Hexachlorobutadiene Concentrations Research Articles

Quantifying Concentrations and Emissions of Hexachlorobutadiene - A New Atmospheric Persistent Organic Pollutant in northern China

Hexachlorobutadiene (HCBD) was listed as a new persistent organic pollutant for global regulation under Stockholm Convention in 2015, and there has been scarce information on its atmospheric concentrations, distributions, and emission sources. HCBD air samples were collected and analyzed to characterize concentrations and distributions at high elevation and urban sites as well as emission source locations in Northern China. We found ambient concentrations of HCBD in Northern China averaged at 34 ± 16 and 36 ± 28 pptv at urban sites in Jinan and Tai'an, respectively, and 31 ± 21 pptv at a high-elevation site Mount Tai. HCBD concentrations at the high elevation and urban sites were found to be affected by long-range transport under the influence of the East Asian monsoon climate. Over potential sources areas, we found concentrations of 76 ± 33 pptv in a mixed factory park, 59 ± 21 pptv in a rubber plant and 74 ± 8 pptv in a municipal solid waste (MSW) landfill area, which were all several times higher than in urban sites. The large concentration gradient across the various environments revealed strong emission sources of HCBD, especially over MSW landfill and Cl-compound production and application areas. An emission rate of 9.2 × 104 kg/yr and an oxidation rate of 32.9 kg/yr for HCBD were estimated for the mixed factory park. OH and Cl are much more active in reaction with HCBD than other oxidants in the atmosphere. Dry deposition and oxidation removed about 5.3% and 0.04%, respectively, of the emitted, suggesting that ∼95% of the emitted HCBD remaining in the atmosphere and could be transported for redistribution. Our findings revealed significant emission sources of HCBD in northern China, which was in turn affected by major sources in East-central China. The regional influence of HCBD pollution warrants serious concerns and points to the need to develop mitigation strategies.

Sources and Distribution Characteristics of HCBD in Rapid Economic Development Areas

In order to understand the sources and distribution characteristics of hexachlorobutadiene (HCBD) in the Yangtze River Delta (YRD), Beijing-Tianjin-Hebei (BTH), and Pearl River Delta (PRD), the emission sources, as well as their distribution in water and soil were analyzed based on the production levels of chlorinated hydrocarbons and wastewater discharge in the three regions. The results showed that the by-products of trichloroethylene (TCE) and tetrachloroethylene (PCE) and wastewater treatment plants were the main sources of HCBD in the three regions. In 2018, the total emissions of HCBD from by-products of TCE and PCE in the three regions were 498.46 t, among which the proportion of by-products of TCE was 66.9%. The HCBD emissions of the three regional industrial and domestic wastewater treatment plants were 628.9 kg and 254.6 kg, respectively. The emissions of HCBD from hydrocarbon chlorination production and wastewater treatment plants in YRD were significantly higher at 497.8 t and 648 kg, respectively, while the emissions from the two sources in BTH were 0.37 t and 125 kg, respectively, and in PRD they were 0.29 t and 110.3 kg, respectively. The average concentrations of HCBD in the natural water of YRD, BTH and PRD were 0.35, 0.25, and 0.64 μg·L-1, respectively, and in the drinking water concentrations were 0.16, 0.09, and 0.04 μg·L-1, respectively. The overall level of HCBD in urban drinking water was relatively low. The concentrations of HCBD in industrial soil were significantly higher than in farmland soil, at 9.3-24.6 ng·g-1 and 0.13-2.67 ng·g-1, respectively. Similar to the situation in water bodies, HCBD pollution in the soil of YRD was the most serious, which was related to the fact that HCBD emissions in YRD were significantly higher than in BTH and PRD.

Hexachlorobutadiene emissions from typical chemical plants

Hexachlorobutadiene (HCBD) was classed as a persistent organic pollutant under the Stockholm Convention in 2015. HCBD is mainly an unintentionally produced by-product of chlorinated hydrocarbon (e.g., trichloroethylene and tetrachloroethylene) synthesis. Few studies of HCBD formation during chemical production processes have been performed, so HCBD emissions from these potentially important sources are not understood. In this study, HCBD concentrations in raw materials, intermediate products, products, and bottom residues from chemical plants producing chlorobenzene, trichloroethylene, and tetrachloroethylene were determined. The results indicated that HCBD is unintentionally produced at much higher concentrations in trichloroethylene and tetrachloroethylene plants than chlorobenzene plants. The sum of the HCBD concentrations in the samples from all of the trichloroethylene and tetrachloroethylene production stages in plant PC was 247000 µg/mL, about three orders of magnitude higher than the concentrations in the tetrachloroethylene production samples (plant PB) and about six orders of magnitude higher than the concentrations in the chlorobenzene production samples (plant PA). The HCBD concentrations were highest in bottom residues from all of the plants. The concentrations in the bottom residue samples contributed 24%–99% of the total HCBD formed in the chemical production plants. The bottom residue, being hazardous waste, could be disposed of by incineration. The HCBD concentrations were much higher in intermediate products than raw materials, indicating that HCBD formed during production of the intended chemicals. The results indicate the concentrations of HCBD unintentionally produced in typical chemical plants and will be useful in developing protocols for controlling HCBD emissions to meet the Stockholm Convention requirements.

Environmentally sound destruction of hexachlorobutadiene during waste incineration in commercial- and pilot-scale rotary kilns

Hexachlorobutadiene (HCBD) is a persistent organic pollutant (POP) that is banned in many countries. To investigate the destruction of HCBD in industrial waste, we conducted incineration tests at a commercial-scale incineration plant equipped with a 130-t/day rotary kiln and at a pilot-scale plant with approximately 2-kg/h of feeding rate. At the commercial-scale plant, waste oil containing 37% by weight of HCBD was co-incinerated at 1058 °C together with the solid and liquid industrial wastes that the plant normally processes. The concentrations of HCBD in the bottom ash (0.25 ng/g-dry), effluent slurry (2.8 ng/L), and stack gas (8.2 ng/m3N) were comparable with those obtained when only the usual industrial waste was incinerated. A destruction efficiency of 99.999996% was obtained from the co-incineration test, with negligible discharge of chlorinated dioxins and furans. At the pilot-scale plant, refuse-derived fuel spiked with HCBD was incinerated. It was found that both decomposition and unintentional generation of HCBD occurred simultaneously in the primary combustion chamber; however, the decomposition rate exceeded the generation rate to afford a destruction efficiency of 99.99993%. Together, these results indicate that HCBD contained in industrial waste can be efficiently destroyed in best available technology (BAT) rotary kiln waste incinerators.

Hexachlorobutadiene (HCBD) contamination in the Arctic environment: A review

Abstract Hexachlorobutadiene (HCBD) is a halogenated hydrocarbon that is primarily produced as an unintentional byproduct in the manufacture of chlorinated solvents. Similarities between HCBD and other persistent organic pollutants (POPs) led to its listing in 2015 for global regulation under the Stockholm Convention on POPs. HCBD's toxicity and propensity for long-range transport means there is special concern for its potential impacts on Arctic ecosystems. The present review comprehensively summarizes all available information of the occurrence of HCBD in the Arctic environment, including its atmospheric, terrestrial, freshwater and marine ecosystems and biota. Overall, reports of HCBD in Arctic environmental media are scarce. HCBD has been measured in Arctic air collected from monitoring stations in Finland and Canada, yet there is a dearth of data for other abiotic matrices (i.e. soils, sediments, glacier ice, freshwaters and seawater). Low HCBD concentrations have been measured in Arctic terrestrial and marine biota, which is consistent with laboratory studies that indicate that HCBD has the potential to bioaccumulate, but not to biomagnify. Available data for Arctic biota suggest that terrestrial birds and mammals and seabirds, have comparatively higher HCBD concentrations than fish and marine mammals, warranting additional research. Although spatial and temporal trends in HCBD concentrations in the Arctic are currently limited, future monitoring of HCBD in the Arctic will be important for assessing the impact of global regulations newly-imposed by the Stockholm Convention on POPs.

Determination of hexachlorobutadiene, pentachlorobenzene, and hexachlorobenzene in waste incineration fly ash using ultrasonic extraction followed by column cleanup and GC-MS analysis.

Hexachlorobutadiene (HCBD) was listed as a new controlling persistent organic pollutant in the Stockholm Convention because of its wide industrial applications and potential genotoxicity and carcinogenicity. However, only limited information exists on the release of HCBD from unintentional sources, such as waste incineration. Identification and quantification of HCBD in fly ash, one of the major outputs of waste incineration, is imperative. This work presents a simple method for determining HCBD in waste incineration fly ash based on ultrasonic extraction coupled with a silica gel-Florisil column cleanup followed by gas chromatography-mass spectrometry detection. Two typical persistent organic pollutants, pentachlorobenzene (PeCB) and hexachlorobenzene (HCB), were measured simultaneously. The parameters that influence the extraction efficiency and the quality of instrument detection were studied. Under the optimum experimental conditions, high sensitivity (detection limit 0.25-0.53 ng g-1), acceptable recoveries (64.0-71.4%) at spiking levels of 5-500 ng g-1, and good repeatability [relative standard deviation (n = 3) of 14% or less] were achieved for all target analytes. The validation of this method was performed by analysis of six real fly ash samples from different waste incinerators in eastern China. The concentrations of HCBD detected in these samples (1.39-97.6 ng g-1) were comparable to those of PeCB (1.22-150 ng g-1) and HCB (0.82-120 ng g-1), indicating that the residual HCBD as well as PeCB and HCB in waste incineration fly ash should not be ignored. The results confirm for the first time that waste incineration is an unintentional source of HCBD in China. Graphical abstract An analytical method for hexachlorobutadiene, pentachlorobenzene, and hexachlorobenzene in fly ash from waste incineration. GC-MS gas chromatography-mass spectrometry, Ph-d10 phenanthrene-d10.

Spatial distributions of hexachlorobutadiene in agricultural soils from the Yangtze River Delta region of China.

Hexachlorobutadiene (HCBD) is one of the persistent organic pollutants (POPs) listed by the Stockholm Convention and poses potential risks to human health and ecosystems. To reveal the regional-scale pollution status of HCBD in agricultural soils from fast-developing areas, an extensive investigation was conducted in the core Yangtze River Delta (YRD), China. The detectable concentrations of HCBD in 241 soil samples ranged from 0.07 to 8.47ngg-1 dry weight, with an average value of 0.32ngg-1 and a detection rate of 59.3%. Industrial emissions and intensive agricultural activities were the potential source of HCBD. The concentrations of HCBD were highly associated with the soil physicochemical properties such as organic matter contents. Higher concentrations of HCBD were found in paddy fields than other land-use types. The concentrations of HCBD were much lower than those of organochlorine pesticides and polychlorinated biphenyls. Significant positive correlations were found between HCBD and most organochlorine pesticides. HCBD was not found in ten vegetable samples due to its low concentration and detection rate. A positive relationship was observed between the level of HCBD and the biomass of fungi, indicating that the fungi in soils might be influenced by the existence of HCBD. The potential risks of HCBD to ecosystems and health of inhabitants were estimated to be negligible. The finding from this study provides an important basis for soil quality assessment and risk management of HCBD in China.

Levels and distribution of organochlorine pesticides and hexachlorobutadiene in soils and terrestrial organisms from a former pesticide-producing area in Southwest China

The contamination of organochlorine pesticides (OCPs) and hexachlorobutadiene (HCBD) in soils, plants, and terrestrial fauna from a former pesticide-producing area in Southwest China was investigated. High levels of OCP residues (ΣHCHs and ΣDDTs of 3.89–13,386 and 23.3–11,186 ng g−1 dw, respectively) were found in the soils within the producing factory, indicating that the former pesticide factory brownfield site poses a high environment risk and that effective soil remediation is needed. The OCP concentrations in soils surrounding the pesticide factory were 1–2 orders of magnitude higher than in the other agricultural areas from China. Grass, vegetables, and tree leaves from the surrounding areas of the point source showed moderate OCP pollution, which was likely to be causing potential negative impacts on terrestrial ecosystem. OCP levels in terrestrial species from the studied area including insects, free-range chickens and birds were moderate, and were generally within accepted safe levels. β-HCH was the most prevalent isomer, implying that hexachlorocyclohexane (HCH) residues were mainly derived from the degradation of technical HCH. The dichlorodiphenyltrichloroethane (DDT) profiles reflected obvious degradation of technical DDT. In the study area, the concentrations of HCBD were <0.02–5.59, 0.03–24.6 ng g−1 dw and 1.65–3.80 ng g−1 lw in soils, plants, and animals, respectively, which were relatively low and not sufficient to cause observable adverse biological effects.

Distribution and accumulation of hexachlorobutadiene in soils and terrestrial organisms from an agricultural area, East China

Hexachlorobutadiene (HCBD) is a potential persistent organic pollutant that has been found in abiotic environments and organisms. However, information on HCBD in soils and its accumulation in terrestrial food chains is scarce. This study investigated the accumulation of HCBD in soils, plants, and terrestrial fauna in a typical agricultural area in Eastern China, and drew comparisons with organochlorine pesticides (OCPs). The HCBD concentrations in soils were <0.02–3.1ng/g dry weight, which were similar to α-endosulfan concentrations but much lower than the concentrations of some other OCPs. The HCBD soil–plant accumulation factors, 8.5–38.1, were similar to those of o,p′-DDT and higher than those of HCHs and p,p′-DDT, indicating that HCBD is strongly bioaccumulated by rice and vegetables. HCBD concentrations of 1.3–8.2ng/g lipid weight were found in herbivorous insects, earthworms, and Chinese toads. The biomagnification factor, the ratio between the lipid-normalized concentrations in the predator and the prey, was found to be 0.16–0.64 for different food chains of Chinese toads, so HCBD was found not to biomagnify, which is in contrast with OCPs. Further research into whether HCBD is biomagnified in high trophic level organisms or through the entire terrestrial food web is required.

Levels and Distributions of Hexachlorobutadiene and Three Chlorobenzenes in Biosolids from Wastewater Treatment Plants and in Soils within and Surrounding a Chemical Plant in China

Although hexachlorobutadiene (HCBD) was recently proposed as a candidate persistent organic pollutant (POP) under the Stockholm Convention, information about its environmental levels and distributions is still very limited. In this work, HCBD was determined in the sewage sludge from 37 wastewater treatment plants (WWTPs) in 23 cities and 17 soils near a chemical plant in China. Three chlorobenzenes (CBs) (1,2,4-trichlorobenzene, 1,2,4,5-tetrachlorobenzene, and hexachlorobenzene) were simultaneously studied to help better understand the environmental behavior of HCBD. Concentrations of HCBD in sludge samples ranged from <0.03 to 74.3 ng/g dry weight (dw) with a median value of 0.30 ng/g dw, which was lower than those of the three CBs. Levels of HCBD were not correlated with capacity of the WWTPs and total organic carbon. For soils, high level of HCBD was found in the sample within the plant, with a rapid decreasing concentration trend with the increase of distance from the plant. It was suspected that releasing as a byproduct during manufacturing of chlorinated chemicals was the primary source of HCBD in the studied location. Further risk assessment indicated that the environmental risk of HCBD to soil organisms and the health risk to employees were very low through soil exposure within the plant.

Pollution topography of chlorobenzenes and hexachlorobutadiene in sediments along the Kaohsiung coast, Taiwan—a comparison of two consecutive years’ survey with statistical interpretation

Forty sediments were analyzed for chlorobenzenes (CBs) and hexachlorobutadiene (HCBD) to investigate their pollution topography along the Kaohsiung coast, Taiwan. Maximum CB concentrations found, varied from 15.4 ng/g dw for 1,2,3-TCB to 56.8 ng/g dw for 1,2,4-TCB, while higher HCBD concentrations were detected among north-bound stations (around the exit of the Tsoying outfall pipe) and its concentration decreases from north to south. Compared to a previous survey executed a year before, there is no statistically significant difference in CB and HCBD congeners between these two surveys ( p = 0.68–0.87, two-tailed paired t-test). The spatial distribution of toxic index reveals that biological effects might occur near Tsoying and Dalinpu outfall pipe outlets which dispose of petro-chemical wastewater. Evidence found in this study also shows distinct CB patterns from the two nearby sources, the Dalinpu outfall pipe outlet and the Kaoping estuary. Principal component analysis shows that four principal components conducting CBs and HCBD distribution were extracted. Both the first two components (accounted for 58.8% of the total variance), comprised all of the CBs except HCB (DCBs to PeCB), were found not capable of differentiating any distinct pollution source. On the other hand, HCBD and HCB were extracted as third and fourth components, respectively, pointing out their distinct sources in this area.

Reducing Ingress of Organic Vapours into Homes Situated on Contaminated Land

The efficacy of current landfill gas and radon mitigation measures for the prevention of ingress of organic vapours was investigated by the study of four houses situated on contaminated land in North West England. The chemical present in the ground of greatest concern for health due to exposure to vapour in the indoor air was hexachlorobutadiene (HCBD) and the concentration of this compound was used to assess the effectiveness of the remedial measures. A two stage remediation was undertaken. For a house with a solid floor the top surface of the floor was sealed and then for the second stage a fan was used to pressurise the soil gas beneath the house. In a house with a suspended timber floor, extra air bricks were installed to increase ventilation of the floor void and then a fan to further increase air exchange in the void. HCBD in air was monitored by both pumped and diffusive sampling methods. Control houses were also monitored that were not subject to remediation. It is concluded that the remedial measures used for radon protection of a suspended floor have the potential to reduce indoor HCBD concentrations by about 80%, at least in downstairs rooms (where initial levels were highest). The two techniques used for properties with solid floors do not appear to be as effective, and no benefit at all was seen without making allowances for changes in concentration that occurred in the control house over the same period. Further work is required to test the efficacy of the techniques over a longer period and under different circumstances of type of contamination and building characteristics.

Three lines of evidence in a sediment toxicity evaluation for hexachlorobutadiene

Three approaches were used in a site-specific sediment toxicity evaluation for hexachlorobutadiene (HCBD), a chemical not previously tested for toxicity in sediment. The results of a sediment dilution study, spiked sediment toxicity tests, and a probabilistic model based on equilibrium partitioning theory were used to estimate ecological effects thresholds for HCBD in sediments of a Gulf Coast estuary. Twenty-nine sediment samples, including 11 undiluted samples and six dilution series, were tested for toxicity under estuarine conditions (10%0 salinity) using Hyalella azteca and Leptocheirus plumulosus. Site sediment was used as diluent, and all samples were assayed for a range of organic and inorganic chemicals. A logistic relationship was observed between HCBD concentrations and organism response, and nonlinear regression explained approximately 90% of the observed variation in amphipod survival as a function of HCBD. Spiked sediment toxicity test results generally agreed with the results of the dilution study, demonstrating the causality of the observed concentration–response relationship. Effects thresholds were estimated as HCBD concentrations corresponding to 80% amphipod survival. The most conservative effects thresholds from the spiked sediment and dilution studies were 0.63 mg/kg normalized to 1% total organic carbon (mg/kg1%OC) for H. azteca and 1.4 mg/kg1%OC for L. plumulosus. Aquatic LC50s for 10 species and a measured acute–chronic ratio from the published literature were used to predict a distribution of sediment effects thresholds for HCBD, with 10th and 90th percentile values of 2.6 and 45 mg/kg1%OC, respectively. The predicted and observed sediment effects thresholds thus agreed relatively well, although the H. azteca and L. plumulosus test results from this study seem to be somewhat more conservative than the majority of published aquatic toxicity test results.

St. Clair River Head and Mouth Water Quality Monitoring, 1987–89

Abstract Water and suspended sediments samples were collected at the head and mouth of the St. Clair River from 1987 to 1989 for organic contaminant analysis. Higher concentrations and higher frequencies of detection of many organic contaminants. in particular penta- and hexachlorobenzenes, hexachlorobutadiene and octachlorostyrene were measured at the river mouth. Year to year comparisons showed substantial reduction in concentrations of hexachlorobutadiene and octachlorostyrene in suspended sediments.

Hexachlorobutadiene residues in aquatic fauna from surface water fed by the river rhine

Hexachlorobutadiene (HCBD) was identified as a component of the residue mixture of chlorinated hydrocarbons in fish from inland waters fed by the Rhine, particularly in the Ketelmeer. The residue level in fish is related to the fat content; no bioaccumulation in the food chain to higher trophic levels was observed. HCBD concentrations in the water of the Ketelmeer appeared to be three orders of magnitude lower than those found in aquatic animals.