Cyclic Volatile Methylsiloxanes Research Articles

Spatial variations of linear and cyclic volatile methyl siloxanes in a river basin and their air-water exchange

Linear and cyclic volatile methylsiloxanes (VMS) are Si and O containing organic compounds that are increasingly subject to scientific studies in recent years. They are used as solvents and coating materials in personal care products, cleaning materials and industrial applications. In this study, it was aimed to investigate the spatial variations of VMS levels in river water and ambient air in Kucuk Menderes Basin and their air-water exchange patterns. Grab river water samples and passive ambient air samples collected from 10 sites throughout Kucuk Menderes Basin located in Izmir region in Turkey, and they were analyzed for VMS. The concentrations of ΣVMS in river water and ambient air ranged from 48.4 to 148 ng L−1 and from 41.7 to 433 ng m−3, respectively. Among the VMS compounds, the predominant compounds were found to be D5 and D3 in ambient air and river water, respectively. In general, concentrations of all VMS congeners increased towards downstream of the river for both water and ambient air samples and there were substantial fluctuations between the sampling points. These fluctuations may be due to wastewater discharges at some sites (increase), followed by loss by volatilization along the river (decrease). VMS concentrations measured in air and river water samples were used to estimate the net air-water exchange fluxes. In all cases, fluxes were negative, ranging between −159 (L4) and −11100 (D3) ng m−2 day, indicating volatilization from water is a source for atmospheric VMS.

Can low-temperature point discharge Be used as atomic emission source for sensitive determination of cyclic volatile methylsiloxanes?

Despite of increased interest in the application of miniature microplasma atomic spectrometry for environmental analytical chemistry, the amenable element detection range is limited to some metal elements and carbon due to it low power consumption. In this work, the generation of silicon atomic emission (251.6 nm and 288.2 nm) from the organosiloxanes was found possible in a low-temperature, low-power, and compact point discharge. Consequence, a tiny point discharge silicon optical emission spectrometer (μPD-OES) was exploited, and used as a novel GC detector for the determination of various cyclic volatile methyl siloxanes (cVMSs). Under the optimized conditions, the developed system provided limits of detection (LODs) of 0.2 mg L−1, 0.04 mg L−1, 0.03 mg L−1 and 0.02 mg L−1 of Si for hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane, respectively. Meanwhile, relative standard deviations (RSDs) of better than 2.3% were obtained. In contrast to gas chromatography mass spectrometer, GC-μPD-OES significantly simplifies the experimental setup with low power consumption and a miniature configuration. As far as we know, this work reports for the first time that silicon atomic emission can be generated in such low temperature microplasma. The accuracy of this system was validated by determining cVMSs in five daily-used shampoo samples collected from retail store, providing satisfactory recoveries (84%–114%) and excellent agreement with values determined by GC-MS at the 95% confidence level.

Cyclic volatile methylsiloxanes (cVMSs) in the air of the wastewater treatment plants in Dalian, China - Levels, emissions, and trends

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.

Photo-electrocatalytic degradation of cyclic volatile methyl siloxane by ZnO-coated aluminum anode: Optimal parameters, kinetics, and reaction pathways

Cyclic volatile methylsiloxanes (cVMSs) are widely used in industrial processes and consumer products, which have been reported to be potentially toxic to human health due to their persistence and bioaccumulation. In this study, a novel photo-catalytic zinc oxide (ZnO)-coated aluminum (ZnO@Al) anode was prepared by a facile hydrothermal epitaxial process for the purpose of degrading cVMSs in practical wastewater. Morphological data and compositional analysis showed a compact coating layer that had the characteristic peaks of ZnO. To optimize the degradation process, central composite design combined with response surface methodology was applied to acquire the optimum parameters of cVMSs removal, and results indicated the cVMSs removal efficiency was approximately 63.3% at the conditions of current density = 17.3 mA/cm2, initial pH of electrolyte = 7.8, plate distance = 18 mm, UV intensity = 90 W, and reaction time = 80 min. Furthermore, the photo-electrocatalytic degradation of cVMSs obeys the pseudo-first order kinetic reaction, and the anode exhibited high durability as the attenuation of cVMSs removal efficiency was <6% after four times reuse. It was also observed that with the application period of the anode was extended, the electroflocculation reaction gradually occurred. The FT-IR of the generated flocs and the total ion gas chromatograms mass spectrometer analysis unraveled the methyl groups in Si-CH3 could be easily attacked by hydroxyl radicals to form the intermediates of monohydroxy substituted products (m/z = 298, 372, and 446) and eventually short-chain carboxylic acids, alkyl radical and silicate. The effective removal of cVMSs by photo-electrocatalytic process using ZnO@Al anode provide significant implication in treatment of practical wastewater.

Reducing sampling artifacts in active air sampling methodology for remote monitoring and atmospheric fate assessment of cyclic volatile methylsiloxanes

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 13C-labelled octamethylcyclotetrasiloxane (13C4-D4), decamethylcyclopentasiloxane (13C5-D5) and dodecamethylcyclohexasiloxane (13C6-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 %). 13C4-D4 formed on ENV+ spiked with 13C5-D5, and both 13C4-D4 and 13C5-D5 formed on ENV+ spiked with 13C6-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.

Assessment of Gas–Particle Phase Distribution and Source Apportionment of Atmospheric Phthalate Esters and Volatile Methyl Siloxanes in Vietnamese Micro-Environments

In this study, the gas–particle distribution characteristics and emission sources of phthalate esters (PAEs) and volatile methyl siloxanes (VMSs) were evaluated for indoor air samples collected from different micro-environments such as homes, offices, kindergartens, hair salons, laboratories, and cars in 4 cities and provinces of Hanoi, Bac Ninh, Thai Binh, and Tuyen Quang, northern Vietnam. In general, total concentrations of PAEs and VMSs were higher in gas phase as compared to particle phase; however, phase distribution profiles of individual compounds were strongly related to their structures and physicochemical properties. For examples, low-molecular-weight compounds such as dimethyl phthalate, diethyl phthalate, D3, D4, L4, and L5 were more abundant in gas phase, while heavier compounds like di(2-ethylhexyl) phthalate and L8 were preferentially associated with particle phase. Assessment of PAE emission sources is relatively difficult because they have been applied in different consumer products and materials. Significant correlation between cyclic VMSs (e.g., D4, D5, and D6) was observed, suggesting their applications in cosmetics and personal care products.&#x0D; Keywords: Phthalate esters, volatile methyl siloxanes, indoor air, phase distribution, source apportionment.&#x0D;

Indoor levels of volatile organic compounds at Florentine museum environments in Italy.

Indoor Air Quality monitoring in cultural institutions is of particular concern to protect these places and the cultural heritage content. An indoor monitoring campaign was performed in three museums in Florence (Italy) to determine the occurrence and levels of volatile organic compounds (VOCs). VOCs of interest included BTEX (benzene, toluene, ethylbenzene, xylenes), terpenes, aldehydes, organic acids, and cyclic volatile methyl siloxanes (cVMS). The most abundant VOCs in all samples analyzed were BTEX, which were strictly related to the traffic source, followed by siloxanes and terpenes. Among BTEX, toluene was always the most abundant followed by xylenes, ethylbenzene, and benzene. cVMS in exhibition rooms with the presence of visitors showed higher values compared to samples collected when the museums were closed. Terpenes showed not only the influence of vegetation-biogenic sources surrounding a museum but could also be related to the wood used for the construction of showcases and furniture and the use of cleaning products. Data obtained also showed the presence of organic acids and aldehydes whose source can be traced back to exhibits themselves and wood-based furniture. Assessing the levels of organic acids in museums is important because, over time, it can cause deterioration of the artifacts.

Chemicals of emerging concern in marine specimens of the German Environmental Specimen Bank

BackgroundDescriptor 8 of the Marine Strategy Framework Directive (MSFD) (Directive 2008/56/EC) addresses the good environmental status with regard to pollution of marine waters by chemical contaminants. Commission decision (EU) 2017/848 lays down the criteria and methodological standards on good environmental status of marine waters. Member States, in regional or subregional cooperation, shall establish lists of relevant contaminants beside those already covered by the Water Framework Directive (WFD). To provide information on emerging contaminants in marine biota, the German Environmental Specimen Bank (ESB) has compiled data of blue mussels and eelpouts from coastal sites in the North and Baltic Seas. Substances identified by the International Council for the Exploration of the Sea (ICES) as of emerging concern for the marine environment have been used as a starting point.Results and conclusionsThe study presents data of 19 emerging flame retardants and degradation products, 40 per- and polyfluoroalkyl substances (PFAS) and three cyclic volatile methylsiloxanes (cVMS). Among the emerging flame retardants, only Dec 602 was detected in all samples of 2015. Dec 604, Cl10-antiDP, 1,5-DPMA, EH-TBB, PBEB, TBP-AE, BATE, BTBPE and HBBz were constantly < limit of quantification (LOQ). Time trends were barely detected. Legacy PBDE still dominates in most samples. PFAS concentrations were usually higher in samples from the North Sea sites compared to samples from the Baltic Sea. PFOS dominated in most samples. Increasing trends over time were detected for PFNA, PFDA and PFDoDA at the Baltic Sea site and for PFDA at one North Sea site. Concentrations of the cVMS D4, D5 and D6 were below the detection limit at the ESB sampling sites. Based on the results, it should be considered to include the emerging flame retardants DP and Dec 602 and the long-chain perfluoroalkyl substances PFNA, PFDA, PFUnDA and PFDoDA in a regular monitoring in the North and Baltic Seas.

Development of a solid-phase microextraction method for fast analysis of cyclic volatile methylsiloxanes in water

Cyclic volatile methylsiloxanes (cVMS) are widely used in consumer products and commonly detected in the environment. There are challenges in the analysis of cVMS because of their ubiquitous use which can introduce high background contamination. The current study introduces a sample preparation method based on headspace of solid-phase microextraction (SPME) for monitoring the cVMS in waters. Efforts were made to reduce the background contamination during sample preparation and instrument analysis. A laboratory prepared MIL-101 coating was prepared using polysulfone instead of polydimethylsiloxane as adhesive to avoid the contamination. The extraction performance of the MIL-101 fiber was optimized and evaluated. The optimized extraction time and temperature were 60 min and 40 °C, respectively. The method quantification limits of the MIL-101 fiber for octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecylcyclohexasiloxane (D6) in water were 0.15 ng mL−1, 0.14 ng mL−1, and 0.27 ng mL−1, respectively. The extraction efficiency of the proposed MIL-101 fiber was comparable to the commercial polydimethylsiloxane/divinylbenzene fiber. The developed method was applied to analyze the cVMS in wastewater treatment plant and the concentrations in the barscreen and in the aeration tank ranged from 0.73 to 3.3 ng mL−1 and 7.74–85.1 ng mL−1, respectively. The MIL-101 fiber was also applied to study the photodegradation of the cVMS in water under simulated sunlight. Approximately 25%, 20%, and 45% of D4, D5, and D6, respectively, were degraded after 10 h exposure.

Headspace gas chromatography for the determination of volatile methylsiloxanes in personal care products.

Most of the reported methods for the analysis of volatile methylsiloxanes focus on their environmental fate or possible health effects, aiming at trace level analysis by using direct injection gas chromatography. However, system contamination as carry over and side reactions at the injector are commonly reported in those cases. In this article, we explore the use of headspace gas chromatography combined with the total vaporization technique as an alternative to avoid such issues for the analysis of linear (L2-L5) and cyclic (D3-D5) volatile methylsiloxanes. The proposed method showed good linearity with R2 values higher than 0.9961 and no significant contribution (α = 0.05) of the intercept. The limit of detection was always below 0.11μg/vial (0.0025% m/m). Finally, the method was applied to real samples like an adhesive remover, hair oil, shampoo, and cream. After simple sample pretreatment, recoveries higher than 86% were achieved. Graphical abstract.

Typical indoor concentrations and mass flow of cyclic volatile methylsiloxanes (cVMSs) in Dalian, China

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.

Tube-type passive sampling of cyclic volatile methyl siloxanes (cVMSs) and benzene series simultaneously in indoor air: uptake rate determination and field application.

Cyclic volatile methyl siloxanes (cVMSs) and benzene series compounds have attracted increasing attention because they are associated with various adverse health effects. In this study, we developed and validated a novel passive air sampling method (PAS), using Tenax-TA as the sorbent, to measure the concentrations of cVMSs (D4, D5, and D6) and benzene series compounds simultaneously in indoor air. The uptake rates (R), which were calibrated side-by-side by an active air sampling method (Tenax-TA-AAS), ranged from 0.10 to 0.56 mL min-1 depending on chemicals, and the R of the TD tube with Tenax-TA was controlled by the sampler material-side and not the air-side. The passive sampling efficiency (PSE) of styrene and m,p-xylene was close to 1. Based on Pearson correlation analysis, a negative correlation was found between the molecular weight of compounds and their uptake rates. Furthermore, the calibrated Tenax-TA-PAS method was used to quantify cVMSs and benzene series compounds in a living room and an office environment in the urban area of Dalian, China. The concentrations of toluene were the highest in both the living room (10.4 μg m-3) and office (7.02 μg m-3) among the target compounds.

Investigating the presence and persistence of volatile methylsiloxanes in Arctic sediments.

Volatile methylsiloxanes (VMS) have been identified as contaminants of emerging concern in aquatic systems. Here, we report on the presence of VMS in sediment and wastewater from Arctic regions in 2014 to 2016 and model their persistence in Adventfjorden in Longyearbyen, Svalbard. Total concentrations of VMS in sediment were dominated by D4 and D5 and ranged from 0.0024 to 1.7 ng g-1 at Svalbard (Longyearbyen), from 4.0 to 43 ng g-1 in Greenland (Nuuk) and from 0.19 to 21 ng g-1 in the Canadian Archipelago. Concentrations in wastewater samples from Svalbard ranged from 12 to 156 ng L-1. Large variability in reported values of the partition ratio between organic carbon and water (KOC) and enthalpy of sorption (ΔHOC; often estimated from enthalpy of phase change between octanol and water, ΔHOW) of VMS has resulted in high uncertainty in evaluating persistence in aquatic systems. We evaluated previously reported KOC and ΔHOC values from the literature in predicting measured VMS concentrations in sediment and wastewater in scenarios using a fugacity-based multimedia model for VMS concentrations in Svalbard. We tested two different model scenarios: (1) KOC and ΔHOW measurements for three cyclic VMS previously reported by Kozerski et al. (Environ. Toxicol. Chem., 2014, 33, 1937-1945) and Xu and Kropscott (Environ. Chem., 2014, 33, 2702-2710) and (2) the KOC and ΔHOC measurements from Panagopoulos et al. (Environ. Sci. Technol., 2015, 49, 12161-12168 and Environ. Sci. Technol. Lett., 2017, 4(6), 240-245). Concentrations of VMS in sediment predicted from concentrations in wastewater in scenario 2 were in good agreement with measured concentrations, whereas in scenario 1, predicted concentrations were 2 to 4 orders of magnitude lower. Such large discrepancies indicate that the differences in the predicted concentrations are more likely to be attributed to KOC and ΔHOC than to uncertainty in environmental parameters or emission rates.

Toxicity identification and evaluation of palm oil mill effluent and its effects on the planktonic crustacean Daphnia magna

Palm oil mill effluent (POME) contains complex and highly biodegradable organic matters so discharging it without appropriate treatment may lead to environmental problems. POME final discharge quality is normally determined based on conventional chemical detection such as by biological oxygen demand (BOD) and chemical oxygen demand (COD). The novelty of the present study is that the toxicity effects of the POME final discharge samples were evaluated based on whole effluent toxicity (WET) and toxicity identification evaluation (TIE) tests using Daphnia magna. The toxicity unit (TU) values were recorded to be in the range from TU = 1.1–11 obtained from WET, and the TIE manipulation tests suggested that a substantial amount of toxic compounds was contained in the POME final discharge. Phenol, 2,6-bis (1,1-dimethylethyl)- and heavy metals such as Cu and Zn were detected in all the effluents and were recognized as being the main toxicants in the POME final discharge. GC/MS analyses also successfully identified cyclic volatile methyl siloxanes; cyclotetrasiloxane, octamethyl- (D4), cyclopentasiloxane, decamethyl- (D5), cyclohexasiloxane, dodecamethyl- (D6). D4 was detected at 0.0148–0.0357 mg/L, which could be potentially toxic. The palm oil industry used only water in the form of steam to process the fruits, and the presence of these compounds might be derived from the detergents and grease used in palm oil mill cleaning and maintenance operations. An appropriate treatment process is thus required to eliminate these toxicants from the POME final discharge. It is recommended that two approaches, chemical-based monitoring as well as biological toxicity-based monitoring, should be utilized for achieving an acceptable quality of POME final discharge in the future.

Retrospective analysis of cyclic volatile methylsiloxanes in archived German fish samples covering a period of two decades

Cyclic volatile methylsiloxanes (cVMS) are widely applied chemicals used as intermediates in the production of silicon polymers or as ingredients in personal care products. cVMS are under scrutiny due to their environmental properties and their potential for long-range atmospheric transport, persistence and food web magnification. In 2018, the cVMS octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6) were identified as Substances of Very High Concern (SVHC) under the European REACH regulation. To obtain current data on the presence of cVMS in German waters, the spatial and temporal occurrence of D4, D5 and D6 in fillets of bream from major rivers archived in the German Environmental Specimen Bank (ESB) was analyzed with a GC-ICP-MS/MS coupling method. The spatial comparison of 17 sites for the year 2017 revealed that highest cVMS burdens occurred in samples from the Saar river (near to the French/German border). cVMS levels in fish from a lake in northern Germany did not exceed the limits of detection. For selected sites, time series covering the period from 1995 to 2017 were investigated. In most years D5 concentrations in fish were clearly higher than the observed D4 and D6 concentrations. Overall maximum D4 and D5 concentrations (about 320 and 7600 ng g−1 wet weight, respectively) were found at one Saar site in 2009. In three of five analyzed time series D5 concentrations peaked 2007–2011. In recent years, cVMS levels in fish decreased at almost all sites. To allow an assessment of the relevance of the detected cVMS fish concentrations these were compared to environmental quality standards (EQS) for D4 and D5 which were recently enacted in the context of the Swedish implementation of the European Water Framework Directive (WFD). The D5 EQS in fish was exceeded at four sites in several years in the investigated period and in the Saar even till 2017.

Lung cell exposure to secondary photochemical aerosols generated from OH oxidation of cyclic siloxanes.

To study the fate of cyclic volatile methyl siloxanes (cVMS) undergoing photooxidation in the environment and to assess the acute toxicity of inhaled secondary aerosols from cVMS, we used an oxidative flow reactor (OFR) to produce aerosols from oxidation of decamethylcyclopentasiloxane (D5). The aerosols produced from this process were characterized for size, shape, and chemical composition. We found that the OFR produced aerosols composed of silicon and oxygen, arranged in chain agglomerates, with primary particles of approximately 31 nm in diameter. Lung cells were exposed to the secondary organosilicon aerosols at estimated doses of 54-116 ng/cm2 using a Vitrocell air-liquid interface system, and organic gases and ozone exposure was minimized through a series of denuders. Siloxane aerosols were not found to be highly toxic.

Long-range transport potential and atmospheric persistence of cyclic volatile methylsiloxanes based on global measurements

This study investigates persistence (P) and long-range transport potential (LRTP) of cyclic volatile methylsiloxanes (cVMS) based on the field measurements in the Northern Hemisphere. The field data consisted of published outdoor air concentrations of octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6) at urban, suburban, rural and remote locations excluding the point sources. Three major trends were observed. First, D4 and D6 concentrations were correlated with measured concentrations for D5 at the same times and locations in the majority of the datasets, reflecting the common sources and similar removal mechanism(s) for these compounds. Second, as the sampling sites changed from the source to remote locations along a south-to-north transect, average cVMS concentrations in air decreased in an exponential manner. The empirical characteristic travel distances (eCTD) extracted from these spatial patterns were smaller than model estimated values and differed in order among individual compounds (D4 ∼ D5 < D6). Finally, D5/D6 concentration ratios were also found to decrease exponentially along the same spatial gradient, contrary to model predictions of an increase based on current knowledge of mechanisms controlling atmospheric cVMS degradation. These findings suggest that there may be additional removal process(es) for airborne cVMS, currently not accounted for, that requires further elucidation.

Chlorinated-Methylsiloxanes in Shengli Oilfield: Their Generation in Oil-Production Wastewater Treatment Plant and Presence in the Surrounding Soils.

In two oil-wastewater treatment stations of Shengli Oilfield, cyclic volatile methylsiloxanes (cVMS, D4-D6) in the wastewater stream were found to undergo chlorination during electro-oxidation process for wastewater containing chlorine ions (16.1-42.0 g/L). Their converted fractions were 4.71-28.0% for monochlorinated D4-D6 and 0.22-7.96% for dichlorinated D4, which were ∼2 orders of magnitude higher than those for hydroxylated products. Furthermore, portions of chlorinated methylsiloxanes retained in excess sludge were released to the surrounding soils. In soil samples ( n = 500), chlorinated methylsiloxanes concentrations (<LOD-586 ng/g dw (dry weight), detection frequency (df) = 6.60-45.6%) decreased roughly exponentially with respect to the distance away from these two stations. During 2008-2017, the measured total chlorinated cVMS kept increasing in the dewatered-sludge (from 58.5 to 120 μg/g dw), while their concentrations in the surrounding soils doubled (from 93.4 to 184 ng/g dw) in first 6 years, but decreased since then (48.0 ng/g at 2017). Simulating experiments showed that monochlorinated D4-D6 in soil had 1.1-2.4 times longer hydrolysis (6.92-234 days) and volatilization (4.62-325 days) half-lives than their paired nonchlorinated cVMS. Among isomers of dichlorinated D4, D3D(CHCl2) had greatest hydrolysis (7.75-33.8 days) and volatilization (135-271 days) rates, followed by D3D(CH2Cl)2, D2(D(CH2Cl))2 and DD(CH2Cl)DD(CH2Cl).

Siloxane in baking moulds, emission to indoor air and migration to food during baking with an electric oven

Linear and cyclic volatile methylsiloxanes (l-VMS and c-VMS) are man-made chemicals with no natural source. They have been widely used in cosmetics, personal care products, coatings and many other products. As a consequence of their wide use, VMS can be found in different environmental media, as well as in humans.We bought 14 new silicone baking moulds and 3 metallic moulds from the market and used them in different baking experiments. Four of the silicone baking moulds were produced in Germany, two in Italy, four in China, and for the other moulds were no information available. The metal forms were all produced in Germany.VMS were measured in the indoor air throughout the baking process and at the edge and in the center of the finished cakes using a GC/MS system. Additionally, the particle number concentration (PNC) and particle size distribution were measured in the indoor air.The highest median concentrations of VMS were observed immediately following baking: 301 μg/m3 of D7, 212 μg/m3 of D6, and 130 μg/m3 of D8. The silicone moulds containing the highest concentrations of c-VMS corresponded with distinctly higher concentrations of the compounds in indoor air. Using a mould for more than one baking cycle reduced the indoor air concentrations substantially. Samples collected from the edge of the cake had higher concentrations relative to samples from the center, with a mean initial concentration of 6.6 mg/kg of D15, 3.9 mg/kg of D9, 3.7 mg/kg of D12, and 4.8 mg/kg of D18. D3 to D5 were measured only at very low concentrations.Before starting the experiment, an average PNC of 7300 particles/cm3 was observed in the room's air, while a PNC of 140,000 particles/cm3 was observed around the electric stove while it was baking, but this PNC slowly decreased after the oven was switched off.Baking with 4 of the moulds exceeded the German indoor precaution guide value for c-VMS, but the health hazard guide value was not reached during every experiment.Compared to other exposure routes, c-VMS contamination of cake from silicone moulds seems to be low, as demonstrated by the low concentrations of D4 and D6 measured. For less volatile c-VMS > D6 the results of the study indicate that food might play a more important role for daily intake. As a general rule, silicone moulds should be used only after precleaning and while strictly following the temperature suggestions of the producers.

Physical properties of secondary photochemical aerosol from OH oxidation of a cyclic siloxane.

Cyclic volatile methyl siloxanes (cVMS) are high-production chemicals present in many personal care products. They are volatile, hydrophobic, and relatively long-lived due to slow oxidation kinetics. Evidence from chamber and ambient studies indicates that oxidation products may be found in the condensed aerosol phase. In this work, we use an oxidation flow reactor to produce ~ 100 μgm-3 of organosilicon aerosol from OH oxidation of decamethyl-cyclopentasiloxane (D5) with aerosol mass fractions (i.e., yields) of 0.2-0.5. The aerosols were assessed for concentration, size distribution, morphology, sensitivity to seed aerosol, hygroscopicity, volatility and chemical composition through a combination of aerosol size distribution measurement, tandem differential mobility analysis, and electron microscopy. Similar aerosols were produced when vapor from solid antiperspirant was used as the reaction precursor. Aerosol yield was sensitive to chamber OH and to seed aerosol, suggesting sensitivity of lower-volatility species and recovered yields to oxidation conditions and chamber operation. The D5 oxidation aerosol products were relatively non-hygroscopic, with an average hygroscopicity kappa of ~ 0.01, and nearly non-volatile up to 190 °C temperature. Parameters for exploratory treatment as a semi-volatile organic aerosol in atmospheric models are provided.