In vitro assessment of potential endocrine disrupting activities of chlorinated paraffins of various chain lengths.

The production of chlorinated paraffins (CPs) has risen in the past two decades due to their versatile industrial applications. Consequently, CPs are now widely detected in human food sources, the environment, and in human matrices such as serum, the placenta and breast milk. This raises concern about prenatal and postnatal exposure. While some studies suggest that certain short-chained CPs (SCCPs) may have endocrine disrupting properties, knowledge about potential endocrine disrupting potential of medium- (MCCP) and long-chained CPs (LCCPs) remains relativity sparse. Here, we used a panel of in vitro assays to investigate seven pure CPs and two technical mixtures of CPs. These varied in chain length and, chlorination degree. The in vitro panel covered androgen, estrogen, and retinoic acid receptor activities, transthyretin displacement, and steroidogenesis. One of the SCCPs inhibited androgen receptor (AR) activity. All SCCPs induced estrogen receptor (ER) activity. Some SCCPs and MCCPs increased 17ß-estradiol levels in the steroidogenesis assay, though not consistently across all substances in these groups. SCCPs exhibited the most pronounced effects in multiple in vitro assays, while the tested LCCPs showed no effects. Based on our results, some CPs can have endocrine disrupting potential in vitro. These findings warrant further examinations to ensure that CPs do not cause issues in intact organisms, including humans.

Tissue-Specific Accumulation of Orally Administered Short- and Medium-Chain Chlorinated Paraffins in Honeybees (Apis mellifera L.).

The prevalence and distribution of chlorinated paraffins (CPs) have been extensively studied in various matrices and organisms; however, there is a lack of information about insects, particularly in honeybees. To address this gap, we studied young honeybee workers exposed to short- and medium-chain CPs (SCCPs and MCCPs) at an environmentally relevant concentration of 10 mg/L for 7 days, followed by a 7-day elimination period. Results indicated that CPs could transfer into the head after oral consumption and SCCPs and MCCPs exhibited clear bioaccumulation trends: midgut > hindgut > head. An evaluation of congener group distribution patterns demonstrated that the dominant congener groups in all target tissues were C11-13Cl7-8 and C14Cl7-8 for SCCPs and MCCPs, respectively, consistent with the treated CP standards. In honeybees, a significant negative relationship was observed for the log concentration of MCCP congener groups and their log KOW, but not with their log KOA. Conversely, no such correlation was found for SCCPs. These findings suggest that honeybees have a high potential to bioaccumulate MCCPs, particularly those with a low log KOW, and exhibit weak selectivity for SCCPs.

Remarkable Contamination of Short- and Medium-Chain Chlorinated Paraffins in Free-Range Chicken Eggs from Rural Tibetan Plateau.

Rapid social-economic development introduces modern lifestyles into rural areas, not only bringing numerous modern products but also new pollutants, such as chlorinated paraffins (CPs). The rural Tibetan Plateau has limited industrial activities and is a unique place to investigate this issue. Herein we collected 90 free-range chicken egg pool samples across the rural Tibetan Plateau to evaluate the pollution status of CPs. Meanwhile, CPs in related soils, free-range chicken eggs from Jiangxi, and farmed eggs from markets were also analyzed. The median concentrations of SCCPs (159 ng g-1 wet weight (ww)) and MCCPs (1390 ng g-1 ww) in Tibetan free-range chicken eggs were comparable to those from Jiangxi (259 and 938 ng g-1 ww) and significantly higher than those in farmed eggs (22.0 and 81.7 ng g-1 ww). In the rural Tibetan Plateau, the median EDI of CPs via egg consumption by adults and children were estimated to be 81.6 and 220.2 ng kg-1 bw day-1 for SCCPs and 483.4 and 1291 ng kg-1 bw day-1 for MCCPs, respectively. MCCPs might pose potential health risks for both adults and children in the worst scenario. Our study demonstrates that new pollutants should not be ignored and need further attention in remote rural areas.

Exposure to Short- and Medium-Chain Chlorinated Paraffins and the Risk of Gestational Diabetes Mellitus: A Nested Case-Control Study in Eastern China.

Toxicological studies have indicated that exposure to chlorinated paraffins (CPs) may disrupt intracellular glucose and energy metabolism. However, limited information exists regarding the impact of human CP exposure on glucose homeostasis and its potential association with an increased risk of developing gestational diabetes mellitus (GDM). Here, we conducted a prospective study with a nested case-control design to evaluate the link between short- and medium-chain CP (SCCPs and MCCPs) exposures during pregnancy and the risk of GDM. Serum samples from 102 GDM-diagnosed pregnant women and 204 healthy controls were collected in Hangzhou, Eastern China. The median (interquartile range, IQR) concentration of SCCPs was 161 (127, 236) ng/mL in the GDM group compared to 127 (96.9, 176) ng/mL in the non-GDM group (p < 0.01). For MCCPs, the GDM group had a median concentration of 144 (117, 174) ng/mL, while the control group was 114 (78.1, 162) ng/mL (p < 0.01). Compared to the lowest quartile as the reference, the adjusted odds ratios (ORs) of GDM were 7.07 (95% CI: 2.87, 17.40) and 3.34 (95% CI: 1.48, 7.53) in the highest quartile of ∑SCCP and ∑MCCP levels, respectively, with MCCPs demonstrating an inverted U-shaped association with GDM. Weighted quantile sum regression evaluated the joint effects of all CPs on GDM and glucose homeostasis. Among all CP congeners, C13H23Cl5 and C10H16Cl6 were the crucial variables driving the positive association with the GDM risk. Our results demonstrated a significant positive association between CP concentration in maternal serum and GDM risk, and exposure to SCCPs and MCCPs may disturb maternal glucose homeostasis. These findings contribute to a better understanding of the health risks of CP exposure and the role of environmental contaminants in the pathogenesis of GDM.

Medium-Chain Chlorinated Paraffins Trigger Thyroid Hormone Synthesis and Interfere with Mitochondrial Function in the Thyroid Gland.

Medium-chain chlorinated paraffins (MCCPs, C14-C17) are frequently detected in diverse environmental media. It has been proposed to be listed in Annex A of the Convention on Persistent Organic Pollutants in 2023. Although MCCPs are a crucial health concern, their toxicity remains unclear. This study investigated the toxic effects of MCCPs (0.1-50 mg/kg body weight/day) on the thyroid gland of female Sprague-Dawley rats and characterized the potential toxic pathways via transcriptomics and metabolomics approaches. MCCPs exposure caused histopathological changes to the endoplasmic reticula and mitochondria in thyroid follicular cells at a dose of 50 mg/kg bw/d and increased serum thyrotropin-releasing hormone, thyroid-stimulating hormones, and thyroxine when exposed to a higher dose of MCCPs. Transcriptomic analysis indicated the excessive expression of key genes related to thyroid hormone synthesis induced by MCCPs. Integrating the dual-omics analysis revealed mitochondrial dysfunction of the thyroid by mediating fatty acid oxidation, Kreb's cycle, and oxidative phosphorylation. Significant metabolic toxicity on the thyroid might be linked to the characteristics of the chlorine content of MCCPs. This study revealed the toxicity of MCCPs to the thyroid gland via triggering thyroid hormone synthesis and interfering with mitochondrial function, which can provide new insights into the modes of action and mechanism-based risk assessment of MCCPs.

Identification of Sulfur-Containing Chlorinated Paraffin Structural Analogues in Human Serum: Origination from Biotransformation or Bioaccumulation?

Chlorinated paraffins (CPs) are manufactured and used in high quantities and have diverse structural analogues. It is generally recognized that sulfur-containing structural analogues of CPs are mainly derived from sulfate-conjugated phase II metabolism. In this study, we non-targeted identified three classes of sulfur-containing CP structural analogues (CPs-S) in human serum, including 44 CP sulfates (CPs-SO4H/CPs-SO4H-OH), 14 chlorinated benzene sulfates (CBs-SO4H), and 19 CP sulfite esters (CPs-SO3/CPs-S2O6), which were generated during the production of commercial mixtures of CPs and, thus, bioaccumulated via environmental exposures. We first wrote a program to screen CPs-S, which were baseline-separated from CPs according to their polar functional groups. Then, mass spectral analyses of alkalization-acidification liquid-liquid extracts of serum samples and Orbitrap mass spectrometry analyses in the presence and absence of tetraphenylphosphonium chloride (Ph4PCl), respectively, were performed to determine the ionization forms ([M + Cl]- or [M - H]-) of CPs-S. The presence of fragment ions (SO4H-, SO3-, SO2Cl-, and HSO3-) revealed the structures of CPs-S, which were validated by their detections in commercial mixtures of CPs. The estimated total concentrations of CPs-S in the human serum samples were higher than the concentrations of medium- and long-chain CPs. The profiles of CPs-S in human serum were similar to those detected in CP commercial mixtures and rats exposed to the commercial mixtures, but CPs-S were not detected in human liver S9 fractions or rat tissues after exposure to CP standards. These results, together with the knowledge of the processes used to chemically synthesize CPs, demonstrate that CPs-S in humans originates from environmental bioaccumulation.

Effects of environmentally relevant concentration of short-chain chlorinated paraffins on BV2 microglia activation and lipid metabolism, implicating altered neurogenesis.

Short-chain chlorinated paraffins (SCCPs), a class of persistent organic pollutants, have been found to cause diverse organ and systemic toxicity. However, little is known about their neurotoxic effects. In this study, we exposed BV2, a mouse microglia cell line, to environmentally relevant concentration of SCCPs (1 µg/L, 10 µg/L, 100 µg/L) for 24 h to investigate their impacts on the nervous system. Our observations revealed that SCCPs induced the activation of BV2 microglia, as indicated by altered morphology, stimulated cell proliferation, enhanced phagocytic and migratory capabilities. Analysis at the mRNA level confirmed the activation status, with the downregulation of TMEM119 and Tgfbr1, and upregulation of Iba1 and CD11b. The upregulated expression of genes such as cenpe, mki67, Axl, APOE and LPL also validated alterations in cell functions. Moreover, BV2 microglia presented an M2 alternative phenotype upon SCCPs exposure, substantiated by the reduction of NF-κB, TNF-α, IL-1ß, and the elevation of TGF-ß. Additionally, SCCPs caused lipid metabolic changes in BV2 microglia, characterized by the upregulations of long-chain fatty acids and acylcarnitines, reflecting an enhancement of ß-oxidation. This aligns with our findings of increased ATP production upon SCCPs exposure. Intriguingly, cell activation coincided with elevated levels of omega-3 polyunsaturated fatty acids. Furthermore, activated microglial medium remarkably altered the proliferation and differentiation of mouse neural stem cells. Collectively, exposure to environmentally relevant concentrations of SCCPs resulted in activation and lipid metabolic alterations in BV2 microglia, potentially impacting neurogenesis. These findings provide valuable insights for further research on the neurotoxic effect of SCCPs.

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.

Stress Response in the Honeybee (Apis mellifera L.) Gut Induced by Chlorinated Paraffins at Residue Levels Found in Bee Products.

Chlorinated paraffins (CPs) have become global pollutants and are of considerable concern as a result of their persistence and long-distance transmission in the environment and toxicity to mammals. However, their risks to pollinating insects are unknown. Honeybees are classical pollinators and sensitive indicators of environmental pollution. Herein, the effects of CPs on the gut microenvironment and underlying mechanisms were evaluated and explored using Apis mellifera L. Both short- and medium-chain CPs had significant sublethal effects on honeybees at a residue dose of 10 mg/L detected in bee products but did not significantly alter the composition or diversity of the gut microbiota. However, this concentration did induce significant immune, detoxification, and antioxidation responses and metabolic imbalances in the midgut. The mechanisms of CP toxicity in bees are complicated by the complex composition of these chemicals, but this study indicated that CPs could substantially affect intestinal physiology and metabolic homeostasis. Therefore, CPs in the environment could have long-lasting impacts on bee health. Future studies are encouraged to identify novel bioindicators of CP exposure to detect early contamination and uncover the detailed mechanisms underlying the adverse effects of CPs on living organisms, especially pollinating insects.

In Vivo Profiling and Quantification of Chlorinated Paraffin Homologues in Living Fish.

Herein, we demonstrate the ability of a dual-purpose periodic mesoporous organosilica (PMO) probe to track the complex chlorinated paraffin (CP) composition in living animals by assembling it as an adsorbent-assisted atmospheric pressure chemical ionization Fourier-transform ion cyclotron resonance mass spectrometry (APCI-FT-ICR-MS) platform and synchronously performing it as the in vivo sampling device. First, synchronous solvent-free ionization and in-source thermal desorption of CP homologues were achieved by the introduction of the PMO adsorbent-assisted APCI module, generating exclusive adduct ions ([M - H]-) of individual CP homologues (CnClm) with enhanced ionization efficiency. Improved detection limits of short- and medium-chain CPs (0.10-24 and 0.48-5.0 pg/µL) were achieved versus those of the chloride-anion attachment APCI-MS methods. Second, the dual-purpose PMO probe was applied to extract the complex CP compositions in living animals, following APCI-FT-ICR-MS analysis. A modified pattern-deconvolution algorithm coupled with the sampling-rate calibration method was used for the quantification of CPs in living fish. In vivo quantification of a tilapia exposed to technical CPs for 7 days was successfully achieved, with ∑SCCPs and ∑MCCPs of the sampled fish calculated to be 1108 ± 289 and 831 ± 266 µg/kg, respectively. Meanwhile, 58 potential CP metabolites were identified in living fish for the first time during in vivo sampling of CPs, a capacity that could provide an important tool for future study regarding its expected risks to humans and its environmental fate.

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.

Calibration and Application of PUF Disk Passive Air Samplers To Assess Chlorinated Paraffins in Ambient Air in Australia, China, and Vietnam.

Ambient air samples were collected in Brisbane (Australia), Dalian (China), and Hanoi (Vietnam) during Mar 2013-Feb 2018 using polyurethane foam based passive air samplers. A sampling rate calibration experiment was conducted for chlorinated paraffins (CPs, i.e., short-chain, medium-chain, and long-chain CPs), where the sampling rates were 4.5 ± 0.7, 4.8 ± 0.3, and 4.8 ± 2.1 m3 day-1 for SCCPs, MCCPs, and LCCPs, respectively. The atmospheric concentration of CPs was then calculated and the medians of ∑CPs were 0.079, 1.0, and 0.89 ng m-3 in Brisbane, Dalian, and Hanoi, respectively. The concentration of CPs in Brisbane's air remained at low levels, with no significant differences observed between the city background site and the city center site, indicating limited usage and production of CPs in this city. The highest concentration of MCCPs was detected in Dalian, while the highest concentration of SCCPs was detected in Hanoi. A decrease of SCCP concentration and an increase of MCCPs' were found in Brisbane's air from 2016 to 2018, while increasing trends for both SCCPs and MCCPs were observed in Dalian. These results indicated impacts from different sources of CPs in the investigated cities.

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.

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.

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 (6.70-495 µg g-1), followed by short-chain CPs (SCCPs, C10-13) (4.23-304 µg g-1) and long-chain (LCCPs, C≥18) CPs (3.68-331 µg g-1). Low levels (not detected-0.469 µg 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.

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 (0-45 cm) 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 977.1 ng/g dry weight (dw), respectively. ∑MCCP levels were comparatively higher and ranged from 417.2 to 1690.8 and 370.9 to 10,712.7 ng/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 the soils 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 × 10-2 µg kg-1 day-1) and adults (2.56 ± 0.99 × 10-4 and 7.94 ± 4.87 × 10-4 µg kg-1 day-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.

Short- and medium-chain chlorinated paraffins in urban road dust of Shanghai, China: concentrations, source apportionment and human exposure assessment.

Chlorinated paraffins (CPs) are ubiquitous anthropogenic contaminants that have been found in various environmental media. The objective of this study was to determine concentrations, spatial distribution, possible sources and potential health risk of SCCPs and MCCPs in urban road dust collected from Shanghai, China. The concentrations ranged from 9.74 to 11,400 ng g-1 for ΣSCCPs, 44.1 to 49,900 ng g-1 for ΣMCCPs and 53.9 to 61,400 ng g-1 for total CPs, respectively. MCCPs were the dominant component in all road dust, averagely accounting for 82.8% of total CPs. The concentrations of CPs in dust collected from traffic and commercial areas were significantly higher than those from campus, industrial, park and residential areas (p < 0.01), which could be attributed to tire wear in heavy traffic. All dust samples were divided into two groups by hierarchical cluster analysis for both SCCPs and MCCPs, and the most abundant homologue groups in most samples were C10Cl7-10 and C13Cl7-9 for SCCPs, and C14Cl7-9 and C15Cl8-9 for MCCPs. Correlation analysis showed that all carbon homologues in road dusts were highly correlated each other, suggesting SCCPs and MCCPs in dust maybe came from similar sources. Three sources for CPs in dust samples were apportioned by the PMF model; their relative contributions to the total CPs burden in dust were 25.6% for factor 1 (commercial CP mixture), 13.7% for factor 2 (long-distance transport) and 60.7% for factor 3 (commercial CP mixture). The median estimated daily intakes of total CPs via road dust were 1.78 × 10-5 for children and 3.0 × 10-6 mg kg-1 day-1 for adults, respectively. Quantitative risk assessment using non-cancer hazard index and total margin of exposure of total CPs indicated that total CPs at the present level in road dust pose no significant risk for both children and adults in Shanghai.

Novel biomonitoring method for determining five classes of legacy and alternative flame retardants in human serum samples.

Flame retardants (FRs) are ubiquitous in environment and biota and may pose harm to human health. In recent years, concern regarding legacy and alternative FRs has been intensified due to their widespread production and increasing contamination in environmental and human matrices. In this study, we developed and validated a novel analytical method for simultaneous determination of legacy and alternative FRs, including polychlorinated naphthalenes (PCNs), short- and middle-chain chlorinated paraffins (SCCPs and MCCPs), novel brominated flame retardants (NBFRs), and organophosphate esters (OPEs) in human serum. Serum samples were prepared by liquid-liquid extraction using ethyl acetate, and purified with Oasis® HLB cartridge and Florisil-silica gel columns. Instrumental analyses were carried out using gas chromatography-triple quadrupole mass spectrometry, high-resolution gas chromatography coupled with high-resolution mass spectrometry, and gas chromatography coupled with quadrupole time-of-flight mass spectrometry, respectively. The proposed method was validated for linearity, sensitivity, precision, accuracy, and matrix effects. Method detection limits for NBFRs, OPEs, PCNs, SCCPs, and MCCPs were 4.6 × 10-4-8.6 × 10-2, 4.3 × 10-3-1.3, 1.1 × 10-5-1.0 × 10-4, 1.5, and 9.0 × 10-1 ng/mL, respectively. Matrix spike recoveries ranged from 73%-122%, 71%-124%, 75%-129%, 92%-126%, and 94%-126% for NBFRs, OPEs, PCNs, SCCPs, and MCCPs, respectively. The analytical method was applied for detection of real human serum. CPs were the dominant FRs in serum, indicating CPs were widely presented in human serum and should be pay more attention for their health risk.

Dietary Intake Contributed the Most to Chlorinated Paraffin Body Burden in a Norwegian Cohort.

Determining the major human exposure pathways is a prerequisite for the development of effective management strategies for environmental pollutants such as chlorinated paraffins (CPs). As a first step, the internal and external exposure to CPs were quantified for a well-defined human cohort. CPs in participants' plasma and diet samples were analyzed in the present study, and previous results on paired air, dust, and hand wipe samples were used for the total exposure assessment. Both one compartment pharmacokinetic modeling and forensic fingerprinting indicate that dietary intake contributed the most to body burden of CPs in this cohort, contributing a median of 60-88% of the total daily intakes. The contribution from dust ingestion and dermal exposure was greater for the intake of long-chain CPs (LCCPs) than short-chain CPs (SCCPs), while the contribution from inhalation was greater for the intake of SCCPs than medium-chain CPs (MCCPs) and LCCPs. Significantly higher concentrations of SCCPs and MCCPs were observed in diets containing butter and eggs, respectively (p < 0.05). Additionally, other exposure sources were correlated to plasma levels of CPs, including residence construction parameters such as the construction year (p < 0.05). This human exposure to CPs is not a local case. From a global perspective, there are major knowledge gaps in biomonitoring and exposure data for CPs from regions other than China and European countries.

Levels of Short- and Medium-Chain Chlorinated Paraffins in Edible Insects and Implications for Human Exposure.

This study reports on the occurrence and distribution of short- and medium-chain chlorinated paraffins (SCCPs and MCCPs, respectively) in edible insects purchased from Asia and Europe. A total of 36 edible insect samples (n = 24 from Asia, n = 12 from Europe) authorized and prepared for human consumption were purchased and analyzed for SCCPs and MCCPs via gas chromatography and mass spectrometry. SCCPs were detected in 83% of all edible insect samples with an overall median ∑SCCP concentration of 8.7 ng/g dry weight (dw) and a range of <2.0 to 410 ng/g dw, while MCCPs were present in 92% of samples with a median ∑MCCP concentration of 51 ng/g dw and a range of <6.0 to 380 ng/g dw. Median ∑SCCP and ∑MCCP levels in edible insects purchased in Asia were approximately two- and four-times higher, respectively, than those from Europe, while the difference was statistically significant for ∑MCCPs (p < 0.001). Differences in homologue patterns were also observed between Asian and European samples to suggest diverse sources of CP contamination to insects which may include environmental accumulation, industrial processing equipment and food additives. Estimated daily intake of SCCPs and MCCPs via consumption of edible insects suggested that adverse health outcomes were very unlikely, but that continued monitoring of insect farming and processing practices are warranted.