Cyclic Volatile Methylsiloxanes Research Articles

Presence, behaviour, and risk assessment of volatile methylsiloxanes in wastewater: A year-long comprehensive study within a wastewater treatment plant

The awareness of possible environmental hazards caused by the widespread global use of volatile methylsiloxanes (VMSs) in personal care products (PCPs) and industrial processes has been increasing. Sewage containing these compounds may reach wastewater treatment plants (WWTPs), which are hotspots of their release into the environment. The levels, distribution, and potential risks of VMSs were studied in an unprecedently comprehensive sampling strategy (four seasonal campaigns) along the water line of a WWTP: the main influent entrance (SA1), after the preliminary treatment (SA2), after the primary treatment (SA3) and after the secondary treatment (the treated effluent; SA4). This WWTP was selected as a representative of the conventional set up based on a secondary treatment, allowing a similar approach in numerous facilities worldwide. Seven VMSs (L3, L4, L5, D3, D4, D5, D6) were analysed in wastewater samples by a small-scale liquid-liquid extraction (LLE) protocol, followed by gas chromatography–mass spectrometry (GC–MS), and the cyclic VMSs were dominant at all sampling sites and in all seasons. Considering the whole year, the total VMSs ranged from 0.4 to 22.5 μg L−1 for SA1, 0.03 to 33.7 μg L−1 for SA2, below method detection limit (MDL) to 13.2 μg L−1 for SA3 and <MDL to 0.8 μg L−1 for SA4. D5 prevailed, together with D6 and D4. The mean VMS mass flows dropped from 119 g day−1 in SA1 to 1.9 g day−1 in SA4, resulting in high removal efficiencies from the water line (>98 %). According to the risk quotients (RQ), only 18 SA4 samples (32 %) presented a minimal risk to the receiving media (0.01 ≤ RQ < 0.1). However, considering the absence of a secondary treatment or a direct discharge without treatment, there may be a risk to the environment.

The Stockholm Convention at a Crossroads: Questionable Nominations and Inadequate Compliance Threaten Its Acceptance and Utility.

Twenty years since coming into force, the Stockholm Convention has become a "living" global agreement that has allowed for the addition of substances that are likely, as a result of their long-range environmental transport (LRET), to lead to significant adverse effects. The recent listing of the phenolic benzotriazole UV-328 in Annex A and a draft nomination of three cyclic volatile methylsiloxanes (cVMS) for Annex B draw attention to the fact that many chemicals are subject to LRET and that this can lead to questionable nominations. The nomination of UV-328 and the draft nomination of cVMS also raise the spectre of regrettable substitutions. At the same time, atmospheric monitoring across the globe reveals that environmental releases of several unintentionally produced POPs listed in Annex C, such as hexachlorobenzene and hexachlorobutadiene, are continuing unabated, highlighting shortcomings in the enforcement of the minimum measures required under Article 5. There is also no evidence of efforts to substitute a chemical whose use has been known for three decades to unintentionally produce polychlorinated biphenyls. These developments need to be rectified to safeguard the long-term viability and acceptance of a global treaty of undeniable importance.

Batch equilibrium experiments and modeling reveal weak temperature dependence of cyclic volatile methylsiloxane sorption in soil/sediment organic carbon-water systems

The organic carbon normalized partition coefficient, KOC, describes the equilibrium distribution of a chemical between water and organic carbon in soil or sediment. It is a key parameter in evaluating chemical persistence, mass distribution, and transport using multimedia fate and transport models. Considerable uncertainty remains about the KOC values of cyclic volatile methylsiloxane (cVMS) compounds, and in particular the dependence of KOC on temperature. In this study, we used a batch equilibrium (BE) method to measure KOC values and their temperature dependence between ∼5 and 25 °C for octamethylcyclotetrasiloxane (D4) and decamethylcyclopentasiloxane (D5) with soil and sediments. Approximate log KOC values at 25 °C were 4.5–5.0 for D4 and 5.5–6.1 for D5 with different sorbents, and decreased by 0.3 log units or less at 4–5 °C. Enthalpies of sorption, ΔHOC, obtained for the different sorbents ranged from +7.2 to +16 kJ mol−1, with average values of +7.9 and +13 kJ mol−1 for D4 and D5, respectively. These values differ in magnitude and direction from those reported elsewhere based on KOC values determined by a novel dynamic purge-and-trap (PnT) method, but are consistent with predictions based on their solvation properties. A new fugacity-based multimedia model incorporating sorption/desorption kinetics was developed and used to predict concentrations in the phases of BE and PnT systems during desorption of cVMS under different experimental and ideal conditions. Model simulations suggested that KOC values for cVMS compounds derived from the PnT systems could be influenced by sorption disequilibrium between water and solids controlled by desorption rates from the particle phase to water, and subsequent losses due to volatilization and degradation. This has the potential to result in overestimation of KOC values when fitting the experimental data of cVMS mass remaining in a PnT system over time, which could explain the observed differences between the methods.

Are Cyclic Volatile Methylsiloxanes POPs? For Rigorous Science in Regulatory Decision Making.

Are Cyclic Volatile Methylsiloxanes POPs? For Rigorous Science in Regulatory Decision Making.

Distribution and spatial variation of volatile methylsiloxanes in surface water and wastewater from the Yangtze River Basin, China

Volatile methylsiloxanes (VMSs) earned serious concerns due to their detection and toxicities after their release to the environments. They were also detected in rivers around the globe, but their distribution remained to be explored in larger rivers with longer length, higher water volume and wider watershed. In the present study, 8 cyclic VMSs (cVMSs) and 7 linear ones (lVMSs) were investigated in 42 water samples (27 surface water (including 7 drinking source water) and 15 wastewater) from the Yangtze River Basin, China. Results showed that VMSs were detected in all sampling sites. In surface water, the concentrations of total cVMSs ranged from 17.3 to 4.57 × 103 ng/L, while those of lVMSs ranged from 1.72 to 81.6 ng/L. In wastewater, the total concentrations of cVMSs and lVMSs showed ranges of 17.6–1.66 × 103 ng/L and 2.59–252 ng/L, respectively. Apparently, cVMSs showed significantly higher concentrations than lVMSs. The concentrations of cVMSs followed an order of lower > upper > middle reaches, while those of lVMSs did not show clear distribution patterns. Among cVMSs, those with less Si numbers were dominant, while those with more Si numbers were dominant in lVMSs. Notably, the VMSs were also detected in 7 surface waters that served as drinking source waters, which earned them further concerns. In addition, the VMSs in surface water showed positive correlation with those in wastewater, which led to necessity in management on industrial emissions in the future.

Interference of the gas chromatography- mass spectrometry instrumental background on the determination of trace cyclic volatile methylsiloxanes and exclusion of it by delayed injection

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.

Directed evolution of enzymatic silicon-carbon bond cleavage in siloxanes.

Volatile methylsiloxanes (VMS) are man-made, nonbiodegradable chemicals produced at a megaton-per-year scale, which leads to concern over their potential for environmental persistence, long-range transport, and bioaccumulation. We used directed evolution to engineer a variant of bacterial cytochrome P450BM3 to break silicon-carbon bonds in linear and cyclic VMS. To accomplish silicon-carbon bond cleavage, the enzyme catalyzes two tandem oxidations of a siloxane methyl group, which is followed by putative [1,2]-Brook rearrangement and hydrolysis. Discovery of this so-called siloxane oxidase opens possibilities for the eventual biodegradation of VMS.

Determination of cyclic volatile methylsiloxanes in sludge samples collected from To Lich River, Hanoi, Vietnam

Cyclic volatile methylsiloxanes (cVMSs) are synthesis chemicals used widely in consumer products such as building materials, households, electrical and medical devices, and personal care products. Due to being used in many applications, cVMSs are released into various micro-environments. Recently, the pollution level of cVMSs in the environment including sewage sludge has been gradually concerned. In this work, four typical cVMSs: hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylhexasiloxane (D6) were measured in 20 sludge samples collected from a sewage river (To Lich River) in Ha Noi metropolitan by using the gas chromatography-tandem mass spectrometry (GC-MS) method. The method detection limits (MDLs) and the method qualification limits (MQLs) of cVMSs in sewage sludge were a range of (1.20-3.00) ng/g-dw (dry weight) and (3.60-9.00) ng/g-dw, respectively. Recoveries of the surrogate compound (tetrakis-(trimethyl siloxane)-silane: M4Q) in blank and real samples were from (89.4 to 112) % (RSD: 9.2 %). The total concentrations of cVMSs in sewage sludge samples from To Lich River ranged from (260 to 13,800) ng/g-dw. Among the studied cVMSs, D5 was found at the highest levels in a range of (150-6,040) ng/g-dw. To our knowledge, this is the first report on the occurrence of cVMSs in sewage sludge samples in Ha Noi as well as Vietnam. The results indicate that the distribution of cVMSs in environments is significantly high and further studies should be conducted. ® 2023 Journal of Science and Technology - NTTU

Unraveling the distribution characteristic of cyclic volatile methylsiloxanes in various environmental media of a wastewater treatment plant

Cyclic volatile methylsiloxane (cVMS) is extensively used in consumer products and frequently detected in various environmental media, including water and air. In this study, we developed reliable and convenient methods to sample three cVMS compounds: octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) in water and air samples collected from different tanks within a wastewater treatment plant (WWTP). The concentrations of D4, D5, and D6 in the water samples ranged from 0.40 to 8.0 μg L−1, 0.35 to 91 μg L−1, and 0.54 to 17 μg L−1, respectively. In the air samples, these concentrations varied from 0.34 to 20 μg m−3, 0.34 to 128 μg m−3, and 0.08 to 12 μg m−3, respectively. It is worth noting that the air-water distribution coefficient (Kaw) for these three cVMS exhibited a strong correlation with their water solubility. Moreover, fugacity fractions indicated a net evaporation process from water to the atmosphere. Furthermore, we investigated the distribution of cVMS between the gaseous and particulate phases. The results revealed a significant fraction, exceeding 72 %, of cVMS resided in the gas phase. D4 and D5 predominate in the gaseous phase, while D5 and D6 are the principal constituents within the particulate phase. The distribution coefficient characterizing the partitioning of cVMS compounds between the gaseous and particulate (Kp) exhibited a strong correlation with their corresponding octanol-air partitioning coefficients (Koa). These findings contribute to a better understanding of the distribution of cVMS in diverse environmental media and the underlying mechanism governing their dispersion.

Volatile Methyl Siloxane Atmospheric Oxidation Mechanism from a Theoretical Perspective─How is the Siloxanol Formed?

Despite several investigations on the atmospheric fate of cyclic volatile methyl siloxanes (VMS), the oxidation chemistry of these purely anthropogenic, high production volume compounds is poorly understood. This led to uncertainties in the environmental impact and fate of the oxidation products. According to laboratory measurements, the main VMS oxidation product is the siloxanol (a -CH3 replaced with an -OH); however, none of the mechanisms proposed to date satisfactorily explain its formation. Motivated by our previous experimental observations of VMS oxidation products, we use theoretical quantum chemical calculations to (1) explore a previously unconsidered reaction pathway to form the siloxanol from a reaction of a siloxy radical with gas-phase water, (2) investigate differences in reaction rates of radical intermediates in hexamethylcyclotrisiloxane (D3) and octamethylcyclotetrasiloxane (D4) oxidation, and (3) attempt to explain the experimentally observed products. Our results suggest that while the proposed reaction of the siloxy radical with water to form the siloxanol can occur, it is too slow to compete with other unimolecular reactions and thus cannot explain the observed siloxanol formation. We also find that the reaction between the initial D3 peroxy radical (RO2•) with HO2• is slower than previously anticipated (calculated as 3 × 10-13 cm3 molecule-1 s-1 for D3 and 2 × 10-11 cm3 molecule-1 s-1 for D4 compared to the general rate of ∼1 × 10-11 cm3 molecule-1 s-1). Finally, we compare the anticipated fates of the RO2• under a variety of conditions and find that a reaction with NO (assuming a general RO2• + NO bimolecular rate constant of 9 × 10-12 cm3 molecule-1 s-1) will likely be the dominant fate in urban conditions, while isomerization can be important in cleaner environments.

Siloxane Emissions and Exposures during the Use of Hair Care Products in Buildings.

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.

Co-occurrence of phthalic acid esters (PAEs) and cyclic volatile methylsiloxanes (cVMSs) in fine particulate matter (PM0.5 and PM0.1) collected from an industrial area in Vietnam

Distribution patterns of 10 phthalic acid diesters (PAEs) and four cyclic volatile methylsiloxanes (cVMSs) were investigated in fine particulate matter (PM0.1 and PM0.5) collected from Bac Ninh, an industrial province in Vietnam during September–October in 2021. Total concentrations of PAEs found in PM0.1 and PM0.5 were in the ranges of 1.76–372 (median: 34.0 ng/m3) and 2.23–895 ng/m3 (median: 15.4 ng/m3), respectively. Among PAEs, di-n-butyl phthalate (DBP) was the most abundant compound found in PM0.1, whereas, di-2-(ethyl)hexyl phthalate (DEHP) was measured at the highest concentration in PM0.5. Total concentrations of cVMSs measured in PM0.1 and PM0.5 were in the ranges of method quantification limit (MQL)–203 (median: 2.10 ng/m3) and MQL–537 ng/m3 (median: 0.389 ng/m3), respectively. Among cVMSs, decamethylcyclopentasiloxane (D5) was found at the highest concentration in both PM0.1 and PM0.5 fractions of particulate matter. The concentration ratios between PAEs and cVMSs in PM0.1/PM0.5 were greater than 1 (except di-n-octyl phthalate: DnOP), suggesting that these chemicals tend to sorb to PM0.1 more preferentially than PM0.5. Among sampling locations, high concentrations of PAEs and cVMSs were found at traffic intersections (Que Vo district) and a craft village (Tu Son city). Relatively stronger correlations existed between cVMSs pairs in PM0.1 and PM0.5 (correlation coefficient: 0.73–1) than those of PAEs (−0.83–0.90). The human exposure doses to PAEs and cVMSs through inhalation of particulate matter were estimated based on the measured concentrations in PM0.1 and PM0.5 fractions. The estimated exposure doses of PAEs and cVMSs for infants (7.1 ng/kg-bw/d and 2.5 ng/kg-bw/d) were higher than those for adults (2.6 ng/kg-bw/d and 0.9 ng/kg-bw/d).

Determination of cyclic volatile methylsiloxanes in sludge samples collected from To Lich River, Hanoi, Vietnam

Cyclic volatile methylsiloxanes (cVMSs) are synthesis chemicals used widely in consumer products such as building materials, households, electrical and medical devices, and personal care products. Due to being used in many applications, cVMSs are released into various micro-environments. Recently, the pollution level of cVMSs in the environment including sewage sludge has been gradually concerned. In this work, four typical cVMSs: hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylhexasiloxane (D6) were measured in 20 sludge samples collected from a sewage river (To Lich River) in Ha Noi metropolitan by using the gas chromatography-tandem mass spectrometry (GC-MS) method. The method detection limits (MDLs) and the method qualification limits (MQLs) of cVMSs in sewage sludge were a range of (1.20-3.00) ng/g-dw (dry weight) and (3.60-9.00) ng/g-dw, respectively. Recoveries of the surrogate compound (tetrakis-(trimethyl siloxane)-silane: M4Q) in blank and real samples were from (89.4 to 112) % (RSD: 9.2 %). The total concentrations of cVMSs in sewage sludge samples from To Lich River ranged from (260 to 13,800) ng/g-dw. Among the studied cVMSs, D5 was found at the highest levels in a range of (150-6,040) ng/g-dw. To our knowledge, this is the first report on the occurrence of cVMSs in sewage sludge samples in Ha Noi as well as Vietnam. The results indicate that the distribution of cVMSs in environments is significantly high and further studies should be conducted.&#x0D; ® 2023 Journal of Science and Technology - NTTU

Association of volatile methylsiloxanes exposure with non-alcoholic fatty liver disease among Chinese adults

Owing to the wide use of volatile methylsiloxanes (VMSs) in various industries and consumer products, both cyclic VMSs (cVMS) and linear VMSs (lVMS) have been detected in human plasma. Experimental studies suggest that exposure to cVMSs may induce liver disease. Whereas, there is no human evidence of the potential health effects of VMSs yet.In this cross-sectional study, we evaluated the association of plasma VMSs concentrations with liver enzymes and Nonalcoholic fatty liver disease (NAFLD) among adults located in southwestern China. We used the fibrosis 4 calculator (FIB-4) as the NAFLD index and defined FIB-4≥1.45 as the NAFLD case.Among 372 participants, 45 (12.1%) of them were classified as NAFLD. Positive associations of plasma cVMSs concentrations with liver enzymes and NAFLD were observed among all participants. With per doubling increase in the total cVMSs, we observed a 1.40 (95%CI: 0.31, 2.48) increase in Alanine aminotransferase (ALT), a 1.56 (95%CI: 0.52, 2.61) increase in aspartate aminotransferase (AST) and a 0.04 (0.00, 0.09) increase in NAFLD index. A 19% increased risk of NAFLD was also found to be associated with per doubling increase in total cVMSs. In addition, positive associations of total lVMSs with ALT, AST and NAFLD were also detected when restricting our analyses to 230 participants living in industrial areas. Our study first provides epidemiological evidence on the association between VMSs and liver health, indicating more careful usage of VMSs may potentially reduce the burden of NAFLD, though more well-designed cohort studies are needed to confirm these findings.

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

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

Cyclic volatile methyl siloxanes (D4, D5, and D6) as the emerging pollutants in environment: environmental distribution, fate, and toxicological assessments.

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.

Comparison of the Yield and Chemical Composition of Secondary Organic Aerosol Generated from the OH and Cl Oxidation of Decamethylcyclopentasiloxane

Cyclic volatile methyl siloxanes (cVMS) that are emitted from industrial processes and consumer products often dominate the burden of volatile organic compounds (VOCs) in occupied spaces. cVMS may contribute to oxygenated VOC and secondary organic aerosol (SOA) formation following oxidation by gas-phase radicals in both indoor and outdoor source regions. Several recent studies examined the SOA formation potential of decamethylcyclopentasiloxane (D5) following exposure to hydroxyl radicals (OH) and found that this reaction generates SOA in high yield following multiple days of oxidative aging. Chlorine atoms (Cl) may compete with OH for the oxidative loss of D5 in indoor and outdoor source regions with active chlorine chemistry, but the SOA formation potential of D5 + Cl reactions has not been studied. Here, we characterized the yield and chemical composition of SOA generated from Cl oxidation of D5 in an oxidation flow reactor (OFR) under dry [relative humidity (RH) < 5%] and humid (RH = 40%) conditions and compared results to the yield and composition of SOA generated from OH oxidation of D5. D5 was oxidized using integrated OH and Cl exposures (OHexp and Clexp) ranging from 1.1 × 1012 to 8.2 × 1012 cm–3 s and from 1.6 × 1010 to 1.6 × 1012 cm–3 s, respectively. Like OH, Cl facilitated multistep SOA oxidative aging over the range of OFR conditions that were studied, with maximum SOA mass yields of 1.5 and 1.3 obtained following OH and Cl oxidation of D5 under humid conditions. These results suggest that indoor and outdoor source regions that are significantly influenced by chlorine chemistry may enhance the atmospheric SOA formation potential of D5.

Seasonal and latitudinal variability in the atmospheric concentrations of cyclic volatile methyl siloxanes in the Northern Hemisphere.

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.

Research progress of the POP fugacity model: a bibliometrics-based analysis.

With the emergence of environmental issues regarding persistent organic pollutants (POPs), fugacity models have been widely used in the concentration prediction and exposure assessment of POPs. Based on 778 relevant research articles published between 1979 and 2020 in the Web of Science Core Collection (WOSCC), the current research progress of the fugacity model on predicting the fate and transportation of POPs in the environment was analyzed by CiteSpace software. The results showed that the research subject has low interdisciplinarity, mainly involving environmental science and environmental engineering. The USA was the most paper-published country, followed by Canada and China. The publications of the Chinese Academy of Sciences, Lancaster University, and Environment Canada were leading. Collaboration between institutions was inactive and low intensity. Keyword co-occurrence analysis showed that polychlorinated biphenyls, organochlorine pesticides, and polycyclic aromatic hydrocarbons were the most concerning compounds, while air, water, soil, and sediment were the most concerning environmental media. Through co-citation cluster analysis, in addition to the in-depth exploration of traditional POPs, research on emerging POPs such as cyclic volatile methyl siloxane and dechlorane plus were new research frontiers. The distribution and transfer of POPs in the soil-air environment have attracted the most attention, and the regional grid model based on fugacity has been gradually improved and developed. The co-citation high-burst detection showed that the research hotspots gradually shifted from pollutant persistence and long-range transport potential to pollutant distribution rules among the different environmental media and the long-distance transmission simulation.

Seasonal occurrence, concentrations, and occupational exposure to VMSs in different environments of a WWTP

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 m3/day) than outdoors (0.32–0.49 m3/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/m3) 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.