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Cyclic methylsiloxanes (CMSs), widely found in wastewater treatment plants (WWTPs), are potentially hazardous to the environment and human health. In this study, the environmental behavior and human exposure risks of three CMSs (D4-D6) were evaluated in WWTPs located in Beijing and Kunming, Yunnan province. D5 had the highest concentrations in air, water, and sludge, with seasonal variation that consisted of a high concentration in summer and low concentration in winter. The CMS concentrations in air were 3-4-fold higher in the A 2 /O (Anaerobic-Anoxic-Oxic) treatment units than in the other units. CMS emissions to air, soil, and water from the Beijing WWTP were in the ranges of 3.4 × 10 4 -5.0 × 10 4  kg·a -1 , 4.5 × 10 2 -7.5 × 10 2  kg·a -1 , and 2.5 × 10 2 -2.9 × 10 2  kg·a -1 , constituting 98 %, 1.3 %, and 0.7 % of the total emissions, respectively. Total daily inhalation exposure doses of CMSs (ADD inh,CMSs ) associated with four different jobs in WWTPs showed that wastewater treatment technicians had the highest ADD inh,CMSs (51 μg/kg/day), indicating that these people had the highest occupational exposure risk in WWTPs. Therefore, this study identified that atmospheric emission was the main environmental fate of CMSs in WWTPs, and provide a basis for the improvement of WWTP process and risk management decisions. ENVIRONMENTAL IMPLICATION: Assessing the environmental fate and occupational exposure risk of cyclic methylsiloxanes (CMSs) found in wastewater treatment plants (WWTPs) is crucial. This is the first study to identify that atmospheric emission was the main environmental fate of CMSs in WWTPs, especially D5; the inhalation exposure doses of CMSs were all significantly higher in the occupational population working in WWTPs. The results described in our study will help enhance the understanding of current knowledge base of environmental fate and exposure risk of CMSs in WWTPs, and provide a basis for the improvement of WWTP process and risk management decisions., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Simulated landfill bioreactors were established and operated for 635 days to investigate the dynamic release of seven siloxanes in landfill biogas (denoted by octamethyltrisiloxane (L3), decamethyltetrasiloxane (L4), dodecamethylpentasiloxane (L5), hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4) and decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6)). In total, 259.45, 252.73, 233.30, 80.40, 4.35, 1.67 and 1.10 mg of D5, D3, D4, D6, L4, L5 and L3 were discharged from 57 kg of municipal solid waste (MSW). More than 70 % of the siloxanes were released before day 119, indicating that the peak period of siloxane discharge occurred during the hydrolysis and acid production stage. The cyclosiloxanes (D3, D4, D5 and D6) were the dominant siloxane species in the biogas. The mass load of discharged cyclosiloxanes was more than 98 % of that of the total siloxanes. In addition to the variation in the concentration distribution profiles of the different siloxane species in the MSW, transformations among species may have an important effect on the release of siloxanes. The main transformation products were D3 and D4 with high release rates (>20 %) and high measured contents of trimethylsilanol (TMSOH) and functional microorganisms (Pseudomonas) were observed during landfilling. These results suggested that MSW degradation and transformation of siloxanes both drive the dynamic release of siloxanes during long-term landfilling., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Cyclic volatile methylsiloxanes (cVMS) have been widely found in various types of environmental media and attracted increasing attention as new pollutants. However, there is still a great challenge in the accurate quantification of trace cVMS, due to their volatility, and the high background originating from GC/MS accessories and surroundings. In this work, the main sources of the high background were investigated in detail for octamethylcyclotetrasiloxane (D4), decmethylcyclopentasiloxane (D5) and dodecmethylcyclohexosiloxane (D6). Several effective measures were employed to minimize these backgrounds, including the delayed injection method to minimize the interference from the injection septum. Then, a GC-MS method was developed for the accurate determination of D4, D5 and D6, with a linear range of 2 - 200 μg/L. The coefficient of determination was 0.9982-0.9986, the limit of detection (LOD) was 0.40-0.52 μg/L, and the quantitative range was 1.88-190 μg/L. Good reproducibility and recovery were obtained, indicating the reliability of the established analytical method., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Cyclic volatile methyl siloxanes (cVMS) have now become a subject of environmental contamination and risk assessment due to their widespread use and occurrence in different environmental matrices. Due to their exceptional physio-chemical properties, these compounds are diversely used for formulations of consumer products and others implying their continuous and significant release to environmental compartments. This has captured the major attention of the concerned communities on the grounds of potential health hazards to human and biota. The present study aims at comprehensively reviewing its occurrence in air, water, soil, sediments, sludge, dusts, biogas, biosolids, and biota and their environmental behavior as well. Concentrations of cVMS in indoor air and biosolids were higher; however, no significant concentrations were observed in water, soil, and sediments except for wastewaters. No threat to the aquatic organisms has been identified as their concentrations do not exceed the NOEC (maximum no observed effect concentration) thresholds. Mammalian (rodents) toxicity hazards were not very evident except for the occurrence of uterine tumors in very rare cases under long-term chronic and repeated dose exposures in laboratory conditions. Human relevancy to rodents were also not strongly enough established. Therefore, more careful examinations are required to develop stringent weight of evidences in scientific domain and ease the policy making with respect to their production and use so as to combat any environmental consequences., (© 2023. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Volatile methyl siloxanes (VMS) are a group of organosilicon compounds of interest because of their potential health effects, their ability to form secondary organic aerosols, and their use as tracer compounds. VMS are emitted in the gas-phase from using consumer and personal care products, including deodorants, lotions, and hair conditioners. Because of this emission route, airborne concentrations are expected to increase with population density, although there are few studies in large urban centers. Here, we report summertime concentrations and daily variations of VMS congeners measured in New York City. Median concentrations of the 6 studied congeners, D3 (20 ng m -3 ), D4 (57 ng m -3 ), D5 (230 ng m -3 ), D6 (11 ng m -3 ), L5 (2.5 ng m -3 ), and L7 (1.3 ng m -3 ) are among the highest reported outdoor concentrations in the literature to date. Average congener ratios of D5:D4 and D5:D6 were consistent with previously reported emissions ratios, suggesting that concentrations were dominated by local emissions. Measured concentrations agree with previously published results from a Community Multiscale Air Quality model and support commonly accepted emissions rates for D4, D5, and D6 of 32.8, 135, and 6.1 mg per capita per day. Concentrations of D4, D5, D6, L5, and L7 and total VMS were significantly lower during the day than during the night, consistent with daytime oxidation reactivity. Concentrations of D3 did not show the same diurnal trend but exhibited a strong directional dependence, suggesting that it may be emitted by industrial point sources in the area rather than personal care product use. Concentrations of all congeners had large temporal variations but showed relatively weak relationships with wind speed, temperature, and mixing height.

Siloxanes have been commonly used as additives in a variety of industrial and consumer products. Media and government investigations have revealed that defoamers containing siloxanes are used in the effluent of thermal power plants in Korea. However, investigations of the source impact of siloxane contamination from the discharge of thermal power plants into coastal environments are scarce. In this study, sediment and invertebrates were collected around a thermal power plant to assess source impact, seasonal variation, and a potential for bioaccumulation. Although siloxanes were detectable in sediment and invertebrates, the spatial distribution and composition (which differed between the siloxanes found in sediment and invertebrates and those in defoamer used in the plant) suggest they were likely transported by long-distance migration as well as the discharge of thermal power plant. Seasonal differences might affect sedimentary contamination and the bioaccumulation potential of siloxanes. Specifically, octamethylcyclotetrasiloxane (D4) may have limited adsorption capacity and potential for long-distance migration, as its contribution in sediment far from the coastline was greater than that of decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6). However, higher D5 accumulation in invertebrates, and D5 has a potential bioaccumulation. A molecular docking analysis showed that the binding affinity between D5 and the cytochrome enzyme in invertebrates was weaker than that with other siloxanes, which could lead to higher D5 accumulation in invertebrates., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Siloxanes, widely used in various consumer and industrial products, are emerging concerns of contaminants. Despite this, limited studies have been conducted on contamination and time trends on siloxanes in coastal environments. In the present study, four cyclic and 15 linear siloxanes were measured in sediments collected from an artificial saltwater lake in Korea during 2001-2016 to investigate contamination, time trends, and ecotoxicological concerns. Cyclic siloxanes were detected in all sediment samples, whereas linear siloxanes were not frequently detected. The highest siloxane concentrations were observed in creeks passing through various industrial complexes, indicating that industrial activities predominantly contributed to siloxane contamination in coastal environments. Decamethylcyclopentasiloxane (D5) and dodecylcyclohexasiloxane (D6) were predominant siloxanes in sediments over the last two decades. Siloxane concentrations significantly increased in creek sediments from 2008 to 2016, whereas those in inshore and offshore regions significantly decreased due to a strong dilution effect by the operation of tidal power plant. This suggests that consumption patterns and coastal development activities are crucial factors determining the contamination and time trends in the sedimentary siloxanes. The sedimentary concentrations of octamethylcyclotetrasiloxane (D4) and D5 exceeded several thresholds, raising the potentials for ecological risks to aquatic organisms., Competing Interests: Declaration of Competing Interest The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2023 The Authors. Published by Elsevier Inc. All rights reserved.)

Volatile methylsiloxanes (VMSs) are massively produced chemicals having applications in industry and home because of their physical and chemical characteristics. They are used in personal care products such as cosmetics, household coatings, cleaners, skin care products, and others. Resultantly, large number of VMSs are discharged into air where they can be subjected to atmospheric migrations over long distances causing toxic and estrogenic effects, persistence, and bioaccumulations. Many institutions have taken measures to control VMSs. They require accurate, rapid, and sensitive pretreatment and analysis methods for diverse samples. Herein, the pretreatment and determination methods of VMSs as reported in recent years are reviewed and summarized. Pretreatments include commonly methods such as membrane-assisted solvent extraction, liquid-liquid extraction, and others, while novel methods are solid phase extraction, solid phase microextraction, diverse liquid phase microextraction and others. Analyses are made through gas chromatography-based methods. In addition, the advantages, and disadvantages of techniques are compared, and the prospects of pretreatment and analysis methods are discussed.

The bioaccumulation behavior, including the uptake, internal distribution, depuration, and biotransformation rates, of three widely used linear methyl-siloxanes was investigated in rainbow trout. Dietary uptake efficiencies of octamethyltrisiloxane (L3), decamethyltetrasiloxane (L4), and dodecamethylpentasiloxane (L5) were 15% (3.3% standard error [SE]), 8.6% (1.4% SE), and 15% (1.8% SE), respectively, and for L3 and L4 were well below those of nonmetabolizable reference chemicals with similar octanol-water partition coefficients, suggesting significant intestinal biotransformation of L3 and L4. Somatic biotransformation rate constants were 0.024 (0.003 SE) day -1 for L3 and 0.0045 (0.0053 SE) day -1 for L4 and could not be determined for L5. Lipid-normalized biomagnification factors for L3, L4, and L5 were 0.24 (0.02 SE), 0.24 (0.01 SE), and 0.62 (0.05 SE) kg-lipid kg-lipid -1 , respectively. Bioconcentration factors standardized to a 5% lipid content fish for water in Canadian oligotrophic lakes with a dissolved organic carbon content of 7.1 mg L -1 were 2787 (354 SE) for L3, 2689 (312 SE) for L4, and 1705 (418 SE) L kg-wet weight -1 , respectively, and 3085 (392 SE) for L3, 4227 (490 SE) for L4, and 3831 (938 SE) L kg-wet weight -1 in water with a dissolved organic carbon content of 2.0 mg L -1 . A comparison of 238 bioaccumulation profiles for 166 different chemicals shows that the bioaccumulation profiles for L3, L4, and L5 are vastly different from those of other very hydrophobic compounds found in the environment. Environ Toxicol Chem 2024;43:42-51. © 2023 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC., (© 2023 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.)

Cyclic volatile methyl siloxanes (cVMS) are ubiquitous in hair care products (HCPs). cVMS emissions from HCPs are of concern, given the potential adverse impact of siloxanes on the environment and human health. To characterize cVMS emissions and exposures during the use of HCPs, realistic hair care experiments were conducted in a residential building. Siloxane-based HCPs were tested using common hair styling techniques, including straightening, curling, waving, and oiling. VOC concentrations were measured via proton-transfer-reaction time-of-flight mass spectrometry. HCP use drove rapid changes in the chemical composition of the indoor atmosphere. cVMS dominated VOC emissions from HCP use, and decamethylcyclopentasiloxane (D5) contributed the most to cVMS emissions. cVMS emission factors (EFs) during hair care routines ranged from 110-1500 mg/person and were influenced by HCP type, styling tools, operation temperatures, and hair length. The high temperature of styling tools and the high surface area of hair enhanced VOC emissions. Increasing the hair straightener temperature from room temperature to 210 °C increased cVMS EFs by 50-310%. Elevated indoor cVMS concentrations can result in substantial indoor-to-outdoor transport of cVMS via ventilation (0.4-6 tons D5/year in the U.S.); thus, hair care routines may augment the abundance of cVMS in the outdoor atmosphere.

Siloxanes and synthetic musk compounds (SMCs) have been widely used as additives in household and personal care products. Humans are easily exposed to siloxanes and SMCs originating from these products through ingestion and dermal absorption of indoor dust. In the present study, indoor dust samples were analyzed for 19 siloxanes (cyclic and linear) and 12 SMCs (polycyclic, macrocyclic, and nitro musks) to assess their occurrence, time trends over time, source, and health risks. A total of 18 siloxanes and 10 SMCs were detected in all indoor dust samples obtained from 2011⎯2021, indicating widespread and long-term contamination. Higher detection frequencies and concentrations were associated with siloxanes and SMCs with higher use and strong resistance against degradation processes. Indoor dust samples were dominated by linear siloxanes (L11-L13), 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-(g)-2-benzopyran (HHCB), musk ketone (MK), and 7-acetyl-1,1,3,4,4,6-hexamethyl-1,2,3,4-tetrahydronaphthalene (AHTN). The frequent use of household and personal care products is likely an important source of siloxane and SMC contamination in indoor environments. The concentrations of siloxanes and SMCs in indoor dust increased from 2011 to 2021, particularly, those of linear siloxanes, reflecting the impact of regulatory actions addressing cyclic siloxanes. The profiles of siloxanes remained stable throughout the study period, whereas those of SMCs shifted from nitro to polycyclic musks. The estimated daily intakes (EDIs) of siloxanes and SMCs arising from ingestion were greater than from dermal absorption of indoor dust. The EDIs of siloxanes and SMCs associated with indoor dust indicated that children are exposed to these pollutants., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Authors. Published by Elsevier Inc. All rights reserved.)

Volatile methylsiloxanes (VMSs) are a group of additives employed in different consumer products that can affect the quality of the biogas produced in wastewater treatment plants (WWTPs). The main objective of this study is to understand the fate of different VMSs along the treatment process of a WWTP located in Aveiro (Portugal). Thus, wastewater, sludge, biogas, and air were sampled in different units for two weeks. Subsequently, these samples were extracted and analyzed by different environment-friendly protocols to obtain their VMS (L3-L5, D3-D6) concentrations and profiles. Finally, considering the different matrix flows at every sampling moment, the mass distribution of VMSs within the plant was estimated. The levels of ∑VMSs were similar to those showed in the literature (0.1-50 μg/L in entry wastewater and 1-100 μg/g dw in primary sludge). However, the entry wastewater profile showed higher variability in D3 concentrations (from non detected to 49 μg/L) than found in previous studies (0.10-1.00 μg/L), likely caused by isolated releases of this compound that could be related to industrial sources. Outdoor air samples showed a prevalence of D5, while indoor air locations were characterized by a predominance of D3 and D4. Differences in sources and the presence of an indoor air filtration system may explain this divergence. Biogas was characterized by ∑VMSs concentrations (8.00 ± 0.22 mg/m 3 ) above the limits recommended by some engine manufacturers and mainly composed of D5 (89%). Overall, 81% of the total incoming mass of VMSs is reduced along the WWTP, being the primary decanter and the secondary treatment responsible for the highest decrease (30.6% and 29.4% of the initial mass, respectively). This reduction, however, is congener dependant. The present study demonstrates the importance of extending sampling periods and matrices (i.e., sludge and air) to improve sample representativity, time-sensitivity, and the accuracy of mass balance exercises., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Authors. Published by Elsevier Inc. All rights reserved.)

A simple mixing-pressing followed by thermal curing and pyrolysis process was used to upcycle coal waste into high-value composites. Three coal wastes of different physicochemical properties were investigated. The hypothetical mechanisms of bonding between the coal particles and the preceramic polymer are presented. The textural properties of the coals indicated that the lowest volatile coal waste (PCD) had a dense structure. This limited the diffusion and reaction of the preceramic polymer with the coal waste during pyrolysis, thereby leading to low-quality composites. The water contact angles of the composites up to 104° imply hydrophobic surfaces, hence, no external coating might be required. Analysis of the carbon phase confirmed that the amorphous carbon structure is prevalent in the composites compared to the coal wastes. The dc volume resistivity of the composites in the range of 22 to 82 Ω-cm infers that the composites are unlikely to suffer electrostatic discharge, which makes them useful in creating self-heating building parts. The leached concentrations of heavy metal elements from the composites based on the end-of-life scenario were below the Toxicity Characteristic Leaching Procedure regulatory limits. Additionally, the release potential or mobility of the metals from the composites was not influenced by the pH of the eluants used. On the basis of the reported results, these carbon/ceramic composites show tremendous prospects as building materials due to these properties., (© 2023. The Author(s).)

Comprehensive studies on emerging contaminants like volatile methyl siloxanes in settled dust from different micro-environments are still limited. In this study, concentrations and distribution of cyclic volatile methyl siloxanes (CVMSs) including D3, D4, D5, and D6 were examined in indoor dust samples collected from various micro-environments in northern and central Vietnam. Concentrations of total CVMSs in the dust samples ranged from 86.0 to 5890 (median 755) ng/g and decreased in the order: waste processing workshops (median 1560; range 329-5890) > common houses (650; 115-1680) > university classrooms (480; 86.0-1540) > vehicle repair shops (295; 126-1950) ng/g. This observation suggests that informal waste processing activities are sources of CVMSs. Among the studied CVMSs, D5 was the most predominant compound (41 ± 14%), followed by D6 (26 ± 13%), D4 (23 ± 12%), and D3 (11 ± 11%). Moderate positive correlations between D3/D4, D4/D5, and D5/D6 were found. Median daily intake doses of D3, D4, D5, and D6 through dust ingestion were 0.016, 0.051, 0.11, and 0.054 ng/kg/d, respectively, which were comparable to water consumption and markedly lower than the air inhalation pathway., (© 2022. The Author(s), under exclusive licence to Springer Nature B.V.)

The study reports on the atmospheric concentrations of per- and polyfluoroalkyl substances (PFAS) and volatile methyl siloxanes (VMS) measured using sorbent-impregnated polyurethane foam disks (SIPs) passive air samplers. New results are reported for samples collected in 2017, which extends temporal trend information to the period 2009-2017, for 21 sites where SIPs have been deployed since 2009. Among neutral PFAS, fluorotelomer alcohols (FTOHs) had higher concentrations than perfluoroalkane sulfonamides (FOSAs) and perfluoroalkane sulfonamido ethanols (FOSEs) with levels of ND‒228, ND‒15.8, ND‒10.4 pg/m 3 , respectively. Among ionizable PFAS, the sum of perfluoroalkyl carboxylic acids (PFCAs) and perfluoroalkyl sulfonic acids (PFSAs) in air were 0.128-781 and 6.85-124 pg/m 3 , respectively. Longer-chain i.e. C 9 -C 14 PFAS, which are relevant to the recent proposal by Canada for a listing of long-chain (C 9 -C 21 ) PFCAs to the Stockholm Convention, were also detected in the environment at all site categories including Arctic sites. Cyclic and linear VMS ranged between 1.34‒452 and 0.01-12.1 ng/m 3 , respectively, showing dominance in urban areas. Despite the wide range of levels observed across different site categories, geometric means of the PFAS and VMS groups were fairly similar when grouped according to the five United Nations regions. Variable temporal trends in air (2009-2017) were observed for both PFAS and VMS. PFOS, which has been listed in the Stockholm Convention since 2009, is still showing increasing tendencies at several sites, indicating constant input from direct and/or indirect sources. These new data inform international chemicals management for PFAS and VMS., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Crown Copyright © 2023. Published by Elsevier Ltd. All rights reserved.)

Field data from two latitudinal transects in Europe and Canada were gathered to better characterize the atmospheric fate of three cyclic methylsiloxanes (cVMSs), i.e. , octamethyl-cyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6). During a year-long, seasonally resolved outdoor air sampling campaign, passive samplers with an ultra-clean sorbent were deployed at 15 sampling sites covering latitudes ranging from the source regions (43.7-50.7 °N) to the Arctic (79-82.5 °N). For each site, one of two passive samplers and one of two field blanks were separately extracted and analyzed for the cVMSs at two different laboratories using gas-chromatography-mass spectrometry. Whereas the use of a particular batch of sorbent and the applied cleaning procedure to a large extent controlled the levels of cVMS in field blanks, and therefore also the method detection and quantification limits, minor site-specific differences in field blank contamination were apparent. Excellent agreement between duplicates was obtained, with 95% of the concentrations reported by the two laboratories falling within a factor of 1.6 of each other. Nearly all data show a monotonic relationship between the concentration and distance from the major source regions. Concentrations in source regions were comparatively constant throughout the year, while the concentration gradient towards remote regions became steeper during summer when removal via OH radicals is at its maximum. Concentrations of the different cVMS oligomers were highly correlated within a given transect. Changes in relative abundance of cVMS oligomers along the transect were in agreement with relative atmospheric degradation rates via OH radicals.

Mono-chlorinated products of cyclic volatile methylsiloxanes (cVMS), i.e., Monochlormet-hylheptamethylcyclotetrasiloxane [D3D(CH 2 Cl)], monochlormethylnonamethylcyclopenta-siloxane [D4D(CH 2 Cl)], and monochlormethylundemethylcyclohexasiloxane [D5D(CH 2 Cl)], were detected in water [

Methylsiloxanes are synthetic molecules with versatile and extensive applications. Because of their volatile properties, they are easily released from manufactured products and contaminate indoor environments, causing high human exposure. However, available information on their presence in specific microenvironments, and on the related potential risks for human health, is limited. We conducted a survey of sixteen methylsiloxanes species, including three cyclic (D 4 -D 6 ) and thirteen linear (L 4 -L 16 ) chemicals, in indoor dust samples from twenty-eight stores representative of six store categories in Beijing, China. Total methylsiloxane concentrations in store dust were 176-54,825 ng/g, depending on the store, with a median of 2196 ng/g. Linear chemicals represented a median proportion of 90.8% of total methylsiloxanes. The measured methylsiloxane concentrations in this study were marginally higher than those reported previously for standard living and working environments. The highest linear and total methylsiloxane concentrations were measured in electronic stores, while the highest cyclic methylsiloxane concentrations were measured in department stores. The presence of methylsiloxanes in the store dust samples was attributed mainly to their release from chemical additives in marketed products. Estimated median total exposure doses under normal and worst-case exposure scenarios were 0.237 and 0.888 ng/kg bw/d, respectively. Further investigation is needed to characterize methylsiloxane distribution in other microenvironments and to evaluate the associated health risks., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Inc. All rights reserved.)

Volatile methylsiloxanes (VMS) are a class of non-biodegradable anthropogenic compounds with propensity for long-range transport and potential for bioaccumulation in the environment. As a proof-of-principle for biological degradation of these compounds, we engineered P450 enzymes to oxidatively cleave Si-C bonds in linear and cyclic VMS. Enzymatic reactions with VMS are challenging to screen with conventional tools, however, due to their volatility, poor aqueous solubility, and tendency to extract polypropylene from standard 96-well deep-well plates. To address these challenges, we developed a new biocatalytic reactor consisting of individual 2-mL glass shells assembled in conventional 96-well plate format. In this chapter, we provide a detailed account of the assembly and use of the 96-well glass shell reactors for screening biocatalytic reactions. Additionally, we discuss the application of GC/MS analysis techniques for VMS oxidase reactions and modified procedures for validating improved variants. This protocol can be adopted broadly for biocatalytic reactions with substrates that are volatile or not suitable for polypropylene plates., Competing Interests: Declaration of competing interest The Dow Chemical Company and the California Institute of Technology have filed a patent application describing enzymatic siloxane degradation., (Copyright © 2023. Published by Elsevier Inc.)

In the present study, indoor and outdoor environments of a wastewater treatment plant (WWTP) were monitored by passive air samplers to assess the presence and seasonal trends of three linear (L3-L5) and four cyclic (D3-D6) volatile methylsiloxanes (VMSs). Furthermore, passive sampling rates (PSRs) were estimated from literature values to calculate VMSs air concentrations and occupational exposure to potentially toxic (D4-D6) congeners. Results showed a seasonal pattern of VMSs in outdoor locations (especially in the aeration tank and preliminary treatment), being the highest levels of total VMSs reached in Summer and the lowest in Spring, caused by the confluence of changing weather conditions and VMSs consumption patterns. This seasonality was not found in indoor sites. The congener profiles of VMSs were consistent throughout the year, showing a prevalence of D5 outdoors, and of D3 and D4 in strictly indoor environments. Different sources of VMSs, together with an air filtering system installed in the sampled buildings explain these differences. Estimated PSRs yielded lower values indoors (0.16-0.21 m 3 /day) than outdoors (0.32-0.49 m 3 /day), due to different wind speeds. Overall, outdoor locations showed higher VMSs concentrations in air than indoors. However, the values detected in both environments (∑VMSs between 8.00 and 2000 ng/m 3 ) were within the ranges described in the literature for these locations. The occupational exposure to D4-D6 estimated for three different activities in the WWTP showed the highest values for Maintenance Technicians (8010 ± 722 ng/(kg·year)) and the lowest for Laboratory Technicians (5410 ± 874 ng/(kg·year)), in direct correlation with the higher amount of time spent outdoors by the former. In any case, the exposure was below the inhalation threshold of 150 μg/(kg·day) proposed as safe by other authors., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

Monitoring studies that aim to quantify volatile methyl siloxanes (VMS) in environmental matrices may encounter a multitude of issues, most of which relate to the unique combination of physical-chemical characteristics of VMS that distinguish them from other classes of organic compounds. These properties, which are critical to their function in various applications, also control their fate and distribution in the environment, as well as the analytical chemistry of their measurement. Polycondensation and rearrangement reactions of VMS oligomers are possible during sample storage and analysis. Thus, care should be exercised to suppress these types of reactions by avoiding any catalytic substances or surfaces in sample collection and analysis equipment. Another factor complicating sample integrity in the analysis of trace levels of VMS, is their ubiquitous presence in many common products and components of instrumentation in the laboratory. For example, some gas chromatography columns and inlet septa have been identified as sources of VMS due to surface-catalyzed transformation of silicones to VMS promoted by moisture under high temperature in some silicone-based GC columns. Possible chemical transformation of the analytes, contamination from other sources, and potential loss of analytes need to be assessed throughout all aspects of the study, from sample collection through analysis, by establishing a rigorous quality assurance and quality control program. The implementation of such a robust QA/QC program facilitates the identification and minimization of potential analytical biases and ensures the validity and usability of data generated from environmental monitoring campaigns for VMS. The objective of this paper is to focus on aspects of collection, processing, and analysis of environmental samples that may influence the quality of the VMS analytical results. This information should then be employed in the design and implementation of future monitoring studies and can used to assess the validity of analytical results from VMS monitoring studies., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: R Gerhards, R Seston, and S Xu are independent consultants who received compensation for their time from the Global Silicones Council. The other authors are employed by member companies of the Global Silicones Council. The review paper could, therefore, have been subject to biases that could constitute a potential conflict of interest. However, we maintain that this review paper was constructed objectively and was not influenced by commercial or other drivers, from either funders or employers., (Copyright © 2022 The Authors. Published by Elsevier B.V. All rights reserved.)

Contamination of coastal environments by siloxanes is of growing concern. Sediment and bivalves were collected from 50 locations along the Korean coast to assess the geographical distribution, sources, and bioaccumulation potential of siloxanes. Cyclic and linear siloxanes were detectable in all sediment and bivalve samples. The highest siloxane concentrations were detected in sediment (656 ng/g dw) and bivalves (3273 ng/g dw) from highly industrialized bays and harbor-zones, suggesting that industrial and shipping activities are major sources of siloxanes in coastal environment. The geographical distribution of siloxanes was similar in sediment and bivalves. Sedimentary siloxanes were dominated by cyclic siloxanes, while linear siloxanes were predominant in bivalves. Bioaccumulation of linear siloxanes in bivalves originated mainly from the sedimentary environment. Mean biota-sediment accumulation factors (BSAFs) of seven siloxanes ranged from 1.26 to 6.03, indicating potential for bioaccumulation. This is the first report on the nationwide survey on siloxanes in Korean coastal waters., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

Volatile methyl siloxanes (VMS) are ubiquitous in indoor environments due to their use in personal care products. This paper builds on previous work identifying sources of VMS by synthesizing time-resolved proton-transfer reaction time-of-flight mass spectrometer VMS concentration measurements from four multiweek indoor air campaigns to elucidate emission sources and removal processes. Temporal patterns of VMS emissions display both continuous and episodic behavior, with the relative importance varying among species. We find that the cyclic siloxane D5 is consistently the most abundant VMS species, mainly attributable to personal care product use. Two other cyclic siloxanes, D3 and D4, are emitted from oven and personal care product use, with continuous sources also apparent. Two linear siloxanes, L4 and L5, are also emitted from personal care product use, with apparent additional continuous sources. We report measurements for three other organosilicon compounds found in personal care products. The primary air removal pathway of the species examined in this paper is ventilation to the outdoors, which has implications for atmospheric chemistry. The net removal rate is slower for linear siloxanes, which persist for days indoors after episodic release events. This work highlights the diversity in sources of organosilicon species and their persistence indoors.

Methylsiloxanes (MSs) are widely used as solvents or emollients in various personal care products (PCPs) and may pose a health risk. In this study, we assessed external and internal exposure to MSs among students at two universities in southwestern China. Samples of air, dust, and PCPs were collected to evaluate indoor non-dietary exposure to MSs via multiple pathways among the students. Indoor MS levels were approximately 1-3 orders of magnitude higher in the dormitories of female students than in either classrooms or the dormitories of male students. Lipstick contained the highest MS levels. Cyclic MS (CMS: D4-D6) levels were 1 order of magnitude higher in female students than in male students. Among the three CMSs, D5 levels were highest in the plasma of all students (1.3-15 ng/mL). In dormitories, dermal contact with PCPs was the major route of exposure to CMSs for all students. Among linear MSs (LMSs: L5-L16), dermal PCP absorption and dust ingestion were the predominant exposure routes for male and female students, respectively. Although the overall risk of exposure to D4 and D5 was below the chronic reference dose for all exposure routes and all students, the total daily doses of exposure to D4 and D5 via dermal PCP absorption approached the chronic reference dose in four female students. Therefore, the effects of MSs on female students should be further investigated in future studies., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Methylsiloxanes (MSs), used in industrial production and personal care products, are released in various environmental media. In this study, we combined monitoring and modeling to investigate the occurrence and behavior of MSs in the urban environment in China. MSs were widely found in the air, water, soil and sediment of four cities in China. The concentrations of MSs in all four environmental media of Zhangjiagang were higher than those in the other three cities (Beijing, Kunming and Lijiang), indicating that the siloxane production plant had a significant impact on the pollution level of MSs in the surrounding environment. The samples with high MS concentrations were all from the sample sites near the outlet of the WWTPs, which showed that the effluent of the WWTPs was the main source of MS pollution in the surrounding environment. The modeling results of the EQC level III model showed that D4 discharged into the environment was mainly distributed in the air, while D5 and D6 were mainly distributed in the sediment. CMSs (D4-D6) discharged into various environmental media could exist in the urban environment for a long time with low temperatures in cities. When the temperature was 0 °C, the residence time of D5 and D6 could be 68.1 days and 243 days in the whole environmental system in Beijing. This study illustrates the importance of CMSs (D4-D6) in low-temperature environments and the potential environmental risks that they may pose.

The growing global energy demand requires the continuous development and optimization of the production of alternative energy sources. According to the circular economy approach, waste conversion into biogas and biomethane represent an interesting energy source. The input into the distribution network and energy conversion systems of biomethane requires quality monitoring and the use of cleaning up systems. Therefore, there is a need to constantly invest in the development of sampling and analysis systems that save time, costs, and materials. The purpose of this study was to use activated porous carbon fiber (APCF), an extremely versatile material for sampling and analysis by thermal desorption, to show the advantages it has over the adsorbents traditionally used for siloxane monitoring. Siloxanes are among the contaminating compounds that are mainly present in biogas and biomethane, and if not removed sufficiently, they endanger the quality and use of the gas. These are highly harmful compounds since during combustion, they produce quartz particles that are abrasive to the surfaces of the materials involved in the energy production process. In addition, siloxanes directly hinder the energy properties of biomethane during combustion, due to their radical scavenger properties. In this work, the efficiency of APCF tube was evaluated by comparing it with common multilayer tube thought sampling and analyzing siloxanes in lab scale and in real scale (biogas plant). Thermal desorption analysis coupled with GC-MS for the determination of siloxanes showed that the use of APCF allows to obtain better performance. This allows to deduce that APCF is an innovative material for the establishment of a better sampling and analysis method than the current ones, enabling better results to be achieved in the process of monitoring fuel quality in biomethane production and storage facilities.

In this report, four cVMSs including hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) were determined in 85 sediment samples collected from three rivers in northern Vietnam during the period from May to November 2020. Total mean concentrations of cVMSs ranged from 75.4 to 15,000 ng/g-dw. The highest levels of cVMS were found in sediment samples collected from the To Lich River (range, 260-15,000 ng/g-dw; median, 2840 ng/g-dw), followed by the Nhue River (range, 188-6800 ng/g-dw; median, 1370 ng/g-dw), and the Day River (range, 75.4-4600 ng/g-dw; median, 666 ng/g-dw). Among cVMSs, decamethylcyclopentasiloxane (D5) was found at the highest levels in all samples and ranged from 9.00 to 11,000 ng/g-dw. Significant correlations exist between the concentrations of D4/D6 and D5/D6 pairs in river sediment samples. Although the calculated ecological risk was not high, the presence of cVMSs in the sediment raises concerns about the impact on aquatic life because of their long-term accumulation capacity., (© 2022. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Despite the extensive usage of synthetic musk compounds (SMCs) and siloxanes in various personal care products (PCPs), trophic magnification of such chemicals in aquatic environments remains unexplored. In June and September 2020, eleven SMCs and nineteen siloxanes were measured in water, sediments, and biota. Samples were collected from two sites where levels were expected to be influenced by the distance from the wastewater treatment plant (WWTP) in the Geum River, Republic of Korea, were expected. High concentrations of SMCs and siloxanes entered through WWTP were measured in water, sediment, and biota at the both sites and both seasons. The δ 15 N of amino acids provided a high-resolution food web and accurate trophic position (TP), which is an important factor for determining the trophic magnification factor (TMF). Among 24 TMFs, 19 of them were <1, ranging 0.7-0.8 for 1,3,4,6,7,8‑hexahydro‑4,6,6,7,8,8‑hexamethyl‑cyclopenta‑γ‑2‑benzopyran (HHCB), 0.6-0.8 for 6-Acetyl-1,1,2,4,4,7-hexamethyltetralin (AHTN), 0.7-0.8 for 4-tert-Butyl-3,5-dinitro-2,6-dimethylacetophenone (MK), 0.7-0.9 for octamethylcyclotetrasiloxane (D4), 0.1-0.4 for decamethylcyclopentasiloxane (D5), and 0.04-0.8 for dodecamethylcyclohexasiloxane (D6), and the remaining ones including HHCB, AHTN, MK, and D4 showed values close to 1 or slightly higher (TMF range: 1.0-2.3) indicating no or a little trophic magnification. The TMFs of these compounds were constant across sites and seasons. The TMF values of PCPs might be affected by species specificity and food web structure rather than by chemical properties such as log K ow , which describes a wide range of TMF values in various environments. This study presents valuable implications for assessing risk and managing environmental fate and trophic transfer of SMCs and siloxanes in freshwater environments., (Copyright © 2022 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Microalgae are widely used in the bioremediation of wastewaters due to their efficient removal of pollutants such as nitrogen, phosphorus, and contaminants of emerging concern (CECs). Siloxanes are CECs that reach wastewater treatment plants (WWTPs), leading to the production of biogas enriched with these compounds, associated with the breakdown of cogeneration equipment. The biological removal of siloxanes from wastewaters could be a sustainable alternative to the costly existing technologies, but no investigation has been performed using microalgal cultures for this purpose. This study evaluated the ability of Chlorella vulgaris to bioremediate primary (PE) and secondary (SE) urban effluents and remove volatile methylsiloxanes (VMSs). C. vulgaris grew successfully in both effluents, and approximately 86% of nitrogen and 80% of phosphorus were efficiently removed from the PE, while 52% of nitrogen and 87% of phosphorus were removed from the SE, and the presence of VMSs does not seem to have a negative influence on nutrient removal. Three out of the seven of the analysed VMSs were detected in the microalgal biomass at the end of the PE assay. However, dodecamethylcyclohexasiloxane (D6) was the one that accumulated to a greater extent, since 48% of the initial mass of D6 was detected in the biomass samples. D6 is one of the most lipophilic VMSs, which might contribute to the higher adsorption onto the surface of microalgae. Overall, the results indicate C. vulgaris ' potential to remove specific VMSs from effluents.

The bioaccumulation of cyclic volatile methylsiloxanes (D3 to D6) as well as linear siloxanes (L3 to L5) was studied in a food web in the St. Lawrence River downstream of the effluent of the municipal wastewater treatment plant in Montreal, Canada. For most species, differences in δ 15 N in fish and prey showed a clear separation of individual fish feeding in food webs influenced by the wastewater plume from those feeding outside the plume. Cyclic siloxanes were detected in all biotic samples from the individuals identified as feeding in the effluent plume. Siloxane D5 accounted for more than 80% of the total siloxanes. Linear siloxane L5 was also abundant in walleye and gull eggs. Total siloxane concentrations in suspended sediments were 17.3 times higher than in surface sediments in the region of the river in the effluent plume. Caged freshwater mussels (Elliptio sp.), placed in the effluent plume, bioaccumulated 43 times more total siloxanes than PBDEs in 30 days, demonstrating how readily siloxanes are taken up in biota and what a significant component of the contaminant body burden they can account for. The sediment-biota accumulation factors (BSAF) for total siloxanes (∑ D3 to D6 and L3 to L5) showed values of 65.4, 27.8, 9.9 and 6.4 for walleye, northern pike, yellow perch and round goby respectively., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Crown Copyright © 2021. Published by Elsevier B.V. All rights reserved.)

We investigated mass loading and the spatial distribution of volatile methylsiloxanes (VMSs) including four cyclic VMSs (D3-D6; cVMSs, the number refers to the number of SiO bonds) and three linear VMSs (L3-L5; lVMSs) in Tokyo Bay, Japan, which is one of the most industrialized, urbanized, and populated areas in the world. Based on the VMS concentrations determined in eight main inflow rivers to the bay, the mass loading of VMSs via inflow rivers and sewage treatment plants located in Tokyo Bay was estimated at 2500 kg/y for total VMSs. Elevated mass loadings of VMSs were found in three of the rivers, inflowing to the inner west of Tokyo Bay. The distribution and deposition characteristics of VMSs were observed depending on the estuarine condition. Estuarine sediments were found to be efficient and effective traps for VMSs and the salting-out effect is one possible mechanism to explain this phenomenon. The overall profiles of D4, D5, and D6 in surface water and sediment were observed across Tokyo Bay; elevated concentrations were identified in the inner west bay with dispersed low concentrations in the outer bay, except for one hotspot of D4 in the sediment, indicating a major emission route of VMSs via inflow rivers. Additionally, the historical pollution profiles of VMSs in Tokyo Bay were reconstructed based on the VMS concentrations determined in a dated sediment core. VMSs were identified throughout the upper 40 cm of the sediment core (representing the mid 1980s); the profiles correspond with the historical use of VMSs in wash-off personal care-products. The noted decreasing trend of D4 might be a reflection of the early 2000s replacement of D4 with D5 in such products. The elevated VMS concentrations in the estuarine sediment raise concerns about the impact on the aquatic environment., Competing Interests: Declaration of competing interest To the best of our knowledge, the named authors have no conflict of interest, financial or otherwise., (Copyright © 2021 Elsevier B.V. All rights reserved.)

The occurrence and distribution of cyclic and linear siloxanes were investigated in South Korean river water and sediment, with a special focus on crucian carp tissues, to evaluate the residual status and potential bioaccumulation of siloxanes. The total siloxanes median concentrations observed in this study were 1495 ng/L in river water, 39.2 ng/g-dry weight [dw] in sediment, and 41.7 ng/g-wet weight [ww] in crucian carp muscle. Cyclic siloxanes (D3-D6) were predominant in all matrices, and D5 (mean: > 81%) was more abundant in biota tissues than in river water (30%) and sediment (26%) samples. Specifically, positive correlations between D5 concentrations and crucian carp sizes (p < 0.01, Spearman) as well as the relatively high estimated biota-sediment accumulation factor value of D5 (D5: 2.31), suggest the high bioaccumulative property of D5 in biota. However, no bioaccumulation potentials were observed for D3, D4, D6, and L3-L17 in this field-scale study. The distributions of major linear siloxanes (L7-L14) in crucian carp gills (17%) and gonads (21%) were higher than in other tissues (brain, 9.6%; liver, 2.6%; muscle, 1.5%). Moreover, relatively high tissue/plasma ratios were observed for linear siloxanes (L7-L10: 1.79-2.12) compared to cyclic siloxanes (D4-D6: 0.829-1.18) (p < 0.01, Mann Whitney U test), which indicated the higher transportability of linear siloxanes to fish tissues than cyclic siloxanes., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Trophic magnification of cyclic volatile methyl siloxanes (cVMS) in a terrestrial food web was investigated by measuring concentrations of octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) and two reference chemicals within air and biota samples from an avian food web located in a mixed urban-agricultural landscape. Terrestrial trophic magnification factors derived from lipid normalized concentrations (TMF L s) for D5 and D6 were 0.94 (0.17 SE) and 1.1 (0.23 SE) and not statistically different from 1 ( p > 0.05); however, the TMF L of D4 was 0.62 (0.11 SE) and statistically less than 1 ( p < 0.001). TMF L s of PCB-153 and p,p' -DDE were 5.6 (2.2 SE) and 6.1 (2.8 SE) and statistically greater than 1 ( p < 0.001). TMF L s of cVMS in this terrestrial system were similar to those reported in aquatic systems. However, trophic magnification factors derived on a fugacity basis (TMF F s), which recognize differences in body temperature and lipid composition between organisms, were greater than corresponding TMF L s primarily because a temperature-induced thermodynamic biomagnification of hydrophobic chemicals occurs when endothermic organisms consume poikilothermic organisms. Therefore, we recommend that biomagnification studies of food webs including endothermic and poikilothermic organisms incorporate differences in body temperature and tissue composition to accurately characterize the biomagnification potential of chemicals.

Methylsiloxanes are widely found in the environment and have been of increasing concern because of their strong resistance to degradation and potential toxicity to organisms. However, little is known about the distributions of these chemicals in street dust and the associated human health risks. This study investigated three cyclic (D 4 -D 6 ) and nine linear methylsiloxanes (L 5 -L 13 ) in street dust from Hefei, China and found total concentrations in the range of 183-1030 (median, 527) ng/g dry weight. The linear congeners were dominant and represented a median of 85.3% of the total methylsiloxanes. D 5 contributed 90.0% of the total concentrations of cyclic methylsiloxanes. In this study, higher concentrations of dust methylsiloxanes were found in the industrial area relative to the other functional areas. A source assessment indicated that the linear and cyclic methylsiloxanes in the street dust were mainly from the industrial and traffic activities, respectively, in addition to important sources of the use of siloxanes-containing products. The estimated median daily intakes of total methylsiloxanes through street dust were 0.037 and 0.476 ng/kg-bw/d for adults and children, respectively, under high-exposure scenarios. More research is needed to characterize the occurrence of methylsiloxane in various exposure sources and the associated adverse effects on human health., (Copyright © 2021 Elsevier Inc. All rights reserved.)

Methyl siloxanes are widely found in the environment, but little is known about the distributions of these chemicals in soils especially in areas where they are manufactured. We determined the concentrations of four cyclic (D 3 -D 6 ) and 13 linear methyl siloxanes (L 4 -L 16 ) in the soils from a siloxane-manufacturing site in China; the total concentrations of these 17 siloxanes (TSi) in the soils were 17.1-3,191 (median, 134) ng/g. We did not find extremely high concentrations of siloxanes in the soils. The median concentrations of total cyclic siloxanes (TCSi) were approximately sevenfold higher than those of total linear congeners. Hexamethylcyclotrisiloxane and octamethylcyclotetrasiloxane contributed a median of 59.7% and 20.3% of the TSi concentrations, respectively. Higher concentrations of soil TCSi were found in the silicone-manufacturing area relative to the other study areas. Source analysis indicated that industrial activities contributed substantially to soil siloxanes, in addition to the contribution of the siloxane emissions from specific consumer products. We calculated that the median values of daily TSi intakes through soil ingestion were 0.021 and 0.138 ng/kg-body weight/day for adults and children, respectively, under high exposure scenarios. Although our estimated daily intakes of the chemicals from soils were low, more research is required to improve our understanding of the health risks posed to humans exposed to siloxanes through other pathways., (© 2021. The Author(s), under exclusive licence to Springer Nature B.V.)

In this study, four cyclic volatile methylsiloxanes (cVMSs) were determined in drinking water, tap water, surface water, and wastewater samples collected from Hanoi metropolitan area, Vietnam, during August to December 2020 (dry season) by using solid phase extraction combined with gas chromatography tandem mass spectrometry. Highest concentrations of cVMSs in the range of 63-7400 ng/L (mean/median: 1840/1310 ng/L) were found in wastewater samples. A significant difference existed in the concentrations of cVMSs between influent and effluent of a wastewater treatment plant. The sum concentrations of four cVMSs in lake water, tap water, and bottled water samples were in the ranges of 67.0-1100 ng/L (mean/median: 350/282 ng/L), 19.8-350 ng/L (12.6/12.3 ng/L), and 2.31-28.1 ng/L (10.3/8.23 ng/L), respectively. Among the four cVMSs, decamethylcyclopentasiloxane (D5) was found at the highest concentrations in all water samples analyzed. The mean exposure doses of cVMSs calculated for adults and children through the consumption of drinking were 0.409 and 0.412 ng/kg-bw/day, respectively. Human exposure to cVMSs calculated through drinking water consumption was significantly lower than that reported for inhalation., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Methylsiloxanes (MSs) are a significant source of indoor environmental pollution due to their high production level and widespread application, and pose a potential health risk. Given the special vulnerability of children to environmental contaminants, assessment of indoor MSs exposure in children is quite essential. In this study, we assessed internal exposure doses and external exposure levels of MSs in children from industrial and residential areas in southwestern China. Indoor air, indoor dust, and personal care product (PCP) samples were collected to evaluate indoor non-dietary MSs exposure in children through various pathways. The concentrations of MSs in indoor environments of industrial areas were approximately one to four orders of magnitude higher than those of residential areas. Sun protection products contained the highest concentrations of MSs. Relatively high levels of cyclic methylsiloxanes (CMSs) were found in plasma of children from industrial areas, which were one to two orders of magnitude higher than those in children from residential areas. The highest MSs levels in plasma were detected in infants (0-1 year), with values of 1.4 × 10 2 ng/mL and 1.3 × 10 2 ng/mL for CMSs (D4-D6) and linear methylsiloxanes (LMSs) (L5-L16), respectively. The internal exposure dose of infants in residential areas is driven by major unknown sources of MSs. The average daily doses via inhalation and dust ingestion in children from industrial areas were one to three orders of magnitude higher than in those from residential areas, indicating that these children should be considered a highly exposed population. Inhalation and dust ingestion were both major exposure pathways to MSs for children of all age groups in industrial areas, whereas dermal absorption from PCPs was the predominant exposure pathway for children of all age groups in residential areas (except for infants). Although the exposure risk to D4 and D5 was at an acceptable level for all children studied, the total daily exposure doses of these two cyclic compounds via inhalation for infants in the industrial areas was near the chronic reference dose. Meanwhile, MSs may accumulate in infant plasma within a short period of time (<6 months). Therefore, infants should be the focus of greater attention in future research. As indoor environments may pose high risks for infants in industrial areas, they should be the focus of future research., (Copyright © 2021 The Authors. Published by Elsevier Ltd.. All rights reserved.)

The ecological harm from methylsiloxanes has drawn worldwide attention. This study investigated three cyclic (D 4 -D 6 ) and four linear siloxanes (L 7 -L 10 ) in the eggs of free-range poultry collected near a rural industrial park in China and found total concentrations in the range of 19.2-1204 (median, 268) ng/g dry weight. Higher concentrations of methylsiloxanes were observed in chicken eggs than duck eggs. Cyclic siloxanes represented a median of 62.2% of the total methylsiloxane concentrations. A source assessment indicated that local soils and outdoor dust were more important sources of egg methylsiloxanes than poultry food. The partitioning of methylsiloxanes between egg yolk and egg albumen was investigated, and preferential distributions of the chemicals in the yolk were observed. This study confirmed that methylsiloxanes were highly prevalent in the study poultry eggs. The results suggested that the potential risks to some wild birds inhabiting this area should be of concern, as their physiologies and feeding ecologies are similar to those of the studied poultry, although available ecotoxicological data of the chemicals to birds remains scarce. Additional research is needed to characterize the accumulation of methylsiloxanes in different bird species and its associated adverse effects on their offspring., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Available information on the bioaccumulation and trophodynamics of cyclic methylsiloxanes in aquatic food webs is insufficient for a reliable understanding of their toxicity and potential ecological harm. The concentrations of four cyclic methylsiloxanes in aquatic species collected from Lake Chaohu (China) were measured and the total concentration was in range of 2.01-36.1 ng/g dry weight. Dodecamethylcyclohexasiloxane (D6) represented 57.7% of the total measured methylsiloxane concentration. The distribution of these methylsiloxanes constitute the first tissue-specific record. The hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4) and decamethylcyclopentasiloxane (D5) tended to accumulate preferentially in fish muscles, while D6 was preferentially accumulated in fish liver and gills. In Lake Chaohu, significant trophic magnification of D3 (p < 0.01) and dilution of D6 (p < 0.05) were observed, and the trophic magnification factors (TMFs) were estimated at 4.94 and 0.68, respectively. No significant trends in D4 and D5 (p > 0.05) were observed within the food web. This study further confirmed the complexity of trophic transfer of the methylsiloxanes in the aquatic food web. The findings suggest that tissue-specific methylsiloxane distribution in aquatic species might also affect the observed TMFs. More research is required to investigate methylsiloxanes in additional species and their trophodynamics in different food webs., (Copyright © 2021 Elsevier B.V. All rights reserved.)

High concentrations (1.08 ng/g-3.61 mg/g) of methylsiloxanes, including cyclic analogs [octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6)], and linear analogs with 3-14 silicon atoms (L3-L14), have been detected in crude oil, additives and petroleum products from one petroleum refinery facility in China. Overall, the total mass load of Σmethylsiloxanes (1320 kg/day) in crude oil and additives was 1.5 times higher than that in petroleum products (857 kg/day), indicating their potential emissions in this facility, which were further confirmed by the find of their obvious emission through exhaust-gas (89.4 kg/day) and wastewater (4.70 kg/day). Σmethylsiloxanes emission from exhaust-gas discharge outlets of deep catalytic cracking units (60.6 kg/day) took up 68% of their total emission from all gas outlets. Overall, Σmethylsiloxanes in air (17.1-743 μg/m 3 ) and soil samples [311 ng/g dw (dry weight) - 34.2 μg/g dw] from this facility were up to four orders of magnitude greater than those from surrounding areas, and plasma concentrations of Σmethylsiloxanes in current workers from this facility (7.4-609 ng/mL) were up to two orders of magnitude larger than those from reference group (

Volatile methylsiloxanes (VMSs) constitute a group of compounds used in a great variety of products, particularly personal care products. Due to their massive use, they are continually discharged into wastewater treatment plants and are increasingly being detected in wastewater and in the environment at low concentrations. The aim of this work was to develop and validate a fast and reliable methodology to screen seven VMSs in water samples, by headspace solid-phase microextraction (HS-SPME) followed by gas chromatography with flame ionization detection (GC-FID). The influence of several factors affecting the extraction efficiency was investigated using a design of experiments approach. The main factors were selected (fiber type, sample volume, ionic strength, extraction and desorption time, extraction and desorption temperature) and optimized, employing a central composite design. The optimal conditions were: 65 µm PDMS/Divinylbenzene fiber, 10 mL sample, 19.5% NaCl, 39 min extraction time, 10 min desorption time, and 33 °C and 240 °C as extraction and desorption temperature, respectively. The methodology was successfully validated, showing low detection limits (up to 24 ng/L), good precision (relative standard deviations below 15%), and accuracy ranging from 62% to 104% in wastewater, tap, and river water samples.

A new passive sampling method was developed and characterized to measure atmospheric volatile methyl siloxanes (VMS). The infrastructure of a commercial passive air sampler (PAS) was used along with XAD-2 resin as the adsorbent. Experimental sampling rates (SR) determined using collocated active and passive samplers ranged between 0.0363 (L5) and 0.0561 (D3) m 3 /day and agreed well with the theoretical ones. VMS uptake was highly linear for eight weeks. The precision of the method was very good (<10%). Compared to the other PASs used for VMS, the new method has several advantages (i.e., the sampler is much smaller, it has commercially available components, and the solvent requirement, equipment needed for extraction, and steps for sample preparation are minimal) while achieving similar or lower method detection limits. The developed method was applied to investigate the spatial distribution and possible sources of atmospheric VMS in the Izmir region. Field sampling covered 42 sites representing different source and land use areas. ΣVMS concentrations ranged between 41.4 and 981 ng/m 3 . The dominant VMS was D5 followed by D3 and D4. Spatial distributions indicated that the main VMS sources in the area were urban areas, wastewater treatment plants, and landfills where the VMS-containing products are used and disposed.

Methyl siloxanes are identified as emerging persistent toxic compounds and the ecological environment risks of these compounds have been caused of great concern worldwide. In this study, the concentrations of methyl siloxanes were reported in dissolved water and crucian carp around a methyl siloxane production factory located in Liaoning Province, Northeast China. D4, D5, D6, D7, L4, L5 and L6 were detectable both in dissolved water and crucian carp. The total concentrations of 7 methyl siloxanes (Σ 7MS ) were 14 ± 6.3 ng/L in dissolved water and 43 ± 22 ng/g ww in crucian carp, respectively. D5 has the highest concentration both in dissolved water (5.5 ± 3.5 ng/L) and crucian carp (17 ± 11 ng/g ww). Based on the monitoring values, bioaccumulation factor (BAF) of these compounds were calculated. Significant bioaccumulation potential was observed for D4 (BAF = 5900 ± 3500 L/kg) based on the bioaccumulation criteria suggested by USEPA and EU (BAF > 5000 L/kg). To our understanding, this is the first report of BAF values of methyl siloxane in field study, which will provide important support for further assessment of bioaccumulation of these compounds., (Copyright © 2021 The Authors. Published by Elsevier Inc. All rights reserved.)

Methyl siloxanes are becoming increasingly prevalent in the environment because of their extensive use in various consumer products. Little is known about the distribution of these chemicals around factories or their presence in road dust. We conducted a survey of four cyclic (D 3 -D 6 ) and 13 linear (L 4 -L 16 ) siloxanes in road dusts around a manufacturing site and found a total siloxane concentration range of 47.3-3.16 × 10 3  ng/g (median 372). The predominant siloxanes in the road dust samples were D 3 , D 4 , D 5 , and D 6 , with median contributions of 65.3%, 17.9%, 6.36%, and 2.16% of the total siloxane concentrations, respectively. Our reported concentrations were comparable to those found in household dusts in previous studies. No high concentrations of siloxanes were observed in the road dust samples from the manufacturing site, which suggests that siloxanes in outdoor dusts are likely affected by many factors. Under a high exposure scenario, the daily intakes of total siloxanes via road dust ingestion at the 95th percentile were 2.13 and 0.313 ng/kg-bw/day for children and adults, respectively. Although the estimated exposure to siloxanes in outdoor dust for humans was low, more studies on the distributions and risks of siloxanes released from manufacturing sites are needed.

A new approach of siloxane sampling based on impinger, micro-impinger, adsorption on active carbon, and direct TedlarBag methods followed by gas chromatography-mass spectrometry (GC-MS) was developed for the analysis of three linear (L2-L4) and four cyclic (D3-D5) volatile methyl siloxanes (VMSs). Three kinds of organic liquid-medium characterized by different polarities, namely acetone, methanol, and d-decane as siloxanes trap were arranged in the experiment which is widely discussed below. Thus, the GC-MS equipped with SUPELCOWAX-10 capillary column was employed to perform monitoring of VMS content in the analyzed biogas samples originating from landfill, wastewater treatment plants, and agriculture biogas plants. In all samples that have undergone the analysis, cyclic and linear VMSs were found in quantities exceeding 107.9 and 3.8 mg/m 3 , respectively. Significant differences between siloxanes concentrations depending on biogas origin were observed. Moreover, the high range of linearity (0.1 to 70.06 mg/m 3 ), low LoD (0.01 mg/m 3 ), low LoQ (0.04 mg/m 3 ), and high recovery (244.1%) indicate that the procedure and can be applied in sensitive analyses of silica biogas contaminants. In addition to the above, the impinger method of sampling performed better than active-carbon Tube and TedlarBag, particularly for quantifying low concentrations of siloxanes. Overall, the evaluation of sampling methods for biogas collection simplified the analytical procedure by reducing the procedural steps, avoiding the use of solvents, as well as demonstrated its applicability for the testing of biogas quality.

Contamination status and distribution characteristics of ten phthalic acid esters (PAEs) and three cyclic volatile methyl siloxanes (CSs) were determined in the air (gas and particle) samples collected from indoor and outdoor spaces of several chemistry laboratories, offices, and homes from urban area of Hanoi, the capital city of Vietnam. Air concentrations of Σ10PAEs (median 688; range 142-2390 ng m -3 ) and Σ3CSs (171; not detected-1100 ng m -3 ) in the indoor air samples were significantly higher than those measured in the outdoor ones (Σ10PAEs: 161; 34.1-515 ng m -3 and Σ3CSs: 43.2; not detected-258 ng m -3 ), partly suggesting the predominance of indoor emission sources of these substances. There were significant positive correlations in total air concentrations of phthalates and siloxanes between the indoor and outdoor air samples. The most predominant phthalates were diethyl-, di-n-butyl-, diisobutyl-, and di(2-ethylhexyl) phthalate. For siloxanes, D5 and D6 were more abundant than D4 in most samples. Except for di(2-ethylhexyl)- and di-n-octyl phthalate in some locations, almost all the compounds were likely associated with gas phase than particle phase. Daily intake doses of airborne phthalates and siloxanes, and non-cancer and cancer risks of selected phthalates were estimated for different exposure groups such as adults, children, and university subjects (e.g., laboratory staff and students), indicating relatively low levels of risk., Competing Interests: Declaration of competing interest The authors declare no competing financial interest., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Passive air samplers comprising sorbent-Tenax-TA thermal desorption tubes were applied for monitoring cyclic volatile methyl siloxanes (cVMSs) in the air above the aeration tanks of eight wastewater treatment plants (WWTPs, including five "open" and three "close" plants) in Dalian, China. The aim was to investigate the inputs of cVMSs from WWTPs to the air throughout a year (June 2016-July 2017). The ∑cVMS concentrations were averaged at 3.14 ± 6.84 μg·m - ³ with D5 as the dominant compound (contributing to 63.8% of the ∑cVMS concentration). The annual average concentrations of D4, D5, and D6 in the air of the "close" WWTPs were 5.33 ± 4.63, 13.4 ± 14.4, and 1.05 ± 1.47 μg·m - ³, and 1.31 ± 1.29, 1.57 ± 2.01, and 0.301 ± 0.340 μg·m - ³ in the air from the "open" WWTPs, respectively. For both the close and open aeration tanks, the concentration of ∑cVMSs was the highest in summer and the lowest in winter, showing a significant correlation with ambient temperature (linear regression; p < 0.01). A simplified Gaussian dispersion model and a single chamber model were introduced to estimate annual emissions (kg·yr -1 ) of cVMSs from "open" and "close" WWTPs, ranging from 86.9 to 165 kg yr -1 and from 203 to 278 kg yr -1 , respectively. Examining the relationship between the per capita emissions of cVMSs and average property prices, our results indicated that a greater amount of personal care products were used/discharged by people with relatively higher socioeconomic status., Competing Interests: Declaration of competing interest The authors declare no competing financial interest., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Methylsiloxanes (MSs) are ubiquitous in indoor air and pose an important health risk. Thus, assessments of indoor inhalation exposure by measuring MSs levels in plasma are needed. In this study, we measured plasma MSs concentrations and evaluated daily indoor inhalation exposure in potentially exposed populations, including residents of industrial areas, university campus, and residential areas, all located in southwestern China. The concentrations of MSs in indoor air (gas-phase and PM 2.5 ) collected from factory housing and from girls' dormitories on university campus were approximately one to three orders of magnitude higher than in parallel samples from other areas. The consequences of MSs exposure were investigated by measuring MSs levels in the plasma samples of the exposed populations. Relatively high levels of cyclic MSs (CMSs: D4-D6) were found in the plasma of the co-resident family members of factory workers and in female college students living in campus dormitories. The highest levels of CMSs (D4-D6) and linear MSs (L5-L16), 2.3 × 10 2 and 2.0 × 10 2 ng/mL, respectively, were detected in the very young (0-3 years old) co-resident children of factory workers. The average daily dose via inhalation (ADD inh ) in different groups showed that the ADD inh values of all MSs (D4-D6, L5-L16) were one to two orders of magnitude higher in the co-resident family members of factory workers and in female college students than in other groups, indicating that both populations should be considered as potentially highly exposed to MSs. A further assessment showed that inhalation exposure is the main source of CMSs (D4-D6) in plasma for people exposed to high indoor air levels of these compounds. Although the health risk assessment showed that the health risk from inhalation exposure to D4 and D5 was acceptable for all of the studied groups based on the current chronic reference dose (cRfD), the maximum ADD inh,CMSs value in 0- to 3-year-old children was only 7.9-fold below the cRfD. Because the toxicity of other MSs is unknown, the potential health risk of MSs to very young children via inhalation exposure should be further analysed., (Copyright © 2020 The Author(s). Published by Elsevier Ltd.. All rights reserved.)

Active sampling methodology for atmospheric monitoring of cyclic volatile methylsiloxanes (cVMS) was improved to reduce sampling artifacts. A new sorbent, ABN Express (ABN), was evaluated for storage stability and measurement accuracy. Storage stability of cVMS on ABN showed less than 1% degradation of the individual 13 C-labelled octamethylcyclotetrasiloxane ( 13 C 4 -D4), decamethylcyclopentasiloxane ( 13 C 5 -D5) and dodecamethylcyclohexasiloxane ( 13 C 6 -D6) after 14 days storage at room temperature and at -20 °C whereas significant degradation was observed on ENV+ sorbent at room temperature (37-62 %) and -20 °C (9-16 %). 13 C 4 -D4 formed on ENV+ spiked with 13 C 5 -D5, and both 13 C 4 -D4 and 13 C 5 -D5 formed on ENV+ spiked with 13 C 6 -D6. However, this was not observed on the ABN sorbent. Performance of ABN was compared to ENV+ through an 8-month Arctic sampling campaign at the Zeppelin Observatory (Ny Ålesund, Svalbard). Good agreement between ABN and ENV+ was observed for D4 in the spring/summer months. However, D5 and D6 was found to be consistently higher on the ABN sorbent during this time period with D6 showing the greatest deviation. During the winter months, larger deviations were observed between ABN and ENV+ sorbents with a factor of 4 times higher atmospheric concentrations of both D5 and D6 found on ABN; indicating sorbent related degradation on ENV+. Our findings show that the ABN sorbent provides greater stability and accuracy for atmospheric monitoring of cVMS. Implications of these improvements towards atmospheric fate processes will be discussed., Competing Interests: Declaration of competing interest The authors declare no competing financial interests., (Copyright © 2020 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Cyclic volatile methylsiloxaes (cVMSs), namely hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6), were studied for a typical indoor environment of male and female dormitories in the campus of Dalian Maritime University (DMU) in China. An empty, frit-fitted SPE cartridge was placed on top of an Isolute ENV + cartridge, sampling cVMSs in particulate and gas phases, respectively. The highest concentration of D3, D4, D5, and D6 was 190, 460, 37,000, and 670 ng m -3 , respectively. All cVMSs, especially D5, were higher in female dormitories than that in male dormitories. Emission rate from different sources of cVMSs in dormitories was calculated from a survey of the use of personal care products (PCPs) by students living in the dormitory during the sampling period. The mean emission rate (ER, mg·d -1 ) of D4 and D5 in male dormitories was 0.12 ± 0.01 and 0.49 ± 0.03 mg d -1 , respectively, and that in female dormitories was 0.21 ± 0.05 and 46 ± 17 mg d -1 , respectively. Then, we modified an existing mass balance model to predict the indoor air levels of D4 and D5 in both male and female dormitories based on the usage of PCPs. There was a good agreement for D4 and D5 concentrations in female dormitories between modeled and measured concentrations with the ratio of predicted to measured values to be 1.5 and 1.2, respectively, which indicated that use of PCPs was the main source of cVMSs in university dormitories., Competing Interests: Declaration of competing interest The authors declare no competing financial interest., (Copyright © 2020 Elsevier Ltd. All rights reserved.)