Brominated flame retardants in surface sediment from Western Guangdong, South China: Occurrence, distribution and toxicity in Caenorhabditis elegans.

Sediment is the ultimate sink of environmental pollutants. A total of 128 surface sediment samples were collected from 8 rivers and 3 reservoirs in Maoming City, Guangdong Province. This study assessed the content and distribution of brominated flame retardants in sediments. The acute toxicity effects of tetrabromobisphenol A (TBBPA) and hexabromocyclododecane (HBCDs) in sediments were evaluated using Caenorhabditis elegans as model organisms. The concentration of TBBPA in sediments ranged from not detected (ND) to 12.59 µg/kg and was mainly distributed in the central area, which was affected by the emission of TBBPA from residential and factory. The concentration of HBCDs ranged from ND to 6.31 µg/kg, and the diastereoisomer distribution was consistent, showing a trend close to the South China Sea. The composition pattern of HBCDs in the surface sediments from rivers were 41.73%-62.33%, 7.89%-25.54%, and 18.76%-40.65% for α-, ß-, and γ-HBCD, respectively, and in the sediments from reservoirs were 26.15%-45.52%, 7.44%-19.23%, and 47.04%-61.89% for α-, ß-, and γ-HBCD, respectively. When the sum of concentrations of TBBPA and HBCD in sediments were above high levels, reactive oxygen species in nematodes significantly increased, resulting in an oxidative stress response. Intestinal permeability was also enhanced, causing intestinal damage. In addition, in terms of this study, TBBPA had a greater impact on biotoxicity compared to HBCDs, and more attention should be paid to the toxic effects of the river ecosystem organisms in Maoming City, Guangdong Province. This study can complement the pollution database in the study area and provide basic data for pollution control.

Prediction of Thermogravimetric Data in Bromine Captured from Brominated Flame Retardants (BFRs) in e-Waste Treatment Using Machine Learning Approaches.

The principal objective in the treatment of e-waste is to capture the bromine released from the brominated flame retardants (BFRs) added to the polymeric constituents of printed circuits boards (PCBs) and to produce pure bromine-free hydrocarbons. Metal oxides such as calcium hydroxide (Ca(OH)2) have been shown to exhibit high debromination capacity when added to BFRs in e-waste and capturing the released HBr. Tetrabromobisphenol A (TBBA) is the most commonly utilized model compound as a representative for BFRs. Our coauthors had previously studied the pyrolytic and oxidative decomposition of the TBBA:Ca(OH)2 mixture at four different heating rates, 5, 10, 15, and 20 °C/min, using a thermogravimetric (TGA) analyzer and reported the mass loss data between room temperature and 800 °C. However, in the current work, we applied different machine learning (ML) and chemometric techniques involving regression models to predict the TGA data at different heating rates. The motivation of this work was to reproduce the TGA data with high accuracy in order to eliminate the physical need of the instrument itself, so that this could save significant experimental time involving sample preparation and subsequently minimizing human errors. The novelty of our work lies in the application of ML techniques to predict the TGA data from e-waste pyrolysis since this has not been conducted previously. The significance of our work lies in the fact that e-waste is ever increasing, and predicting the mass loss curves faster will enable better compositional analysis of the e-waste samples in the industry. Three ML models were employed in our work, namely Linear, random forest (RF), and support vector regression (SVR), out of which the RF method exhibited the highest coefficient of determination (R2) of 0.999 and least error of prediction as estimated by the root mean squared error (RMSEP) at all 4 heating rates for both pyrolysis and oxidation conditions. An 80:20 split was used for calibration and validation data sets. Furthermore, for showing versatility and robustness of the best-predicting RF model, it was also trained using all the data points in the lower heating rates of 5 and 10 °C/min and predicted on all the data points for the higher heating rates of 15 and 20 °C/min to again obtain a high R2 of 0.999. The excellent performance of the RF model showed that ML techniques can be used to eliminate the physical use of TGA equipment, thus saving experimental time and potential human errors, and can further be applied in other real-time e-waste recycling scenarios.

Association between brominated flame retardants exposure and markers of oxidative stress in US adults: An analysis based on the National Health and Nutrition Examination Survey 2007-2016.

We aimed to investigate the relationship between oxidative stress indicators and brominated flame retardant (BFR) levels in US adults. Using data from the NHANES (National Health and Nutrition Examination Survey) from 2007 to 2016, 8028 participants aged 18 and over were enrolled in this study. PBDE28, PBDE47, PBDE85, PBDE99, PBDE100, PBDE153, PBDE154, PBDE209, and PBB153, with over 75 % detection rates, were extracted in this study. Survey-weighted linear regression model, weighted quantile sum (WQS) model, and quantile-based g calculation (QGC) model were used to assess the correlation between serum BFRs levels and oxidative stress indicators (serum bilirubin and gamma-glutamyl transferase [GGT]). Besides, the nonlinear association was explored using restricted cubic splines (RCS). Each of the BFRs was confirmed by the survey-weighted linear regression model to be positively associated with GGT after controlling for variables, and BFRs except for PBDE153 were positively associated with serum bilirubin. Except for PBDE153, serum bilirubin in the highest quartile of BFRs was significantly higher than in the lowest high quartile. Additionally, except for PBDE85, serum GGT in the highest quartile of BFRs was higher than in the lowest high quartile. A significant nonlinear association between all BFRs with bilirubin and the PBDE153, PBDE209, and PBB153 with GGT was identified by RCS analysis. By WQS analysis, combined BFR exposure was associated with serum GGT (ß: 0.093; 95 % CI = 0.066-0.121; P < 0.0001) and bilirubin (ß: 0.090; 95 % CI = 0.068-0.113; P < 0.0001). QGC analysis found a similar correlation between BFR mixtures with serum GGT (ß: 0.098; 95 % CI = 0.075-0.120; P < 0.0001) and bilirubin (ß: 0.073; 95 % CI = 0.048-0.097; P < 0.0001). Exposure to BFRs is positively associated with markers of oxidative stress (serum bilirubin and GGT) in US adults, which needs further exploration by a large-scale cohort study.

Occurrence of hexabromocyclododecanes (HBCDs) and tetrabromobisphenol A (TBBPA) in indoor dust from different microenvironments: levels, profiles, and human exposure.

The levels and distributions of hexabromocyclododecane diastereoisomers (HBCDs) (including α, ß, and γ-HBCD) and tetrabromobisphenol A (TBBPA) were investigated in indoor dust from bedrooms and offices. HBCDs diastereoisomers were the most abundant compounds in the dust samples, and the concentrations of ∑HBCDs in the bedrooms and offices ranged from 10.6 to 290.1 ng/g and 17.6 to 1521.9 ng/g, respectively. The concentrations of target compounds in the offices were generally higher than those in the bedrooms, probably due to the presence of more electrical equipment in the offices. In this study, highest levels of target compounds were all found in the electronics. In the bedrooms, the highest mean level of ∑HBCDs was found in air conditioning filter dust (118.57 ng/g), while the personal computer table surface dust showed the peak mean concentrations of ∑HBCDs (290.74 ng/g) and TBBPA (539.69 ng/g) in the offices. Interestingly, a significantly positive correlation was observed between the concentrations of ∑HBCDs in windowsills and beddings dust in the bedrooms, suggesting beddings was one of the crucial sources of ∑HBCDs in the bedrooms. The high dust ingestion values of ∑HBCDs and TBBPA were 0.046 and 0.086 ng/kg bw/day for adults, while 0.811 and 0.04 ng/kg bw/day for toddlers, respectively. The high dermal exposure values of ∑HBCDs were 0.026 and 0.226 ng/kg bw/day for adults and toddlers, respectively. Except for dust ingestion, other human exposure pathways (such as the dermal contact with beddings and furniture) should be paid attention.

The interaction mechanisms of co-existing polybrominated diphenyl ethers and engineered nanoparticles in environmental waters: A critical review.

This review focuses on the occurrence and interactions of engineered nanoparticles (ENPs) and brominated flame retardants (BFRs) such as polybrominated diphenyl ethers (PBDEs) in water systems and the generation of highly complex compounds in the environment. The release of ENPs and BFRs (e.g. PBDEs) to aquatic environments during their usage and disposal are summarised together with their key interaction mechanisms. The major interaction mechanisms including electrostatic, van der Waals, hydrophobic, molecular bridging and steric, hydrogen and π-bonding, cation bridging and ligand exchange were identified. The presence of ENPs could influence the fate and behaviour of PBDEs through the interactions as well as induced reactions under certain conditions which increases the formation of complex compounds. The interaction leads to alteration of behaviour for PBDEs and their toxic effects to ecological receptors. The intermingled compound (ENPs-BFRs) would show different behaviour from the parental ENPs or BFRs, which are currently lack of investigation. This review provided insights on the interactions of ENPs and BFRs in artificial, environmental water systems and wastewater treatment plants (WWTPs), which are important for a comprehensive risk assessment.

Novel Brominated Flame Retardants (NBFRs) in a Tropical Marine Food Web from the South China Sea: The Influence of Hydrophobicity and Biotransformation on Structure-Related Trophodynamics.

The increasing discharge and ubiquitous occurrence of novel brominated flame retardants (NBFRs) in aquatic environments have initiated intense global concerns; however, little information is available regarding their structure-related trophodynamics in marine food webs. In this study, a tropical marine food web including 29 species (18 fish and 11 invertebrate species) was collected from coral reef waters of the Xisha Islands, the South China Sea, for an analysis of 11 representative NBFRs. The mean ∑NBFR concentrations generally increased in the following sequence: sea cucumbers (0.330 ng/g lw) < crabs (0.380 ng/g lw) < shells (2.10 ng/g lw) < herbivorous fishes (2.30 ng/g lw) < carnivorous fishes (4.13 ng/g lw), with decabromodiphenyl ethane (DBDPE) and hexabromobenzene (HBB) as the predominant components. Trophic magnification was observed for all of the investigated NBFRs, with trophic magnification factors (TMFs) ranging from 1.53 (tetrabromobisphenol A bis(dibromopropyl ether)) to 5.32 (HBB). Significant negative correlations were also found between the TMFs and the tested in vitro transformation clearance rates (CLin vitro) for the target NBFRs except for bis(2-ethylhexyl)-3,4,5,6-tetrabromo-phthalate (TBPH) (p < 0.05). Multiple linear regression analysis confirmed that the transformation rate is a more powerful predictor for TMFs than the hydrophobicity of NBFRs in this marine food web.

Integrated assessment of endocrine disrupting potential of four novel brominated flame retardants.

Novel brominated flame retardants (NBFRs) have emerged as alternatives to the legacy BFRs due to BFRs' persistence, bioaccumulation and evidence of adverse health effects. The increasing production of NBFRs has led to the frequent detection in environmental media and even in organisms. Thus the potential health risks of these novel NBFRs need to be taken into account. Herein, the endocrine disrupting effects of the four NBFRs (α/ß-TBCO, PBEB, EHTBB and BEHTBP) were evaluated by constructing an estrogen receptor (ERα), glucocorticoid receptor (GR), and mineralocorticoid receptor (MR) mediated dual-luciferase reporter gene assays on the CHO cells, in combination with steroid experiments on the H295R cells and molecular docking. The results revealed that α/ß-TBCO, PBEB and EHTBB induced anti-estrogenic activity at certain concentrations while none of the four NBFRs was agonistic to ERα. For reporter gene assay, only PBEB exhibited GR antagonistic effects. Notably, none of the four NBFRs possess neither agonistic nor antagonistic activity of MR. The molecular docking results were generally consistent with the reporter gene assay, which showed the different binding affinities between NBFRs and the receptors. For steroidogenesis, α/ß-TBCO, PBEB, and EHTBB all upregulated genes encoding for steroid synthesis enzymes, including 17ßHSD, CYP11B1 and CYP17. Altogether, the data clarified that NBFRs may pose risks of endocrine disruption.

Bromine K-Edge X-Ray Absorption Near-Edge Structure Analysis on Hydrobromide-Salt Crystals and the Solid Dispersion of Active Pharmaceutical Ingredients.

Bromine K-edge X-ray absorption near-edge structure (XANES) spectroscopy analyses were used to evaluate the crystals of the active pharmaceutical ingredients, eletriptan hydrobromide, dextromethorphan hydrobromide and scopolamine hydrobromide salts and the solid dispersion of eletriptan hydrobromide. The crystals and the solid dispersion of the active pharmaceutical ingredient (API) salts could be discriminated based on the shape of the XANES spectra. The differences in the shape of XANES spectra was ascribable to the differences in the interatomic interactions of the bromine ions based on the crystal structures. Ratio of the eletriptan hydrobromide α-form crystal in mixed powders of α-form and monohydrate crystals could be quantified by the linear-combination fitting using their XANES spectra. These results indicated that the XANES spectroscopy are a potent method for evaluating the APIs of pharmaceutical formulations even at the higher energy region around the bromine K-edge of 13470 eV.

An updated review on environmental occurrence, scientific assessment and removal of brominated flame retardants by engineered nanomaterials.

Due to the extensive manufacturing and use of brominated flame retardants (BFRs), they are known to be hazardous, bioaccumulative, and recalcitrant pollutants in various environmental matrices. BFRs make flame-resistant items for industrial purposes (textiles, electronics, and plastics equipment) that are disposed of in massive amounts and leak off in various environmental matrices. The consumption of plastic items has expanded tremendously during the COVID-19 pandemic which has resulted into the increasing load of solid waste on land and water. Some BFRs, such as polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCDs), are no longer utilized or manufactured owing to their negative impacts, which promotes the utilization of new BFRs as alternatives. BFRs have been discovered worldwide in soil, sludge, water, and other contamination sources. Various approaches such as photocatalysis-based oxidation/reduction, adsorption, and heat treatment have been found to eradicate BFRs from the environment. Nanomaterials with unique properties are one of the most successful methodologies for removing BFRs via photocatalysis. These methods have been praised for being low-cost, quick, and highly efficient. Engineered nanoparticles degraded BFRs when exposed to light and either convert them into safer metabolites or completely mineralize. Scientific assessment of research taking place in this area during the past five years has been discussed. This review offers comprehensive details on environmental occurrence, toxicity, and removal of BFRs from various sources. Degradation pathways and different removal strategies related to data have also been presented. An attempt has also been made to highlight the research gaps prevailing in the current research area.

Levels, distribution and risk assessment of hexabromocyclododecane (HBCD) in fish in Xiamen, China.

In this study, hexabromocyclododecane (HBCD) was detected in 114 fish samples collected from 6 administrative regions of Xiamen city, China. HBCD amounts ranged between ND (not detected) and 2.216 ng g-1 ww (mean, 0.127 ± 0.318 ng g-1 ww). Besides, α-HBCD was the main diastereoisomer in these fish specimens, followed by ß-HBCD. Meanwhile, γ-HBCD was not detected in any of the samples. Significant differences were recorded among fish species. The results indicated that the levels and detection rates of HBCD were higher in Trachinotus ovatus compared with other aquatic organisms. Therefore, Trachinotus ovatus could be used as a marine biological indicator of HBCD. Within the regions investigated, Siming was significantly different from Jimei, Haicang, and Xiang'an. The spatial distribution of HBCD concentrations indicated higher mean levels in samples collected from Haicang, Jimei, and Xiang'an, respectively, with the highest detection rates in Jimei and Xiang'an, which might be related to geographical location and intense industrial and urban activities. Estimation of daily HBCD intake was performed according to fish consumption in Xiamen residents. The medium bound HBCD amounts in fish were approximately 0.073 and 0.088 ng kg bw-1d-1 for male and female residents of Xiamen, respectively. Exposure doses of HBCD indicated no health concern for Xiamen residents.

Occurrence, Spatial Distribution and Health Risk of Hexabromocyclododecane (HBCD) in Source Water in the Lower Yangtze River, China.

The occurrence and health risk of hexabromocyclododecane (HBCD), a brominated flame retardant with its three diastereoisomers, in drinking water sources in the lower Yangtze River in China was investigated. Its concentration ranged from 0.58 to 3.71 ng/L and averaged at 1.18 ng/L. Among the three diastereoisomers of α-, ß- and γ-HBCD, γ-HBCD was the dominant one accounting for 44% (ranging 27-82%) to the total concentration. Source of HBCD in the contaminated site was discussed according to its spatial distribution and diastereoisomer profile. The margin of exposure (MOE) approach was applied to evaluate the health risk of HBCD through drinking water by estimated exposure and derived reference dose. The MOE was 17 for adults and 12 for children in the worst-case scenario, suggesting a trivial health concern.

Stability Assessment of a Polymeric Brominated Flame Retardant in Polystyrene Foams under Application-Relevant Conditions.

The flame retardant (FR) BLUEDGE polymeric flame retardant (PFR) has been in use since 2011 and was developed as a replacement FR for hexabromocyclododecane in polystyrene (PS)-based insulation foams. To better understand the degradation behavior of the PFR used within PS foams, we examined the degradation of PFR under application-relevant conditions. Thermo-oxidative and photolytic pathways represent the most relevant degradation pathways. Separately, both the thermal and oxidative degradations of PFR at ambient conditions were shown to be negligible based on kinetic models of thermogravimetric analysis data obtained at elevated temperatures; the models predict that it would take 100 years to degrade 1% of PFR at 50 °C and 1000 years at 20 °C. Photodegradation was shown to degrade PFR after accelerated ultraviolet (UV) aging/exposure. UV radiation did not significantly penetrate the foam insulation (<2000 µm); the degradation process took place primarily at the surface. The molecular weight of the polymer changed with degradation, but there was minimal loss of bromine from the foam with degradation. The data from the liquid chromatography-mass spectrometry analysis focused primarily on several small-molecule polar products formed, which included two brominated species. These species were predicted using computer-based modeling to be biodegradable, to not be persistent in the environment, and to exhibit a low toxicity to aquatic organisms.

Development and validation of a liquid chromatography-mass spectrometry method for simultaneous analysis of triazine-based brominated flame retardants in environmental samples.

In the present study, a novel and reliable analytical method was developed and validated for the simultaneous determination of 1,3,5-tris(2,3-dibromopropyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (TDBP-TAZTO) and 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine (TTBP-TAZ) in environmental samples using high-performance liquid chromatography coupled to a tandem mass spectrometer. Firstly, for optimization of the liquid chromatography separation, mobile phases, oven temperatures, modifiers, and buffers were varied. Afterwards, the extraction efficiency of sediment and fish samples was tested with different techniques (pressurized liquid, solid-liquid, ultrasound-assisted, and Soxhlet extraction). Additionally, cleanup using modified multilayer silica gel (sediment) and gel permeation chromatography as well as Florisil® columns (fish) with several solvent mixtures were performed. The best results were obtained with the pressurized liquid extraction (optimal conditions: extraction solvent 100% toluene, extraction time 20 min, cycles two, extraction temperature 100 °C, and flushing volume 60%) compared to other solvent extraction methods. On the basis of this optimized analytical procedure, the method was validated with satisfactory values of correlation coefficient (R2) between 0.998 and 0.999 for both matrices in the calibration range of 2.0-502.0 µg kg-1 for TDBP-TAZTO and 16.6-770.6 µg kg-1 for TTBP-TAZ in sediment samples as well as 4.8-303.5 µg kg-1 and 47.4-742.5 µg kg-1 in fish samples (bream), respectively. Mean recoveries (n = 5) were calculated for both analytes with spiked matrices at one concentration level (100 µg kg-1) between 98 and 114% with intra-day relative standard deviations less than 11%. The inter-day precision (n = 15) was also acceptable for both compounds < 11%. It was found that the limit of detection and limit of quantification were in the range of 0.4-1.3 µg kg-1 for TDBP-TAZTO and 10-28 µg kg-1 for TTBP-TAZ in surface sediment samples and 7-25 µg kg-1 and 22-80 µg kg-1 in fish samples (bream), respectively. The results indicated that these analytical methods could provide reliable and efficient approaches for quantification of TDBP-TAZTO and TTBP-TAZ in sediment and fish samples. Graphical abstract.

Microbial debromination of hexabromocyclododecanes.

Hexabromocyclododecanes (HBCDs), a new sort of brominated flame retardants (BFRs), are globally prevalent and recalcitrant toxic environmental pollutants. HBCDs have been found in many environmental media and even in the human body, leading to serious health concerns. HBCDs are biodegradable in the environment. By now, dozens of bacteria have been discovered with the ability to transform HBCDs. Microbial debromination of HBCDs is via HBr-elimination, HBr-dihaloelimination, and hydrolytic debromination. Biotic transformation of HBCDs yields many hydroxylated and lower brominated compounds which lack assessment of ecological toxicity. Bioremediation of HBCD pollution has only been applied in the laboratory. Here, we review the current knowledge about microbial debromination of HBCDs, aiming to promote the bioremediation applied in HBCD contaminated sites. KEY POINTS: • Microbial debromination of HBCDs is via hydrolytic debromination, HBr-elimination, and HBr-dihaloelimination. • Newly occurred halogenated contaminants such as HBCDs hitch the degradation pathway tamed by previously discharged anthropogenic organohalides. • Strategy that combines bioaugmentation with phytoremediation for bioremediation of HBCD pollution is promising.

A low-volume air sampling method for legacy and novel brominated flame retardants in indoor environment using a newly developed sorbent mixture.

Brominated flame retardants (BFRs) are a series of stable and outstanding flame retardants bringing human exposure risks in indoor environment. However, sampling methods now available for BFRs are solvent-consuming and relatively complicated. This study provides a new option of low-volume air sampling device using cartridges with a sorbent mixture for different types of legacy and novel BFRs. In this study, we found that HC-C18 sorbent is most suitable for polybrominated diphenyl ethers (PBDEs) and novel BFRs (NBFRs) enrichment, and that NH2 for hexabromocyclododecanes (HBCDs). The sorbent mixture was optimized using a complex of HC-C18 and NH2 sorbents with elution recovery of 69.4% ± 7.9-117% ± 10%, pumping-through recovery of 84.5% ± 7.9-127% ± 36%, and breakthrough recovery of 70.8% ± 3.4-118% ± 6% for PBDEs, NBFRs, and HBCDs in indoor air. A sequential elution was also achieved using hexane for PBDEs and NBFRs and ethyl acetate for HBCDs. The method was validated with field sampling at nine student dormitory rooms. For legacy BFRs, all the isomers of HBCDs were detected in the air of nine rooms with the median concentrations of 91, 33, and 25 pg/m3 for (±)α-HBCD, (±)ß-HBCD, (±)γ-HBCD, respectively, while PBDEs were hardly detected. In contrast, NBFRs were detected at total concentrations of 15-811 pg/m3. Pentabromotoluene (PBT) was the most frequently detected NBFRs with a median concentration of 4 pg/m3, followed by EHTBB at 56 pg/m3 and HBBZ at 21 pg/m3. For the risk assessment, the total hazard index value for air inhalation of BFRs was estimated at 6.1⎓10-4-0.35, which are consistently lower than 1, indicating no immediate health risk, while their long-term effects remain worth concerns.

New understanding of novel brominated flame retardants (NBFRs): Neuro(endocrine) toxicity.

Traditional brominated flame retardants (BFRs) negatively affect the environment and human health, especially in the sensitive (developing) nervous system. Considering the physicochemical similarities between novel brominated flame retardants (NBFRs) and BFRs, more and more evidence reveals the neurotoxic effects of NBFRs. We reviewed the neuro(endocrine) toxic effects of NBFRs in vivo and in vitro and discussed their action mechanisms based on the available information. The neurotoxic potential of NBFRs has been demonstrated through direct neurotoxicity and disruption of the neuroendocrine system, with adverse effects on neurobehavioral and reproductive development. Mechanistic studies have shown that the impact of NBFRs is related to the complex interaction of neural and endocrine signals. From disrupting the gender differentiation of the brain, altering serum thyroid/sex hormone levels, gene/protein expression, and so on, to interfere with the feedback effect between different levels of the HPG/HPT axis. In this paper, the mechanism of neurotoxic effects of NBFRs is explored from a new perspective-neuro and endocrine interactions. Gaps in the toxicity data of NBFRs in the neuroendocrine system are supplemented and provide a broader dataset for a complete risk assessment.

Determination of Polybrominated Diphenyl Ethers in Water Samples Using Effervescent-Assisted Dispersive Liquid-Liquid Icroextraction with Solidification of the Aqueous Phase.

An effective and sensitive method is necessary for the determination of polybrominated diphenyl ethers (PBDEs) pollutants in water. In this study, effervescent-assisted dispersive liquid-liquid microextraction with solidification of the aqueous phase (EA-DLLME-SAP), followed by Gas Chromatography-Tandem Mass Spectrometry (GC-MS-MS) quantitative analysis, was established for the preconcentration and determination of PBDEs in real environmental water samples. 1,1,2,2-Tetrachloroethane was used as the extractant and directly dispersed into the water phase of the aqueous samples with the aid of a large number of carbon dioxide bubbles generated via the acid-base reaction of acetic acid and sodium bicarbonate, which did not require the use of a dispersant during the extraction process. The key factors affecting the extraction recovery were optimized, and an internal standard was used for quantitative analysis, which gave good linearity ranges of 1-100 ng·L-1 (BDEs 28, 47, 99, and 100), 2-200 ng·L-1 (BDEs 153, 154, and 183) and 5-500 ng·L-1 (BDE 209) with limits of quantification in the range of 1.0-5.0 ng·L-1. The accuracy was verified with relative standard deviations < 8.5% observed in tap, lake, river and reservoir water samples with relative recoveries ranging from 67.2 to 102.6%. The presented method contributes to the determination of PBDEs in environmental water samples.

Monitoring and Statistical Analysis of Formation of Organochlorine and Organobromine Compounds in Drinking Water of Different Water Intakes.

The main drawback of drinking water chlorination involves the formation of quite hazardous disinfection by-products (DBPs), represented mainly by halogenated species. Based on the authors' monitoring data since 2002, the prevalence of chlorine over bromine in the composition of volatile DBPs was shown for the drinking water in Ufa (Russia). However, the situation was completely reversed in the case of semi-volatile DBPs. The principal goal of the present study involved rationalization of the results of the long-term monitoring. Gas chromatography-mass spectrometry (GC-MS) was used for the qualitative and quantitative analysis of volatile DBPs. Identification of semi-volatile compounds was carried out with GC-MS, while gas chromatography with an atomic emission detector (GC-AED) was used for their quantification. A significant contribution of oxygen to the composition of semi-volatile compounds proves the decisive role of the dissolved organic matter oxidative destructive processes. Statistical analysis revealed notable linear correlations for trihalomethane and haloacetic acid formation vs. chlorine dose. On the contrary, halogenated semi-volatile products do not demonstrate any correlations with the water quality parameters or chlorine dose. Principal component analysis (PCA) placed them into separate groups. The results allow for proposing that formation of the organohalogenated species involved the fast penetration of bromine into the humic matter molecules and, further, their oxidative destruction by active chlorine.

Variations in methyl bromide concentration with distance and time during quarantine fumigation.

Methyl bromide (MB) is a highly toxic and ozone-depleting substance and should be replaced. Worker exposure to high MB concentrations during fumigation has been previously reported. However, variations in MB concentration as a function of distance from fumigated objects or of time after degassing have not been reported so far. In this study, air samples were collected at various distances from fumigated objects (oranges, wood in containers, and wood in tarpaulin) during injection and degassing and analyzed via gas chromatography according to the Occupational Safety and Health Agency method. In addition, MB concentrations were directly measured over time using a gas detector during degassing. Non-linear regression analysis of the logarithmically transformed data indicated a clear decrease in MB concentration with distance as well as time. Non-linear regression models were constructed to describe the decrease in MB concentration with distance from the objects and with time during degassing (P < 0.05 for all models). The results of this study could aid in establishing appropriate safety guidelines, and hence, in preventing risks related to MB exposure.

Development and Application of a High-Precision Algorithm for Nontarget Identification of Organohalogens Based on Ultrahigh-Resolution Mass Spectrometry.

Brominated and/or chlorinated organic compounds (referred to as organohalogens) are frequently detected in natural and engineered environments. However, ultrahigh-resolution mass spectrometry (UHR-MS)-based nontargeted identification of organohalogens remains challenging because of the coexistence of a vast number of halogenated and nonhalogenated organic molecules. In this study, a new algorithm, namely, the NOMDBP code, was developed to simultaneously identify organohalogens and non-organohalogens from the UHR-MS spectra of natural and engineered waters. In addition to isotopic patterns, for the first time, three optional filter rules [i.e., selection for minimum nonoxygen heteroatoms, inspection of the presence of newly formed halogenated disinfection byproducts (Xn-DBPs), and of their precursors] were incorporated into our code, which can accurately identify DBP-associated peaks and further elucidate Xn-DBP generation and transformation mechanisms. The formula assignment ratio against 2815 previously reported organohalogens, and their 11,583 isotopologues exceeded 97%. Application of our algorithm to disinfected natural organic matter indicated that oxygen-containing Xn-DBP species accounted for a majority of the Xn-DBPs. Furthermore, brominated Xn-DBPs (Br-DBPs) were characterized by a higher degree of unsaturation compared to chlorinated Xn-DBPs. In addition to electrophilic substitution and electrophilic addition reactions, the decomposition/transformation pathway was found to be another important mechanism in Br-DBP formation. The results of this study highlight the superior potential of our code for the efficient detection of yet unknown organohalogens (including organohalogens bearing nonoxygen heteroatoms) in a nontargeted manner and for the identification of their generation mechanism occurring during the disinfection process.