Methylsiloxanes from Vehicle Emissions Detected in Aerosol Particles.

Methylsiloxanes have gained growing attention as emerging pollutants due to their toxicity to organisms. As man-made chemicals with no natural source, most research to date has focused on volatile methylsiloxanes from personal care or household products and industrial processes. Here, we show that methylsiloxanes can be found in primary aerosol particles emitted by vehicles based on aerosol samples collected in two tunnels in São Paulo, Brazil. The aerosol samples were analyzed with thermal desorption-proton transfer reaction-mass spectrometry (TD-PTR-MS), and methylsiloxanes were identified and quantified in the mass spectra based on the natural abundance of silicon isotopes. Various methylsiloxanes and derivatives were found in aerosol particles from both tunnels. The concentrations of methylsiloxanes and derivatives ranged 37.7-377 ng m-3, and the relative fractions in organic aerosols were 0.78-1.9%. The concentrations of methylsiloxanes exhibited a significant correlation with both unburned lubricating oils and organic aerosol mass. The emission factors of methylsiloxanes averaged 1.16 ± 0.59 mg kg-1 of burned fuel for light-duty vehicles and 1.53 ± 0.37 mg kg-1 for heavy-duty vehicles. Global annual emissions of methylsiloxanes in vehicle-emitted aerosols were estimated to range from 0.0035 to 0.0060 Tg, underscoring the significant yet largely unknown potential for health and climate impacts.

Distribution of methylsiloxanes in benthic mollusks from the Chinese Bohai Sea.

Methylsiloxanes are a class of silicone compounds that have been widely used in various industrial processes and personal care products for several decades. This study investigated the spatial distribution of three cyclic methylsiloxanes (D4-D6) and twelve linear methylsiloxanes (L5-L16) in mollusks collected from seven cities along the Bohai Sea. D4-D6 (df = 71%-81%) and L8-L16 (df = 32%-40%) were frequently detectable in the mollusk samples, while L5-L7 were not found in any mollusk samples. Cyclic methylsiloxanes (D4-D6) were found in mollusks with the mean concentrations of 15.7 ±â€¯12.3 ng/g ww for D4, 24.6 ±â€¯15.8 ng/g ww for D5 and 34.0 ±â€¯23.0 ng/g ww for D6. Among the seven sampling cities, the cyclic methylsiloxanes were predominant in mollusks, with the total cyclic methylsiloxanes (sum of D4-D6, ∑CMS) accounting for 74.2%-80.7% of the total methylsiloxanes. ∑CMS along the coastline demonstrated a clear gradient, with the highest concentrations in mollusks at the sampling sites located in the western part of the Bohai Sea and the lowest concentrations in mollusks from cities located in the eastern part of the Bohai Sea. The biota-sediment accumulation factors for cyclic methylsiloxanes (D4-D6) and linear methylsiloxanes (L8-L16) were estimated as 0.42 ±â€¯0.06-0.53 ±â€¯0.06 and 0.13 ±â€¯0.03-0.19 ±â€¯0.05, respectively.

Exposure to cyclic volatile methylsiloxanes (cVMS) causes anchorage-independent growth and reduction of BRCA1 in non-transformed human breast epithelial cells.

Dermal absorption of components of personal care products (PCPs) may contribute to breast cancer development. Cyclic volatile methylsiloxanes (cVMS) are used widely in the formulation of PCPs, and their presence has been recently detected in human blood. The objectives of this study were to investigate any genotoxic effects after short- (1 week) or longer-term (30 weeks) exposure to hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4) or decamethylcyclopentasiloxane (D5) in MCF-10 A and MCF-10F immortalized non-transformed human breast epithelial cells. Genotoxic effects were assessed by an ability of cells to grow in suspension culture, from DNA damage measured by comet assays, and from a reduction in levels of DNA repair proteins measured by RT-PCR and western immunoblotting. Dose-dependent anchorage-independent growth in methocel culture was observed after exposure to D3 (10-13 M-10-5 M) and D4/D5 (10-9 M-10-5 M). DNA damage was measured by the comet assay after 1-h exposure to D3 (10-6 M-10-5 M) and D4 (10-5 M). BRCA1 mRNA and BRCA1 protein levels were reduced after 30-week exposure to 10-5 M D4 and D5 in both cell lines. Reduced levels of mRNAs for other DNA repair proteins (BRCA2, ATM, ATR, CHK1 and CHK2) were also observed after exposure to 10-5 M D5 in both cell lines, and some reductions after exposure to D3 and D4. If cVMS can not only enable anchorage-independent growth of non-transformed breast epithelial cells and damage DNA, but also compromise DNA repair systems, then there is the potential for them to impact on breast carcinogenesis. Further risk assessment now requires information concerning the extent to which cVMS may be present in human breast tissues. Copyright © 2016 John Wiley & Sons, Ltd.

Preparation and characterization of high molecular weight vinyl-containing poly[(3,3,3-trifluoropropyl)methylsiloxane.

Prior to crosslinking and vulcanization, fluorosilicone rubber is a linear polymer. This linear polymer contains 3,3,3,-trifluoropropyl methyl siloxane links, a few methyl vinyl siloxane links, and is formed by co-polymerization of 1,3,5-trimethyl-1,3,5-tris(3,3,3-trifluoropropyl) cyclotrisiloxane (D3F) with 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane (V4) under alkaline conditions. To improve the performance of fluorosilicone rubber, three key points should be considered during the synthesis of vinyl-containing high-molecular-weight linear fluorosilicone polymers (fluorosilicone raw rubber): first, avoid the generation of low molecular weight equilibrium by-products; second, eliminate the influence of impurities; and third, increase the copolymerization participation rate of monomer V4. From the three aspects above, this study optimized the reaction conditions for the synthesis of high-molecular-weight linear fluorosilicone polymers containing vinyl. Various factors influencing polymerization were thoroughly investigated. These factors include the initiation system, accelerator, equilibrium reaction, feeding ratio, feeding sequence, neutralization mode, impurity content, etc.

Occurrence and Behavior of Methylsiloxanes in Urban Environment in Four Cities of China.

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.

Application of multimedia models for understanding the environmental behavior of volatile methylsiloxanes: Fate, transport, and bioaccumulation.

Multimedia fate and transport models (MFTMs) describe how chemicals behave in the environment based on their inherent properties and the characteristics of receiving systems. We critically review the use of MFTMs for understanding the behavior of volatile methylsiloxanes (VMS). MFTMs have been used to predict the fate of VMS in wastewater treatment, rivers, lakes, marine systems, and the atmosphere, and to assess bioaccumulation and trophic transfers. More widely, they have been used to assess the overall persistence, long-range transport potential (LRTP), and the propensity for atmosphere-surface exchange. The application of MFTMs for VMS requires particularly careful selection of model inputs because the properties of VMS differ from those of most organic compounds. For example, although n-octanol/water partition coefficient (KOW ) values are high, air:water partition coefficient (KAW ) values are also high and n-octanol/air partition coefficient (KOA ) values are relatively low. In addition, organic carbon/water partition coefficient (KOC ) values are substantially lower than expectations based on KOW . This means that most empirical relationships between KOC and KOW are not appropriate. Good agreement between modeled and measured concentrations in air, sediment, and biota indicates that our understanding of environmental fate is reasonable. VMS compounds are "fliers" that principally partition to the atmosphere, implying high LRTP, although they have low redeposition potential. They are degraded in air (half-lives 3-10 days) and, thus, have low overall persistence. In water, exposure can be limited by hydrolysis, volatilization, and partitioning to sediments (where degradation half-lives are likely to be high). In food webs, they are influenced by metabolism in biota, which tends to drive trophic dilution (i.e., trophic magnification factors are often but not always <1). Key remaining uncertainties include the following: (i) the strength and direction of the temperature dependence for KOC ; (ii) the fate of atmospheric reaction products; and (iii) the magnitude of emissions to wastewater. Integr Environ Assess Manag 2022;18:599-621. © 2021 The Authors. Integrated Environmental Assessment and Management published by Wiley Periodicals LLC on behalf of Society of Environmental Toxicology & Chemistry (SETAC).

A large contribution of methylsiloxanes to particulate matter from ship emissions.

The chemical and stable carbon isotopic composition of the organic aerosol particles (OA) emitted by a shuttle passenger ship between mainland Naples and island Capri in Italy were investigated. Various methylsiloxanes and derivatives were found in particulate ship emissions for the first time, as identified in the mass spectra of a thermal desorption - proton transfer reaction - mass spectrometer (TD-PTR-MS) based on the natural abundance of silicon isotopes. Large contributions of methylsiloxanes to OA (up to 59.3%) were found under inefficient combustion conditions, and considerably lower methylsiloxane emissions were observed under cruise conditions (1.2% of OA). Furthermore, the stable carbon isotopic composition can provide a fingerprint for methylsiloxanes, as they have low δ13C values in the range of -44.91‰ ± 4.29‰. The occurrence of methylsiloxanes was therefore further supported by low δ13C values of particulate organic carbon (OC), ranging from -34.7‰ to -39.4‰, when carbon fractions of methylsiloxanes in OC were high. The δ13C values of OC increased up to around -26.7‰ under cruise conditions, when carbon fractions of methylsiloxanes in OC were low. Overall, the δ13C value of OC decreased linearly with increasing carbon fraction of methylsiloxanes in OC, and the slope is consistent with a mixture of methylsiloxanes and fuel combustion products. The methylsiloxanes in ship emissions may come from engine lubricants.

Methylsiloxanes in children silicone-containing products from China: Profiles, leaching, and children exposure.

Methylsiloxanes (D4-D6, L5-L16) were detected in children silicone-containing products (n=190, detected frequencies=46-89%) marketed in China. For the 15 target compounds, the average concentrations ranged from

Occurrence of cyclic and linear siloxanes in indoor air from Albany, New York, USA, and its implications for inhalation exposure.

Cyclic and linear siloxanes are used in a wide variety of household and consumer products. Nevertheless, very few studies have reported the occurrence of these compounds in indoor air or inhalation exposure to these compounds. In this study, five cyclic (D3-D7) and nine linear siloxanes (L3-L11) were determined in 60 indoor air samples collected in Albany, New York, USA. The mean concentrations of individual siloxanes in particulate and vapor phases ranged from <12 µg g(-1) (for octamethyltrisiloxane [L3], decamethyltetrasiloxane [L4]) to 2420 µg g(-1) (for decamethylcyclopentasiloxane [D5]) and from 1.05 ng m(-3) to 543 ng m(-3), respectively. The mean concentrations of individual siloxanes in combined particulate and vapor phases of bulk indoor air ranged from 1.41 ng m(-3) (for L4) to 721 ng m(-3) (for D5). Cyclic siloxanes hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), D5, dodecamethylcyclohexasiloxane (D6), and octadecamethylcycloheptasiloxane (D7) were found in all indoor air samples. The mean concentrations of total siloxanes (i.e., sum of cyclic and linear siloxanes) ranged from 249 ng m(-3) in laboratories to 6210 ng m(-3) in salons, with an overall mean concentration of 1470 ng m(-3) in bulk indoor air samples. The calculated mean daily inhalation exposure doses of total siloxanes (sum of 14 siloxanes) for infants, toddlers, children, teenagers, and adults were 3.18, 1.59, 0.76, 0.34, and 0.27 µg/kg-bw/day, respectively.

Polymethacrylate monoliths with immobilized poly-3-mercaptopropyl methylsiloxane film for high-coverage surface functionalization by thiol-ene click reaction.

In this work, new polythiol-functionalized macroporous monolithic polymethacrylate-polysiloxane composite materials are presented which can be useful substrates for highly efficient immobilization of (chiral) catalysts, chromatographic ligands, and other functional moieties by thiol-ene click reaction. Poly(glycidyl methacrylate-co-ethylene dimethacrylate) (poly(GMA-co-EDMA)) monoliths were coated with a poly-3-mercaptopropyl methylsiloxane (PMPMS) film and subsequently the polymer was covalently immobilized by formation of crosslinks via nucleophilic substitution reaction with pendent 2,3-epoxypropyl groups on the monolith surface. This monolith, though, showed similar levels of surface coverage as a reference monolith obtained by opening of the epoxide groups with sodium hydrogen sulfide. However, a 3-step functionalization by amination of the epoxy monolith, followed by its vinylation with allylglycidyl ether and subsequent thiolation by coating of a thin polythiol (PMPMS) film and crosslinking by click reaction furnished a monolith with more than 2-fold elevated thiol coverage. Its further functionalization with a clickable chiral quinine carbamate selector clearly documented the benefit of highly dense thiol surfaces for such reactions and synthesis of functional materials with proper ligand loadings. The new monoliths were chromatographically tested in capillary electrochromatography mode using N-3,5-dinitrobenzoyl-leucine as chiral probe and the capillary column with the monolith having the highest selector coverage, produced from the precursor with the most thiols on the surface, showed the largest separation factor. By performic acid oxidation the surface characteristic could be tuned and strongly altered due to a delicate balance of enantioselective and non-specific interactions.