Chlorinated Paraffins Research Articles

Short- and medium-chain chlorinated paraffins in T-shirts and socks

The short- and medium-chain chlorinated paraffins (SCCPs and MCCPs) are complex mixtures of persistent compounds used mainly as plastic additives. They can have a negative impact on human health as they are suspected of disrupting the endocrine system and being carcinogenic, which is why monitoring their presence in the human environment is desirable.Clothing was selected for this study because they are produced in large quantities worldwide and the final products are worn for long periods throughout the day, in direct contact with human skin. The concentrations of CPs in this type of sample have not been sufficiently reported.We determined SCCPs and MCCPs in 28 samples of T-shirts and socks by gas chromatography coupled with high-resolution mass spectrometry in negative chemical ionisation mode (GC–NCI–HRMS). CPs were found above the limits of quantification in all samples, with concentrations ranging from 33.9 to 5940 ng/g (mean 1260 ng/g, median 417 ng/g). The samples with a substantial proportion of synthetic fibres contained higher CP concentrations (22 times higher mean for SCCPs and 7 times higher mean for MCCPs) than garments composed exclusively of cotton.Finally, the effect of washing in the washing machine was investigated. The individual samples behaved differently: (i) excessively emitting CPs; (ii) being contaminated; (iii) retaining the original CP levels. The CP profiles also changed for some samples (with a substantial proportion of synthetic fibres and samples composed exclusively of cotton).

Short- and medium-chain chlorinated paraffins in agricultural and industrial soils from Shanghai, China: surface and vertical distribution, penetration behavior, and health risk assessment.

The widespread contamination of chlorinated paraffins (CPs) of the soil environment has raised global concern due to their highly persistent and toxic properties. However, little information is available regarding these industrial toxicants' spatial-vertical distribution and penetration potentials. In this study, short- and medium-chain chlorinated paraffins (SCCPs and MCCPs, respectively) were analyzed in pooled surface and core soils (0-45cm) samples collected from agricultural and industrial areas in Shanghai. ∑SCCP concentrations in agricultural and industrial surface soils ranged from 52.6 to 237.6 and 98.3 to 977.1ng/g dry weight (dw), respectively. ∑MCCP levels were comparatively higher and ranged from 417.2 to 1690.8 and 370.9 to 10,712.7ng/g dw in agricultural and industrial soils, respectively. C10Cl5-10 SCCPs and C14-15Cl5-7 MCCPs were the predominant homologues in all samples. Analysis of the soil vertical profiles revealed that MCCP concentrations decreased significantly with depth (P < 0.01). SCCPs more efficiently penetrated into thesoils than MCCPs because of their higher water solubility and less octanol-water partition coefficient (Kow) values. A preliminary risk assessment suggested no potential health risks caused by non-dietary exposure. The daily exposure doses of CPs via ingestion were significantly (P < 0.01) higher for children (5.41 ± 2.11 × 10-3 and 1.68 ± 1.03 × 10-2μgkg-1day-1) and adults (2.56 ± 0.99 × 10-4 and 7.94 ± 4.87 × 10-4μgkg-1day-1) than dermal permeation exposure. Furthermore, CPs at current levels posed low ecological risks (0.1 ≤ RQ < 1) according to the risk quotient model. This study enhanced our understanding of the fates and behaviors of CPs in the terrestrial environment.

Characterizing the Organohalogen Iceberg: Extractable, Multihalogen Mass Balance Determination in Municipal Wastewater Treatment Plant Sludge.

The large number and diversity of organohalogen compounds (OHCs) occurring in the environment poses a grand challenge to analytical chemists. Since no single targeted method can identify and quantify all OHCs, the size of the OHC "iceberg" may be underestimated. We sought to address this problem in municipal wastewater treatment plant (WWTP) sludge by quantifying the unidentified fraction of the OHC iceberg using targeted analyses of major OHCs together with measurements of total and extractable (organo)halogen (TX and EOX, respectively; where X = F, Cl, or Br). In addition to extensive method validation via spike/recovery and combustion efficiency experiments, TX and/or EOX were determined in reference materials (BCR-461 and NIST SRMs 2585 and 2781) for the first time. Application of the method to WWTP sludge revealed that chlorinated paraffins (CPs) accounted for most (∼92%) of the EOCl, while brominated flame retardants and per- and polyfluoroalkyl substances (PFAS) accounted for only 54% of the EOBr and 2% of the EOF, respectively. Moreover, unidentified EOF in nonpolar CP extracts points to the existence of organofluorine(s) with physical-chemical properties unlike those of target PFAS. This study represents the first multihalogen mass balance in WWTP sludge and offers a novel approach to prioritization of sample extracts for follow-up investigation.

An international investigation of chlorinated paraffin concentrations and homologue distributions in indoor dust

In this study, very short-, short-, medium-, and long-chain chlorinated paraffins (vSCCPs, SCCPs, MCCPs and LCCPs, respectively) were measured in 40 indoor dust samples from four countries including Japan (n = 10), Australia (n = 10), Colombia (n = 10) and Thailand (n = 10). Homologues of the chemical formula CxH(2x+2−y)Cly ranging C6-36 and Cl3-30 were analysed using liquid chromatography coupled to Orbitrap high resolution mass spectrometry (LC-Orbitrap-HRMS) and integrated using novel custom-built CP-Seeker software. CPs were detected in all dust samples with MCCPs the dominant homologue group in all countries. Overall median ∑SCCP, ∑MCCP and ∑LCCP (C18-20) concentrations determined in dust samples were 30 μg/g (range; 4.0–290 μg/g), 65 μg/g (range; 6.9–540 μg/g) and 8.6 μg/g (range; <1.0–230 μg/g), respectively. Of the quantified CP classes, overall concentrations were generally highest in the samples from Thailand and Colombia, followed by Australia and Japan. vSCCPs with C≤9 were detected in dust from each country with an overall frequency of 48%, while LCCPs (C21-36) were present in 100% of samples. Estimated daily intakes (EDIs) calculated for SCCPs and MCCPs relating to ingestion of contaminated indoor dust were considered not to represent health risks based on currently available toxicological data using the margin of exposure (MOE) approach. To the authors’ knowledge, this study provides the first data on CPs in indoor dust from Japan, Colombia and Thailand, and is among the first reports of vSCCPs in indoor dust, globally. These findings indicate that further toxicological data and the availability of appropriate analytical standards are needed to evaluate the potential for negative health outcomes deriving from exposure to vSCCPs and LCCPs.

Concentrations and homologue patterns of SCCPs and MCCPs in the serum of the general population of adults in Hangzhou, China

Due to their ubiquitous presence in the environment and humans, chlorinated paraffins (CPs) are a major environmental and public health concern. CPs are known to persist, bioaccumulate and potentially threaten human health, but reports on their internal exposure in the adult general population are still scarce. In this study, serum samples collected from adults living in Hangzhou, China, were quantified for SCCPs and MCCPs using GC-NCI-MS methods. A total of 150 samples were collected and subjected to analysis. ∑SCCPs were detected in 98% of the samples with a median concentration of 721 ng/g lw. MCCPs were found in all serum samples with a median concentration of 2210 ng/g lw, indicating that MCCPs were the dominant homologous group. For SCCPs and MCCPs, ∑C10 and ∑C14 were found to be the dominant carbon chain length homologues. Our results showed that age, BMI and lifestyle were not found to be significantly associated with internal exposure to CPs for the samples in this study. Based on PCA analysis, an age-specific distribution of CP homologues was observed. This suggests that internal exposure to CPs in the general population is related to exposure scenarios and history. The results of this study may contribute to a better understanding of the internal exposure to CPs in the general population and may provide a direction for the investigation of the source of exposure to CPs in the environment and daily life.

Synthesis, identification, chiral separation and crystal structure of (3R,4R,7S,8S)-3,4,7,8-tetrachlorodecane and its stereoisomers

Chlorinated paraffins (CPs) are a notoriously known class of compounds that stand amongst the most wide-spread persistent organic pollutants. Therefore, their reliable, repeatable, and reproducible quantitative analysis using well-defined reference standards is of utmost importance. In view of the increasing demand for constitutionally and stereochemically defined CP standards, we have synthesized a stereoisomeric mixture of 3,4,7,8-tetrachlorodecane. One stereoisomer – (3R,4R,7S,8S)-3,4,7,8-tetrachlorodecane was separated from the mixture, and enriched fractions of residual stereoisomers were achieved through crystallisation of the residual mother liquors. The molecular structure of the single isolated stereoisomer was confirmed through single-crystal X-ray crystallographic data. One fraction of 3,4,7,8-tetrachlorodecane stereoisomers was successfully separated on a chiral stationary phase using supercritical fluid chromatography hyphenated to mass spectrometry (column: Chiral ART Amylose-C; mobile phase: CO2/MeOH (96/4 v/v) with 0.1% diethylamine). The reported separation of stereoisomers is unprecedented in CP analysis so far.

(096) Chronic Oral Exposure to Short Chain - Chlorinated Paraffins Induced Testicular Toxicity by Promoting NRF2-mediated Oxidative Stress

Abstract Introduction Chlorinated paraffins (CPs) are important additives in a variety of chemical processing. Based on the lengths of the carbon chains, CPs are classified into short-chain CPs (SCCPs, C10-13), medium-chain CPs (MCCPs, C14-17) and long-chain CPs (LCCPs, C18-30) with the chlorine content ranging from 30%-70%. SCCPs were listed in the persistent organic pollutants (POPs) by Stockholm Convention due to its toxicity, bioaccumulation potential, long range transport potential and environmental persistence. Numerous studies have analyzed the toxicities of SCCPs in various organisms, with the toxic effects including lethality and carcinogenicity, developmental toxicity, endocrine disrupting effect and immunomodulatory effect. Objectives As a widespread environmental contaminant, short chain chlorinated paraffins (SCCPs) has attracted great attention. However, the toxicity of SCCPs on male reproductive system remains ambiguous. In this study, we investigated the toxic effects of SCCPs on testis. Methods We treated mice with 1,10 or 100 mg/kg bm/d SCCPs by gavage once a day for 35 days. The tissues and blood samples were collected after treatment. The weight of mice and testes were measured. The organ index is the body weight divided by the weight of the testis. The left testes were used for protein extraction, RNA extraction and measurement of SOD, CAT, GST and MDA. The left epididymis was used for analysis of sperm parameters. The right testis and epididymis were fixed in Bouin’s solution for H&amp;E and TUNEL staining. GC2 cell (mouse spermatocyte) treated with SCCPs was used to examined the cell viability by CCK8 kits. Cellular ROS generation was evaluated by 2',7'Dichlorodihydrofluorescein diacetate (DCFH-DA). We used Apoptosis Detection Kit to detect the cell apoptosis by dual staining cells with Annexin V-fluorescein isothiocyanate (FITC) and propidium iodide (PI). Results SCCPs resulted in disorderly arranged seminiferous epithelium and increased apoptotic cells in testes. Both in vivo and in vitro experiments indicated that the oxidative stress was induced after SCCPs exposure, and dysfunction of nuclear factor erythroid-related factor (NRF2) signaling pathway played a role in this process. Moreover, resveratrol, an NRF2 activator, could alleviate the damage of SCCPs on spermatogenetic cells in vitro. Our study indicated that oxidative stress is the key point for explaining the testicular toxicity caused by SCCPs, and NRF2 could be used as a potential target for clinical treatment to alleviate the reproductive toxicity induced by SCCPs. Conclusions Our study is the first to evaluate the toxic effects of SCCPs on male reproductive system, which is associated with overproduction of ROS. This study also indicates that NRF2/ARE pathway plays the vital role in the toxic effects of SCCPs in spermatogenesis, thus providing a target for the prophylaxis and treatment. Disclosure No

Identification and yield of metabolites of chlorinated paraffins incubated with chicken liver microsomes: Assessment of their potential to convert into metabolites

Chlorinated paraffins (CPs) are emerging environmental pollutants. Although metabolism has been shown to affect the differential accumulation of short-chain (SCCPs), medium-chain (MCCPs) and long-chain (LCCPs) CPs in birds, CP metabolites have rarely been reported and the extent to which they are formed is still unclear. In this study, single and mixed CP standards were incubated with chicken liver microsomes in vitro to study the generation of CP metabolites. Putative aldehyde/ketone and carboxylic acid metabolites identified by mass spectroscopy data were shown to be false positive results. Phase I metabolism of CPs first formed monohydroxylated ([M-Cl+OH]) and then dihydroxylated ([M-2Cl+2OH]) products. The yields of monohydroxylated metabolites of CPs decreased with increasing carbon chain length and chlorine content at the initial stage of reaction. Notably, the yield of monohydroxylated metabolites of SCCPs with 51.5% Cl content reached 21%, and that of 1,2,5,6,9,10-hexachlorodecane (C10H16Cl6) was as high as 71%. Thus, monohydroxy metabolites of CPs in birds should not be ignored, especially those of SCCPs. This study provides important data that could support improvements to the ecological/health risk assessment of CPs.

Characterization of short-, medium- and long-chain chlorinated paraffins in ambient PM2.5 from the Pearl River Delta, China

Research on the environmental occurrence of long-chain chlorinated paraffins (LCCPs) in ambient fine particulate matter (PM2.5) is still scarce. In the present study, short-chain chlorinated paraffins (SCCPs), medium-chain chlorinated paraffins (MCCPs) and LCCPs were simultaneously quantified and profiled in PM2.5 samples collected from 96 primary or secondary schools in the Pearl River Delta of South China. SCCPs, MCCPs and LCCPs were detected in higher than 90% samples with concentrations in the range of 0.832–109, 1.02–110, and 0.173–17.4 ng/m3, respectively. The dominant congener groups of SCCPs, MCCPs and LCCPs were C13Cl6-8, C14Cl7-8, and C18Cl7-9, respectively. The concentrations of SCCPs and MCCPs were higher in summer than in winter, while an opposite seasonal trend was observed for LCCPs. Principal components analysis showed there were seasonal variations in the congener group patterns with C13Cl6-7 and C14Cl7 more abundant in summer than in winter. Concentrations of CPs also exhibited slight spatial variations. Exposure risk assessment based on different age groups suggested exposure to PM2.5-associated CPs would not pose significant health risk. The present study expands the existing knowledge of CPs contamination in atmospheric environment.

Physical and chemical processes driving remote seasonal atmospheric exposure to cyclic volatile methysiloxanes and short-chain chlorinated paraffins

Cyclic volatile methylsiloxanes (cVMS) and short-chain chlorinated paraffins (SCCPs) use has been restricted in recent years due to environmental health concerns. Both of these classes of emerging contaminants possess long range transport potential (LRTP), highlighting the need for continuous monitoring to assess effectiveness of implemented regulations. However, emission source elucidation and understanding processes affecting atmospheric transport remain challenging. Atmospheric levels of cVMSs and SCCPs were simultaneously monitored at a background monitoring site in Norway from January–July 2020. Concentrations obtained from active air samplers ranged from 49.9 to 845 (mean: 208) pg/m3 for ƩSCCPs and from 0.4 to 3.5 (mean: 1.5), 1.1–15 (mean: 5.6) and 0.1–0.9 (mean: 0.4) ng/m3 for octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6), respectively. As SCCPs pose several challenges to analysts, different quantification methodologies and blank handling procedures were investigated to ensure reliable environmental measurements. Simulations using a Lagrangian atmospheric transport model (FLEXPART) revealed air masses impacting sampling measurements were of Oceanic origin, but periodic emission events from Europe and Russia were also observed. Seasonal pattern in cVMS concentrations was mainly driven by atmospheric degradation via hydroxyl radical reaction, whereas SCCP concentrations were more influenced by periodic anthropogenic inputs from local and continental Europe. No clear correlation could be observed with SCCP atmospheric concentrations and temperature over the entire sampling campaign. However, increased volatilization at elevated temperatures may be important with emissions originating from local sources. Higher chlorinated homologue groups dominated during the winter season and declined towards spring and summer, whereas reverse was found for the lower and more volatile chlorinated homologue groups.

Short- and medium-chain chlorinated paraffins in fish from an anthropized south-western Atlantic estuary, Bahía Blanca, Argentina

Chlorinated paraffins (CPs) are synthetic organic compounds of growing environmental and social concern. Short-chain chlorinated paraffins (SCCPs) were listed under the Stockholm Convention on Persistent Organic Pollutants (POPs) in 2017. Further, in 2021, medium-chain chlorinated paraffins (MCCPs) were proposed to be listed as POPs. We investigated SCCP and MCCP amounts and homolog profiles in four wild fish species from Bahía Blanca Estuary, a South Atlantic Ocean coastal habitat in Argentina. SCCPs and MCCPs were detected in 41% and 36% of the samples, respectively. SCCP amounts ranged from <12 to 29 ng g−1 wet weight and <750–5887 ng g−1 lipid weight, whereas MCCP amounts ranged from <7 to 19 ng g−1 wet weight and <440–2848 ng g−1 lipid weight. Amounts were equivalent to those found in fish from the Arctic and Antarctic Oceans and from some North American and Tibetan Plateau lakes. We performed a human health risk assessment and found no direct risks to human health for SCCP or MCCP ingestion, according to present knowledge. Regarding their environmental behavior, no significant differences were observed among SCCP amounts, sampling locations, species, sizes, lipid content, and age of the specimens. However, there were significant differences in MCCP amounts across species, which could be attributed to fish size and feeding habits. Homolog profiles in all fish were dominated by the medium-chlorinated (Cl6 and Cl7) CPs and shorter chain length CPs were the most abundant, with C10Cl6 (12.8%) and C11Cl6 (10.1%) being the predominant SCCPs and C14Cl6 (19.2%) and C14Cl7 (12.4%) the predominant MCCPs. To the best of our knowledge, this is the first study on the presence of CPs in the environment in Argentina and the South Atlantic Ocean. CP occurrence in the environment, particularly in the food chain, promotes the need for further research on their occurrence and behavior, and the impact of CPs in marine ecosystems in Argentina.

Health Risks Posed by Dermal and Inhalation Exposure to High Concentrations of Chlorinated Paraffins Found in Soft Poly(vinyl chloride) Curtains

Chlorinated paraffins (CPs) are used in many products, including soft poly(vinyl chloride) curtains, which are used in many indoor environments. Health hazards posed by CPs in curtains are poorly understood. Here, chamber tests and an indoor fugacity model were used to predict CP emissions from soft poly(vinyl chloride) curtains, and dermal uptake through direct contact was assessed using surface wipes. Short-chain and medium-chain CPs accounted for 30% by weight of the curtains. Evaporation drives CP migration, like for other semivolatile organic plasticizers, at room temperature. The CP emission rate to air was 7.09 ng/(cm2 h), and the estimated short-chain and medium-chain CP concentrations were 583 and 95.3 ng/m3 in indoor air 21.2 and 172 μg/g in dust, respectively. Curtains could be important indoor sources of CPs to dust and air. The calculated total daily CP intakes from air and dust were 165 ng/(kg day) for an adult and 514 ng/(kg day) for a toddler, and an assessment of dermal intake through direct contact indicated that touching just once could increase intake by 274 μg. The results indicated that curtains, which are common in houses, could pose considerable health risks through inhalation of and dermal contact with CPs.

Levels and diverse composition profiles of chlorinated paraffins in indoor dust: possible sources and potential human health related concerns.

Chlorinated paraffins (CPs), a group of mixtures with different carbon chain lengths and chlorine contents, are widely used as plasticizers and flame retardants in various indoor materials. CPs could be released from CP-containing materials into the ambient environment and then enter the human body via inhalation, dust ingestion and dermal absorption, resulting in potential effects on human health. In this study, we collected residential indoor dust in Wuhan, the largest city in central China, and focused on the co-occurrence and composition profiles of CPs as well as the resultant human risk via dust ingestion and dermal absorption. The results indicated that CPs with C9-40 were ubiquity in indoor dust with medium-chain CPs (MCCPs, C14-17) as the main components (6.70-495μg g-1), followed by short-chain CPs (SCCPs, C10-13) (4.23-304μg g-1) and long-chain (LCCPs, C≥18) CPs (3.68-331μg g-1). Low levels (not detected-0.469μg g-1) of very short-chain CPs (vSCCPs, C9) were also found in partial indoor dust. The dominant homolog groups were C9 and Cl6-7 groups for vSCCPs, C13 and Cl6-8 groups for SCCPs, C14 and Cl6-8 groups for MCCPs, and C18 and Cl8-9 groups for LCCPs. Based on the measured concentrations, vSCCPs, SCCPs, MCCPs, and LCCPs posed limited human health risks to local residents via dust ingestion and dermal absorption.

Chlorinated paraffins in nut-nougat and chocolate spreads from the German market

Chlorinated paraffins (CPs) are amongst the most discussed polyhalogenated pollutants in recent years. Their ubiquitous occurrence in the environment and especially foodstuff has given rise to concerns about CP uptake levels. Especially animal products and oils, i.e. foodstuff with high fat contents showed comparably high CP contaminations. In this study, nut-nougat and chocolate spread samples (n = 30) from the German market were analyzed on the occurrence of short-chain CPs (SCCPs) and medium-chain CPs (MCCPs) via gas chromatography coupled with electron capture negative ion mass spectrometry (GC/ECNI-MS). Fifteen (= 50%) of the samples contained CPs, with MCCPs being much higher abundant (17–270 ng/g fresh weight (fw)) in most samples than SCCPs (7.5–50 ng/g fw). No statistical correlation could be established between SCCP or MCCP occurrence on one hand and manufacturer or ingredients, such as palm oil on the other hand. A preliminary risk assessment of the detected levels gave margins of exposure (MOE) to CPs from consumption of chocolate and nut-nougat spreads ranging from approx. 16,000 to 48,000. Since health concerns are expected at an MOE of <1,000, this indicated no risk from CP intake for the consumer by consumption of these products, based on current knowledge. • CPs were analyzed in 30 nut-nougat and chocolate spreads from the German market. • Short-chain CPs (SCCPs) and medium-chain CPs (MCCPs) were separately quantified. • Fifteen samples (50%) contained CPs between 7.5 and 270 ng/g fat. • MCCPs were higher abundant than SCCPs in most samples. • A preliminary risk assessment indicated no risk from CP intake for consumers.

Bioaccumulation of emerging persistent organic pollutants in the deep-sea cold seep ecosystems: Evidence from chlorinated paraffin.

Persistent organic pollutants (POPs) are highly toxic and can accumulate in marine organisms, causing nonnegligible harm to the global marine ecosystem. The Cold seep is an essential marine ecosystem with the critical ecological function of maintaining the deep-sea carbon cycle and buffering global climate change. However, the environmental impact of emerging POPs in the deep-sea cold seep ecosystem is unknown. Here, we investigated the potential pollution of chlorinated paraffins (CPs) and their bioaccumulation in the cold seep ecosystem. High concentrations of CPs were detected in the cold seep ecosystems, where CPs bioaccumulated by the keystone species of deep-sea mussels can be released into the surface sediment and vertically migrate into the deeper sediment. Furthermore, more toxic CPs were accumulated from transforming other CPs in the cold seep ecosystem. Our study provides the first evidence that high concentrations of POPs are bioaccumulated by deep-sea mussels in the cold seep ecosystem, causing adverse ecological effects. The discovery of CPs bioaccumulation in the deep-sea cold seep ecosystem is a crucial mechanism affecting deep-sea carbon transport and cycling. This study has important guiding significance for revealing the deep-sea carbon cycle process, addressing global climate change, and making deep-sea ecological and environmental protection policies.

Objective Review

Leather industry uses a great number of processing chemicals to make leather from animal hides. The toxicity, health and environmental impacts of many of these chemicals have been established leading to significant regulatory certifications and programs helping in trade and policy making. The focus of this review are the hazardous chemicals and auxiliaries relevant to leather industry, their categories, possible origins, analysis and toxicity with respect to humans and the environment and the regulatory mechanisms suggested for them through manufacturing restricted substance list (MRSL) 2.0.** Informative guidelines are provided about the most probable leather processing stage for the origin of these chemicals. Some alternative technologies, chemicals and ideas gaining popularity are also suggested as probable remedies. Recommended test methods are stated for the adequate monitoring of the hazardous chemicals. The nature and severity of chemical toxicity and corresponding limits set for their allowed use in formulations are graphically expressed for clarity and ease of understanding. The maximum number of compounds / isomers belong to classes comprising chlorinated paraffins, perfluorooctanoic acids (PFOA), perfluorooctanesulfonates (PFOS) and banned aromatic amines. Similarly, most of the restricted chemicals are used during the finishing stage and may be considered for eco-friendly alternatives. Likewise, the analytical equipment covering most testing requirements is GC-MS among other hyphenated techniques. Additionally, most critical chemicals from toxicity point of view are arsenic, cadmium and chromium (VI), whereas navy blue colorants and chlorinated aromatic compounds may be considered as less toxic among the restricted chemicals under the current scope. Surprisingly, the latest UV absorbents and polymeric fatliquors are comparatively non-toxic. Similarly, the most relaxed formulation limits are given for UV absorbers and 2-methoxypropylacetate whereas strict limits have been set for PFOA, PFOS, mercury, triclosan permethrin, sensitizing dyes etc. in MRSL 2.0.

Assessment of silicone wristbands for monitoring personal exposure to chlorinated paraffins (C8-36): A pilot study

Chlorinated paraffins (CPs) are a major environmental concern due to their ubiquitous presence in the environment. Since human exposure to CPs can significantly differ among individuals, it is essential to have an effective tool for monitoring personal exposure to CPs. In this pilot study, silicone wristbands (SWBs) were employed as a personal passive sampler to measure time-weighted average exposure to CPs. Twelve participants were asked to wear a pre-cleaned wristband for a week during the summer of 2022, and three field samplers (FSs) in different micro-environments were also deployed. The samples were then analyzed for CP homologs by LC-Q-TOFMS. In worn SWBs, the median concentrations of quantifiable CP classes were 19 ng/g wb, 110 ng/g wb, and 13 ng/g wb for ∑SCCPs, ∑MCCPs, and ∑LCCPs (C18-20), respectively. For the first time, lipid content is reported in worn SWBs, which could be a potential impact factor in the kinetics of the accumulation process for CPs. Results showed that micro-environments were key contributors to dermal exposure to CPs, while a few outliers suggested other sources of exposure. CP exposure via dermal contact showed an increased contribution and thus poses a nonnegligible potential risk to humans in daily life. Results presented here provide proof of concept of the use of SWBs as a cheap and non-invasive personal sampler in exposure studies.

Release Mechanism of Short- and Medium-Chain Chlorinated Paraffins from PVC Materials under Thermal Treatment.

Chlorinated paraffins (CPs) as plasticizers are massively added to polyvinyl chloride (PVC) products, during whose life cycle CPs can be continuously released especially under thermal stress. In this study, a PVC cable sheath was adopted as a representative kind of PVC material to investigate the release behaviors of short- and medium-chain CPs (SCCPs and MCCPs) under thermal treatment. Release percentages of CPs with increasing temperature followed a Gaussian-like curve. At the unmolten stage of 80 °C, heating for 10 min caused 0.051% of added SCCPs and 0.029% of added MCCPs to be released. At the molten stage of 270 °C, accumulative release rates of SCCPs and MCCPs within 10 min were up to 30 and 14%, respectively. The developed emission model indicated that material-gas partitioning and internal diffusion simultaneously governed the release of CPs. During thermal treatment, the release of CPs could be remarkably affected by the thermal expansion of the PVC material and the formation of breakage and micropores. Congener group profiles of released CPs indicated a slight fractionation effect for SCCPs during the release process. Furthermore, the release risk of CPs from the whole life cycle of PVC products was preliminarily evaluated.

Understanding inter-individual variability in short-chain chlorinated paraffin concentrations in human blood.

Chlorinated paraffins (CPs), particularly short-chain CPs (SCCPs), have been reported in human blood with high detection frequency and often high variation among individuals. However, factors associated with and their contributions to inter-individual variability in SCCP concentrations in human blood have not been assessed. In this study, we first measured SCCP concentrations in 57 human blood samples collected from individuals living in the same vicinity in China. We then used the PROduction-To-Exposure model to investigate the impacts of variations in sociodemographic data, biotransformation rates, dietary patterns, and indoor contamination on inter-individual variability in SCCP concentrations in human blood. Measured ∑SCCP concentrations varied by a factor of 10 among individuals with values ranging from 122 to 1230ng/g, wet weight. Model results show that age, sex, body weight, and dietary composition played a minor role in causing variability in ∑SCCP concentrations in human blood given that modeled ∑SCCP concentrations ranged over a factor of 2 - 3 correlated to the variations of these factors. In contrast, variations in the modeled ΣSCCP concentrations increased to factors of 6 and 8 when variability in biotransformation rates and indoor contamination were considered, respectively, indicating these two factors could be the most influential on inter-individual variability in SCCP concentrations in human blood.

Online Quantitative Analysis of Chlorine Contents in Chlorinated Paraffins by Facile Raman Spectroscopy.

Online analysis of industrial chemicals is extremely important for managing product quality and performance. The chlorine (Cl) content is one of the most important technical metrics for chlorinated paraffins (CPs), and the conventional approaches to estimate Cl contents require transforming the Cl element to chloride followed by quantitative analysis with either titration or instrumentation, which are normally tedious and time-consuming and cannot simultaneously guide the industrial production. Here, we developed a rapid, real-time, and online approach to determine the Cl content of CPs with facile Raman spectroscopy. The chlorination of paraffins generated two new Raman peaks at 610-618 and 668-690 cm-1, which are associated with the vibrational modes of the SHH and SHC conformations of the C-Cl bond in CPs, respectively. More importantly, the corresponding peak of the SHH conformation decreased and that of the SHC conformation increased with the enhancement of the chlorination degree of CPs. The ratiometric calculation of the two respective Raman peak areas leads to a quantitative analysis of the Cl content of CPs. The developed approach can online provide the Cl contents of CPs within seconds accurately but without the tedious sample treatment required by conventional approaches. The strategy of integrating Raman analysis with the industrial pipeline will help in managing the production and quality control of industrial chemicals.