Hexachlorocyclohexane Isomers Research Articles

Co-metabolic growth and microbial diversity: Keys for the depletion of the α, δ, β and γ-HCH isomers

The objective of this study was the isolation and enrichment of microbiomes capable of degrading the main hexachlorocyclohexane isomers quantified in environmental matrices, e.g.: the α, δ, β and γ-HCH isomers. Four microbiomes were isolated and enriched from an HCH-contaminated dumpsite in Italy, both in the presence of HCH isomers (1:1:1:1) as the sole carbon sources and under co-metabolic growth conditions in presence of glucose (0.1 % v/v). The microbiomes were assessed for their relevant metabolic capabilities. A quantitative metabarcoding approach was employed to analyze the compositional evolution of the four microbiomes during the enrichment phase and the phase of testing of the HCH isomers degradation kinetics. The use of a co-metabolic substrate during enrichment process was essential for selecting microbiomes with higher biodiversity. All microbiomes efficiently degraded the α, δ, and γ-HCH isomers. The highest efficiency in the β-HCH degradation capacity was positively correlated to the highest biodiversity of the microbiome, and the involvement of Chryseobacterium and Asinibacterium sps. have been proposed for a recorded increment in bacterial load during the HCH degradation process.

Hydrogeochemical analysis of processes affecting HCH removal using ZVI-based treatment technology

In the 1960s, ca. 3000–5000 tons of HCH residue were disposed of in an overburden dump at the Hájek kaolin/uranium mine site (Czech Republic). The dump leachate, which has a 136 μg/l average total content of hexachlorocyclohexane (HCH) isomers, discharges into a local creek and contaminates the ecosystem. A full-scale prototype for the treatment of dump leachate comprised three sequential stages: 1) permeable reactive modules filled with macro-zerovalent iron (mZVI), 2) a biosorption module and 3) an aerobic wetland module. After commissioning, HCH removal efficiency reached 95%, but decreased to 70% over the following 230 days, primarily due to the efficiency of the mZVI modules dropping from 76% to 39%. Hydrogeochemical analysis and geochemical modelling revealed that the reduction in efficiency was mainly caused by passivation of mZVI surfaces and clogging of mZVI pore spaces through precipitation of goethite, calcite and rhodochrosite, or siderite and magnetite instead of goethite where boundary conditions for O2 differed. XRD analysis of the solid phase from the mZVI modules confirmed the geochemical modelling results. The major part of the precipitated products (46–66 wt%) comprised a ferric hydroxide amorphous phase, especially in the initial mZVI module inlet, with goethite the second most abundant precipitate (10–40 wt%). Siderite and calcite also mainly precipitated in the initial module inlet. In conclusion, mZVI appears to be a suitable reductant for HCH; however, the longevity of the ZVI-based treatment system was negatively affected by precipitates in the presence of high concentrations of iron, manganese and carbonate species.

Lindane degradation potential of methanotrophs and soil microbial biomass from HCH contaminated sites

In the present study, soil physico-chemical properties, hexachlorocyclohexane (HCH) isomers, lindane degrading soil methanotrophs and soil microbial biomass-C, N and P were investigated by selecting 6 study sites in Lucknow and Renukoot region of Uttar Pradesh, Northern India. The ANOVA revealed significant variations soil physico-chemical properties (P<0.001), HCH residues concentrations (P<0.001) and lindane degradation by soil methanotrophs (P<0.001), across different study sites. The GC and GC-MS/MS analysis revealed soil contamination by α, β-, γ-, and δ-HCH, along with organochlorine pesticides (OCPs) including aldrin, β-endosulphan, and dichlorodiphenyltrichloroethane (DDT). The concentration of soil HCH isomers (0.43-310.97 μg g−1) was higher in the soil samples of Lucknow region, compared to the Renukoot (0.12–194.44 μg g−1) region. These results depict that methanotrophic isolates SBRJS01, SBIJS02 and SBJS03 compared to control, showed better growth at selected environmental parameters. During lindane degradation the maximum Cl− release among the methanotrophic isolates showed the trend as SBJS03> SBRJS01> SBIJS02> ControlURRH3. A positive linear relationship (R2=0.7951) was noted between lindane degradation and Cl− release during the methanotrophic isolates incubation period. A greater SMB–C, –N and –P values (365.2, 65.5, and 26.8 μg g−1 soil, respectively), having higher HCH residues were, recorded in the soil samples of Renukoot region, compared to the soils of Lucknow region.The negative correlation between SMB–C, –N, and –P values and different soil HCH isomers suggests that higher concentrations of lethal HCH residues persisting in soils negatively impacts the quantity of soil microbial biomass. Therefore, on-site monitoring and methanotrophic mediated bioremediation of HCH soil residues might be a viable and eco-friendly option in removal of this particular persistent soil pesticide from the contaminated area.

Comprehensive review on Haloalkane dehalogenase (LinB): a β-hexachlorocyclohexane (HCH) degrading enzyme.

Haloalkane dehalogenase, LinB, is a member of the α/β hydrolase family of enzymes. It has a wide range of halogenated substrates, but, has been mostly studied in context of degradation of hexachlorocyclohexane (HCH) isomers, especially β-HCH (5-12% of total HCH isomers), which is the most recalcitrant and persistent among all the HCH isomers. LinB was identified to directly act on β-HCH in a one or two step transformation which decreases its toxicity manifold. Thereafter, many studies focused on LinB including its structure determination using X-ray crystallographic studies, structure comparison with other haloalkane dehalogenases, substrate specificity and kinetic studies, protein engineering and site-directed mutagenesis studies in search of better catalytic activity of the enzyme. LinB was mainly identified and characterized in bacteria belonging to sphingomonads. Detailed sequence comparison of LinB from different sphingomonads further revealed the residues critical for its activity and ability to catalyze either one or two step transformation of β-HCH. Association of LinB with IS6100 elements is also being discussed in detail in sphingomonads. In this review, we summarized vigorous efforts done by different research groups on LinB for developing better bioremediation strategies against HCH contamination. Also, kinetic studies, protein engineering and site directed mutagenesis studies discussed here forms the basis of further exploration of LinB's role as an efficient enzyme in bioremediation projects.

Removal of hexachlorocyclohexane isomers from wastewater using activated carbon from Musa paradisiaca peel: Adsorption isotherms, kinetic, and thermodynamic studies

The potential usage of activated carbon from plantain peel (Musa paradisiaca) (TPPC) and unactivated carbon from plantain peel (UPPC) for the removal of Hexachlorocyclohexanes (HCHs) from water systems was investigated. The TPPC and UPPC were characterized using Fourier transform infrared spectroscopy (FT-IR), and scanning electron microscopy (SEM). Adsorption experiments were conducted as a function of adsorbent weight (2 – 10 g), temperature (30 -50 °C), and solution pH (2 - 9) under an adsorbent packed column. The Optimum removal efficiency of 98.23 % was achieved in the column studies under the following conditions: pH = 5, the dosage of adsorbent = 5 g/100 mL, temperature = 30 °C. The batch adsorption process was employed to evaluate the kinetics, equilibrium, and thermodynamics of the adsorption processes. The equilibrium study showed that Langmuir among other isotherm models applied performed better in fitting the data. Additionally, the kinetic data was best described by the pseudo-second-order model (R2 > 0.97), indicating a chemisorption mechanism. Furthermore, the thermodynamic calculations of the adsorption process suggest that HCH adsorption was exothermic (ΔH = -110.87) and spontaneous (-ΔG).

Breast cancer immunophenotypes and serum organochlorine pesticides in Mexican women: Mixture exposure approach

Epidemiological studies on associations between breast cancer (BC) and organochlorine pesticides (OCP) are inconclusive. The majority of studies have evaluated the effect of single compounds without considering multiple OCP exposures and immunophenotypes of BC. We aimed to evaluate the association between BC immunophenotypes and serum OCP mixtures, and identify the main contributors within mixtures. We included 767 histopathologically confirmed incident BC cases and 908 controls from a population-based case-control study conducted from 2007 to 2011 in Northern Mexico. We obtained direct information about sociodemographic, lifestyle and reproductive characteristics. We collected data from clinical records about hormonal receptors (HR) and epidermal growth factor receptor 2 (HER2) expressions. Immunophenotypes were determined as HR+/HER2−, HER2+ or HR−/HER2−. We quantified OCP and metabolites by gas chromatography using an electron capture micro detector. We used Weighted Quantile Sum regression to assess the association of BC and exposure to multiple OCP, and their contribution within the mixture. We found a positive adjusted association between BC and an OCP mixture (OR: 3.48, 95%CI: 2.58, 4.69), whose primary contribution arose from the isomers of hexachlorocyclohexane and endosulfan, as well as endosulfan sulfate. We also identified a mixture negatively associated (OR: 0.13, 95%CI: 0.08, 0.20), characterized by p,p'-DDT and chlordane metabolites. All these associations remained regardless BC immunophenotypes. This is the first epidemiological report that identified serum OCP mixtures associated with BC immunophenotypes. Due to OCP ubiquity, biomagnification, and continuous exposure, they constitute a global problem of persistent exposure that might be related to BC risk.

Wetland technology for the treatment of HCH-contaminated water – Case study at Hajek site

Hexachlorocyclohexanes (HCH) isomers and their transformation products, such as chlorobenzenes (ClB), generate severe and persistent environmental problems at many sites worldwide. The Wetland technology employing oxidation-reduction, biosorption, biodegradation and phytoremediation methods can sufficiently treat HCH-contaminated water. The treatment process is inherently natural and requires no supplementary chemicals or energy. The prototype with a capacity of 3 L/s was installed at Hajek quarry spoil heap (CZ), to optimize the technology on a full scale. The system is fed by drainage water with an average concentration of HCH 129 μg/L, ClB 640 μg/L and chlorophenols (ClPh) of 16 μg/L. The system was tested in two years of operation, regularly monitored for HCH, ClB and ClPh, and maintained to improve its efficiency. The assessment was not only for environmental effects but also for socio and economic indicators. During the operation, the removal efficiency of HCH ranged from 53.5 % to 96.9 % (83.9 % on average) depending on the flow rate. Removal efficiency was not uniform for individual HCH isomers but exhibited the trend: α = γ = δ > β = ε. The improved water quality was reflected in a biodiversity increase expressed by a number of phytobenthos (diatoms) species, a common biomarker of aquatic environment quality. The Wetland outranked the conventional WWTP in 10 out of the 15 general categories, and it is the most relevant scenario from the socio, environmental, and economic aspects.

Remediation of groundwater polluted with lindane production wastes by conductive-diamond electrochemical oxidation

This work studies the remediation of groundwater saturated with dense non-aqueous phase liquid (DNAPL) from lindane production wastes by electrochemical oxidation. DNAPL-saturated groundwater contains up to 26 chlorinated organic compounds (COCs), including different isomers of hexachlorocyclohexane (HCH). To do this, polluted groundwater was electrolysed using boron-doped diamond (BDD) and stainless steel (SS) as anode and cathode, respectively, and the influence of the current density on COCs removal was evaluated in the range from 5 to 50 mA cm−2. Results show that current densities higher than 25 mA cm−2 lead to the complete removal and mineralisation of all COCs identified in groundwater. The higher the current density, the higher the COCs removal rate. At lower current densities (5 mA cm−2), chlorobenzenes were completely removed, and degradations above 90 % were reached for COCs with more than five chlorine atoms in their molecules. The use of BDD anodes promotes the electrochemical generation of powerful reactive species, such as persulfate, hypochlorite or hydroxyl radicals, that contribute to the degradation and mineralisation of COCs. The applied current density also influences the generation of these species. Finally, no acute toxicity towards Vibrio fischeri was observed for the treated groundwater after the electrochemical oxidation performed at 5 and 10 mA cm−2. These findings demonstrate that electrochemical oxidation with BDD anodes at moderate current densities is a promising alternative for the remediation of actual groundwater contaminated with DNAPLs.

Anaerobic biotransformation of hexachlorocyclohexane isomers in aqueous condition: Dual C[sbnd]Cl isotope fractionation and impact on microbial community compositions

Hexachlorocyclohexane (HCH) isomers are persistent organic pollutants (POPs) with high toxicity, lipid solubility, chemical stability. Despite the current ban on usage of Lindane, residual contamination cannot be ignored, and HCH are frequently detected in groundwater and threaten human health. Cultures capable of degrading α-HCH, β-HCH, γ-HCH, and δ-HCH individually have been enriched in anoxic aqueous conditions. Compound-Specific Isotope Analysis (CSIA) was applied to examine the transformation mechanisms of different HCH isomers by the four enrichment cultures. 16S rRNA sequencing techniques were employed to examine the community composition of the enrichment cultures and detect changes in these communities resulting from adding individual HCH isomers. The results indicated that the ability of the enrichment cultures for dichloroelimination of HCH isomers was inconsistent. During dichloroelimination, different bond cleavage mode of β- and δ-HCH led to distinct isotopic effects. HCH isomers had significant impact on the microbial community, while different microbial communities showed comparable isotopic effects during the transformation of a specific HCH isomer. In addition, bacteria in the phyla Proteobacteria and Firmicutes were proposed as the dominant dechlorinators. This study provides a novel perspective on the mode of bond cleavage during HCH dichloroelimination and the effect of HCH on microbial communities, which could potentially support the evaluation of HCH transformation by CSIA and their effects on the microecosystems of groundwater.

Enhancing hexachlorocyclohexane solubility with surfactants and ionic liquids

Surfactant-enhanced remediation of soil can increase the solubility of hydrophobic organic contaminants in water and improve their removal. In this study, the effect of 24 traditional surfactants and surface-active ionic liquids (SAILs) on the solubility of hexachlorocyclohexane isomers (α-, β-, γ-, δ-HCH) was evaluated in batch-type experiments. The combination of two different proportions of a cationic SAIL and an anionic surfactant was also assessed. The solubilisation capacity of the surfactant varied depending on its concentration and structure, but also the HCH isomer considered. In general, the anionic surfactants yielded the best results, increasing solubilisation of HCH up to 2.4 times compared to the control (pure water). α-HCH and γ-HCH isomers were more easily solubilised than β-HCH and δ-HCH regardless of the surfactant’s type. The main advantage of ionic liquids being their tunability, some clues are given for formulating surfactants to enhance the solubilisation of HCH. The combination of a traditional surfactant and a SAIL influenced the critical micelle concentration, but not the solubilisation of the contaminant. Further studies on the use of blends for this application are required. The increase of solubility achieved with the studied surfactants encourages their application in washing HCH-contaminated soils through solubility enhancement.

Assessing HCH isomer uptake in Alnus glutinosa: implications for phytoremediation and microbial response

Although the pesticide hexachlorocyclohexane (HCH) and its isomers have long been banned, their presence in the environment is still reported worldwide. In this study, we investigated the bioaccumulation potential of α, β, and δ hexachlorocyclohexane (HCH) isomers in black alder saplings (Alnus glutinosa) to assess their environmental impact. Each isomer, at a concentration of 50 mg/kg, was individually mixed with soil, and triplicate setups, including a control without HCH, were monitored for three months with access to water. Gas chromatography–mass spectrometry revealed the highest concentrations of HCH isomers in roots, decreasing towards branches and leaves, with δ-HCH exhibiting the highest uptake (roots—14.7 µg/g, trunk—7.2 µg/g, branches—1.53 µg/g, leaves—1.88 µg/g). Interestingly, α-HCH was detected in high concentrations in β-HCH polluted soil. Phytohormone analysis indicated altered cytokinin, jasmonate, abscisate, and gibberellin levels in A. glutinosa in response to HCH contamination. In addition, amplicon 16S rRNA sequencing was used to study the rhizosphere and soil microbial community. While rhizosphere microbial populations were generally similar in all HCH isomer samples, Pseudomonas spp. decreased across all HCH-amended samples, and Tomentella dominated in β-HCH and control rhizosphere samples but was lowest in δ-HCH samples.

Chemical analysis of wetland plants to evaluate the bioaccumulation and metabolism of hexachlorocyclohexane (HCH)

Hexachlorocyclohexanes (HCH) belong to the banned pesticides with short-time production and use during the last century. However, the consequences of this short period are still present as persistent environmental contamination. This study represents the large lab-scale experiment focused on the HCH accumulation and metabolism in selected wetland plants (Juncus effuses, Typha latifolia, Phragmites australis) and trees (Alnus glutinosa) after the exposure to the technical mix of HCH isomers (t-HCH) or δ-HCH at three different concentration. During the three-month exposure, morphological (biomass, height, relative chlorophyll content) and physiological (photosynthetic measurements - photosynthetic rate, stomatal conductance, transpiration and dark transpiration) parameters were measured to assess the HCH effect on plant's growth. The results showed that all selected plant species supported HCH removal from the soil. The total removal efficiency was lower for the t-HCH than for δ-HCH exposure, and the best results were provided by Alnus glutinosa tree. Also, no isomer preference was observed in plants exposed to t-HCH. Most HCH remained accumulated in the root biomass, and mainly α-HCH and δ-HCH were transported to the above-ground parts due to their physicochemical properties. Simultaneously, HCH uptake and metabolization to chlorobenzenes (CB) and chlorophenols (CP) occur. Non-targeted analysis showed that CP could be conjugated to glucose and malonyl in plant tissue, and secondary plant metabolism is affected positively and negatively after exposure to t-HCH depending on plant species and chemical concentration. Luteolin, quercetin and quercetin-3-O-glucoside found common to all species showed quantitative changes due to HCH. Nevertheless, most morphological and physiological parameters were adversely affected without statistical significance. This large-scale study provides information on the fate of HCH in the soil-plant system, the suitability of selected plants and their adaptation to chemical stress for use in the phytoremediation process.

Organochlorine Pesticides in Dairy Cows’ Diet and the Carryover into Milk in NW Romania

Since modern agriculture relies on high volumes of chemical pesticides, monitoring the exposure to these dangerous substances in feed and the food chain is crucial. This study investigates the transfer of organochlorine pesticide (OCP) from water, soil, and feed to milk in free-range dairy cows using the carryover rates (CORs) and biotransfer factors (BTFs) from feed to milk as tools that can be used for human and animal risk assessments. BTFs can predict the transfer of OCPs into milk due to cows’ ingestion of contaminated feed. Samples were collected from ten small-scale dairy cow farms located near Baia Mare city, NW Romania, identified for distributing fresh milk in the local market. After the appropriate extraction was performed, the OCP concentrations were measured by gas chromatography equipped with an electron capture detector and randomly confirmed using mass spectrometry. The most prominent compounds in the soil, feed, and milk samples were hexachlorocyclohexane (HCH) isomers and dichlorodiphenyltrichloroethane (DDT) and its metabolites. The concentrations of OCPs were lower than the maximum admissible values in feed, water, soil, and milk. The CORs of OCPs varied over four orders of magnitudes, from 0.10% (2,4′–dichlorodiphenylchloroethylene, 2,4′–DDE) to 250% (4,4′–dichlorodiphenyltrichloroethane, 4,4′–DDT). Similar to CORs, the values of BTFs varied largely, from 0.0001 to 1.408. Additionally, the values higher than the unit for some BTFs could be due to the accumulation and biomagnification of these organochlorine compounds in the animal body. The cows’ dietary exposure was evaluated by the estimated daily intake (EDI), considering the three components of ingestion (feed, water, and soil), and varied in the range of 0.0008–0.3509 µg/day/body weight (bw).

Solar-assisted oxidation of organochlorine pesticides in groundwater using persulfate and ferrioxalate

The oxidation of hexachlorocyclohexane isomers in the aqueous phase (Milli-Q and groundwater) was studied using persulfate activated by ferrioxalate and solar light at circumneutral pH. The experiments were conducted in a solar simulator reactor with local radiation fluxes qw= 1.12·10−7 E cm−2s−1 and in compound parabolic collectors with solar light (qw≈10−7 E cm−2s−1) for 390 min. The effect of activator dosage (18–125 μM ferrioxalate) and persulfate concentration (520–2600 μM) on hexachlorocyclohexane conversion and oxalate and oxidant consumption was analyzed. Conversion of about 95% of β isomer was achieved at 390 min using 1300 μM of initial persulfate and 63 μM of Fe3+ concentration despite this β isomer being the most recalcitrant to oxidation (XHexachlorocyclohexanes=0.98). Dechlorination above 80% was achieved under these conditions, analyzing the chlorides released into the water.The influence of chloride and bicarbonate on hexachlorocyclohexanes degradation was analyzed in milli-Q water and in groundwater. Hexachlorocyclohexane conversion at 390 min decreases from 98% to 83, 75 and 65% in the presence of chloride, bicarbonate or groundwater, respectively. Results obtained with compound parabolic collectors and solar light using 2600 μM Na2S2O8 and 63 μM Fe for removing hexachlorocyclohexanes agreed with those from the solar simulator reactor, supporting using solar light to activate persulfate for sustainable abatement of persistent organic pollutants in aqueous matrixes.

Biodiversity in wetland+ system: a passive solution for HCH dump effluents.

The hexachlorocyclohexane isomers (HCH) are long-banned pesticides. Even though their use has been prohibited for decades, their presence in the environment is still reported worldwide. Wetland + is a registered trademark of the remedial treatment technology consisting of an aerobic sedimentary tank, a permeable reactive barrier, a biosorption system, and an aerobic wetland. This proven method combines a reductive treatment known from PRBs with the natural wetland self-cleaning processes. The average efficiency of the system is 96.8% for chlorobenzenes (ClB) and 81.7% for HCH, during the first 12 months of the system operation. The presence of the genes encoding enzymes involved in the degradation of the HCH compounds indicates that the removal of HCH and ClB occurs not only by chemical removal but also through aerobic and anaerobic combining biodegradation. Changes in abundance and the composition of the diatom community were found to be suitable indicators of the water quality and of the impact of the Wetland + operation on the water ecosystem. The system's annual operation exhibited a markedly higher number of diatom species in the closing profiles of the Ostrovský Creek, the Wetland + effluent recipient.

Selected pesticidal POPs and metabolites in the soil of five Vietnamese cities: Sources, fate, and health risk implications

Large quantities of organochlorine pesticides (OCPs) have been used in tropical regions. The fate processes and risks of these legacy contaminants in the tropics are poorly understood. Herein, we investigated the occurrence of three classes of widely used OCPs and their metabolites in surface and core soil from five cities across Vietnam with a prevalent tropical monsoon climate and a long history of OCP application. We aimed to elucidate migration potentials, degradation conditions, and transformation pathways and assess current health risks of these contaminants. Generally, the concentrations of OCPs and metabolites in the soil core were slightly lower than those in surface soil except for hexachlorocyclohexane (HCH) isomers. 2,2-bis(4-chlorophenyl)-1,1,1-trichloroethane (p,p’-DDT), 2,2-bis(4-chlorophenyl)-1,1-dichloroethylene (p,p’-DDE), the sum of dicofol and 4,4′-dichlorobenzophenone (p,p’-DBP), and 2,2-bis(4-chlorophenyl)-1,1-dichloroethane (p,p’-DDD) were the most abundant compounds in both surface and core soils. A uniform distribution of HCHs (the sum of α-, β-, γ-, and δ-HCH) at trace levels was found in almost all soils, serving as evidence of the lack of recent use of HCH pesticides. Higher concentrations of DDTs (the sum of DDT, DDD, and DDE) were observed in north-central Vietnamese soil, whereas appreciable concentrations of ENDs (the sum of α- and β-endosulfan and endosulfan sulfate) were only found in southern Vietnamese soils. Empirical diagnostic ratios indicated residuals of DDTs were mainly from technical DDT rather than dicofol, whereas aged HCHs could be explained by the mixture of lindane and technical HCH. Both historical applications and recent input explain DDTs and ENDs in Vietnamese soil. Total organic carbon performs well in preventing vertical migration of more hydrophobic DDTs and ENDs. The dominant transformation pathway of DDT in surface soil followed p,p’-DDE→2,2-bis(4-chlorophenyl)-1-chloroethylene or p,p’-DDMU→1,1-bis(4-chlorophenyl)ethylene or p,p’-DDNU→p,p’-DBP, whereas the amount of p,p’-DDMU converted from p,p’-DDD and p,p’-DDE is similar in soil core. Non-cancer risks of OCPs and metabolites in all soils and cancer risks of those chemicals in core soils were below the safety threshold, whereas a small proportion of surface soil exhibited potential cancer risk after considering the exposure pathway of vegetable intake. This study implied that organic matter in non-rainforest tropical deep soils still could hinder the leaching of hydrophobic organic contaminants as in subtropical and temperate soils. When lands with a history of OCP application are used for agricultural purposes, dietary-related risks need to be carefully assessed.

New approaches to the determination of organochlorine pesticides in food products and food raw materials

Introduction. The current methods for determining the residual amounts of organochlorine pesticides – 4,4-dichlorodiphenyltrichloromethylmethane (DDT) and its metabolites, hexachlorocyclohexane (HCH) (α, β, γ isomers) in food products and food raw materials, subject to mandatory declaration for their content, despite a fairly high sensitivity, are characterized by low measurement selectivity and are based on the use of obsolete equipment, time-consuming sample preparation. &#x0D; Material and methods. In the work, the method of gas chromatography with mass spectrometric detection on a gas chromatograph “Khromatek-Kristall 5000.2” was used. Sample preparation was carried out by the method of matrix solid-phase dispersion, based on the destruction and dispersion of the analysed sample together with florisil in order to obtain a free-flowing dry mixture.&#x0D; Results. The effectiveness of the method has been proven by validation on 16 model samples of food products of animal origin of various compositions. The versatility of the analysis procedure is ensured by the systematization of food products according to their structural and mechanical properties into groups: liquid, having a finely dispersed structure and a high water content (group A); viscous and pasty products having a fine structure (group B); products of animal origin requiring grinding and dispersion (semi-solid and solid), having a high water and/or fat content, not free-flowing (Group B); dry products of animal origin (dried or freeze-dried), and/or free-flowing powdered products with a low water content that require wetting, grinding and dispersion (Group D). Ingredient composition (water, fat, protein, hydrocarbons) does not significantly affect the stability and reproducibility of the developed method.&#x0D; Limitations. The method has been tested and validated on samples of food products of animal origin. &#x0D; Conclusion. The developed method for the determination of DDT and its metabolites, HCH (isomers α, β, γ), providing a range of measured concentrations (0.01–1.0 mg/kg) will make it possible to control the content of substances in all groups of food products of animal origin identified in the TR CU 021/11 “On food safety”, including products for baby food.

Determination of Stable Hydrogen Isotopic Composition and Isotope Enrichment Factor at Low Hydrogen Concentration.

Determination of stable hydrogen isotopic compositions (δ2H) is currently challenged to achieve a high detection limit for reaching the linear range where δ2H values are independent of concentration. Therefore, it is difficult to assess precise δ2H values for calculating the hydrogen isotope enrichment factor (εH) and for field application where the concentrations of contaminants are relatively low. In this study, a data treatment approach was developed to obtain accurate δ2H values below the linear range. The core concept was to use a logarithmic function to fit the δ2H values below the linear range and then adjust the δ2H values below the linear range into the linear range by using the fitted logarithmic equation. Moreover, the adjusted δ2H values were calibrated by using laboratory reference materials, e.g., n-alkanes. Tris(2-chloroethyl) phosphate (TCEP) and hexachlorocyclohexane (HCH) isomers were selected as examples of complex heteroatom-bearing compounds to develop the data treatment approach. This data treatment approach was then tested using δ2H values from a TCEP transformation experiment with OH radicals. Comparable δ2H values and εH between the low-concentration experiment and the reference experiment were obtained using the developed approach. Therefore, the developed data treatment approach enables a possibility of determining the hydrogen isotopic compositions of organic components in low concentrations. It is especially valuable for determining organic contaminants in environmental samples, which are usually present in low concentrations.

Targets for pollutants in rat and human pancreatic beta-cells: The effect of prolonged exposure to sub-lethal concentrations of hexachlorocyclohexane isomers on the expression of function- and survival-related proteins

Decades after most countries banned hexachlorocyclohexane, HCH isomers still pollute the environment. Many studies described HCH as a pro-diabetic factor; nevertheless, the effect of HCH isomers on pancreatic beta-cells remains unexplored. This study investigated the effects of a one-month exposure to α-HCH, β-HCH, and γ-HCH on protein expression in human (NES2Y) and rat (INS1E) pancreatic beta-cell lines. α-HCH and γ-HCH increased proinsulin and insulin levels in INS1E cells, while β-HCH showed the opposite trend. α-HCH altered the expression of PKA, ATF3, and PLIN2. β-HCH affected the expression of GLUT1, GLUT2, PKA, ATF3, p-eIF2α, ATP-CL, and PLIN2. γ-HCH altered the expression of PKA, ATF3, PLIN2, PLIN5, and IDH1. From the tested proteins, PKA, ATF3, and PLIN-2 were the most sensitive to HCH exposure and have the potential to be used as biomarkers.

Degradation of real lindane wastes using advanced oxidation technologies based on electrogenerated hydrogen peroxide

In this work, hydrogen peroxide (H2O2) is produced using an optimized electrochemical cell equipped with a gas diffusion electrode (GDE) as cathode, reaching efficiencies as high as 20.1%, when operating in a single compartment configuration, which increases up to the range 50–60, when a proton exchange membrane is used to separate the anodic and cathodic compartments, pointing out the great significance of the anodic oxidation of H2O2 and the scavenging effects of the oxidants produced on the anode surface. As compared to previous materials tested, the GDE implemented in this cell underwent a more sustainable manufacturing procedure and exhibited an outstanding performance. The H2O2 produced electrochemically is dosed to the real leachate of an industrial dump, strongly polluted with derivatives of lindane. This waste is associated to the operation of a large facility in the seventies and contains different isomers of hexachlorocyclohexane and other chlorinated hydrocarbons, produced during the ageing of the dump. Effects of the addition of iron (II) sulfate salts and irradiation of UVC were also evaluated. All electrochemically-assisted technologies evaluated (named as chemical (EACO), Fenton (EAFO), photolysis (EAPO) and photo-Fenton (EAPFO) oxidations) were able to successfully remove the pollutants, although with important differences in the efficiencies reached. Results demonstrate that EACO, that is, oxidation by molecular H2O2 is the most effective treatment for the treatment of this type of wastes, pointing out that activation of H2O2 to hydroxyl radicals, either by electrochemically assisted Fenton or photolysis is not positive for this waste. As well, among the different pollutants contained in the raw waste, removal of hexachlorocyclohexane (HCHs) and non-chlorinated volatile organic compounds (VOCs) stands out (both groups being the primary species contained in the wastes). These results are very important not only because of the outstanding productions of H2O2 reached with the novel approach of electrochemical cell used, but also because of the implications of the mechanistic understanding of the attack of H2O2 species in the design of a full-scale application to remediate this real important problem.