethe shielding of the hormonally active phenolic OH and markedly decreaseelectrostatic interactions favorable for agonistic activities towardPPARγ, but unfavorable for agonistic activities toward ERα.The halogenation at the phenolic rings of BPAs exerts more impacton molecular electrostatic potential distribution than halogenationat the bridging alkyl moiety. Different halogenations further alterhydrogen bond interactions of BPAs and induce conformational changesof PPARγ ligand binding domain (LBD) and ERα LBD, specificallyaffecting the stabilization of helix H12 attributable to the differentagonistic activities. Our results indicate that structural variationsin halogenation patterns result in different interactions of BPAswith PPARγ LBD and ERα LBD, potentially causing distinctagonistic/antagonistic toxic effects. The various halogenation patternsshould be fully considered for the design of future environmentallybenign chemicals with reduced toxicities and desired properties. [ABSTRACT FROM AUTHOR]

3,3',5,5'-Tetrabromobiphenyl (BB-80) was once used as additive flame retardants. Whether its early exposure and discontinued exposure alter thyroid function remains unknown. We investigate adverse effects after early-life exposure and discontinued exposure to BB-80 and hydroxylated BB-80 (OH-BB-80) on thyroid hormone (TH) levels, thyroid tissue, and transcriptome profiles in zebrafish larvae. BB-80 at 10 μg/L induces pathological changes of thyroid with reduced thyroid follicles in larvae ( P < 0.05), whereas OH-BB-80 significantly increases T4 and T3 contents (1.8 and 2.5 times of the control, P < 0.05) at 14 days postfertilization (dpf) without morphological thyroid alterations. BB-80 and OH-BB-80 cause transcriptome aberrations with key differentially expressed genes involved in the disruption of TH synthesis and signal transduction (BB-80 at 14 dpf) or TH pathway activation (OH-BB-80 at 21 dpf). After 7 days of discontinued exposure, thyroglobulin ( tg ) and thyroid peroxidase ( tpo ) genes are downregulated ( P < 0.05) by 52 and 48% for BB-80 and by 49 and 39% for OH-BB-80, respectively; however, the whole-body TH levels fail to fully recover, and the locomotor activity is impaired more by BB-80. Our results indicate significant adverse impacts of BB-80 and OH-BB-80 on TH homeostasis and thyroid function of zebrafish.

Thousands of contaminants are used worldwide and eventually released into the environment, presenting a challenge of health risk assessment. The identification of key toxic pathways and characterization of interactions with target biomacromolecules are essential for health risk assessments. The adverse outcome pathway (AOP) incorporates toxic mechanisms into health risk assessment by emphasizing the relationship among molecular initiating events (MIEs), key events (KEs), and adverse outcome (AO). Herein, we attempted the use of AOP to decipher the toxic effects of 2,6-di- tert -butylphenol (2,6-DTBP) and its para-quinone metabolite 2,6-di- tert -butyl-1,4-benzoquinone (2,6-DTBQ) based on integrated transcriptomics, molecular modeling, and cell-based assays. Through transcriptomics and quantitative real-time PCR validation, we identified retinoic acid receptor β (RARβ) as the key target biomacromolecule. The epigenetic analysis and molecular modeling revealed RARβ interference as one MIE, including DNA methylation and conformational changes. In vitro assays extended subsequent KEs, including altered protein expression of p-Erk1/2 and COX-2, and promoted cancer cell H4IIE proliferation and metastasis. These toxic effects altogether led to carcinogenic risk as the AO of 2,6-DTBP and 2,6-DTBQ, in line with chemical carcinogenesis identified from transcriptome profiling. Overall, our simplified AOP network of 2,6-DTBP and 2,6-DTBQ facilitates relevant health risk assessment.

Nitrated and oxygenated polycyclic aromatic hydrocarbons (NPAHs and OPAHs) from the direct atmospheric emission or the degradation of parent PAHs are increasingly recognized because of their potential health risks. Herein, we investigated the effects of four NPAHs/OPAHs (1-NNAP, 9-NANT, 9,10-AQ, and 9-FLU) and their parent PAHs (NAP, ANT, and FLU) on endothelium function with regard to endothelial nitric oxide synthase (eNOS) and endothelium-derived nitric oxide (NO) production in human umbilical vein endothelial cells. The eNOS enzymatic activity and NO production were promoted by NAP, ANT, and FLU; however, eNOS activity was dropped by 52.8, 52.1, 52.5, and 44.5%, and NO production was decreased by 31.1, 50.3, 65.0, and 35.0% after 24 h exposure to 0.01 μM 1-NNAP, 9-NANT, 9,10-AQ, and 9-FLU, respectively. The mRNA expression of eNOS and protein expression of phosphorylated eNOS (Ser1177) were increased by three PAHs but decreased by four NPAHs/OPAHs. The 100 ns molecular dynamics simulations reveal the conformational alteration in the key propionate of heme upon the binding of NPAHs/OPAHs. Our findings provide the first in silico and in vitro evidence for the potential endothelial dysfunction of nitrated and oxygenated PAHs. The health risk implications of NPAHs/OPAHs and corresponding parent PAHs warrant further research.

The environmental issue caused by atmospheric hexachlorocyclohexanes (HCHs) has been a worldwide concern due to their long-range transport potential. Tree bark is an excellent passive sampler for monitoring atmospheric pollutants. In this study, bark samples from agricultural regions across China were collected and analyzed to elucidate the contamination status of atmospheric HCHs and the enantiomeric composition of chiral α-HCH. Average contents of α-HCH, β-HCH, γ-HCH, δ-HCH, and ∑HCHs in bark were 1.16, 2.51, 1.67, 0.368, and 5.71 ng/g (dry basis), respectively. Jing-Jin-Tang region was identified as the "hot-spot" of bark HCHs in China. Their residues were likely from the combined sources of historical applications of technical HCHs and lindane through long-distance transport. HCH contents were found inversely correlated with annual precipitation and temperature, but positively correlated with PM10 or PM2.5 due to the bioaccumulation of both vapor- and particle-phase HCHs by tree bark. Most bark samples preferentially accumulated (+)-α-HCH, and the enantiomeric fractions (EFs) of α-HCH were positively correlated with α-HCH concentrations and the elevations of sampling locations. Compared to atmospheric analysis, tree bark analysis and enantiomeric signatures provide valuable time-integrated information on the spatial distribution and transport pathways of atmospheric HCHs on the national scale in China.

As the substitute of polybrominated diphenyl ethers (PBDEs), further assessments about the potential ecological safety and health risks of phosphorus-containing flame retardants (PFRs) are required because the worldwide demand for PFRs has been increasing every year. In this study, we examined the agonistic/antagonistic activity of a group of PFRs by three in vitro models (luciferase reporter gene assay, yeast two-hybrid assay, and E-screen assay). Molecule docking was used to further explain the interactions between ERα and PFRs. Data from luciferase reporter gene analysis showed three members of the nine tested PFRs significantly induced estrogenic effects, with the order of TPP > TCP > TDCPP, while TCEP and TEHP have remarkable antiestrogenic properties with calculated REC20 and RIC20 values of 10(-6) M or lower. Results from the luciferase reporter gene method are generally consistent with results obtained from the yeast two-hybrid assay and E-screen, except for the positive estrogenic activity of TBP in E-screen testing. Docking results showed that binding between ligands and ERα was stabilized by hydrophobic interactions. As a proposed alternative for brominated flame retardant, PFRs may have anti/estrogenic activity via ERα at the low dose typical of residue in environmental matrix or animals. PFRs with a short chain, halogen, and benzene ring in the substituent group tend to be estrogenic. Our research suggests that comprehensive evaluations, including health and ecological assessments, are required in determining whether PFRs are preferable as an emerging industrial substitute.

Micellar partitioning of volatile chlorinated hydrocarbons in surfactant solutions and its effects on vapor-liquid equilibrium is fundamental to the overall design and implementation of surfactant-enhanced aquifer remediation. Surfactant micelles greatly enhance contaminant recovery from the subsurface; however, the reduced volatility of organic compounds compromises the aboveground treatment of surfactant-laden wastewaters using air-stripping process. Batch equilibrium tests were performed to acquire micellar partition coefficients (Km) and apparent Henry's law constants (H*) of three prominent groundwater contaminants (tetrachloroethylene, trichloroethylene, cis-dichlorethylene) in the presence of two anionic surfactants (sodium dodecyl sulfate, SDS; sodium dodecylbenzene sulfonate, SDBS) and two nonionic surfactants (Triton X-100 and Tween 80). The H* values were significantly reduced in the presence of all four surfactants over their critical micelle concentrations (cmc's). On a cmc basis, the anionic surfactant SDS had the greatest effect on H*, followed by SDBS, Triton X-100, and Tween 80. Anionic surfactants decreased H* to an order of magnitude lower than nonionic surfactants, although nonionic surfactants decreased the H* at concentrations significantly lower than the anionic surfactants due to their lower cmc's. Nonionic surfactants present higher Km and molar solubilization ratio than anionic surfactants. Tetrachloroethylene has the highest Km values among three chlorinated solvents, which agrees well with the hydrophobicity (Kow) of these chemicals. An empirical correlation between log Km and log Kow is developed on the basis of data from this study and the Km values reported for a number of chlorinated and nonchlorinated hydrocarbons. Equilibrium data were also tested against three sets of models that describe the partitioning of volatile compounds in vapor-water-micelle phases. Applications of these models in experimentally determining Km from batch vapor-water equilibrium data are discussed.

High concentrations of 2,4-dinitrotoluene (2,4-DNT) and 2,6-dinitrotoluene (2,6-DNT) are present in vadose zone soils at many facilities where explosives manufacturing has taken place. Both DNT isomers can be biodegraded under aerobic conditions, but rates of intrinsic biodegradation observed in vadose zone soils are not appreciable. Studies presented herein demonstrate that nutrient limitations control the onset of rapid 2,4-DNT biodegradation in such soils. In column studies conducted at field capacity, high levels of 2,4-DNT biodegradation were rapidly stimulated by the addition of a complete mineral medium but not by bicarbonate-buffered distilled deionized water or by phosphate-amended tap water. Biodegradation of 2,6-DNT was not observed under any conditions. Microcosm studies using a DNT-degrading culture from column effluent suggest that, after the onset of 2,4-DNT degradation, nitrite evolution will eventually control the extent of degradation achieved by two mechanisms. First, high levels of nitrite (40 mM) were found to strongly inhibit 2,4-DNT degradation. Second, nitrite production reduces the solution pH, and at pH levels below 6.0, 2,4-DNT degradation slows rapidly. Under conditions evaluated in laboratory-scale studies, 2,4-DNT biodegradation enhanced the rate of contaminant loss from the vadose zone by a factor of 10 when compared to the washout due to leaching.