Abundant Congeners Research Articles

Determination of Carbonyl Compounds in Different Work Environments: Comparison between LC-UV/DAD and LC-MS/MS Detection Methods.

There were two analytical methods for the determination of 12 carbonyl compounds (CCs) by using liquid chromatography (LC) coupled with mass spectrometry (MS/MS) and diode array detector (UV/DAD) that were developed and applied to 52 samples that were collected in 10 workplaces. Linearity (0.996 < R2 < 0.999), intra-day repeatability (0.7 < RSD% < 10), and inter-day repeatability (5 < RSD% < 16) were acceptable for both techniques, but the highest sensibility of the MS/MS method allowed us to correctly quantify 98% of the samples (versus 32% by UV/DAD). The comparison of the concentrations that were obtained by quantifying the same sample with both techniques showed good agreement for acetaldehyde and formaldehyde (0.1 < % deviation < 30) but much higher for the less abundant congeners. In real samples, formaldehyde was the most abundant congener (concentrations between 2.7 and 77 µg m−3), followed by acetaldehyde (concentrations between 1.5 and 79 µg m−3) and butyraldehyde (concentrations between 0.4 and 13 µg m−3). In all the beauty salon samples, instead, the most abundant congener was acetaldehyde (concentrations between 19 and 79 µg m−3), probably associated with the use of beauty products. Principal components analysis (PCA) confirms the ubiquitous character of formaldehyde and highlights the influence of minority CCs on different workplaces.

New emerging polybromobiphenyls in serum of general population and their disruption on thyroid hormone receptor β1.

After the PBBs pollution incident in Michigan, a large number of studies focused on the exposure of people to 2,2',4,4',5,5'-hexabromobiphenyl (BB-153), but paid less attention to other PBBs congeners in human serum. In this study, three monobromobiphenyls (BB-1, BB-2 and BB-3), five dibromobiphenyls (BB-4, BB-7, BB-9, BB-10 and BB-15), decabromobiphenyl (BB-209) and BB-153 in the serum of the general population in Wuxi from 2012 to 2016 were detected by GC-MS/MS. The most abundant congeners in serum samples were BB-1(median 254ng·g-1 lw), BB-10 (median 141ng·g-1 lw) and BB-209 (median 68.4ng·g-1 lw). The detection rate of BB-153 is less than 10%, and the concentration is far lower than that in other areas. The concentrations of BB-1, BB-10 and BB-209 are 3-4 orders of magnitude higher than the maximum concentration of BB-153. Serum concentrations of BB-209 increased significantly from 2012 to 2016 (p=0.025). In addition, the concentrations of BB-1 in serum of females were significantly higher than that of males, and the concentrations of BB-1, BB-10 and BB-209 in serum of young adults were significantly higher than that of middle-aged adults. Finally, we found that BB-1 and BB-10 may have similar disruption on the binding of T3 and TRβ1 as BB-153, while BB-209 has little effect on the binding of T3 and TRβ1. This suggests that we should pay more attention to the damage of BB-1 and BB-10 to thyroid in the future.

A retrospective study on dioxins and dioxin-like polychlorinated biphenyls in milk and dairy products from the Latium region (Italy) over a 7-year study period (2011-2017).

This study reports the data of polychlorinated dibenzo-p-dioxins (PCDDs), -furans (PCDFs), and polychlorinated biphenyls dioxin-like (dl PCBs) measured in a total of 260 samples of the dairy supply chain collected over a period of 7 years (2011–2017) in the Latium region (Italy). Levels and average profiles of congeners were reported for each group of the analyzed dairy matrices, and any differences between different sampling strategies were considered (around likely pollutant sources or casual sampling). Of the samples, 95.4% resulted compliant with the regulated levels; only samples belonging to the “sheep bulk milk” matrix were found to be above either the action levels or the maximum levels (tot. 12 samples). Raw milk of the sheep species showed the highest averages (PCDD/F 0.248 and dl PCB 0.966 WHO TEQ pg/g of fat) compared to the milk of other species. The buffalo milk showed a content of dl PCB significantly lower (dl PCB: 0.371 WHO TEQ pg/g of fat) than the sheep milk (p<0.05). Dioxins were found to be superior to furans in almost all dairy products, except in the noncompliant samples where furans were higher. The OCDD was found to be the most abundant congener in almost all dairy products. This study provides a first list of reference values for background contamination of the dairy supply chain in the Latium region. These pre-existing values will be useful in all cases of environmental pollution to identify critical situations.

Priority Organic Pollutants and Endocrine-Disrupting Compounds in Arctic Marine Sediments (Svalbard Islands, Norway).

The present study investigated the occurrence and distribution of polycyclic aromatic hydrocarbons (PAHs) and phenolic endocrine-disrupting compounds (PEDCs), including bisphenol A (BPA), 4-nonylphenol (4-NP), and its monoethoxylate (NP1EO) and diethoxylate precursors in marine sediments in an Arctic fjord (Svalbard, Norway). The contribution of different local sources of contamination was also evaluated, together with a risk assessment for the marine environment. Samples were collected during two consecutive summer seasons (2018 and 2019), and target contaminants were analyzed with gas chromatography-mass spectrometry (MS) and high-performance liquid chromatography-MS/MS. The results showed no statistical differences between total PAH concentrations measured in 2018 (mean value 53.7 ± 54.3 ng/g) and 2019 (mean value 58.1 ± 63.6 ng/g). Low-ring (three or four rings) PAHs were the most abundant congeners, and single PAH ratios indicated a predominance of petrogenic sources (i.e., coal and liquid fossil fuel combustion). Nonylphenols and BPA showed a significant decrease in 2019 compared to 2018; 4-NP and NP1EO prevailed in both years, particularly in sediments close to the Ny-Ålesund research village. Overall, the results indicate that local anthropic activities are the major source of contamination in the Kongsfjorden ecosystem, but also melting waters from glaciers in the summer season can play an important role as a secondary source of pollutants previously trapped in ice. Comparison between our data and empirical and mechanistic indices derived from sediment quality guidelines suggests that the occurrence of PAHs and PEDCs in sediments does not currently pose a risk for this Arctic ecosystem, but further investigation is needed on the spread of hazardous contaminants and their effects on these fragile environments. Environ Toxicol Chem 2023;42:953-965. SETAC.

Body burden and influencing factors of polychlorinated dibenzodioxins and dibenzofurans (PCDD/Fs) in male workers from a municipal waste incineration plant in China

Emissions of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) from municipal solid waste incinerators (MSWIs) have aroused public concern around the world. However, biomonitoring evidence regarding the influence of MSWIs on the human body burden of PCDD/Fs is scarce. The aim of this study is to investigate the human body burden levels of PCDD/Fs in MSWI workers and to further explore the potential influencing factors, including duration of occupation and dietary habits, on the PCDD/F levels. A total of 98 paired serum samples from MSWI workers and non-MSWI workers were collected. Seventeen 2,3,7,8-chlorine substituted PCDD/Fs in the serums were analyzed using an isotope dilution high-resolution gas chromatograph/high-resolution mass spectrometer (HRGC/HRMS). The results showed that the mean levels of toxic equivalent (TEQ)-PCDD/Fs for the MSWI workers and the control group were 18.28 pg TEQ g−1 lipid and 5.81 pg TEQ g−1 lipid, respectively. Significantly higher concentrations of PCDD/Fs existed in the incinerator workers compared with the control subjects after adjustment of the confounding factors. OCDD was the most abundant congener in both the MSWI workers and the control subjects, accounting for 82.2% and 89.4% of the ∑17PCDD/Fs, respectively. The serum levels of PCDFs in the MSWI workers increased with the duration of occupation (β = 0.498, P = 0.031), and a higher total concentration of PCDD/Fs were present in senior workers classified as production supervisors than routine operation staff (β = 8.809, P = 0.008). No significant relationship was found between the PCDD/F concentrations and dietary habits. This study was the first to explore the associations between the body burden of PCDD/Fs and occupational exposure as well as dietary intake of MSWI workers in China. The findings provide scientific information for health risk assessments of human exposure to PCDD/Fs.

A nationwide survey of 20 legacy brominated flame retardants in indoor dust from China: continuing occurrence, national distribution, and implication for human exposure.

Despite the restrictions on polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecanes (HBCDDs), these chemicals are still ubiquitous environmental pollutants. In this study, we measured the concentrations and profiles of 17 PBDE congeners and 3 HBCDD isomers in indoor dust samples collected from 23 provinces and cities across China. The summed concentrations of PBDEs (Σ17PBDEs) ranged from 4.19 to 817ng/g, with an average of 171 ± 184ng/g. BDE-209 was the most abundant congener. The concentrations of HBCDDs ranged from 6.65 to 1335ng/g, with an average of 236 ± 324ng/g. Unlike commercial HBCDD formulations, α-HBCDD was the predominant isomer in the indoor dust samples analyzed. Geographical distributions showed that the concentrations of PBDEs and HBCDDs varied significantly among different regions. Higher PBDE and HBCDD levels were observed in samples from eastern coastal and economically developed regions. Further, we estimated the daily intakes of PBDEs and HBCDDs through the routes of dust ingestion and dust dermal absorption for different age groups. Dust dermal absorption is an unneglectable exposure pathway to PBDEs and HBCDs for the Chinese population. Among the age groups, infants had the highest exposure via dust dermal absorption, and toddlers had the highest exposure via dust ingestion. Compared with the threshold values, the exposure doses of PBDEs and HBCDDs are unlikely to pose significant health concerns for both infants and adults in China. This is the first national survey of PBDEs and HBCDDs in indoor dust samples across China after the restriction.

Occurrence and air-water diffusive exchange legacy persistent organic pollutants in an oligotrophic north Patagonian lake.

In this study, the occurrence and diffusive air-water exchange of POPs in Panguipulli Lake (39°42'S-72°13'W), an oligotrophic lake located in northern Patagonia (Chile), were determined. Air and water samples were collected between March and August 2017 (autumn-winter) and analyzed for concentrations of OCPs (α-HCH, β-HCH, γ-HCH and HCB) and PCBs (PCB-28,-52,-101,-118,-153,-158,-180) using gas chromatography coupled with an electron capture detector. The direction of air-water exchange direction was evaluated using a fugacity approach (ƒw ƒa-1), and net diffusive exchange fluxes (FAW, ng m-2 d-1) were also estimated. Total ∑4OCP levels in air ranged from 0.31 to 37pgm-3, with a maximum for β-HCH, while Σ7PCB levels ranged from 3.05 to 43pgm-3. The most abundant congener was PCB-153, accounting for 60% of the total PCBs in air. Surface water ∑4OCPs measured in this study ranged from 1.01 to 3.9pgL-1, with γ-HCH predominating, while surface water Σ7PCB levels ranged from 0.32 to 24pgL-1, with PCB-101, PCB-118, and PCB-153 presenting the highest levels. Diffusive air-water exchanges of HCB, α-HCH, γ-HCH and PCBs in the form of volatilization from the lake to air predominated; in contrast, for β-HCH net deposition dominated during the sampling period. Estimates suggested faster microbial degradation in the dissolved phase compared to atmospheric degradation for all analyzed POPs. Overall, these results could indicate that the oligotrophic lakes of northern Patagonia act as a secondary source of atmospheric POPs, mainly PCBs and some OCPs. This study is a first attempt to understand the occurrence of POPs in air and water, as well as their dynamics in oligotrophic lakes in the southern hemisphere.

Distribution, Source and Potential Risk Assessment of Polychlorinated Biphenyls (PCBs) in Sediments from the Liaohe River Protected Area, China

This study aimed to assess the occurrence, distribution, toxicity equivalency and health risks of dl-PCBs (dioxin-like PCBs) from nine sites collected in surface sediments from Liaohe River Protected Area. ∑dl-PCBs concentrations in sediments range from 79.2 to 365.1 pg/g. Sediment profiles showed that pentachlorobiphenyl is the most abundant congener among all sampling sites. The results of principal component analysis and cluster analysis indicated that PCBs were mainly derived from electronic waste and paint additives in the sediments of Liaohe River Protected Area. Toxic equivalent quantity (TEQ) values of the PCBs in the Liaohe River Protected Area sediments are at comparatively lower levels compared with the previously reported data. Hazardous ratio (HR) for human health risk assessment allied to cancer was found to be lower than the non-carcinogenic risk assessment within an acceptable range.

BDE-47 induced PC-12 cell differentiation via TrkA downstream pathways and caused the loss of hippocampal neurons in BALB/c mice

As the most abundant congener of polybrominated diphenyl ethers (PBDEs) detected in environment and human biotic samples, 2, 2′, 4, 4′-tetrabromodiphenyl ether (BDE-47) has been found to accumulate in brain and induce neurotoxicity, however, the detailed mechanism has not been clearly elucidated. To investigate the neurotoxicity of BDE-47, undifferentiated PC-12 cells were exposed to different doses of BDE-47, and BDE-47 dissolved in corn oil was orally administered to mice for 8 consecutive weeks. Our data showed that BDE-47 obviously changed cell morphology, altered cell viability, promoted cell apoptosis, and induced reactive oxygen species (ROS) production. BDE-47 promoted the differentiation of PC-12 cells by enhancing the expression of TrkA receptor and the phosphorylation levels of ERK and Akt. Moreover, BDE-47-induced differentiation of PC-12 cells was suppressed by inhibitors of corresponding pathways (MAPK/ERK and PI3K/Akt). H&E staining of brain showed neurons in DG and CA1 areas of hippocampus decreased after BDE-47 exposure. Transcriptome sequencing of brain tissue suggested that multiple signaling pathways related to neuron death and nerve function were significantly regulated. In conclusion, these results provided new evidence for revealing the neurotoxicity of BDE-47, and offered important experimental basis for environmental controlling and post-exposure health risk assessment of BDE-47.

Associations between phthalic acid esters in house dust and home characteristics/living habits in a rural region of Taiwan.

Phthalic acid esters (PAEs) commonly used as plasticizers are distributed ubiquitously in the living environment. We conducted a field study to examine the associations between PAE residue in dust and home characteristics/living habits in 47 rural homes in Taiwan. A questionnaire regarding home characteristics/living habits and composite sampling of house dust were conducted in each participating home. Five PAEs were selected for analysis on gas chromatography-mass spectrometry with the limits of quantification being 0.5 ng/g or lower. Uni- and multivariate linear regression analyses were performed for examining the associations. The five PAEs were prevalently detected from the samples, and the concentrations were below 1000 ng/g; di(2-ethylhexyl) phthalate (DEHP) was the most frequently detected PAE (85%), whereas di-isobutyl phthalate (DiBP) appeared to the most abundant congener with the maximum concentration of 807.65 ng/g. Floor cleaning frequency and use of detergents for floor cleaning were significantly associated with DEHP in dust (P < 0.05), suggesting additives of plasticizers in detergent products. The factors of plastic wraps in storage and use of disposable cups were both significantly related to DiBP (P < 0.01), which could be extensively used in food packaging products. We confirmed that several home characteristics/living habits were related to certain PAE residue in dust.

Thyroid hormones in relation to polybrominated diphenyl ether and metals exposure among rural adult residents along the Yangtze River, China.

Although several studies indicate that exposure to polybrominated diphenyl ethers (PBDEs) and metals may influence thyroid function, the evidence is limited and inconsistent in general population. The current study was conducted to determine the levels of plasma PBDEs and urinary metals and evaluate the associations of co-exposure to both with thyroid hormones (THs) among rural adult residents along the Yangtze River, China. A total of 329 subjects were included in current analyses, and 8 PBDEs congeners and 14 urinary metals were measured to reflect the levels of environmental exposure. Multiple linear regression models were used to evaluate the association between PBDEs, metals and THs levels. Bayesian Kernel Machine Regression (BKMR) was used to examine PBDEs and metals mixtures in relation to THs. The geometric mean (GM) and 95% confidence interval (CI) of total measured PBDEs was 65.10 (59.96, 70.68) ng/g lipid weights (lw). BDE-209 was the most abundant congener, with a GM (95% CI) of 47.91 (42.95, 53.26) ng/g lw, accounting for 73.6% of the total PBDEs. Free thyroxine (FT4) was significantly negatively associated with BDE-28, 47, 99, 100, 154, and 183, and urinary strontium [β (95% CI): -0.04 (-0.07, -0.02)], but positively associated with selenium [β (95% CI): 0.04 (0.02, 0.06)]. Free triiodothyronine (FT3) was negatively associated with BDE-28 [β (95% CI): -0.03 (-0.05, -0.01)] and urinary arsenic [β (95% CI): -0.01 (-0.02, -0.001)]. The current study did not observe a statistically significant association of thyroid-stimulating hormone (TSH) with PBDEs and urinary metals. BKMR analyses showed similar trends when these chemicals were taken into consideration simultaneously. We found no significant interaction in the association between individual chemical at the 25th versus 75th percentiles and THs estimates, comparing the results when other chemicals were set at their 10th, 50th, and 90th percentile levels. Further study is required to confirm these findings and determine potential mechanisms.

Exposure and risk assessment of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and dioxin-like polychlorinated biphenyls (dl-PCBs) for primiparous mothers and breastfed infants in Penang, Malaysia

ABSTRACT An average 50 ml breast milk samples were collected from 21 lactating primiparous mothers (range 25 to 45 years, mean 33 years), 4–8 weeks after delivery in Penang Island, Malaysia. The geometric mean concentration of the most toxic congeners, 2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8-TCDD) was 0.14 pg WHO2005-TEQ g−1 zlipid. The most abundant congeners of PCDD/Fs were octachlorodibenzo-p-dioxin (OCDD) (5.9–75.4%), followed by 1,2,3,4,6,7,8-heptachlorodibenzo-p-dioxin (1,2,3,4,6,7,8-HpCDD) (1.1–30.7%). The geometric mean level of total dioxins and dl-PCBs was 2.2 pg WHO2005-TEQ g−1 lipid, significantly lower than those in developed countries or highly contaminated areas. The total dioxins and dl-PCBs in pg WHO2005-TEQ levels in breast milk were significantly correlated with years of residence at potential contaminated site. The average daily intake of 11.8 pg WHO2005-TEQ kg−1 body weight was estimated for a breastfed infant at 6 months of age. This demonstrates the exposure risk to infants, especially from Penang region, to these pollutants from human milk intake are potentially high during the lactation period.

Novel microsatellite markers reveal low genetic diversity and evidence of heterospecific introgression in the critically endangered Chinese Crested Tern (Thalasseus bernsteini)

The Chinese Crested Tern, Thalasseus bernsteini, is one of the most endangered seabird species in the world, with only small breeding populations of around 100 individuals. To profile the genetic properties of this population, we screened 200 short tandem repeat sequences from a de novo assembled genome of the Great Crested Tern, T. bergii, which is the sister species of T. bernsteini. We designed a panel of 12 novel microsatellites, and genotyped nine and 23 individuals of T. bernsteini and T. bergii, respectively. The results showed that T. bernsteini genetic diversity was lower than that of T. bergii, and no inbreeding was detected. There was no sign of recent bottleneck events in the two species, but T. bernsteini showed signals of a post-bottleneck population expansion. Gene flow analysis indicated introgression between the two species, but the magnitude from T. bernsteini to T. bergii was higher than the opposite. This could be explained by Hubb’s principle, which states that there is a propensity of rarer species to reproduce with abundant congeners. Overall, our efforts provide useful genetic tools for conservation genetic studies of T. bernsteini and potentially other crested terns which face several natural and anthropogenic threats. The findings of this study further highlight that introgression may be a neglected factor in species conservation that needs to be seriously considered for conservation management. Availability of data and materialsThe dataset of all microsatellite are available from the corresponding author upon request.

Nontargeted Discovery of Novel Contaminants in the Great Lakes Region: A Comparison of Fish Fillets and Fish Consumers.

Sport fish fillets and human sera (fish consumers) were collected in the Lake Superior and Lake Michigan basin and screened for novel contaminants using the isotopic profile deconvoluted chromatogram (IPDC) algorithm. The IPDC algorithm was extended beyond traditional Cl/Br filters to detect additional potential bioaccumulative and toxic (PBT) such as perfluoroalkyl substances (PFAS). The IPDC algorithm screened for approximately 13.5 million theoretical molecular formulas. Additional algorithm modules were developed to detect data independent MS/MS fragmentation products and a retention time index calculator using a series of 13C-labeled perfluoroalkyl carboxylic acids (13C-PFCAs). Ten potential compound classes were isolated including six untargeted PFAS, six homologue groups of polyfluorinated carboxylic acids, polyfluorinated telomer alcohols (PoFTOHs), two hydroxylated polychlorobiphenyls, pesticides, herbicides, antifungals, pharmaceuticals, artificial sweeteners, and personal care products with minimal postprocessing efforts. The algorithm isolated 48 ubiquitous PoFTOHs in both fish fillet and serum of fish consumers suggesting a region wide distribution of this class of compounds. The 3, 4, and 7 fluorine substituted PoFTOH were the most abundant congeners in both biological matrices.

Permeability of the Cyanotoxin Microcystin-RR across a Caco-2 Cells Monolayer.

Microcystins (MCs) are toxins produced by several cyanobacterial species found worldwide. While MCs have a common structure, the variation of two amino acids in their structure affects their toxicity. As toxicodynamics are very similar between the MC variants, their differential toxicity could rather be explained by toxicokinetic parameters. Microcystin-RR (MC-RR) is the second most abundant congener and induces toxicity through oral exposure. As intestinal permeability is a key parameter of oral toxicokinetics, the apparent permeability of MC-RR across a differentiated intestinal Caco-2 cell monolayer was investigated. We observed a rapid and large decrease of MC-RR levels in the donor compartment. However, irrespective of the loaded concentration and exposure time, the permeabilities were very low from apical to basolateral compartments (from 4 to 15 × 10−8 cm·s−1) and from basolateral to apical compartments (from 2 to 37 × 10−8 cm·s−1). Our results suggested that MC-RR would be poorly absorbed orally. As similar low permeability was reported for the most abundant congener microcystin-LR, and this variant presented a greater acute oral toxicity than MC-RR, we concluded that the intestinal permeability was probably not involved in the differential toxicity between them, in contrast to the hepatic uptake and metabolism.

Estimation of dietary intake and sources of organohalogenated contaminants among infants: 24-h duplicate diet survey in Fukuoka, Japan

The widespread occurrence of persistent organic pollutants (POPs) in the environment is a matter of concern. In this study, selected organohalogenated contaminants, including dichlorodiphenyltrichloroethane and its metabolites (DDTs) polychlorinated biphenyls (PCBs), chlordanes (CHLs), hexachlorobenzene (HCB), polybrominated diphenyl ethers (PBDEs), hexabromocyclododecanes (HBCDs), tetrabromobisphenol A (TBBPA), 2,4,6-tribromophenol (TBP), were measured in complete meal sets (24-h duplicate-diet) of Japanese infants to investigate the levels, profiles, and possible sources of contamination. In total, 46 whole-day meals of infants (7–24-months old) were collected during 2017 from Fukuoka, Japan. To the best of our knowledge, this is the first report based on the duplicate-diet method for infants. The median intakes among the POP groups were highest for ΣDDTs (18 ng/day, maximum 251 ng/day), followed by ΣPCBs (17 ng/day, maximum 198 ng/day), ΣCHLs (14 ng/day, maximum 105 ng/day), HCB (11 ng/day, maximum 64 ng/day), TBP (3.5 ng/day, maximum 109 ng/day), ΣHBCDs (1.9 ng/day, maximum 70 ng/day), TBBPA (0.72 ng/day, maximum 34 ng/day), and ΣPBDEs (0.11 ng/day, maximum 4.5 ng/day). Among the PCBs, PCB-138 and PCB-153 were the most abundant congeners (27% and 23%, respectively). p,p’-DDE, the major DDT metabolite, accounted for 96% of total DDTs. Among PBDEs, BDE47 was the only detected congener (present in 4% of the samples). The dietary intake of the targeted compounds was lower than the intake via breast milk, suggesting that the exposure from baby food was limited. In the principal component analysis, chlorinated and brominated compounds were separated on principal component 1, while TBP and α-HBCD were separated on principal component 2, likely suggesting a differing emission time trend or source. PCB-153, PCB-138, trans-chlordane, cis-chlordane, and trans-nonachlor were correlated with seafood consumption (Spearman's ρ = 0.45 to 0.57, p < 0.05), while TBP was correlated with seaweed consumption (Spearman's ρ = 0.46, p < 0.05). Also, four species of commercial edible seaweed in Japan were analyzed to confirm the findings of the duplicate-diet study. The relatively high concentration of TBP (5.5 ± 6.6 ng/g wet weight) was observed in the seaweed samples, indicating that seaweed is a potential exposure source of TBP.

Contamination levels and temporal trends of legacy and current-use brominated flame retardants in a dated sediment core from Beppu Bay, southwestern Japan

Contamination levels and temporal trends of polybrominated diphenyl ethers (PBDEs) and some alternative brominated flame retardants (BFRs) were examined in a dated sediment core from the deepest part of the Beppu Bay, southwestern Japan. PBDEs were found in the upper layers of 0–15 cm depth at concentrations ranging from 5200 to 32,600 pg g−1 with the peak estimated at 1995. Decabromodiphenyl ether (BDE-209) was the most abundant congener, accounting for 96% in average of total PBDEs. The vertical profile of BDE-209 observed in our sediment core generally agreed with the historical pattern of domestic demand of commercial deca-BDE mixtures in Japan, and perfectly matched with maximum stock of these products (i.e., 42,000 tons in 1995). Among alternative BFRs, only decabromodiphenyl ethane (DBDPE), a replacement of deca-BDE, was found at significant levels with concentrations of 69–850 pg g−1 in sediment layers dated between 1991 and 2011. Ratios of DBDPE to BDE-209 gradually increased during this period, implying opposite trends of these two compounds and the role of DBDPE as a deca-BDE’s alternative. The occurrence of deca-BDE components in sediments may pose medium risk to benthic aquatic life, while the ecological risk of other PBDE homologs and DBDPE was negligible.

BFRs (PBDEs and HBCDs) in freshwater species from Lake Trasimeno (Italy): The singular case of HBCDs in red swamp crayfish

Eighty-six samples belonging to five different species (crucian carp, Carassius carassius; European perch, Perca fluviatilis; tench, Tinca tinca; eel, Anguilla anguilla; red swamp crayfish, Procambarus clarkii) collected from Lake Trasimeno (Italy) were analyzed to assess polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecanes (HBCDs) contamination. The Trasimeno is the largest Italian peninsular lake located in Umbria (Central Italy), in a rural area with low anthropogenic impact. All the samples were analyzed by an in-house developed analytical procedure involving a single sample preparation with dual detection: Gas- and Liquid-Chromatography coupled to tandem Mass Spectrometry (GC–MS/MS for PBDEs and LC-MS/MS for HBCDs). BFRs levels in crucian carp, tench and European perch were negligible and mostly below quantification limits (LOQs). In eel, the species with the higher fat content, PBDE sum (15 congeners) ranged from 0.269 to 0.916 ng/g w.w. BDE-47, -100 and -154 accounted for roughly 57%, 16% and 11% of the PBDE sum, respectively, while BDE-99 (usually one of the most abundant congeners in biota), only for 3%. HBCDs (sum of α-, β-, γ-isomers) were found between 0.157 and 1.14 ng/g w.w. with α- as predominant isomer (92% of the sum), followed by γ- (5%) and β- (2%). Peculiar was the contamination in red swamp crayfish characterized by negligible PBDEs and very high HBCDs levels with a singular contamination pattern. In female pools (n = 9) the mean HBCDs sum was 0.150 ng/g w.w., while in males higher concentrations were measured (mean = 2.77 ng/g w.w.). A significant correlation seems to exist between the contamination level and the seasonal cycle only in male crayfish. Interestingly, among the HBCDs, the γ-isomer was the highest (67% of the total) while α- contributes only for 20%.

Legacy and novel flame retardants from indoor dust in Antarctica: Sources and human exposure

The air humidity in Antarctica is very low and this peculiar weather parameter make the use of flame retardants in research facilities highly needed for safety reasons, as fires are a major risk. Legacy and novel flame retardants (nFRs) including polybrominated diphenyl ethers (PBDEs), hexabromocyclododecanes (HBCDs), 1,2-bis(2,4,6-tribromophenoxy) ethane (BTBPE), Dechlorane Plus (DP), and other nFRs were measured in indoor dust samples collected at research Stations in Antarctica: Gabriel de Castilla, Spain (GCS), Julio Escudero, Chile (JES), and onboard the RRS James Clark Ross, United Kingdom (RRS JCR). The GC-HRMS and LC-MS-MS analyses of dust samples revealed ∑7PBDEs of 41.5 ± 43.8 ng/g in rooms at GCS, 18.7 ± 11.6 ng/g at JES, and 27.2 ± 37.9 ng/g onboard the RRS JCR. PBDE pattern was different between the sites and most abundant congeners were BDE-183 (40%) at GCS, BDE-99 (50%) at JES, and BDE-153 (37%) onboard the RRS JCR. The ∑(4)HBCDs were 257 ± 407 ng/g, 14.9 ± 14.5 ng/g, and 761 ± 1043 ng/g in indoor dust collected in rooms at GCS, JES, and RRS JCR, respectively. The ∑9nFRs were 224 ± 178 ng/g at GCS, 14.1 ± 13.8 ng/g at JES, and 194 ± 392 ng/g on the RRS JCR. Syn- and anti-DP were detected in most of the samples and both isomers showed the highest concentrations at GCS: 163 ± 93.6 and 48.5 ± 61.1 ng/g, respectively. The laboratory and living room showed the highest concentration of HBCDs, DPs, BTBPE. The wide variations in FR levels in dust from the three research facilities and between differently used rooms reflect the different origin of furnishing, building materials and equipment. The potential health risk associated to a daily exposure via dust ingestion was assessed for selected FRs: BDEs 47, 99, and 153, α-, β-, and γ-HBCD, BTBPE, syn- and anti-DP. Although the estimated exposures are below the available reference doses, caution is needed given the expected increasing use of novel chemicals without a comprehensive toxicological profile.

Brominated flame retardants in home dust and its contribution to brominated flame retardants bioaccumulation in children hair

Brominated flame retardants (BFRs) in house dust have raised significant concern around the world. However, few studies have reported the correlation between BFR concentrations in house dust and children’s hair samples. In this study, BFR concentrations in house dust and children’s hair were measured. Chemical analysis showed that the total concentrations of polybrominated diphenyl ethers (PBDEs) in house dust ranged from 334 to 4444 ng g−1, with a median of 442 ng g−1, and the concentrations in children’s hair ranged from 352 to 655 ng g−1, with a median of 530 ng g−1. In addition, two alternative flame retardants, pentabromoethylbenzene (PBEB) and hexabromobenzene, were frequently detected in house dust and human hair. BDE209 was the most abundant PBDE congener detected in both house dust and children’s hair. A significant correlation was found between the integrated PCA score of BFR concentrations in house dust and in children’s hair (r2 = 0.31, P < 0.05), indicating the great contribution of house dust to the bodily burden of PBDEs in children. Risk assessment indicated that children’s exposure to PBDEs via non-dietary intake of house dust should be recognized as an important exposure pathway.