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Landfill biogas is a potential alternative for fossil fuel, but the containing impurities, volatile methyl siloxanes (simplified as siloxanes), often cause serious problems in gas turbines when applied to generate electricity. In this research, a collecting and analyzing method based on solvent adsorption and purge and trap-gas chromatography-mass spectrometry was established to determine the siloxanes in biogas from a landfill in Jinan, China, and adjacent ambient samples, such as soil, air, and leachate of the landfill. The results showed that, octamethylcyclotetrasiloxane (D4) and decamethylcyclopentasiloxane (D5) accounted for 63% of total siloxanes; and without considering D4 and D5, the order of detected siloxanes in concentration was found relating to Gibbs free energies of molecules, namely that higher abundant siloxane (except for D4 and D5) usually had lower Gibbs free energy. Additionally, the mass ratio between D4 and octamethyltrisiloxane (L3) in the biogas varied with different garbage age in landfills, possibly revealing the breaking-down of larger siloxane molecules with time. The samples, which were collected from environmental samples adjacent to the landfill, such as soil, water, and air, presented much higher siloxane level than urban or rural area away from landfills. The current H 2 S scrubber of the landfill biogas could decrease the total siloxanes from 10.7 to 5.75 mg/m 3 due to Fe 2 O 3 and a refrigerant drier in a purification system and cyclic siloxanes were more easily removed than linear ones., (Copyright © 2020. Published by Elsevier B.V.)

Volatile methylsiloxanes (VMS) are a special kind of impurity that exist in biogas and seriously hamper its utilization; therefore, their removal has attracted great attention in recent years. Adsorption is the only technology that is currently capable of industrial-scale removal of VMS. In this research, three carbons with various porous structures, including ordered mesoporous carbon (OMC), activated carbon fiber (ACF) and granular activated carbon (GAC), were selected as potential adsorbents to investigate their adsorption properties toward hexamethyldisiloxane (L2), which is a typical linear VMS pollutant. The adsorption isotherms and kinetics of L2 on the three carbons were studied, and the isosteric heats of adsorption were calculated in accordance with the isotherms under different temperatures by using the Van't Hoff equation. Additionally, the influences of the topological structures of the carbons on the adsorption kinetics were compared. Generally, adsorption isotherms of the three carbons can be well-fitted by the Dubinin-Astakhov equation, and the variation of the isosteric heats and adsorption kinetics are presumed to be closely related to the pore sizes of the carbons. These new findings reveal the adsorption mechanisms of L2 on carbons and make it possible that the proper adsorption system is set up to fulfill higher removal efficiency., Competing Interests: Declaration of competing interest The authors declare no conflict of interest., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

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.

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 R 2 values higher than 0.9961 and no significant contribution (α = 0.05) of the intercept. The limit of detection was always below 0.11 μg/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.

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., (Copyright © 2019 The Authors. Published by Elsevier B.V. All rights reserved.)

Siloxanes are organo-silicon compounds containing Si-O-Si linkages and methyl branches. Depending on the structure, siloxanes can be divided into cyclic and linear compounds. Methyl siloxanes with small and medium molecular weights (molecular weights less than 500 g mol -1 ), are volatile under normal conditions, and hence are referred to as volatile methyl siloxanes (VMSs). VMSs are additive ingredients in many products such as plastics, rubber, personal care products, and household items. This review provides information on the distribution of VMSs in consumer products, indoor air and dust, and their implications for human exposure. VMSs have been used in personal care products and household items at concentrations on the order of hundreds to thousands of micrograms per gram which are the main sources of contamination in the indoor environments. VMSs have been found widely in indoor air and dust. A significant correlation existed between VMS concentrations in indoor air and dust. Among typical VMSs, dodecamethylcylcopentasiloxane (D5) is the major compound found in indoor environments. The human exposure doses to VMSs through dermal absorption, dust ingestion, and inhalation were compiled; Inhalation is a dominant pathway of exposure to VMSs, especially in indoor environments of occupational settings like hair salons. The human exposure doses were higher in children than in adults., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Siloxanes have been used as chemical additives in various products since the 1940s. They are known to have potentially toxic effects, to be environmentally persistent, and to be bioaccumulative. Previous studies have reported high levels of siloxanes in various environmental matrices. In this study, 6 cyclic siloxanes (D4-D9) and 13 linear siloxanes (L3-L15) in coastal sediment collected from southeastern bays adjacent to industrial zones in South Korea (Busan, Ulsan, Jinhae, and Gwangyang) were analyzed. The contamination levels and spatial distribution of siloxanes in the coastal sediment samples were investigated, with the hazard quotients (HQs) for siloxanes evaluated using Monte Carlo simulation. Across all samples, the total concentration (Σ 19 ) of siloxanes was in the range of 11.6-3877 (mean: 305; median: 133) ng/g dry weight (dw). The highest average concentration of Σ 19 siloxanes was found in Busan (mean: 580; median: 233 ng/g dw), followed by Ulsan (mean: 316; median: 209 ng/g dw), Jinhae (mean: 266; median: 125 ng/g dw), and Gwangyang (mean: 33; median: 27 ng/g dw), all of which are suggested to be affected by both industrial and domestic activities. The highest contributions were from D5 (18%) and D6 (34%), followed by D9 (7.3%) and L11 (5.8%). The HQs for siloxanes were less than 1, indicating that there was no risk to benthic organisms in the study areas; however, further monitoring of various environmental matrices is required to fully assess the potential ecological risks., (Copyright © 2019 Elsevier Inc. All rights reserved.)

Numerous chemicals have been manufactured through industrial activities and used as consumer products since the late 18th century. Non-target analysis is a new analytical tool to detect many chemicals in environmental samples and to prioritize emerging contaminants. In this study, suspect and non-target analytical methods were optimized using gas chromatography coupled with time-of-flight (GC/TOF) to propose contaminants of emerging concern for the Arctic environment. A suspect analytical method was developed with qualification and qualifier ions, isotopic ratios, and retention times of 215 contaminants including persistent organic pollutants (POPs) to establish an in-house library. Non-target analytical method was also optimized with a deconvoluted ion chromatogram, which is a form that can possibly match the mass spectrum of the NIST library. Multiple environmental samples, such as seawater, air, soil, sediment, sludge, and iceberg, collected from the Arctic region were analyzed with suspect and non-target analysis of GC/TOF after the clean-up procedure with a solid phase extraction (SPE) cartridge. The commonly detected contaminants in the Arctic environmental samples were siloxanes, organophosphate flame retardants, phthalates, synthetic musk compounds, polychlorinated biphenyls, and polycyclic aromatic hydrocarbons. Among them, siloxanes and organophosphate flame retardants were proposed to be contaminants of emerging concerns for the Arctic environment. This is the first report to prioritize emerging contaminants in the Arctic environment with suspect and non-target analysis of GC/TOF., (Copyright © 2019 Elsevier Inc. All rights reserved.)

Wastewater, aeration gas, dewatered sludge, and incineration ash and flue gas (from dewatered sludge) were collected from 9 sewage treatment plants (STPs) located in Saitama Prefecture, Japan, and analyzed for seven cyclic and linear volatile methylsiloxanes (VMSs) namely, D3, D4, D5, D6, L3, L4, and L5. The mass loadings and distribution of VMSs in STPs were estimated based on measured concentrations in liquid, solid, and gaseous samples, including incinerated dewatered sludge. Mass loading of ΣVMS varied widely from 21 kg y -1 to 3740 kg y -1 , depending on the volume of wastewater treated in each STP. Mass % of ΣVMS distributed in aeration gas was 15% and that in activated sludge was 78%. Approximately 6.6% of ΣVMS remained in the final effluent. Overall, partitioning onto the activated sludge was the dominant removal mechanism for D4, D5, and D6, whereas volatilization was also an important removal mechanism for D4. Incineration was effective to degrade VMSs in dewatered sludge, with a reduction rate of >99%. Activated carbon treatment removed >99% of VMSs from the aeration gas. In Saitama Prefecture, total emission of ΣVMS via STPs was estimated at 434 kg y -1 , 86 kg y -1 , and 0.065 kg y -1 , to aquatic, atmospheric, and terrestrial environments, respectively, which accounted for 83%, 17%, and 0.01% of the total environmental emissions. Our results indicate that majority of VMSs in dewatered sludge can be removed by incineration and emission of VMSs through incineration ash landfill is negligible., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Dynamic production of cyclic siloxanes: octamethylcyclotetrasiloxane D4, decamethylcyclopentasiloxane D5 and dodecamethylcyclohexasiloxane D6 increases their concentrations in environment. It is considered that both environmental pollution and the usage of personal care products and cosmetics containing cyclic siloxanes can be the main source of the human exposure by transdermal route. The aim of the study was to verify the possibility to overcome the skin barrier by cyclic siloxanes (ATR-FTIR and GC-FID), evaluation of diffusion pathway to stratum corneum SC (Fluorescence microscopy), and determination of depth of permeation to deeper skin layers: epidermis and dermis (ATR-FTIR) and also of potential interaction with SC lipids and proteins (Fluorescence microscopy, ATR-FTIR) and the cytotoxicity studies against HaCaT cells (MTT test). The results show that D4, D5 and D5 can penetrate to SC and permeate into the deeper layers of the skin: epidermis and dermis. The quantitative analysis (GC-FID) showed that total cumulative doses for D4, D5 and D6 were: 42.50; 95.37 and 77.19 μg/cm2/24 h, respectively. The microscopic analysis proved, transepidermal route through the lipid matrix as well as through the canyons (intercluster spaces) were a diffusion pathway to the SC as well as disruption of human SC lipid structure by: D4 (the most), D5 and D6 (the least). The cytotoxicity studies demonstrated that the tested range of concentrations of D5 and D6 (up to 300 mM, 111 300 mg and 133 500 mg respectively) did not impaired the HaCaT growth, while D4 had IC50 value of 40 098 mM ± 7.94 (10 906 ± 872,5 mg)., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Trophic transfer of cyclic methyl siloxanes (CMS) in aquatic ecosystems is an important criterion for assessing its environmental risks. This study researched the trophic transfer of four CMS (octamethylcyclotetrasiloxane (D 4 ), decamethylcyclopentasiloxane (D 5 ), dodecamethylcyclohexasiloxane (D 6 ), and tetradecamethylcycloheptasiloxane (D 7 )) in marine food web from zooplankton up to seabirds in the Chinese Bohai Sea. In the zooplankton-invertebrate-fish-seabird based food web, the significant trophic magnifications were found for D 4 to D 6 (D 4 : R 2  = 0.040, p < 0.05, D 5 : R 2  = 0.26, p < 0.0001, D 6 : R 2  = 0.071, p < 0.001), and the significant trophic dilution was found for D 7 (R 2  = 0.026 and p < 0.05). The trophic magnification factors (TMF) for D 4 to D 7 were 1.7 (95% confidence interval: 1.1-2.6), 3.5 (2.5-5.0), 1.8 (1.3-2.6), and 0.63 (95% CI: 0.40-0.99) respectively. In the zooplankton-invertebrate-fish based food web, both significant trophic magnification for D 5 (R 2  = 0.16, p < 0.0001, TMF = 3.0) and significant trophic dilution for D 7 (R 2  = 0.073, p < 0.01, TMF = 0.4) were found, but for D 4 and D 6 , the trophic magnifications were not significant (D 4 : R 2  = 0.010, p = 0.23, D 6 : R 2  = 0.010, p = 0.23). The trophic transfer of the legacy contaminant BDE-47 and BDE-99 were also conducted as the benchmark chemicals and significant positive correlation was found. As far as we know, this is the first research on the trophic transfer of CMS in the zooplankton-invertebrate-fish-bird food chain which provided new insight of these compounds in the area., (Copyright © 2019 Elsevier Inc. All rights reserved.)

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., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Multi-media fate and transport models (MFTMs) are invaluable tools in understanding and predicting the likely behaviour of organic pollutants in the environment. However, some parameters describing the properties of both the environmental system and the chemical pollutant under consideration are uncertain and or variable in space and time. Furthermore, model performance is often evaluated using sparse data sets on chemical concentrations in different media. This can result in equifinality - the phenomenon in which several different combinations of model parameters can result in similar predictions of environmental concentrations. We explore this idea for MFTMs for the first time using, as examples, three cyclic volatile methyl siloxanes (cVMS: D4, D5 and D6) and the QWASI lake model applied to Tokyo Bay. Monte Carlo simulation was employed with parameters selected from probability distributions representing estimated uncertainty in a large number of iterations. This generated distributions of predicted chemical concentrations in water (CW) and sediment (CS) which represent the aleatory uncertainty envelope but which also demonstrate significant equifinality. For all three compounds, the uncertainty implied in the CW was lower (coefficient of variation, CV, of the order of 20%) than for CS (CV ca. 45%), reflecting the propensity of cVMS compounds to sorb to sediment and the sensitivity of the model to KOC. Confidence intervals were particularly high for the persistence of D5 and D6 in sediment which both ranged between approximately 1.7 years and approximately 26 years for Tokyo Bay. Predicted concentration distributions matched observations well for D5 and D6 not for D4. Equifinality could be reduced by better constraining acceptable parameter sets using additional measured data from different environmental compartments.

Volatile methylsiloxanes (VMSs) are widely used in various personal-care products and industrial additives and products. This study focused on VMSs exposure in the general population, workers, and the families of workers living in residential and industrial areas of southwestern China. VMSs concentrations in indoor environmental matrices from six industrial facilities were 3.4 × 10 2 to 9.0 × 10 2  μg m -3 in gas-phase samples, 4.7 × 10 2 to 1.5 × 10 4  μg g -1 in PM 2.5 samples, and 2.3 × 10 2 to 7.2 × 10 3  μg g -1 in dust samples, which were two to four orders of magnitude higher than the concentrations measured in residential areas. Exposure to VMSs was investigated by analysis of plasma samples from workers in residential and industrial areas for the presence of cyclic (D4-D6) and linear (L3-L16) VMSs. VMSs concentrations in plasma samples ranged from 84 to 2.3 × 10 2  ng ml -1 in workers, one to two orders of magnitude higher than those in the general population (2.2 ng ml -1 ). Daily VMSs indoor exposure via inhalation and ingestion in individuals from residential and industrial areas were estimated and assessed under working-time and leisure-time conditions. This study showed that exposure to VMSs in industrial areas is approximately two to four or one to two orders of magnitude higher than that in residential areas during the working- or leisure-time scenario, respectively. Furthermore, the families of workers (the non-occupational group) experienced higher levels of exposure to VMSs in their homes compared with the general population. The ratios of exposure to linear VMSs via PM 2.5 inhalation to that via the gas phase ranged from 7.8% to 43.1% in industrial areas. This study suggests that intake of linear VMSs via PM 2.5 inhalation should be considered when estimating human exposure to VMSs in areas with high levels of PM 2.5 air pollution., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Quantitative mapping of oxygen tension (pO 2 ), noninvasively, could potentially be beneficial in cancer and stroke therapy for monitoring therapy and predicting response to certain therapies. Intracellular pO 2 measurements may also prove useful in tracking the health of labeled cells and understanding the dynamics of cell therapy in vivo. Proton Imaging of Siloxanes to map Tissue Oxygenation Levels (PISTOL) is a relatively new oximetry technique that measures the T 1 of administered siloxanes such as hexamethyldisiloxane (HMDSO), to map the tissue pO 2 at various locations with a temporal resolution of 3.5 minutes. We have now developed a siloxane-selective Look-Locker imaging sequence equipped with an echo planar imaging (EPI) readout to accelerate PISTOL acquisitions. The new tissue oximetry sequence, referred to as PISTOL-LL, enables the mapping of HMDSO T 1 , and hence tissue pO 2 in under one minute. PISTOL-LL was tested and compared with PISTOL in vitro and in vivo. Both sequences were used to record dynamic changes in pO 2 of the rat thigh muscle (healthy Fischer rats, n = 6), and showed similar results (P > 0.05) as the other, with each sequence reporting a significant increase in pO 2 (P < 0.05) under hyperoxia compared with steady state normoxia. This study demonstrates the ability of the new sequence in rapidly and accurately mapping the pO 2 changes and accelerating quantitative 1 H MR tissue oximetry by approximately 4-fold. The faster PISTOL-LL technique could enable dynamic 1 H oximetry with higher temporal resolution for assesing tissue oxygentation and tracking the health of transplanted cells labeled with siloxane-based probes. With minor modifications, this sequence can be useful for 19 F applications as well., (© 2019 John Wiley & Sons, Ltd.)

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/m 3 of D7, 212 μg/m 3 of D6, and 130 μg/m 3 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/cm 3 was observed in the room's air, while a PNC of 140,000 particles/cm 3 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., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

This study focused on the determination of seven volatile methylsiloxanes (VMSs) and eleven UV-filters (UVFs) in beach sand from the Oporto's region (Portugal). A QuEChERS methodology ("Quick, Easy, Cheap, Effective, Rugged, and Safe") was used to extract VMSs from the sand, which has never been employed before. To extract the UVFs, a solid-phase microextraction (SPME) was used. The analyses were performed by gas chromatography-mass spectrometry (GC-MS). Twenty-three beach sand samples were analysed, from two campaigns - summer/winter. VMSs were found in all the samples with concentrations ranging from 0.007 ± 0.001 to 17.8 ± 0.9 ng g -1 dw , while UVFs in summer samples from 0.030 ± 0.001 to 373 ± 17 ng g -1 dw . Cyclic VMSs and octocrylene (OC) were detected in higher concentrations. In general, higher levels were detected in summer than winter. Hazard quotients were determined and 3-(4'-methylbenzylidene) camphor (4-MBC), 2-ethylhexyl 4-methoxycinnamate (EMC) and benzophenone-3 (BP3) presented values >1, which may indicate that they may pose an ecotoxicological risk., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

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 ± 12.3 ng/g ww for D4, 24.6 ± 15.8 ng/g ww for D5 and 34.0 ± 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 ± 0.06-0.53 ± 0.06 and 0.13 ± 0.03-0.19 ± 0.05, respectively., (Copyright © 2018. Published by Elsevier B.V.)

Objectives: To assess the efficacy and effect on clinical signs of a polyvinylsiloxane (Tresident; Shütz Dental Group GmbH, Germany) compared with an irreversible hydrocolloid (Orthoprint; Zhermack SpA, Badia Polesine, Italy) for ocular impression-taking., Methods: Twenty subjects were recruited (13 female and 7 male), with mean age 31.1±4.6 years (SD) (range 25.8-39.7). Subjects attended for 2 sessions, each of 1-hr duration, on 2 separate days. Each session was scheduled at the same time on each day. At each visit, the subject underwent an ocular impression procedure, using either Tresident or Orthoprint, in random order and to one eye only. Investigator 2 was blind to this assignment. Two experienced practitioners conducted the study, investigator 1 performed the ocular impression procedures and investigator 2 observed and assessed the clinical signs: logMAR visual acuity, ocular surface staining, tear break-up time (TBUT), and ocular hyperemia., Results: Visual acuity was unaffected by either material; TBUT was marginally disrupted by both materials, but was not clinically significant according to published criteria; ocular redness increased with both materials; and corneal staining was significantly greater after Orthoprint impression. Less redness and clinically insignificant staining after impression-taking, with fewer clinical complications, was found after use of Tresident., Conclusions: Tresident offers a quicker, more effective, and clinically viable method of obtaining ocular impression topography compared with the traditional Orthoprint, and Orthoprint causes significantly more superficial punctuate staining of the corneal epithelium than Tresident.

In this study, three typical cyclic siloxanes (CSis) were found in hair care products, indoor dust and indoor air samples at hair salons in Hanoi, Vietnam. The total concentrations of CSis in three kinds of hair care products ranged from 8.77 to 515 μg g -1 . The mean and median concentrations of CSis in dust samples collected at hair salons were 671 and 654 μg g -1 , respectively. The total concentrations of CSis in indoor air samples collected at the hair salons ranged from 415 to 2610 ng m -3 (mean: 1030; median: 849 ng m -3 , respectively). Among three cyclic siloxanes mentioned in this study, decamethylcyclopentasiloxane (D5) was found at the highest level in all categories of samples. D5 had also a strong correlation between indoor dust and indoor air from hair salons (the coefficient of determination (R 2 ): 0.852); meanwhile dodecamethylcyclohexasiloxane (D6) and octamethylcyclotetrasiloxane (D4) had good correlations (R 2  = 0.618 and 0.585, respectively). This result indicates that hair care products are main emission source of cyclic siloxanes in indoor environments at the hair salons. The average exposure doses to total SCis through both of dust ingestion and inhalation were estimated to be 103 and 79.5 ng kg-bw -1 day -1 for women and men, respectively. These levels were higher than those reported for some Asian countries. This is among the most comprehensive investigations on the emission sources and distributions of cyclic siloxanes in indoor dust and indoor air at hair salons in Vietnam., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Indoor air samples were collected from private homes and various occupational indoor environments using passive air sampler and analysed for fluorotelomer alcohols (FTOHs), brominated flame retardants (BFRs), organophosphorus flame retardants (OPFRs) and cyclic volatile methyl siloxanes (cVMSs). The aim was to investigate their occurrence in indoor air, factors that may affect their presence and human daily exposure dose (DED) via inhalation. In general, levels of cVMSs were 3-4 orders of magnitude greater than the other compound classes. OPFRs concentration was found significantly higher than BFRs in indoor air. The most abundant compounds in each chemical class were 8:2 FTOH, 2,4,6-TBP, TNBP and TCEP and decamethylcyclopentasiloxane (D5). Home samples contained higher level of FTOHs, BFRs and cVMSs than occupational environments, whereas concentration of OPFRs in office samples were higher. BFRs concentrations were significantly correlated with building age and with the number of electronic/electrical devices at the sampling sites. Moreover, significantly lower levels of FTOHs and cVMSs were observed in rooms with forced-ventilation system. Estimated DED via inhalation was significantly higher at home than in office and the total DED was on average 3-5 orders of magnitude lower than the reference value., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Major obstacles to formulating a simple retention mechanism for reversed-phase liquid chromatography have a direct impact on the development of experimental methods for column characterization as they limit our capability to understand observed differences in retention at a system level. These problems arise from the heterogeneous composition of the stationary phase, the difficulty of providing a working definition for the phase ratio, and uncertainty as to whether the distribution mechanism for varied compounds is a partition, adsorption or mixed (combination) of these models. Retention factor and separation factor measurements offer little guidance as they represent an average of various and variable contributing factors that can only be interpreted by assuming a specific model. Column characterization methods have tended to ignore these difficulties by inventing a series of terms to describe column properties, such as hydrophobicity, hydrophilicity, silanol activity, steric resistance, etc., without proper definition. This has allowed multiple scales to be proposed for the same property which generally are only weakly correlated. Against this background we review the major approaches for the characterization of alkylsiloxane-bonded silica stationary phases employing prototypical compounds, the hydrophobic-subtraction model and the solvation parameter model. Those methods using prototypical compounds are limited by the lack of compounds with a singular dominant interaction. The multivariate approaches that extract column characteristic properties from the retention of varied compounds are more hopeful but it is important to be more precise in defining the characteristic column properties and cognizant that general interpretation of these properties for varied columns cannot escape the problem of a poor understanding of the distribution mechanism., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Poly- and per-fluoroalkyl substances (PFAS) and volatile methyl siloxanes (VMS) were monitored at 21 sites in the Global Atmospheric Passive Sampling (GAPS) Network. Atmospheric concentrations previously reported from 2009 were compared to concentrations measured at these sites in 2013 and 2015, to assess trends over 7 years of monitoring. Concentrations of the fluorotelomer alcohols (FTOHs) and fluorinated sulfonamides and sulfonamidoethanols (FOSAs and FOSEs) were stable at these sites from 2009 to 2015 with no significant difference (p > 0.05) in concentrations. Elevated concentrations of all the neutral PFAS were detected at the urban sites as compared to the polar/background sites. The perfluorosulfonic acids (PFSAs), meanwhile, saw a significant increase (p < 0.001) in concentrations from 2009 to 2015. The perfluorocarboxylic acids (PFCAs) had elevated concentrations in 2015, however, the difference was not statistically significant (p > 0.05). Concentrations of the PFSAs and the PFCAs were similar at all location types, showing the global reach of these persistent compounds. Concentrations of the cyclic VMS (cVMS) were at least an order of magnitude higher than the linear VMS (lVMS) and the PFAS. Octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6) saw a weak significant increase in concentrations from 2009 to 2013 (p < 0.05), however, hexamethylcyclotrisiloxane (D3) had a strong significant decrease in concentrations from 2009 to 2015 (p < 0.01)., (Copyright © 2018 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Environmental contamination by siloxanes is a matter of concern due to their widespread consumption in personal care as well as industrial products and potential toxicity. Nevertheless, methods for simultaneous determination of cyclic and linear siloxanes in sediment are lacking. In this study, we developed an optimized analytical method to determine cyclic and linear siloxanes based on gas chromatography coupled to tandem mass spectrometry (GC-MS/MS). This method was applied to determine concentrations of 19 siloxane compounds in surface and core sediments from industrialized bays in Korea to assess contamination status, spatial distribution, and historical trends. Total concentrations of siloxanes ranged from 15.0 to 11730 (mean: 712) ng/g dry weight, which were similar to or higher than those reported in other countries. The highest concentrations of siloxanes were found in rivers/streams that discharge into coastal waters and bays close to industrial complexes, indicating that industrial activities are major sources of siloxane contamination. Cyclic siloxanes such as D5 and D6 were predominant in surface and core sediments. A significant correlation existed between the concentrations of cyclic and linear siloxanes, suggesting similar sources in the marine coastal environment. The historical record of cyclic siloxanes in core sediments revealed a clear increasing trend since the 1970s. This finding is consistent with the history of local industrialization and global production of siloxanes. This is the first study of historical trends in siloxanes in the coastal environment., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

The trophic transfer of cyclic methylsiloxanes (cVMS) in aquatic ecosystems is an important criterion for assessing bioaccumulation and ecological risk. Bioaccumulation and trophic transfer of cVMS, specifically octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6), were evaluated for the marine food webs of the Inner and Outer Oslofjord, Norway. The sampled food webs included zooplankton, benthic macroinvertebrates, shellfish, and finfish species. Zooplankton, benthic macroinvertebrates, and shellfish occupied the lowest trophic levels (TL ≈2 to 3); northern shrimp (Pandalus borealis) and Atlantic herring (Clupea harengus) occupied the middle trophic levels (TL ≈3 to 4), and Atlantic cod (Gadus morhua) occupied the highest tropic level (TL>4.0). Trophic dynamics in the Oslofjord were best described as a compressed food web defined by demersal and pelagic components that were confounded by a diversity in prey organisms and feeding relationships. Lipid-normalized concentrations of D4, D5, and D6 were greatest in the lowest trophic levels and significantly decreased up the food web, with the lowest concentrations being observed in the highest trophic level species. Trophic magnification factors (TMF) for D4, D5, and D6 were <1.0 (range 0.3 to 0.9) and were consistent between the Inner and Outer Oslofjord, indicating that exposure did not impact TMF across the marine food web. There was no evidence to suggest biomagnification of cVMS in the Oslofjord. Rather, results indicated that trophic dilution of cVMS, not trophic magnification, occurred across the sampled food webs., (Copyright © 2017 The Authors. Published by Elsevier B.V. All rights reserved.)

Methyl siloxanes (MSs) have been widely added as emollients or solvents in various personal care products (PCPs) such as soap, shampoo and hair conditioner. A considerable percentage of MSs are released into the atmosphere directly from the use of PCPs in indoor environments. Indoor dust is a major reservoir of MSs, due to their particle-binding affinity. Dust ingestion could be one exposure pathway for special populations (hairdressers, for example). Though the toxicity of MSs is known, there is no information regarding the occurrence of MSs in barbershop dusts and the exposure of hairdressers through indoor dust ingestion. In the present study, the levels of three cyclic siloxanes (D4-D6) and 13 linear siloxanes (L4-L16) were measured in indoor dust samples collected from barbershops, and some other microenvironment including bathhouses, dormitories and households for comparison. The concentrations of ∑MSs in barbershop dusts were one to two orders of magnitude higher than those from the other three indoor microenvironments. The daily intakes of ∑MSs through indoor dust ingestion were estimated using the model of worst-case exposure (95th percentile concentration) and high dust ingestion, For the hairdressers in workplaces (barbershops), the exposure rates were 14.3ng/kg-bw/day, and for the general population, college students and toddlers (1-3yr), the corresponding exposure rates in living spaces were 3.43, 2.00 and 222ng/kg-bw/day, respectively. Such high exposure levels of MSs through dust ingestion indicate that we should not overlook the potential health risks for occupational groups and toddlers., (Published by Elsevier B.V.)

Bituminous coal-based magnetic activated carbon (MAC) was prepared, characterized, and used successfully for removal of cyclic volatile methylsiloxanes (cVMSs) from treated landfill leachate. Batch adsorption studies were performed at different adsorption dosages and contact times. With adsorptive dosage of 0.75 g/L and contact time of 60 min, the removal efficiencies achieved by MAC for octamethylcyclotetrasiloxane (D 4 ), decamethylcyclopentasiloxane (D 5 ), and dodecamethylcyclohexasiloxane (D 6 ) are 100, 82.8, and 71.4%, respectively. The specific magnetization coefficients of MAC before and after adsorption are 4.6 × 10 -7 and 5.2 × 10 -7  m 3 /kg, between 1.26 × 10 -7 and 3.8 × 10 -5  m 3 /kg, which suggests that MAC can be recycled by the high-intensity magnetic separators.

We apply multimedia models to systematically evaluate the fate profile of cyclic volatile methyl siloxanes (VMS) D 4 , D 5 and D 6 , and the linear VMS L 4 and L 5 using recently reported measurements of their partition ratios between organic carbon and water (K OC ), their salting out constants (K s ), and their enthalpy of sorption to organic carbon (ΔH OC ). Our assessment follows a multi-stage strategy where the environmental fate of the chemicals is explored in generic regional models with increasing fidelity to the real system and in a region-specific model. Modeled emissions of VMS to air remained in air and were degraded or advected out of the system with overall residence times ranging from 2.4 to 2.5 days, while emissions to water resulted in accumulation in sediment and longer residence times ranging from 29.5 to 1120 days. When emitted to water the modeled residence times of VMS in the sediment exceeded the REACH criterion for persistence in freshwater sediments. Reported K OC measurements for D 5 differ by 1 log unit, which results in a 500-day difference in the overall residence times calculated in the generic regional modeling. In the specific-region modeling assessment for Adventfjorden, Svalbard in Norway, the different K OC measurements of D 5 resulted in a 200-day difference in overall residence times. Model scenarios that examined combinations of previously published ΔH OC or enthalpy of phase change between octanol and water (ΔH OW ) for D 5 in combination with the range of the K OC measurements resulted in 1100-days difference in overall residence times. Our results demonstrate that residence times of VMS in aquatic systems are highly sensitive to their degree of sorption to organic carbon, and that residence times of VMS likely exceed several persistence criteria and therefore they cannot be considered as non-persistent.

The purpose of this description is to review scientific literature from 1944 to 2017 as a source of information on the reasons for the increased interest in siloxanes (silicones). Not only the research area, but first, the changes in the tendency of research aims are important issues in the evaluation. On the one hand, the authors emphasize the unique properties of linear and cyclic siloxanes, providing many examples of beneficial applications, and on the other hand, there are some warnings of overcoming of the safety barrier of their presence in human environment. Analyzing the results from the SCOPUS database, it can be argued that the increased interest of scientists and government agencies particularly relates to the analysis of siloxanes in biological and environmental samples. This is caused not only by the widespread use of various siloxanes in the pharmaceutical, medical, cosmetic and food industries, but also by the direct contact of these compounds with tissues, as well as an increased access to knowledge and modern research tools that have developed the awareness of hazards. The development of research methods enables not only constant monitoring of progressively lower siloxanes concentrations in various samples, but because of the specificity of these methods, it also enables an identification of specific siloxane compounds and evaluation of their effects on humans and environment. This paper discusses the issues of the evolution of consciousness of exposure to siloxanes due to their increased synthesis and widespread use in many areas of human life, which contributes to environmental pollution., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

The ready availability of butane makes butane abuse frequent. Fatalities are rare. This study presents two cases of death by butane overdose. The postmortem analyses were carried out using headspace gas chromatography-mass spectrometry. It revealed femoral blood butane concentrations of 18 and 22 mg/L, respectively, as well as specific combinations of adjuvants in each victim. In one of the victims, brain and fatty tissue also contained butane, pointing to chronic consumption. The originality of this study is to show that the identification of specific combinations of adjuvants can be helpful for identifying the brand of deodorant used. Also, sampling the skin and mucosa can help identify the method of drug delivery. The histological examination documented both the direct toxic effect of the gas on the respiratory mucosa and signs of chronic abuse. Volatile substance intoxications should be systematically considered in case of sudden death in a teenager., (© 2017 American Academy of Forensic Sciences.)

Objective: Organosiloxanes are prevalent in personal care products (PCPs) due to the desired properties they impart in the usage and application of such products. However, the European Chemical Agency (ECHA) has recently published restriction proposals on the amount of two cyclic siloxanes, octamethylcyclotetrasiloxane (D4) and decamethylcyclotetrasiloxane (D5), allowed in wash off products such as shampoos and conditioners which are discharged down the drain during consumer use. This legislation will require that reliable analytical methods are available for manufacturers and government agencies to use in documenting compliance with the restrictions. This article proposes a simple analytical method to enable accurate measurement of these compounds down to the circa 0.1 weight per cent level in PCPs., Methods: Although gas chromatography methods are reported in the literature for quantitation of D4 and D5 in several matrices including PCPs, the potential for generation of false positives due to contamination, co-elution and in situ generation of cyclic volatile methylsiloxanes (cVMS) is always present and needs to be controlled. This report demonstrates the applicability of using a combination of emulsion break, liquid-liquid extraction and silylation sample preparation followed by GC-FID analysis as a suitable means of analysing PCPs for specific cVMS., Results: The reliability and limitations of such methodology were demonstrated through several round-robin studies conducted in the laboratories of a consortium of silicone manufacturers. In addition, this report presents examples of false positives encountered during development of the method and presents a comparative analysis between this method and a published QuEChERS sample preparation procedure to illustrate the potential for generation of false positives when an inappropriate approach is applied to determination of cVMS in personal care products., Conclusion: This report demonstrates that an approach to determine cVMS levels in personal care products is to perform an emulsion break on the sample, isolate the non-polar phase from the emulsion break and treat with a silylation reagent to abate potential in situ formation of cyclics during the course of GC-FID analysis. Round-robin studies conducted in laboratories representing multiple siloxane manufacturers demonstrated the reliability of the GC-FID method when measuring cVMS in PCPs down to circa 0.1%., (© 2017 CES - Silicones Europe. International Journal of Cosmetic Science published by John Wiley & Sons Ltd on behalf of Society of Cosmetic Scientists and the Société Française de Cosmétologie.)

Earlier studies have reported the occurrence of cyclic and linear siloxanes in personal care and household products. Nevertheless, there is a lack of information on the occurrence of siloxanes in indoor air. In this study, four cyclic and six linear siloxanes were measured in 97 indoor air samples collected from various micro-environments in four cities in northern, Vietnam, during September 2016 to January 2017. The total concentrations of siloxanes (TSi) in particulate and gas phases ranged from 141 to 7220 μg g -1 (mean: 1880) and 23.8-1580 ng m -3 (mean: 321), respectively. The total concentrations of cyclic siloxanes (TCSi), linear siloxanes (TLSi), and TSi in indoor air were 1.91-1500 ng m -3 , 21.8-817 ng m -3 , and 41.8-1950 ng m -3 , respectively. The highest mean concentration of siloxanes was found in indoor air from hair salons in Hanoi. The concentrations of siloxanes in air collected from homes in Hanoi were higher than those from other smaller cities such as Bacninh, Thaibinh, and Tuyenquang. The human exposures to siloxanes through inhalation were estimated for various age groups based on the measured concentrations. The mean inhalation exposure doses to total siloxanes for infants, toddlers, children, teenagers, and adults were 352, 219, 188, 132, and 95.9 ng kg-bw -1 d -1 , respectively., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Volatile methylsiloxanes (VMSs) and organophosphate esters (OPEs) are two suites of chemicals that are of environmental concern as organic contaminants, but little is known about the exposure of wildlife to these contaminants, particularly in birds, in terrestrial and aquatic ecosystems. The present study investigates the spatial distributions of nine cyclic and linear VMSs and 17 OPEs in the eggs of European starlings (Sturnus vulgaris) and three congeneric gull species (i.e., herring gull (Larus argentatus), glaucous-winged gull (L. glaucescens), and California gull (L. californicus)) from nesting sites across Canada. ∑VMS concentrations for all bird eggs were dominated by decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6), and octamethylcyclotetrasiloxane (D4). With European starlings, birds breeding adjacent to landfill sites had eggs containing significantly greater ∑VMS concentrations (median: 178 ng g -1 wet weight (ww)) compared with those from the urban industrial (20 ng g -1 ww) and rural sites (1.3 ng g -1 ww), indicating that the landfills are important sources of VMSs to Canadian terrestrial environments. In gull eggs, the median ∑VMS concentrations were up to 254 ng g -1 ww and suggested greater detection frequencies and levels of VMSs in aquatic- versus terrestrial-feeding birds in Canada. In contrast, the detection frequency of OPEs in all European starling and gull eggs was lower than 16%. This suggested that low dietary exposure or rapid metabolism of accumulated OPEs occurs in aquatic feeding birds and may warrant further investigation for the elucidation of the reasons for these differences.

A reliable and accurate method for collection and analysis of octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) in wastewater treatment plant influent, effluent and surface waters was developed. Due to the use of cyclic volatile methylsiloxanes (cVMS) in industrial and consumer products including some personal care products, the wastewater stream represents a potential post-use disposal route and cVMS may subsequently enter the environment through wastewater treatment plant effluents. cVMS in the environment has come under increased regulatory scrutiny with regard to their potential for persistence, bioaccumulation and toxicity indicating a need for monitoring programs with reliable analytical methods. The developed method is unique in that it utilizes low density polyethylene (LDPE) to inhibit loss of cVMS during sampling and transport to the laboratory. The samples are then processed with a simple solvent extraction and analyzed by gas chromatography mass spectrometry with stable isotope internal standard calibration. This method utilizes readily available laboratory supplies and requires minimal field processing, reducing contamination potential. Method detection limits of 17 ng/L, 57 ng/L, and 20 ng/L were obtained for D4, D5, and D6, respectively. Additionally a robust quality control program was employed to ensure sample integrity. The method described herein can readily be adopted for use in monitoring studies where the amount of cVMS in water samples will be quantified., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Waste-to-energy projects are an increasingly prominent component of future energy portfolios. Landfill gas (LFG)-to-energy (LFGTE) projects are particularly important as they address greenhouse gas emissions. Contaminants in LFG may hamper these projects both from environmental and economic standpoints. The purpose of this review is to highlight key aspects (LFG composition ranges, LFG flowrates, and allowable tolerances for LFGTE technologies, performance and costs for contaminant removal by adsorption). Removal of key contaminants, H 2 S and siloxanes, by adsorption are surveyed in terms of adsorption capacities and regeneration abilities. Based on the open literature, costing analyses are tabulated and discussed. The findings indicate economics of contaminant removal depend heavily on the feed concentrations of contaminants, allowable tolerances for the LFGTE technology, and the current market for the product. Key trends, identification of challenges, and general purification guidelines for purifying LFG for energy projects are also discussed., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

The use of siloxanes has been increasing due to physicochemical properties that are appropriate to be included in the formulations of a large variety of consumer products. This implies a considerable release of these chemicals into the environment, which caught the attention of the scientific community in view of some reports of potential hazardous effects. However, the studies related to the presence and partition of volatile methylsiloxanes (VMSs) in wastewater treatment plants (WWTPs) are still scarce. The aim of this review is to provide a comprehensive assessment of the current state of the knowledge concerning the presence of VMSs in WWTPs and also a discussion of the efficiency of the removal technologies available. Levels, fate and behaviour of VMSs in WWTPs were reviewed, covering not only the water and sludge lines during the treatment processes, but also in the surrounding air. Several approaches for the analysis of VMSs within the WWTPs have been developed to cope with the complexity of the mentioned matrices, which led to sometimes challenging protocols. Hence, an overview of methodologies normally used was also included in the present review. Regarding the wastewater samples, VMSs have been detected in influents in concentrations ranging from a few nanograms to a hundred micrograms per litre, in which linear VMSs were usually detected in lower levels than cyclic siloxanes. The levels of VMSs in effluents were lower than those found in influents, suggesting an effective removal from the water line. However, they are commonly accumulating in the sludge, instead of suffering degradation during the treatment process. Therefore, due to the volatile character of VMSs it can be expected that a fraction may be removed in WWTPs by volatilization, thus completing the mass balances to the whole treatment facilities., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

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

Sand flies are natural hosts of various microorganisms. Due to their epidemiological importance, sand fly colonies are kept in laboratories to be studied in terms of their biology and vector/host/parasite interactions. In order to investigate the presence of oviposition pheromones in Nyssomyia neivai, experiments using Solid Phase Microextraction (SPME) were performed. However, siloxanes which is an external class of contamination, present in breeding containers made by plaster used to maintain sand flies in colonies, may be hindered the experiments., (Published by Elsevier B.V.)

We measured the concentrations of linear and cyclic volatile methylsiloxanes (VMS) concentrations in the blood plasma of turtles, cormorants, and seals collected from Canadian freshwater and marine ecosystems. A modified quick, easy, cheap, effective, rugged, and safe (QuEChERS) method was developed to quantify the levels of linear and cyclic VMS in the plasma samples. The cyclic VMS of hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) were present in the plasma of all three species. Linear VMS compounds were observed only in seal plasma from one contaminated site. There was no statistically significant difference among species and locations for D3, D4, and D6 concentrations. Average D5 concentrations ranged from 0.143 to 7.39ngg -1 ; these concentrations appeared to be associated with diffuse/urban sources. Snapping turtles, cormorants, and seals all exhibited elevated D5 concentrations in contaminated sites relative to the reference sites. Our data indicate that local urban sources of VMS contributed significantly to the observed D5 concentrations in free-ranging wildlife. The presence of cyclic VMS in the plasma of the three species from Canada demonstrates that these chemicals are ubiquitous in aquatic biological systems. This finding raises concerns regarding their persistence in freshwater and marine environments. To the best of our knowledge, this study reports the first measurements of VMS compounds in the plasma of reptiles, birds, and mammals., (Crown Copyright © 2016. Published by Elsevier B.V. All rights reserved.)

The potential of wastewater treatment plants (WWTPs) to act as sources of poly and perfluoroalkyl substances (PFASs), volatile methyl siloxanes (VMSs) and organic UV-filters to the atmosphere was investigated. Target compounds included: PFASs (fluorotelomer alcohols (FTOHs), perfluorooctane sulfonamides/sulfonamidoethanols (FOSAs/FOSEs), perfluroalkyl sulfonic acids (PFSAs) and perfluroalkyl carboxylic acids (PFCAs)), cyclic VMSs (D3 to D6), linear VMSs (L3 to L5) and eight UV-filters. Emissions to air were assessed at eight WWTPs using paired sorbent-impregnated polyurethane foam passive air samplers, deployed during summer 2013 and winter 2014. Samplers were deployed on-site above the active tank and off-site as a reference. Several types of WWTPs were investigated: secondary activated sludge in urban areas (UR-AS), secondary extended aeration in towns (TW-EA) and facultative lagoons in rural areas (RU-LG). The concentrations of target compounds in air were ∼1.7-35 times higher on-site compared to the corresponding off-site location. Highest concentrations in air were observed at UR-AS sites while the lowest were at RU-LG. Higher air concentrations (∼2-9 times) were observed on-site during summer compared to winter, possibly reflecting enhanced volatilization due to higher wastewater temperatures or differences in influent wastewater concentrations. A significant positive correlation was obtained between concentrations in air and WWTP characteristics (influent flow rate and population in the catchment of the WWTP); whereas a weak negative correlation was obtained with hydraulic retention time. Emissions to air were estimated using a simplified dispersion model. Highest emissions to air were seen at the UR-AS locations. Emissions to air (g/year/tank) were highest for VMSs (5000-112,000) followed by UV-filters (16-2000) then ΣPFASs (10-110)., (Copyright © 2016. Published by Elsevier Ltd.)

Organosiloxanes, namely volatile methylsiloxanes (VMSs) are one of the most relevant classes of ingredients incorporated in personal care products (PCPs), such as creams and lotions, bath soaps and hair care products. Their use has caused concern among the scientific community due to their potential toxic behaviour to human health and environment. This manuscript reports the first application of QuEChERS ("Quick, Easy, Cheap, Effective, Rugged and Safe") extraction followed by gas chromatography - mass spectrometry analysis to determine VMSs in cosmetics and personal care products. Eight VMSs, four linear (L2-L5) and four cyclic (D3-D6) were investigated in 36 samples. The validated method was able to remove the interfering matrix components, conducting to high recovery percentages (74-104%) and low relative standard deviations (<18%). A linear behaviour was observed in the range of 0.005-2.50mgL(-1) (correlation coefficient, R(2)>0.996) and limits of detection ranged from 0.17ngg(-1) (L2) to 3.75ngg(-1) (L5). Matrix effects were also investigated for all analysed compounds and matrices and showed not to be significant. Global uncertainty of the proposed methodology was also estimated using a bottom-up approach being between 5% and 35% (on average). Finally, the method was satisfactorily applied to the analysis of 36 personal care products. As expected, results showed the existence of VMSs in all analysed samples in concentrations up to 754µgg(-1). D4 and D5 were more frequently detected while body moisturizers, facial creams and shampoos showed the highest levels of VMSs., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Organosiloxanes are widely used in the formulation of a broad range of cosmetic and personal care products (PCPs), including creams and lotions, bath soaps, shampoo and hair care products to soften, smooth, and moisten. In fact, the intensive and widespread use of organosiloxanes combined with their lipophilic nature, makes them interesting targets for future research, particularly in the toxicology area. This study focused on determining the concentration levels of these compounds in the bestselling brands of PCPs in the Oporto region (Portugal), allowing the estimation of dermal and inhalation exposure to siloxanes and the evaluation of the quantities released to the environment "down-the-drain" and to air. To accomplish this task, a QuEChERS technique ("Quick, Easy, Cheap, Effective, Rugged, and Safe") was employed to extract the siloxanes from the target PCPs, which has never been tested before. The resulting extract was analysed by gas chromatography-mass spectrometry (GC-MS). The limits of detection varied between 0.17 (L2) and 3.75ngg(-1) (L5), being much lower than any values reported in the literature for this kind of products. In general, satisfactory precision (<10%) and accuracy values (average recovery of 84%) were obtained. 123 PCPs were analysed (moisturizers, deodorants, body and hair washes, toilet soaps, toothpastes and shaving products) and volatile methylsiloxanes were detected in 96% of the samples, in concentrations between 0.003μgg(-1) and 1203μgg(-1). Shampoo exhibited the highest concentration for cyclic and aftershaves for linear siloxanes. Combining these results with the daily usage amounts, an average daily dermal exposure of 25.04μgkgbw(-1)day(-1) for adults and 0.35μgkgbw(-1)day(-1) for baby/children was estimated. The main contributors for adult dermal exposure were body moisturizers, followed by facial creams and aftershaves, while for babies/children were body moisturizers, followed by shower gel and shampoo. Similarly, the average daily inhalation exposure was also estimated. Values of 1.56μgkgbw(-1)day(-1) for adults and 0.03μgkgbw(-1)day(-1) for babies/children were calculated. An estimate of the siloxanes amount released "down-the-drain" into the sewage systems through the use of toiletries was also performed. An emission per capita between 49.25 and 9574μgday(-1) (mean: 1817μgday(-1)) is expected and shampoo and shower gel presented the higher mean total values (1008μgday(-1) and 473.3μgday(-1), respectively). In the worst-case scenario, D5 and D3 were the predominant siloxanes in the effluents with 3336μgday(-1) and 3789μgday(-1), respectively. Regarding the air emissions per capita, values between 8.33 and 6109μgday(-1) (mean: 1607μgday(-1)) are expected and D5 and D6 were the predominant siloxanes., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

The occurrence and fate of four cyclic (D3 to D6) and 10 linear (L5 to L14) siloxanes were investigated in influent and effluent wastewater, sludge from a wastewater treatment plant (WWTP), and surrounding air and soil within the WWTP in Harbin, Northeast China. The mean concentrations of total siloxanes in influent and effluent were 4780 and 997 ng/L and in excess sludge and aerobic sludge were 25.1 and 32.3 μg/g dw, respectively. The concentrations in air and soil within the WWTP were 243 ng/m(3) and 4960 ng/g dw, respectively. A similar composition profile of siloxanes in influent and sludge suggests their same source. Seasonal variation with concentration was comprehensively studied. It was found that temperature and rainfall are the two important factors for the seasonal variation of siloxanes. Adsorption with sewage sludge was the major way for the removal of siloxanes during the municipal wastewater treatment process. Overall, on a daily basis, the mass loading of the Σsiloxanes into the WWTP, out of the WWTP with the effluent and sludge, were estimated to be 3.0, 0.6 and 1.3 kg, respectively. In general, 21 % of siloxanes were discharged into the receiving body (Songhua River), 43 % of siloxanes were absorbed on sludge, and 36 % of siloxanes were lost during the whole process of WWTP.

Siloxane levels in biogas can jeopardize the warranties of the engines used at the biogas to energy facilities. The chemical structure of siloxanes consists of silicon and oxygen atoms, alternating in position, with hydrocarbon groups attached to the silicon side chain. Siloxanes can be either in cyclic (D) or linear (L) configuration and referred with a letter corresponding to their structure followed by a number corresponding to the number of silicon atoms present. When siloxanes are burned, the hydrocarbon fraction is lost and silicon is converted to silicates. The purpose of this study was to evaluate the adequacy of activated carbon gas samplers for quantitative analysis of siloxanes in biogas samples. Biogas samples were collected from a landfill and an anaerobic digester using multiple carbon sorbent tubes assembled in series. One set of samples was collected for 30min (sampling 6-L gas), and the second set was collected for 60min (sampling 12-L gas). Carbon particles were thermally desorbed and analyzed by Gas Chromatography Mass Spectrometry (GC/MS). The results showed that biogas sampling using a single tube would not adequately capture octamethyltrisiloxane (L3), hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6). Even with 4 tubes were used in series, D5 was not captured effectively. The single sorbent tube sampling method was adequate only for capturing trimethylsilanol (TMS) and hexamethyldisiloxane (L2). Affinity of siloxanes for activated carbon decreased with increasing molecular weight. Using multiple carbon sorbent tubes in series can be an appropriate method for developing a standard procedure for determining siloxane levels for low molecular weight siloxanes (up to D3). Appropriate quality assurance and quality control procedures should be developed for adequately quantifying the levels of the higher molecular weight siloxanes in biogas with sorbent tubes., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Increasing sensitivity without further preconcentration steps is a major challenge in separation sciences. In this study a macro control approach that allows the implementation of Hadamard encoding on standard HPLC instrumentation was applied to the analysis of polysiloxane and polystyrene polymers by gel permeation chromatography. Here, the use of pseudo-random modulation sequences with 1023 elements (512 sample injections) improved the signal-to-noise ratio (S/N) by up to an order of magnitude. Comparison with conventional single injection confirmed the linearity and accuracy of the deconvolution process for the whole mass range of the column., (Copyright © 2016 Elsevier B.V. All rights reserved.)

A gas chromatography with flame ionization detection (GC-FID) method for analysis of D4, D5, and D6 cyclic siloxanes in silicone emulsions is described. Sample preparation involves breaking the emulsion with methanol and hexanes, and then analyzing the hexanes phase after derivatization with hexamethyldisilazane (HMDS). Silylation is performed to reduce the potential for formation of cyclic siloxanes during the course of the GC analysis. The accuracy of the method was verified by performing analyses on samples spiked with known levels of D4, D5 and D6 and by comparison to a referee method using atmospheric pressure chemical ionization liquid chromatography with mass spectrometry detection (APCI-LC-MS). Absolute differences of the results obtained between the two techniques were 0.03 weight percent or less, and relative differences were 15% or less. The reproducibility and ruggedness of the method was demonstrated by performing a global round robin test at four different geographic sites on four different types of silicone emulsions. The %RSDs obtained were less than 10% for all analytes and all emulsions examined., (Copyright © 2016 Elsevier B.V. All rights reserved.)

This study aimed to contribute to the enhancement of the knowledge of levels, trends and behaviour of eight siloxanes (four linear and four cyclic) in the environment. Adding to the prioritised scrutiny of the incidence in the atmosphere through passive samplers (sorbent-impregnated polyurethane foam disks--SIPs), the sampling of pine needles and soil was also performed, thus closing the circle of atmospheric exposure in the areas of study. Two sampling campaigns (one in summer and one in winter) were done in a total of eight sampling points in the Portuguese territory, which covered a wide range of human presence and land uses (urban, industrial, remote and beach areas). By adopting a "green" approach in terms of analytical methods, namely reducing the clean-up steps for the passive air samples and using the quick, easy, cheap, effective, rugged and safe (QuEChERS) technology for soils and pine needles, the results showed total concentration of siloxanes between 5 and 70 ng g(-1) (dry weight) for soils and from 2 to 118 ng g(-1) (dry weight (dw)) for pine needles, with no clear seasonal trend. For SIPs, the levels varied from 0.6 to 7.8 ng m(-3) and were higher in summer than in winter in all sites. Overall, the cyclic siloxanes were found in much higher concentrations, with D5 and D6 being the most predominant in a great majority of cases. Also, the urban and industrial areas had the highest incidence, suggesting a strong anthropogenic fingerprint, in line with their main uses.

Cyclic volatile methyl siloxanes (cVMSs) are highly volatile and have an unusual combination of physicochemical properties, which are unlike those of halocarbon-based chemicals used to establish criteria for identification of persistent organic pollutants (POPs) that undergo long-range transport (LRT). A transparent quantitative weight of evidence (QWoE) evaluation was conducted to characterize their properties. Measurements of concentrations of cVMSs in the environment are challenging, but currently, concentrations measured in robust studies are all less than thresholds of toxicity. The cVMSs are moderately persistent in air with half-lives ≤11 d (greater than the criterion of 2 d) but these compounds partition into the atmosphere, the final sink. The cVMSs are rapidly degraded in dry soils, partition from wet soils into the atmosphere, and are not classifiable as persistent in soils. Persistence in water and sediment is variable, but the greatest concentrations in the environment are observed in sediments. Based upon the measurements that have been made in the environment, cVMSs should not be classified as persistent. Studies in food webs support a conclusion that the cVMSs do not biomagnify, a conclusion that is consistent with results of toxicokinetic studies. Concentrations in air in remote locations are small and deposition has not been detected. Taken together, evidence indicates that traditional measures of persistence and biomagnification used for legacy POP are not suitable for cVMS. Refined approaches used here suggest that cVMSs are not classifiable as persistent, bioaccumulative, or toxic. Further, these chemicals do not undergo LRT in the sense of legacy POPs.