Degradation behaviors and accumulative effects of coexisting chlorobenzene congeners on the dechlorination of hexachlorobenzene in soil by nanoscale zero-valent iron.

It is well known that many chlorinated organic pollutants can be dechlorinated by nanoscale zero-valent iron. However, in the real chlorinated organic compounds contaminated soil, the congeners of high- and low-chlorinated isomer often coexist and their dechlorination behaviors are poorly known, such as hexachlorobenzene (HCB). In this work, the degradation behaviors of three coexisting chlorobenzene congeners pentachlorobenzene (PeCB), 1,2,4,5-tetrachlorobenzene (1,2,4,5-TeCB) and 1,2,4-trichlorobenzene (1,2,4-TCB) and the influence of initial pH and reaction temperature on the dechlorination of HCB in HCB-contaminated soil by nanoscale zero-valent iron were studied. The amount and extent of accumulated coexisting chlorobenzenes was analyzed under different environmental conditions. The results indicate that nanoscale zero-valent iron can improve the degradation efficiency of highly toxic chlorinated benzenes and reduce the accumulative effects of highly toxic chlorinated benzenes on dechlorination of HCB. The accumulative effects of three coexisting chlorobenzene congeners on the dechlorination of HCB were ranked as follows: 1,2,4-TCB > 1,2,4,5-TeCB > PeCB.

Adsorption of the hydrophobic organic pollutant hexachlorobenzene to phyllosilicate minerals.

Hexachlorobenzene (HCB), a representative of hydrophobic organic chemicals (HOC), belongs to the group of persistent organic pollutants (POPs) that can have harmful effects on humans and other biota. Sorption processes in soils and sediments largely determine the fate of HCB and the risks arising from the compound in the environment. In this context, especially HOC-organic matter interactions are intensively studied, whereas knowledge of HOC adsorption to mineral phases (e.g., clay minerals) is comparatively limited. In this work, we performed batch adsorption experiments of HCB on a set of twelve phyllosilicate mineral sorbents that comprised several smectites, kaolinite, hectorite, chlorite, vermiculite, and illite. The effect of charge and size of exchangeable cations on HCB adsorption was studied using the source clay montmorillonite STx-1b after treatment with nine types of alkali (M+: Li, K, Na, Rb, Cs) and alkaline earth metal cations (M2+: Mg, Ca, Sr, Ba). Molecular modeling simulations based on density functional theory (DFT) calculations to reveal the effect of different cations on the adsorption energy in a selected HCB-clay mineral system accompanied this study. Results for HCB adsorption to minerals showed a large variation of solid-liquid adsorption constants Kd over four orders of magnitude (log Kd 0.9-3.3). Experiments with cation-modified montmorillonite resulted in increasing HCB adsorption with decreasing hydrated radii of exchangeable cations (log Kd 1.3-3.8 for M+ and 1.3-1.4 for M2+). DFT calculations predicted (gas phase) adsorption energies (- 76 to - 24 kJ mol-1 for M+ and - 96 to - 71 kJ mol-1 for M2+) showing a good correlation with Kd values for M2+-modified montmorillonite, whereas a discrepancy was observed for M+-modified montmorillonite. Supported by further calculations, this indicated that the solvent effect plays a relevant role in the adsorption process. Our results provide insight into the influence of minerals on HOC adsorption using HCB as an example and support the relevance of minerals for the environmental fate of HOCs such as for long-term source/sink phenomena in soils and sediments.

Mechanochemical remediation of the chlorinated compounds contaminated soil depending on the minerals inside-the most reasonable approach.

This study explored a possible destruction of hexachlorobenzene (HCB) as example of persistent organic pollutants (POPs) as well as the dechlorination mechanism by directly using minerals in the soil, such as antigorite, talc and olivine. Compared with a stable quartz phase of SiO2, all three Mg silicate minerals demonstrated certain degrading capacity for HCB with different efficiency order as: antigorite > talc > olivine > SiO2 at 2 h of milling time. Interestingly, olivine exhibited a better performance than antigorite at 4 h of milling time, giving destruction percentage of 92.7% over 89.0% even at high concentrated HCB up to 5% added. Raman and ESR characterizations of the ball milled sample with olivine indicated the formation of amorphous carbon and graphitic carbon, and the occurrence of free radicals was observed to play an important role in dechlorination and carbonization of HCB. The first identified effectiveness of directly using Mg silicate minerals, allowed no addition of active chemicals during the ball milling, therefore avoided the concern over extrinsic contaminations on the soil. Olivine was further utilized to deal with actual contaminated soil and showed unique advantages on application prospects.

Dissociative Electron Attachment to Hexachlorobenzene.

Gas phase molecules of hexachlorobenzene (C6 Cl6 ) were investigated by means of dissociative electron attachment spectroscopy (DEAS). Three channels of molecular negative ions decay have been identified: abstraction of Cl- and Cl2- as well as electron detachment (τa ∼250 µs at 343 K). All three channels exhibit temperature dependence. The adiabatic electron affinity estimated using a simple but typically accurate Arrhenius model (EAa =1.6-1.9 eV) turns out to be much higher than the quantum-chemical predictions (EAa =0.9-1.0 eV). We discuss the possible reasons behind the observed discrepancy.

Photochemical transformation of hexachlorobenzene (HCB) in solid-water system: Kinetics, mechanism and toxicity evaluation.

As one of the first batch of persistent organic pollutants (POPs) included in Stockholm Convention, hexachlorobenzene (HCB) has attracted great attention because of its wide occurrence and great environmental risks. Considering the easy adsorption of HCB on solids and the complexity of natural particles, we systematically investigated the photodegradation of HCB on the surface of silica gel (SG) in aqueous solution in this work to reveal its fate in natural waters. Under mercury lamp irradiation, more than 90% of HCB loaded on SG could be removed after 240 min. Moreover, the effects of solution pH and water constituents were examined, and results showed that the presence of NO2-, NO3-, Fe3+ and humic acid (HA) significantly inhibited the reaction due to the scavenging of ROS and/or competitive absorption of light. According to radical quenching experiments and electron paramagnetic resonance (EPR) spectra, hydroxyl radicals and singlet oxygen generated on the surface of SG could participate in the transformation of HCB, but •OH played a dominant role. Based on products identified by high performance liquid chromatography-mass spectrometry (HPLC-MS) and gas chromatography-mass spectrometry (GC-MS), two main pathways were proposed for the removal of HCB, including dechlorination and hydroxylation which represent direct and indirect photodegradation, respectively, and the occurrence of these two reactions was further supported by density functional theory (DFT) calculations. From the quantitative analysis of penta-chlorobenzene, it was estimated that dechlorination and hydroxylation contributed to approximately 44.4% and 55.6% of initial HCB degradation, respectively. Furthermore, toxicity predictions by the ecological structure-activity relationship model (ECOSAR) suggested that the toxicity of HCB was decreased in the photodegradation process. This study would provide important information for understanding the photochemical transformation mechanism of HCB at the solid/water interface.

Association between toxic organochlorine levels in human serum and systemic lupus erythematosus.

Organochlorines (OCs) are groups of highly toxic pesticides with known immunotoxicity. The present work aimed to study the potential association between serum residues of OCs and the risk of developing systemic lupus erythematosus (SLE) as well as correlating to the clinical-laboratory manifestations in a sample of Egyptian SLE patients. A cross-sectional study was conducted on 132 patients environmentally exposed to OCs. Patients were diagnosed as SLE based on the American College of Rheumatology (ACR) revised criteria. Systemic Lupus Erythematosus Disease Activity Index-2000 (SLEDAI-2K) score was calculated to stratify the disease severity. Blood and urine samples were collected to measure the levels of OCs, serological markers, and urinary protein. The most frequently detected OCs were p,p'-DDE; lindane; and hexachlorobenzene (HCB). The risk of developing SLE was significantly associated with detected p,p'-DDE and HCB (B value 7.704 and 14.33, respectively). Hexachlorobenzene, in addition, was significantly associated with increased SLEDAI-2K score and polycythemia. Lindane was significantly associated with hypocomplementemia, cardiac manifestations of SLE, anemia, and leucopenia. In conclusion, the detected OCs p,p'-DDE and HCB are associated with increased risk of SLE in Egyptian patients and correlates to the manifestations of disease severity.

Toxicity studies of hexachlorobenzene administered by gavage to female Sprague Dawley (Hsd:Sprague Dawley SD) rats.

Despite the cessation of its production and use in many parts of the world, hexachlorobenzene (HCB) remains highly persistent in the environment, and chronic, low-dose exposure to HCB in humans continues. Its structural resemblance to 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD), ability to activate the aryl hydrocarbon (Ah) receptor, TCDD-like toxicities, and bioaccumulative nature suggest HCB be included in the toxic equivalency factor (TEF) methodology. Consequently, the National Toxicology Program conducted this subchronic study of HCB, including measurement of a variety of toxicological and biochemical endpoints, to allow comparison to TCDD data obtained in a previous 2-year bioassay. (Abstract Abridged).

Mechanochemical treatment with CaO-activated PDS of HCB contaminated soils.

Mechanochemical methods with co-milling reagents have been widely used to degrade organic pollutants. In this study, calcium oxide and persulfate were employed as co-milling reagents in a mechanochemical process that showed highly effective degradation of hexachlorobenzene in contaminated soil. The influences of soil particle size and organic matter content were also investigated. The interaction between different factors was analyzed by response surface methodology, and a multi-variate regression equation was obtained relating the soil-to-oxidant mass ratio, rotation speed and organic matter content. The existence of SO4- and OH during the mechanochemical reaction was proved by the indirect detection of benzoquinone and p-hydroxybenzoic acid for the first time, providing a new method for testing free radicals in solid-phase reactions. Finally, a possible activation mechanism and hexachlorobenzene degradation pathway were proposed. This study successfully presents a mild degradation method in the field of hexachlorobenzene contaminated site remediation.

Alumina-mediated photocatalytic degradation of hexachlorobenzene in aqueous system: Kinetics and mechanism.

Five kinds of Al2O3 were characterized by SEM, TEM, FT-IR and BET surface area, and then used as carriers to investigate the photochemical removal of hexachlorobenzene (HCB) in aqueous system. The results showed that HCB coated on the surfaces of all Al2O3 could be photodegraded rapidly, and Neutral-Al2O3 presented the best performance. Meanwhile, the efficient removal of HCB in real water matrices, including tap water, river water and secondary clarifier effluent showed the potential practical application of Al2O3. EPR and theoretical calculation revealed the generation of hydroxyl radicals on Al2O3 surface under 500 W Xe lamp irradiation. Nine intermediates and a small amount of Cl- were identified by GC/MS, LC/MS and IC analysis, which was further verified by transition state calculations. These results can provide a new technique for HCB removal in water and wastewaters, and give more insights into the environmental ecological risk assessment of this pollutant.

Deiodination in the presence of Dehalococcoides mccartyi strain CBDB1: comparison of the native enzyme and co-factor vitamin B12.

Triiodinated benzoic acid derivatives are widely used as contrast media for medical examinations and are found at high concentrations in urban aquatic environments. During bank filtration, deiodination of iodinated contrast media has been observed under anoxic/anaerobic conditions. While several bacterial strains capable of dechlorination and debromination have been isolated and characterized, deiodination has not yet been shown for an isolated strain. Here, we investigate dehalogenation of iodinated contrast media (ICM), triiodobenzoic acids (TIBA), and analogous chlorinated compounds by Dehalococcoides mccartyi strain CBDB1 and its corrinoid co-factor vitamin B12. No cell growth of CBDB1 was observed using iodinated compounds as electron acceptor. Only negligible deiodination occurred for ICM, whereas 2,3,5-TIBA was nearly completely deiodinated by CBDB1 without showing cell growth. Furthermore, TIBA inhibited growth with hexachlorobenzene which is usually a well-suited electron acceptor for strain CBDB1, indicating that TIBA is toxic for CBDB1. The involvement of CBDB1 enzymes in the deiodination of TIBA was verified by the absence of deiodination activity after heat inactivation. Adding iodopropane also inhibited the deiodination of TIBA by CBDB1 cells, indicating the involvement of a corrinoid-enzyme in the reductive TIBA deiodination. The results further suggest that the involved electron transport is decoupled from proton translocation and therefore growth. Graphical abstract.

Flavin-N5-oxide intermediates in dibenzothiophene, uracil, and hexachlorobenzene catabolism.

Flavin-N5-oxide is a new intermediate in flavoenzymology. Here we describe the identification of DszA (dibenzothiophene catabolism), RutA (uracil catabolism) and HcbA1 (hexachlorobenzene catabolism) as flavin-N5-oxide-utilizing enzymes. Mechanistic analysis of these reactions suggests a model for the identification of other examples of this catalytic motif.

Degradation kinetics of hexachlorobenzene over zero-valent magnesium/graphite in protic solvent system and modeling of degradation pathways using density functional theory.

Hexachlorobenzene (HCB), like many chlorinated organic compounds, has accumulated in the environment from agricultural and industrial activity. Because of its health risks and adverse impact on various ecosystems, remediation of this contaminant is of vital concern. The objective of this study is to evaluate the proficiency of activated magnesium metal in a protic solvent system to accomplish reductive dechlorination of HCB. Experimental results were compared with those predicted by quantum chemical calculations based on Density Functional Theory (DFT). Multivariate analysis detected complete degradation of HCB within 30 min at room temperature, the reaction having a rate constant of 0.222 min-1. Dechlorination was hypothesized to proceed via an ionic mechanism; the main dechlorination pathways of HCB in 1:1 ethanol:ethyl lactate were HCB → PCBz → 1,2,4,5-TCB; 1,2,3,5-TCB → 1,2,4-TriCB; 1,3,5-TriCB → 1,4-DiCB; 1,3-DiCB. The direct relationship between the decreasing number of Cl substituents and dechlorination reaction kinetics agrees with the ΔG values predicted by the computational model. This methodology shows promise for the development of a practical and sustainable field application for the remediation of other chlorinated aromatic compounds.

Hexachlorobenzene Catabolism Involves a Nucleophilic Aromatic Substitution and Flavin-N5-Oxide Formation.

HcbA1 is a unique flavoenzyme that catalyzes the first step in the bacterial hexachlorobenzene catabolic pathway. Here we report in vitro reconstitution of the HcbA1-catalyzed reaction. Detailed mechanistic studies provide evidence for nucleophilic aromatic substitution and flavin-N5-oxide formation.

The effect of redox capacity of humic acids on hexachlorobenzene dechlorination during the anaerobic digestion process.

Hexachlorobenzene (HCB) dechlorination affected by humic acids (HA) was evaluated in terms of HA redox capacity, HA concentrations, and microbial community, as well as the correlation between HA redox capacity values and HCB concentrations. With addition of HA in the initial stage, redox capacity values increased by 2.19 meq/L (80 mg/L of HA addition, HA80), 2.51 meq/L (120 mg/L of HA addition, HA120), and 3.64 meq/L (200 mg/L of HA addition, HA200), respectively. The addition of HA could prominently enhance the HCB degradation rate. However, the concentration and the redox capacity of HA decreased during the anaerobic digestion process. Illumina MiSeq sequencing showed that microbial community affected by HA. Bacillus, Comamonas, and Pseudomonas were the predominant genera during the HCB dechlorination treatment. Moreover, Bacillus and Pseudomonas can improve HA electron transfer capability and promote the dechlorination of HCB.

Preliminary release inventories of unintentionally generated dl-PCB and HCB from sources in China: Base year 2015.

This research presents release inventories of unintentionally generated dioxin-like polychlorinated biphenyls (dl-PCB) and hexachlorobenzene (HCB), which so far have not been developed or assessed. For the inventory development, the amended Toolkit methodology as developed for reporting under the Stockholm Convention on Persistent Organic Pollutants, has been applied. Based on the activity rate (AR) obtained from various statistical yearbooks, reports, or scientific literature, and the emission factors (EFs) suited to each technology level, we estimated the preliminary release inventories of unintentionally produced dl-PCB and HCB from 36 source categories in China for the reference year 2015. The result showed that in 2015, 656 g TEQ of unintentionally produced dl-PCB and 2,145,504 g (or 2146 kg) of unintentionally generated HCB were released in China from these 36 source categories. Most of dl-PCB and HCB was released to air, 71% or 60%, respectively. For comparison - and for the sources which could be estimated for all three unintentional POPs - the total releases of PCDD/PCDF were 5695 g TEQ per year. Of these, 78% were released to air. For dl-PCB and HCB, the vast majority of the releases from the source group 7 - Production and use of consumer goods - is found in the products and not in air. With respect to source attribution and releases to air, the source groups SG3 - Heat and power generation and SG2 - Ferrous and non-ferrous metal production dominate the air emission inventory. Due to the lack of EFs, the calculated releases to the water and land were not well covered, which overall results in an underestimation of the total releases for all unintentional POPs. For comparison, the release inventories from Japan and from several other countries that were developed using methodologies other than the UNEP Toolkit are presented as well.

Modification of Hexachlorobenzene to Molecules with Lower Long-Range Transport Potentials Using 3D-QSAR Models with a Full Factor Experimental Design.

In this study, the hexachlorobenzene molecule was modified by three-dimensional quantitative structure-activity relationship (3D-QSAR) models and a full factor experimental design to obtain new hexachlorobenzene molecules with low migration ability. The 3D-QSAR models (comparative molecular field analysis (CoMFA) and comparative molecular similarity indices analysis (CoMSIA)) were constructed by SYBLY-X 2.0 software, using experimental data of octanol-air partition coefficients (KOA) for 12 chlorobenzenes (CBs) congeners as the dependent variable, and the structural parameters of CBs as independent variables, respectively. A target molecule (hexachlorobenzene; HCB: its long-distance migration capability leads to pollution of the marine environment in Antarctic and Arctic) was modified using the 3D-QSAR contour maps associated with resolution V of the 210-3 full-factorial experimental design method, and 11 modified HCB molecules were produced with a single chlorine atom (-Cl2) and three chlorine atoms (-Cl1, -Cl3, and -Cl5) replaced with electropositive groups (-COOH, -CN, -CF3, -COF, -NO2, -F, -CHF2, -ONO2, and -SiF3) to increase the logKOA. The new molecules had essentially similar biological enrichment functions and toxicities as HCB but were found to be more easily degraded. A 2D-QSAR model and molecular docking technology indicated that both dipole moments and highest occupied orbital energies of the substituents markedly affected migration and degradation of the new molecules. The abilities of the compounds to undergo long distance migration were assessed. The modified HCB molecules (i.e. 2-CN-HCB, 2-CF3-HCB, 1-F-3-COOH-5-NO2-HCB, 1-NO2-3-CN-5-CHF2-HCB and 1-CN-3-F-5-NO2-HCB) moved from a long-range transport potential of the modified molecules to a relatively low mobility class, and the transport potentials of the remaining modified HCB molecules (i.e. 2-COOH-HCB, 2-COF-HCB, 1-COF-3-ONO2-5-NO2-HCB, 1-F-3-CN-5-SiF3-HCB, 1-F-3-COOH-5-SiF3-HCB and 1-CN-3-SiF3-5-ONO2-HCB) also significantly decreased. These results provide a basic theoretical basis for designing environmentally benign molecules based on HCB.

Dechlorination of Hexachlorobenzene in Contaminated Soils Using a Nanometallic Al/CaO Dispersion Mixture: Optimization through Response Surface Methodology.

Hexachlorobenzene (HCB) contamination of soils remains a significant environmental challenge all over the world. Reductive stabilization is a developing technology that can decompose the HCB with a dechlorination process. A nanometallic Al/CaO (n-Al/CaO) dispersion mixture was developed utilizing ball-milling technology in this study. The dechlorination efficiency of HCB in contaminated soils by the n-Al/CaO grinding treatment was evaluated. Response surface methodology (RSM) was employed to investigate the effects of three variables (soil moisture content, n-Al/CaO dosage and grinding time) and the interactions between these variables under the Box-Behnken Design (BBD). A high regression coefficient value (R² = 0.9807) and low p value (<0.0001) of the quadratic model indicated that the model was accurate in predicting the experimental results. The optimal soil moisture content, n-Al/CaO dosage, and grinding time were found to be 7% (m/m), 17.7% (m/m), and 24 h, respectively, in the experimental ranges and levels. Under optimal conditions, the dechlorination efficiency was 80%. The intermediate product analysis indicated that dechlorination was the process by stepwise loss of chloride atoms. The main pathway observed within 24 h was HCB → pentachlorobenzene (PeCB) → 1,2,3,4-tetrachlorobenzene (TeCB) and 1,2,4,5-TeCB. The results indicated that the moderate soil moisture content was crucial for the hydrodechlorination of HCB. A probable mechanism was proposed wherein water acted like a hydrogen donor and promoted the hydrodechlorination process. The potential application of n-Al/CaO is an environmentally-friendly and cost-effective option for decontamination of HCB-contaminated soils.

Residue behavior of organochlorine pesticides during the production process of yogurt and cheese.

The presence of organochlorine pesticides (OCPs) in dairy products can lead to human exposure. This study investigated the behavior of OCP residues in milk during yogurt and cheese production. Gas chromatography with electron-capture detection (GC-ECD) was used to detect α-hexachlorocyclohexane (HCH), hexachlorobenzene (HCB), γ-HCH, g-chlordane, and α-chlordane in fresh milk, yogurt, and cheese. The results showed that fermentation reduced the residual concentration of OCPs in yogurt, with processing factors (PFs) ranging from 0.42 to 0.64. The reductions in residue levels during fermentation were due to the activity of the starter. The cheese making process increased the residual concentration of OCPs in cheese compared to raw milk, with PFs ranging from 2.37 to 4.93. Additionally, milk, yogurt, and cheese samples were purchased from local markets and OCP levels were analyzed. The target OCPs ranged from ND to 16.50 µg/kg in these samples.

Serum concentrations of selected organochlorine pesticides in a Lebanese population and their associations to sociodemographic, anthropometric and dietary factors: ENASB study.

Organochlorine pesticides (OCPs) were banned by the Stockholm Convention many years ago; however, they are still detected in the environment due to their high persistence, their current illegal use, and their import from countries where they have not been banned. We evaluated the serum concentrations of selected OCPs (hexachlorobenzene (HCB), ß-hexachlorocyclohexanes (ß-HCH), p,p'-dichlorodiphenyltrichloroethane (DDT) and its metabolite p,p'-dichlorodiphenyldichloroethylene (DDE) in a sample of Lebanese adults using gas chromatography coupled to an ion trap mass spectrometer detector. The mean concentrations of HCB, ß-HCH, DDT, and DDE were 7.1, 8.6, 2.1, and 18.9 ng/g of lipids, respectively, and the major contributor among the four OCPs was DDE. The OCP levels in the present study were in general lower than the values observed in several countries worldwide and their concentrations at the 95th percentile were lower than the biomonitoring equivalents (BEs) excluding any appreciable health risk. We observed an inverse association between HCB concentrations and body mass index (BMI) as well as HCB, ß-HCH, and DDE levels, and smoking habits. Milk consumption however was positively associated with an increased serum level of ß-HCH. This study, which was the first to investigate OCP serum levels in a Lebanese population, provides a baseline to which future measurements can be compared.

Energy transfer and kinetics in mechanochemistry.

Mechanochemistry (MC) exerts extraordinary degradation and decomposition effects on many chlorinated, brominated, and even fluorinated persistent organic pollutants (POPs). However, its application is still limited by inadequate study of its reaction kinetic aspects. In the present work, the ball motion and energy transfer in planetary ball mill are investigated in some detail. Almost all milling parameters are summarised in a single factor-total effective impact energy. Furthermore, the MC kinetic between calcium oxide/Al and hexachlorobenzene is well established and modelled. The results indicate that total effective impact energy and reagent ratio are the two factors sufficient for describing the MC degradation degree of POPs. The reaction rate constant only depends on the chemical properties of reactants, so it could be used as an important index to appraise the quality of MC additives. This model successfully predicts the reaction rate for different operating conditions, indicating that it could be suitably applied for conducting MC reactions in other reactors.