Short-chain Chlorinated Paraffins Research Articles

Developmental toxicity of short-chain chlorinated paraffins on early-stage chicken embryos in a shell-less (ex-ovo) incubation system

Short-chain chlorinated paraffins (SCCPs) are listed as a category of globally controlled persistent organic pollutants (POPs) by the Stockholm Convention in 2017. However, SCCP toxicity, particularly their developmental toxicity in avian embryos, has not been well studied. In this study, we observed the early development of chicken embryos (Gallus gallus domesticus) by applying a shell-less (ex-ovo) incubation system developed in our previous studies. After exposing embryos at Hamburger Hamilton stage (HHS) 1 to SCCPs (control, 0.1% DMSO; SCCPs-L, 200 ng/g; SCCPs-M, 2000 ng/g; SCCPs-H, 20,000 ng/g), we observed the development of embryos from the 3rd to 9th incubation day. Exposure to SCCPs-M and -H induced a significant reduction in survival, with an LD50 of 3100 ng/g on the 9th incubation day. Significant dose-dependent decreases in body length were observed from days 4–9. We also found that SCCPs-H decreased the blood vessel length and branch number on the 4th incubation day. Additionally, SCCPs-H significantly reduced the heart rate on the 4th and 5th incubation days. These findings suggest that SCCPs may have potential of developmental and cardiovascular toxicity during the early stages of chicken embryos. Quantitative PCR of the mRNA of genes related to embryonic development showed that SLC16A10 (a triiodothyronine transporter) level decreased in the SCCPs-H group, showing a significant positive correlation with the body length of embryos. THRA level, a thyroid hormone receptor, was significantly decreased in the SCCPs-H group, whereas that of DIO3 level, a deiodinase was significantly increased. These results suggest that SCCPs exposure induces developmental delays via the thyroxine signaling pathway. Analysis of thyroid hormones (THs) in blood plasma also indicated a significant reduction in thyroxine (T4) levels in the SCCPs-H group on the 9th incubation day of embryos. In conclusion, SCCPs induce developmental toxicity by disrupting thyroid functions at the early-life stage of chicken embryos.

Medium-chain chlorinated paraffins (MCCPs) induce renal cell aging and ferroptosis.

Medium-chained chlorinated paraffins (MCCPs) are a class of chlorinated derivatives of straight-chain n-alkanes with complex compositions, which are widely used in industry. The chlorinated paraffins (CPs) are divided into short chain chlorinated paraffins (SCCPs), medium chain chlorinated paraffins (MCCPs) and long chain chlorinated paraffins (LCCPs). SCCPs have been banned due to their severe bioaccumulation and biotoxicity. Therefore, MCCPs are used as a substitute for SCCPs. However, the toxicological data of MCCPs are still very limited. For this, we systematically investigated the toxicological impact of MCCPs on a renal cell model in the current study. Our work provides basic research data for analyzing the toxicological effects of MCCPs, suggesting that MCCPs should be restricted in their usage. A series of biochemical experiments was performed, including Western blot, indirect immunofluorescence assay, and ELISA was performed to analyze the toxicological effects of MCCPs. Two renal cell lines were used as a model for assessing the toxicological effects of MCCPs. Cell proliferation assays showed that MCCPs could inhibit the proliferation of kidney cells in a dose-dependent manner. Further studies showed that MCCPs induced ferroptosis in kidney cells by evaluating a series of ferroptosis marker molecules. Additionally, MCCPs induced inflammatory response and premature senescence in HEK293 and NRK-52E cells. Molecular mechanism experiments showed that ferroptosis induced by MCCPs emerged as a significant contributor to premature aging of kidney cells. The current study provides basic research data to analyze the toxicological effects of MCCPs and their toxicity mechanisms. It also provides a theoretical basis for the assessment of the potential ecological risk of MCCPs, as well as basic experimental data for the rational and standardized use of MCCPs.

Bee colonies map the short- and medium-chain chlorinated paraffin contamination from the apiary environment

Chlorinated paraffins (CPs) are industrial chemicals that have potential adverse effects in the environment and on human health. This study investigated CPs in apiary environment, honeybees, and bee products from two rural areas of Beijing, China. The median concentrations of short-chain CPs (SCCPs) and medium-chain CPs (MCCPs) were 22 and 1.6 ng/m3 in the ambient air, 1350 and 708 ng/g dry mass (dw) in bees, 1050 and 427 ng/g dw in flowers, 37 and 54 ng/g in honey, 78 and 53 ng/g dw in bee pollen, 36 and 30 ng/g dw in soil, and 293 and 319 ng/g dw in bee wax. C10Cl6–7 and C14Cl7–8 dominated SCCPs and MCCPs in these samples, respectively. The concentrations and distributions of CPs in samples from apiaries located in the two regions varied. Long-range transportation of air masses was identified as an important source of CPs in apiaries. A close relationship between CPs in bees and the apiary environment indicated that bees could act as bioindicators for CP contamination in the environment. A human health risk assessment found that there were low risks for adults and children exposed to CPs through consumption of honey and pollen from the studied regions.

Occurrence, distribution and annual emissions of chlorinated paraffins in hazardous byproducts from municipal solid waste incineration plants in South China

Nowadays incineration technology has become the most mainstream way for the disposal of municipal wastes. Short chain chlorinated paraffins (SCCPs) and medium chain chlorinated paraffins (MCCPs) are currently classified as new persistent organic pollutants (POPs) and candidate POPs under the Stockholm Convention, respectively. However, the occurrence and contamination characteristics of these main hazardous byproducts (e.g., leachate, fly ash, and bottom ash) from municipal solid waste incineration (MSWI) plants have remained unknown. This study focused on the SCCPs and MCCPs (defined as CPs) contamination and their annual emissions from leachate, fly ash, and bottom ash among three typical MSWI plants in Shenzhen, South China. Compared to the dissolved phase of the leachate, higher concentrations of CPs were detected in the adsorbed phase. The total concentrations of CPs ranged from lower method detection limits (<MDLs) to 448 ng/g in fly ash and 124 to 7230 ng/g in bottom ash. The ratios of MCCPs to SCCPs were generally >1 in leachate (i.e., adsorbed phase) and bottom ash, while the opposite results were found in fly ash. The dominant SCCP congener groups were C10Cl6–7 in leachate and fly ash, and C13Cl6–7 in bottom ash. The dominant MCCP congener groups were C14Cl7–8 in leachate, fly ash and bottom ash samples. Principal component analysis (PCA) revealed the dominant CPs in fly ash were obviously different from those in leachate and bottom ash. Estimated total annual emissions of CPs from the three main hazardous byproducts generated from typical MSWI plants were estimated between 66.2 and 7510 kg/y and bottom ash contributed the most to the CP emissions. Overall, this study is the first report on CP contamination in hazardous byproducts from MSWI plants, and can provide basic data support for CP contamination control.

Short- and medium-chain chlorinated paraffins in breast milk in Shanghai, China: Occurrence, characteristics, and risk assessment

As novel contaminants, short-chain chlorinated paraffins (SCCPs) and medium-chain chlorinated paraffins (MCCPs) have been of great concern in the past several years. Shanghai was one of the provinces with the largest chlorinated paraffins (CPs) emission in China; nevertheless, there is currently little information on the human exposure to SCCPs and MCCPs, particularly MCCPs. In this study, 25 breast milk samples were collected in Shanghai from 2016 to 2017. The concentrations of SCCPs and MCCPs were determined using two-dimensional gas chromatography coupled with orbitrap high-resolution mass spectrometry (GC × GC-orbitrap-HRMS) to investigate their characteristics and assess the associated health risks for breast-fed infants. Compared with the previous studies in other areas, the current study presented the higher CPs concentrations, with median concentrations of SCCPs and MCCPs up to 771 and 125 ng/g lipid weight (lw), respectively. The exposure profiles of the CPs were characterized by C10 and Cl6-7 as the predominant congeners of SCCPs, while C14 and Cl7–9 were identified as the dominant groups of MCCPs. CP-42 and CP-52 were identified as potential sources of CPs found in breast milk samples collected in Shanghai. The concentrations of MCCPs exhibited a positive correlation (p value < 0.05) with the dietary consumption of meat and poultry. No significant positive correlations were observed for SCCPs and MCCPs with polychlorinated dibenzodioxins/furans (PCDD/Fs) congeners. A preliminary exposure assessment showed that SCCPs in breast milk potentially posed high risks to the breast-fed infants in Shanghai.

Characterization of persistent organic contaminants in the atmosphere of Gadani's ship breaking yards and its surrounding: Implications for sustainable ship recycling practices

Gadani is internationally renowned for its extensive ship-breaking operations, positioning it as one of the globe's primary ship-breaking hubs. A comprehensive study was conducted to evaluate the presence of organic contaminants in the air within Gadani, encompassing the areas surrounding ship-breaking facilities, proximate residential settlements, and adjacent roadways. Passive air samplers were employed to collect a total of 30 air samples. The analytical results unveiled a notably elevated concentration of specific organic compounds, with a pronounced prevalence of polycyclic aromatic hydrocarbons (PAHs), short-chain chlorinated paraffins (SCCPs), and polychlorinated biphenyls (PCBs) at the ship-breaking yard. Notably, dichlorodiphenyltrichloroethanes (DDTs) and DDE were detected at substantially lower levels. In particular, sites in close proximity to ship-breaking activities exhibited elevated concentrations of PCBs (Σ7PCB 0.065429 to 7.345714 ng/sample), PAHs (Σ8PAH 2.44 to 134.23 ng/sample), and SCCPs (0.18 to 25.6 ng/sample). Conversely, DDTs and DDE demonstrated higher concentrations near residential settlements. The evaluation of Molecular Diagnostic Ratios for PAHs revealed anthracene/anthracene + phenanthrene ratios of 0.88, 0.69, and 0.5 for ship-breaking areas, roadside locations, and community surroundings, respectively. Furthermore, the benz[a]anthracene/benz-[a]anthracene + chrysene molecular ratios were measured at 0.77 (ship-breaking sites), 0.82 (roadside), and 0.83 (community), respectively. The molecular ratio of fluoranthene/fluoranthene + pyrene at ship-breaking sites was 0.23, while roadside and community ratios were 0.36 and 0.89, respectively. These findings underscore the significant contribution of ship-recycling activities to the atmospheric release of SCCPs, PCBs, and PAHs, emphasizing the global imperative for responsible ship recycling practices.

Exploring long-term global environmental impacts of chlorinated paraffins (CPs) in waste: Implications for the Stockholm and Basel Conventions and the global plastic treaty

Chlorinated paraffins (CPs), mainly short-chain CPs (SCCPs) and medium-chain CPs (MCCPs), are currently the most produced and used industrial chemicals related to persistent organic pollutants (POPs) globally. These chemicals are widely detected in the environment and in the human body. As the release of SCCPs and MCCPs from products represents only a small fraction of their stock in products, the potential long-term release of CPs from a large variety of products at the waste stage has become an issue of great concern. The results of this study showed that, by 2050, SCCPs and MCCPs used between 2000 and 2021 will cumulatively generate 226.49 Mt of CP-containing wastes, comprising 8610.13 kt of SCCPs and MCCPs. Approximately 79.72 Mt of CP-containing wastes is predicted to be generated abroad through the international trade of products using SCCPs and MCCPs. The magnitude, distribution, and growth of CP-containing wastes subject to environmentally sound disposal will depend largely on the relevant provisions of the Stockholm and Basel Conventions and the forthcoming global plastic treaty. According to multiple scenarios synthesizing the provisions of the three conventions, 26.6–101.1 Mt of CP-containing wastes will be subject to environmentally sound disposal as POP wastes, which would pose a great challenge to the waste disposal capacity of China, as well as for countries importing CP-containing products. The additional 5-year exemption period for MCCPs is expected to see an additional 10 Mt of CP-containing wastes subject to environmentally sound disposal. Thus, there is an urgent need to strengthen the Stockholm and Basel Conventions and the global plastic treaty.

[Metabolomic interference induced by short-chain chlorinated paraffins in human normal hepatic cells].

Short-chain chlorinated paraffins (SCCPs) are an emerging class of persistent organic pollutants (POPs) that are widely detected in environmental matrices and human samples. Because of their environmental persistence, long-range transport potential, bioaccumulation potential, and biotoxicity, SCCPs pose a significant threat to human health. In this study, metabolomics technology was applied to reveal the metabolomic interference in human normal hepatic (L02) cells after exposure to low (1 μg/L), moderate (10 μg/L), and high (100 μg/L) doses of SCCPs. Principal component analysis (PCA) and metabolic effect level index (MELI) values showed that all three SCCP doses caused notable metabolic perturbations in L02 cells. A total of 72 metabolites that were annotated by MS/MS and matched with the experimental spectra in the Human Metabolome Database (HMDB) or validated by commercially available standards were selected as differential metabolites (DMs) across all groups. The low-dose exposure group shared 33 and 36 DMs with the moderate- and high-dose exposure groups, respectively. The moderate-dose exposure group shared 46 DMs with the high-dose exposure group. In addition, 33 DMs were shared among the three exposure groups. Among the 72 DMs, 9, 9, and 45 metabolites participated in the amino acid, nucleotide, and lipid metabolism pathways, respectively. The results of pathway enrichment analysis showed that the most relevant metabolic pathways affected by SCCPs were the lipid metabolism, fatty acid β-oxidation, and nucleotide metabolism pathways, and that compared with low-dose exposure, moderate- and high-dose SCCP exposures caused more notable perturbations of these metabolic pathways in L02 cells. Exposure to SCCPs perturbed glycerophospholipid and sphingolipid metabolism. Significant alterations in the levels of phosphatidylcholines, phosphatidylethanolamines, and sphingomyelins indicated SCCP-induced biomembrane damage. SCCPs inhibited fatty acid β-oxidation by decreasing the levels of short- and medium-chain acylcarnitines in L02 cells, indicating that the energy supplied by fatty acid oxidation was reduced in these cells. Furthermore, compared with low- and moderate-dose SCCPs, high-dose SCCPs produced a significantly stronger inhibition of fatty acid β-oxidation. In addition, SCCPs perturbed nucleotide metabolism. The higher hypoxanthine levels observed in L02 cells after SCCP exposures indicate that SCCPs may induce several adverse effects, including hypoxia, reactive oxygen species production, and mutagenesis in L02 cells.

Short- and medium-chain chlorinated paraffins in sediment from the Haihe River Basin: Sources, distributions, and ecological risk assessment

Chlorinated paraffins (CPs) can accumulate in sediment and pose risks to ecological systems and human health. The Haihe River Basin is one of the seven main river basins in China and is mainly in the Beijing–Tianjin–Hebei region, which is densely populated and very urbanized. There is therefore a high probability of CP pollution in the Haihe River Basin. However, CP pollution and the environmental risks posed by CPs in the Haihe River are not well understood. In this study, the concentrations of short-chain CPs (SCCPs) and medium-chain CPs (MCCPs) in sediment from six rivers in the Haihe River Basin system were determined using two-dimensional gas chromatography electron-capture negative ionization mass spectrometry. The total SCCP and MCCP concentrations in the sediment samples ranged from 131.83 to 1767.71 and from 89.72 to 1442.82 ng/g dry weight, respectively. The total organic carbon content did not significantly correlate with the CP concentrations. The dominant SCCP congener groups were C10Cl6–7 and the dominant MCCP congener groups were C14Cl7–8. Significant relationships (R = 0.700, p < 0.05) were found between the SCCP and MCCP concentrations, indicating that SCCPs and MCCPs may have similar sources. Hierarchical cluster analysis and principal component analysis indicated that sediment in the study area was contaminated with CPs through the use of the CP-42 and CP-52 commercial products in industrial processes and human activities. The ecological risks posed by CPs were assessed and SCCPs were found to pose high risks in the Yongding New River but moderate risks in the other rivers. MCCPs were found to pose minimal risks to the aquatic environment at most of the sampling points.

Characterization of short-, medium-, and long-chain chlorinated paraffins in Tibetan butter and implications for local human exposure

Since short-chain chlorinated paraffins (SCCPs) were severely restricted under the Stockholm Convention in 2017, a shift to the production of other chlorinated paraffin (CP) groups has occurred, particularly medium-chain (MCCPs) and long-chain CPs (LCCPs), although data on the latter are sparser in the literature. This study described the occurrence of three types of CPs in butter samples from six livestock milk sources across 15 sites in Tibet. The median levels of SCCPs, MCCPs, and LCCPs were 132, 456, and 13.2 ng/g lipid, respectively. The detection rate of 97.6% suggests that LCCPs can be transmitted to humans. Thus, all CPs, regardless of their chain length and degree of chlorination, should be treated with caution. The differences in concentration were mainly caused by dynamic wet deposition and thermodynamic cold-trapping effects across the different districts. The homolog pattern of CPs varied widely across livestock species, which was attributed to the diverse impacts of the physicochemical properties of the homologs, especially the heterogeneity in the uptake and transfer of CPs across different organisms. Under three different criteria, the health risks associated with the daily intake of SCCPs should not be neglected, especially considering other intake exposure pathways and the degradation of longer-carbon-chain monomers.

Evolution of chlorinated paraffin and olefin fingerprints in sewage sludge from 1993 to 2020 of a Swiss municipal wastewater treatment plant

Exposure of humans to chlorinated paraffins (CPs) and chlorinated olefins (COs) can occur via contact with CP-containing plastic materials. Such plastic materials can contain short-chain CPs (SCCPs), which are regulated as persistent organic pollutants (POPs) under the Stockholm Convention since 2017. Municipal wastewater treatment plants (WWTP) collect effluents of thousands of households and their sludge is a marker for CP exposure. We investigated digested sewage sludge collected in the years 1993, 2002, 2007, 2012, and 2020 from a Swiss WWTP serving between 20000 and 23000 inhabitants. A liquid chromatography mass spectrometry (R > 100000) method, in combination with an atmospheric pressure chemical ionization source (LC-APCI-MS), was used to detect mass spectra of CPs and olefinic side products. A R-based automated spectra evaluation routine (RASER) was applied to search for ∼23000 ions whereof ∼6000 ions could be assigned to CPs, chlorinated mono- (COs), di- (CdiOs) and tri-olefins (CtriOs). Up to 230 CP-, 120 CO-, 50 CdiO- and 20 CtriO-homologues could be identified in sludge. Characteristic fingerprints were deduced describing C- and Cl-homologue distributions, chlorine- (nCl) and carbon- (nC) numbers of CPs and COs. In addition, proportions of saturated and unsaturated material were determined together with proportions of different chain length classes including short- (SC), medium- (MC), long- (LC) and very long-chain (vLC) material. A substantial reduction of SCCPs of 84% was observed from 1993 to 2020. Respective levels of MCCPs, LCCPs and vLCCPs decreased by 61, 69 and 58%. These trends confirm that banned SCCPs and non-regulated CPs are present in WWTP sludge and higher-chlorinated SCCPs were replaced by lower chlorinated MCCPs. Combining high-resolution mass spectrometry with a selective and fast data evaluation method can produce characteristic fingerprints of sewage sludge describing the long-term trends in a WWTP catchment area.

Uptake, accumulation and toxicity of short chain chlorinated paraffins to wheat (Triticum aestivum L.)

Short chain chlorinated paraffins (SCCPs) are ubiquitous persistent organic pollutants. They have been widely detected in plant-based foods and might cause adverse impacts on humans. Nevertheless, uptake and accumulation mechanisms of SCCPs in plants remain unclear. In this study, the soil culture data indicated that SCCPs were strongly absorbed by roots (root concentration factor, RCF>1) yet limited translocated to shoots (translocation factor<1). The uptake mechanism was explored by hydroponic exposure, showing that hydrophobicity and molecular size influenced the root uptake and translocation of SCCPs. RCFs were significantly correlated with logKow values and molecular weights in a parabolic curve relationship. Besides, it was extremely difficult for SCCPs to translocate from shoots back to roots via phloem. An active energy-dependent process was proposed to be involved in the root uptake of SCCPs, which was supported by the uptake inhibition by the low temperature and metabolic inhibitor. Though SCCPs at environmentally relevant concentrations had no negative impacts on root morphology and chlorophyll contents, it caused obvious changes in cellular ultrastructure of root tip cells and induced a significant increase in superoxide dismutase activity. This information may be beneficial to moderate crop contamination by SCCPs, and to remedy soils polluted by SCCPs with plants.

Interlaboratory trial of short-chain chlorinated paraffin: comparison of mass fractions and homolog profiles in a simulation environmental sample.

Short-chain chlorinated paraffins (SCCPs) are listed in the Stockholm Convention. Therefore, selecting suitable methods for their accurate quantification is essential. Nowadays, the quality of commercial reagents employed as quantification standards is not guaranteed. As a solution, we adopted an SCCP formulation reference material with known homolog composition ratios as the quantification standard to evaluate the appropriateness of the methods. By mixing the SCCP formulation and interferences, an analytical sample was independently prepared and used as the simulation environmental sample. The homolog compositional profiles of the SCCPs resembled those of the quantification standard and the analytical sample. The mass fractions and the homolog profiles, including the carbon chain length and chlorine homologprofiles, of the SCCPs were reported by 14 different laboratories. For the mass fraction, the results reported by participants were consistent, except for the participants that employed low-resolution gas chromatography (GC). The results generated from liquid chromatography (LC) and GC were slightly different, despite of the similar homolog composition ratios between the quantification standard and the analytical sample. Although there were discreet discrepancies in the overall chlorine homolog profiles, the carbon chain length profiles acquired from GC and LC were similar. The differences depended on the method employed. Additionally, compared with the low-resolution data, the high-resolution data displayed less fluctuation since the effect of the interferences on the analytical sample was reduced because of the mass accuracy of high-resolution instruments. Accordingly, the interlaboratory trial employing the similar homolog compositional profiles of the quantification standard and the analytical sample proved valuable in elucidating the differences among methods, considering equipment, resolution specification, and ionization.

Short-chain chlorinated paraffin (SCCP) exposure and type 2 diabetes risk: A population-based case-control study in East China

Exposure to persistent organic pollutants may be associated to type 2 diabetes, but the studies on associations between short-chain chlorinated paraffin (SCCP) exposure and type 2 diabetes risk in humans are still scarce. Here, we conducted a case-control study involving 344 participants in Shandong Province, East China, to explore the effects of SCCPs on type 2 diabetes risk and their correlations with glycemic biomarker and serum lipid parameters. SCCPs were detected in all serum samples with a median concentration of 24 ng mL−1 in cases and 19 ng mL−1 in controls. Exposure to C10-CPs, C11-CPs, and ΣSCCPs were positively associated with the risk of type 2 diabetes after adjusting for confounders. The associations remained consistent in stratified analyses but stronger in male participants and obese individuals. In the control group, there were significant and positive correlations between SCCP exposure and levels of total cholesterol (TC), low-density lipoprotein-cholesterol (LDL-C), total lipid, and non-high-density lipoprotein-cholesterol. Significant joint effects on SCCP exposure and lipid parameters were observed in females when analyzed by the quantile-based g-computation model, and C10-CPs showed the highest contribution. Mediation analysis showed that LDL-C had significant mediation effects on the associations between C10-CPs, C11-CPs, and ΣSCCPs exposure and risk of type 2 diabetes. Moreover, TC and high-density lipoprotein-cholesterol were mediators in the relationship between C11-CPs and type 2 diabetes. Taken together, our study revealed that human exposure to SCCPs may increase the risk of type 2 diabetes and disrupt lipid metabolism.

Chlorinated paraffins (CPs) in vegetable oils from the Dutch market and the effects of the refining process on their levels

Chlorinated paraffins (CPs) are of growing public health concern because of their ubiquitous presence in food samples. To get more insight into levels of CPs in vegetable oils from the Dutch market and human exposure via these oils, two series of samples were analysed in this study for the presence of CPs by UHPLC coupled with Q-Exactive Orbitrap mass spectrometry: 1) 39 vegetable oils from local supermarkets; 2) 13 paired crude and refined vegetable oils obtained from a contract refining company. Short chain CPs (SCCPs) and medium chain CPs (MCCPs) were detected in vegetable oils from supermarkets with an overall range from <LOQ to 78 ng/g lipid weight (lw) and <LOQ to 391 ng/g lw, respectively. The tridecane and tetradecane groups dominated in SCCPs and MCCPs, respectively. As regards to paired crude and refined oils from a refining company, a marked decrease in concentrations of both SCCPs and MCCPs were detected by the refining process (average reduction: 82% and 69% for SCCPs and MCCPs, respectively). Based on the data obtained, it can be concluded that CPs with a relatively short carbon chain length and low chlorination degree are more likely to be removed in the refining process. The estimated margins of exposure (MoEs) due to oil consumption alone were all higher than 1000, indicating no health concern from CPs for the Dutch population.

Occurrence and Formation Mechanism of PCDD/Fs and SCCPs in Chlorinated Paraffin Products.

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and short-chain chlorinated paraffins (SCCPs) can be formed during the production of chlorinated paraffins (CPs). Detection and accurate quantification of PCDD/Fs in CPs are challenging because of their matrix complexity. Therefore, the occurrence and formation mechanisms of PCDD/Fs from CPs have not been studied extensively in the past. In this study, 15 commercial samples including solid and liquid CPs were collected in 2022 from China. The average ΣSCCP concentrations detected in the solid and liquid CPs were 158 and 137 mg/g, respectively. The average International Toxic Equivalent (I-TEQ) values of 2,3,7,8-PCDD/F in solid and liquid CPs were 15.8 pg I-TEQ/g and 15.0 pg I-TEQ/g, respectively. The solid and liquid CPs had different predominant congener groups for SCCPs and PCDD/Fs. Possible formation routes for the generation of PCDD/Fs were analyzed by screening precursors in paraffin and laboratory-scale thermochemical experiments of CPs. The transformation between 2,3,7,8-PCDD/Fs and non-2,3,7,8-PCDD/Fs was recognized by calculating the successive chlorination preference. The first reported occurrence of PCDD/Fs in CP commercial products indicated that exposure to CPs and downstream products might be an assignable source of PCDD/F emission, which is of great significance to further explore the control factors of PCDD/Fs in the whole life cycle of CPs.

An alkali-enhanced subcritical water treatment strategy of short-chain chlorinated paraffins: Dechlorination and hydrocarbons recovery

As persistent organic pollutants, short-chain chlorinated paraffins (SCCPs) have attracted wide attention in the field of environmental health risk and hazardous waste management. Efficient dechlorination of high content of SCCPs in plastic waste is the committed step for its detoxification and safety treatment. In this study, a high-efficiency and low-temperature process for dechlorination and hydrocarbons recovery from typical SCCPs (52#SCCPs) by subcritical water (SubCW) with alkali enhancer was developed. The introduction of alkali enhancer in the SubCW process had significantly enhanced effect on the dechlorination of 52#SCCPs, and the order of the enhanced effect of alkali enhancer for the dechlorination was NaOH > Na2CO3 > NaHCO3 > NH3·H2O > KOH. The dechlorination behaviors of 52#SCCPs in the NaOH-enhanced SubCW process were studied systematically under different conditions including temperature, residence time, alkali concentration, and volume ratio. The results showed that high-efficiency dechlorination (100 %) of 52#SCCPs could be achieved by the NaOH-enhanced SubCW process at low temperature for a short time (250 °C, 5 min). All of the chlorine released from the molecular chain of 52#SCCPs was transferred to the aqueous phase in the form of inorganic chlorine. The continuous HCl elimination reaction was the primary dechlorination mechanism for 52#SCCPs in the NaOH-enhanced SubCW process. After the dechlorination of 52#SCCPs, high value-added hydrocarbons such as 2,4-hexadiyne (31.74 %) could be obtained. The alkali-enhanced SubCW process proposed in this study is believed to be an environmentally friendly and high-efficiency method for dechlorination/detoxification and resource recovery of SCCPs.

Homologue Composition of Technical Chlorinated Paraffins Used in Several Countries over the Last 50 Years─SCCPs Are Still Out There.

Chlorinated paraffins (CPs) are widely produced chemicals, with certain CP subgroups facing global restrictions due to their environmental dispersion, persistence, bioaccumulation, and toxicity. To evaluate the effectiveness of these international restrictions, we assessed the homologue group contribution and the mass fraction of short-chain CPs (SCCPs: C10-C13), medium-chain CPs (MCCPs: C14-C17), and long-chain CPs (LCCPs: ≥C18) in 36 technical CP mixtures used worldwide over the last 50 years. Using low-resolution mass spectrometry (LC-ESI-MS/MS), we quantified 74 CP homologue groups (C10Cl4-C20Cl10). Additionally, high-resolution mass spectrometry (LC-ESI-QTOF-MS) screening was employed to identify unresolved CP contents, covering 375 CP homologue groups (C6Cl4-C30Cl30). Overall, 1 sample was mainly composed of <C10-CPs, 10 of SCCPs, 13 of MCCPs, and 12 of LCCPs. Specific homologue group contributions and mass fractions of CP subgroups varied considerably. However, the predominance of C11Cl6- and C14Cl6-CP homologue groups was in good agreement with that of the dominant homologue groups in environmental matrices and manufactured products. SCCP yields are still high in some technical CP mixtures, and three technical CP mixtures currently produced failed the Stockholm Convention restrictions on SCCPs. This study sheds light on significant challenges in implementing international CP restrictions effectively.

Chlorinated paraffins in food contact materials made of rubber from the German market

Chlorinated paraffins (CPs), also known as polychlorinated alkanes (PCA), are a very complex class of polyhalogenated compounds currently produced in unmatchable amounts for different industrial uses. Short-chain CPs (SCCPs; C10- to C13-CPs) are listed as POPs in the Stockholm Convention and medium-chain CPs (MCCPs; C14- to C17-CPs) are proposed for listing. Here, we investigated the presence of SCCPs and MCCPs in 21 rubber samples used as food contact materials from the German market. For this purpose, an analytical method was developed which consisted of (i) freezing and (ii) grounding of the material, (iii) removal of oligomers by adsorption chromatography, (iv) matrix destruction with sulfuric acid, and (v) GC/ECNI-MS screening and quantification. Three of the rubber samples were found to contain predominantly MCCPs at 69, 113,000 and 341,000 mg/kg. The highest amount (corresponding with 34 weight-% CPs) was determined in one rubber band sample used to bundle a bunch of spring onions. A very high CP content of >300,000 mg/kg in this rubber band sample was confirmed by quantitative 1H NMR (qNMR) analysis. This rubber material was in direct contact with the onions and leaching of CPs into the food cannot be excluded. Even more, micro-abrasions of rubber could be unintentionally swallowed by the consumer and this CP exposure could be higher than the current CP intake via food.

POPs in the Mongolian environment

An environmental and human monitoring project analyzing the persistent organic pollutants (POPs) listed in the Annexes of the Stockholm Convention on POPs was implemented in Mongolia with sampling activities from 2017 until 2019. In support of the global monitoring plan implementation, a total of 51 samples were analyzed for POPs whereby 23 POPs were detected frequently. Two POPs, endrin and hexabromobiphenyl (PBB 153), were not quantified in any of the samples; toxaphene was found only twice in air samples; and dicofol, pentachlorophenol, and short-chain chlorinated paraffins were analyzed only in one human milk sample. Most results were for perfluorooctanoic acid (PFOA, 32 of 43 samples) and perfluorooctanesulfonic acid (PFOS, 31 of 43 samples). With respect to detection frequency, dioxin-like polychlorinated biphenyls (dl-PCB) were detected in 100% of the samples analyzed (N = 28). On scale, highest amounts were found in soil samples, almost 30 000 ng/g for lindane, more than 13 000 ng/g for α-hexachlorocyclohexane (α-HCH), and almost 10 000 ng/g for dichlorochlorodiphenyltrichloroethane (DDT) and its transformation products. The soil and ambient air samples were the drivers towards highest values in the abiotic samples, due to the presence of legacy POPs such as DDT, indicator PCB, HCHs but also hexachlorobenzene (HCB), and pentachlorobenzene (PeCBz). Concentrations of dioxin-like POPs were low in general as were the perfluorinated substances (PFAS). With respect to brominated flame retardants, the presence of hexabromocyclododecane in air samples was surprising. At present, the analytical capacity to analyze POPs in various matrices under the global monitoring plan for POPs is being set-up to strengthen future environmental monitoring activities in Mongolia.