Linear Siloxanes Research Articles

Conformational Analysis of Oligomeric Models of Siloxane, Silazane and Siloxazane Ladder Polymers

Oligomeric models of linear ladder silanes, siloxanes and siloxazanes with seven repeat units consisting of four-, six-, or eight-membered rings were designed and their conformations in chloroform were explored. The Low Mode–Monte Carlo conformational method was used to explore oligomeric flexibility on the OPLS-2005/GBSA(CHCl3) potential energy surface to obtain a set of low energy structures for each oligomer. These structures were then optimized using B3LYP/6-31G*/SCRF-PBF(CHCl3) calculations. The results indicate complex conformational dynamics with mostly non-planar, curved structures. Electron delocalization from the lone pair of electrons on N or O into empty 3d orbitals on Si was not observed.

Factors determining contamination and time trends in cyclic and linear siloxanes in sediments from an industrialized lake in Korea

Siloxanes, widely used in various consumer and industrial products, are emerging concerns of contaminants. Despite this, limited studies have been conducted on contamination and time trends on siloxanes in coastal environments. In the present study, four cyclic and 15 linear siloxanes were measured in sediments collected from an artificial saltwater lake in Korea during 2001–2016 to investigate contamination, time trends, and ecotoxicological concerns. Cyclic siloxanes were detected in all sediment samples, whereas linear siloxanes were not frequently detected. The highest siloxane concentrations were observed in creeks passing through various industrial complexes, indicating that industrial activities predominantly contributed to siloxane contamination in coastal environments. Decamethylcyclopentasiloxane (D5) and dodecylcyclohexasiloxane (D6) were predominant siloxanes in sediments over the last two decades. Siloxane concentrations significantly increased in creek sediments from 2008 to 2016, whereas those in inshore and offshore regions significantly decreased due to a strong dilution effect by the operation of tidal power plant. This suggests that consumption patterns and coastal development activities are crucial factors determining the contamination and time trends in the sedimentary siloxanes. The sedimentary concentrations of octamethylcyclotetrasiloxane (D4) and D5 exceeded several thresholds, raising the potentials for ecological risks to aquatic organisms.

Bioaccumulation of Linear Siloxanes in Fish.

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

Occurrence, time trends, and human exposure of siloxanes and synthetic musk compounds in indoor dust from Korean homes

Siloxanes and synthetic musk compounds (SMCs) have been widely used as additives in household and personal care products. Humans are easily exposed to siloxanes and SMCs originating from these products through ingestion and dermal absorption of indoor dust. In the present study, indoor dust samples were analyzed for 19 siloxanes (cyclic and linear) and 12 SMCs (polycyclic, macrocyclic, and nitro musks) to assess their occurrence, time trends over time, source, and health risks. A total of 18 siloxanes and 10 SMCs were detected in all indoor dust samples obtained from 2011⎯2021, indicating widespread and long-term contamination. Higher detection frequencies and concentrations were associated with siloxanes and SMCs with higher use and strong resistance against degradation processes. Indoor dust samples were dominated by linear siloxanes (L11–L13), 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-(g)-2-benzopyran (HHCB), musk ketone (MK), and 7-acetyl-1,1,3,4,4,6-hexamethyl-1,2,3,4-tetrahydronaphthalene (AHTN). The frequent use of household and personal care products is likely an important source of siloxane and SMC contamination in indoor environments. The concentrations of siloxanes and SMCs in indoor dust increased from 2011 to 2021, particularly, those of linear siloxanes, reflecting the impact of regulatory actions addressing cyclic siloxanes. The profiles of siloxanes remained stable throughout the study period, whereas those of SMCs shifted from nitro to polycyclic musks. The estimated daily intakes (EDIs) of siloxanes and SMCs arising from ingestion were greater than from dermal absorption of indoor dust. The EDIs of siloxanes and SMCs associated with indoor dust indicated that children are exposed to these pollutants.

Quantitative Simulations of Siloxane Adsorption in Metal-Organic Frameworks.

We present a transferable force field (FF) for simulating the bulk properties of linear and cyclic siloxanes and the adsorption of these species in metal-organic frameworks (MOFs). Unlike previous FFs for siloxanes, our FF accurately reproduces the vapor-liquid equilibria of each species in the bulk phase. The quality of our FF combined with the Universal Force Field using standard Lorentz-Berthelot combining rules for MOF atoms was assessed in a wide range of MOFs without open metal sites, showing good agreement with dispersion-corrected density functional theory calculations. Predictions with this FF show good agreement with the limited experimental data for siloxane adsorption in MOFs that is available. As an example of using the FF to predict adsorption properties in MOFs, we present simulations examining entropy effects in binary linear and cyclic siloxane mixture coadsorption in the large-pore MOF with structure code FOTNIN.

Removal of Cyclic and Linear Siloxanes in Effluents from a Cosmetic Wastewater Treatment Plant by Electrochemical Oxidation

Removal of Cyclic and Linear Siloxanes in Effluents from a Cosmetic Wastewater Treatment Plant by Electrochemical Oxidation

Assessment of the mass transfer strategy and the role of the active bacterial population on the biological degradation of siloxanes

Upgrading of biogas to remove siloxanes is mandatory to meet the standards required for its use as a substitute of fossil fuels. The biological degradation of these pollutants is a low cost and environmental friendly alternative to conventional techniques, albeit certain limitations, such as the low solubility of siloxanes, still hinder its application. In the present work, two parameters were optimized in aerobic and anoxic two-phase biotrickling filters (TP-BTF): the trickling liquid velocity (TLV) and the internal gas recirculation, with the aim of improving siloxanes biological removal. The results obtained showed that the increase in TLV from 2 to 10 m h−1 resulted in higher removal efficiency (RE) under both anoxic and aerobic conditions, reaching maximum values of 55 and 47%, respectively. This effect was more significant for the linear siloxanes. On the contrary, a further increase in the TLV to 20 m h−1 together with the implementation of internal gas recirculation caused an excessive turbulence in the liquid side, detaching the biofilm and having a negative effect for the RE. The cyclic siloxanes were more effectively eliminated along the process (maximum REs of 75% were recorded for decamethylcyclopentasiloxane (D5)), but the studied system modifications exerted a minor effect on their RE. The active bacterial population involved in siloxanes degradation (studied throughout RNA extraction and sequencing) was dominated by the clade Acidithiobacillacea KCM-B-112 and the genus Parvibaculum in aerobic conditions, while the members of the family Phyllobacteriacea and the genera Nocardia and Baekduia dominated in anoxic conditions.

Thermal stability of linear siloxanes and their mixtures

The working fluid thermal stability is one of the crucial features of an effective organic Rankine cycle. Hexamethyldisiloxane (MM - C6H18OSi2) and octamethyltrisiloxane (MDM - C8H24O2Si3) are siloxane fluids currently exploited in high temperature organic Rankine cycles. However, data about their thermal stability are scarce or absent in literature. This manuscript presents a study of their behavior and decomposition at operating temperatures in the range 270–420°C.The assessment of thermal stability can be performed with several methods, which are either based on pressure anomalous variation in isothermal stresses or on the deviation of the saturation curves experimentally obtained before and after the fluid is thermally stressed. An enhanced method is proposed here, based on chemical analysis of both vapor and liquid phases of the sample before and after it is subjected to thermal stress. A comparison of the pre- and post-stress vapor–liquid equilibrium curve complements the analysis.Results proved a higher stability for MM than for MDM. Moreover, due to the current interest in applying mixtures in organic Rankine cycles, an equimolar mixture of MM and MDM was also tested, which exhibit a behavior that appears to be different from the simple superimposition of pure fluid ones.

Spatial distribution and temporal trends of cyclic and linear siloxanes in sediment from semi-enclosed and industrialized bays of Korea, in 2013 and 2021

Although siloxanes are contaminants of emerging concerns, limited studies have been conducted on contamination and time trends in siloxanes from aquatic environments worldwide. To date, most previous studies have focused on the environmental relevance of cyclic siloxanes in coastal environments. In the present study, cyclic and linear siloxanes were measured in sediment collected from semi-enclosed bays in Korea in 2013 and 2021 to assess occurrence, spatial distribution, temporal trends, and ecological risks. Almost all siloxanes were detected in all sediment samples, indicating continuous contamination for the last decade. The concentrations of cyclic siloxanes in sediment were approximately two times higher than those of linear siloxanes. Decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6) were predominantly detected in all sediment samples, possibly due to their high consumption and strong resistance. The overall concentrations of siloxanes in sediment gradually decreased from inner to outer parts of the bays, suggesting that industrial activities largely contributed to siloxane contamination. Moreover, the highest concentrations of siloxanes in both sampling years were observed in sediment near the outfall of wastewater treatment plant, implying a potential source in the coastal environment. Siloxane concentrations in sediment were significantly correlated with sedimentary organic carbon. The concentrations of siloxanes in sediment were not significantly different between 2013 and 2021, indicating ongoing contamination. The concentrations of D5 and D6 in our sediment samples showed a limited potential to pose a threat to benthic organisms.

Density and Viscosity of Linear Siloxanes and Their Mixtures

Density and viscosity measurements are performed for ethanol, water, hexamethyldisiloxane (MM), octamethyltrisiloxane (MDM), decamethyltetrasiloxane (MD2M), and their mixtures (ethanol/water, MM/MDM, MM/MD2M, MDM/MD2M) at 100 kPa at different temperatures (293–423 K) and mixture compositions. To measure the density and viscosity, an IMETER measuring system with a combined dynamic and static force measurement method, a density meter with an oscillating U-tube measuring method, and a rheometer with a double-gap measuring system were used. The experimentally determined data for the pure substances show a very good agreement with literature data. However, there is a strong deviation of the mixture viscosity between max 7% for MM/MDM and 31% for MM/MD2M compared to Refprop v.10.0. In order to enable an improvement in the calculation of the density and viscosity for the mixtures, specific parameters for the Jouyban–Acree model are developed for all mixtures and thereby, a better description of the density and viscosity for the mixtures could be achieved.

Nationwide monitoring of cyclic and linear siloxanes in sediment and bivalves from Korean coastal waters: Occurrence, geographical distribution, and bioaccumulation potential.

Contamination of coastal environments by siloxanes is of growing concern. Sediment and bivalves were collected from 50 locations along the Korean coast to assess the geographical distribution, sources, and bioaccumulation potential of siloxanes. Cyclic and linear siloxanes were detectable in all sediment and bivalve samples. The highest siloxane concentrations were detected in sediment (656ng/g dw) and bivalves (3273ng/g dw) from highly industrialized bays and harbor-zones, suggesting that industrial and shipping activities are major sources of siloxanes in coastal environment. The geographical distribution of siloxanes was similar in sediment and bivalves. Sedimentary siloxanes were dominated by cyclic siloxanes, while linear siloxanes were predominant in bivalves. Bioaccumulation of linear siloxanes in bivalves originated mainly from the sedimentary environment. Mean biota-sediment accumulation factors (BSAFs) of seven siloxanes ranged from 1.26 to 6.03, indicating potential for bioaccumulation. This is the first report on the nationwide survey on siloxanes in Korean coastal waters.

Volatile Methyl Siloxanes and Other Organosilicon Compounds in Residential Air.

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

Two Complementary Approaches to Silicon-Supported Soluble [FeFe]-Hydrogenase Mimics

Two series of silicon-supported [(μ-SCH2)2NRFe2(CO)6] (R = p-OHC6H4, 3, and (CH2)2OH, 4a, and (CH2)5OH, 4b) hydrogenase mimics, as well as octamethylsilsesquioxane (POSS)-based nanostructures containing eight [(μ-SCH2)2NRFe2(CO)6] moieties, have been prepared either by reaction of the corresponding silyl and silyloxy chlorides and compounds 3 and 4 or by CuAAC between propargyl derivatives of silyl and silyloxy chlorides and azide 14. Cycloaddition between POSS-derived azide 23b and [(μ-SCH2)2NRFe2(CO)6] (R = alkyne) complexes 24 and 26 is efficient, leading to POSS-based nanostructures containing eight [(μ-SCH2)2NRFe2(CO)6] units. All of the complexes prepared through this work were soluble in organic solvents and hence fully characterizable by spectroscopic media. The electrochemistry of the linear siloxanes 6a and 10 is similar, with a reduction wave around −1.7 V, which is characteristic of these [(μ-SCH2)2NRFe2(CO)6] entities. Complexes 6a and 6b lacking 1,2,3-triazole moieties were electrochemically stable in the presence of AcOH, showing a strong electrocatalytic wave at −2.2 V, while complexes 16 and 18 having the 1,2,3-triazole ring decomposed but were electrocatalytically active in the wave at −2.2 V. POSS-[(μ-SCH2)2NRFe2(CO)6] derivatives 25 and 27 show a strong irreversible reduction event and are deposited in the electrode either when adding AcOH or over time (successive voltammograms). 29Si NMR shows that the integrity of the silicon cage is not affected by time or AcOH addition. These synthetic protocols and electrochemical studies will be applied in the design of silicon-supported [(μ-SCH2)2NRFe2(CO)6] mimics.

Measurement and modeling of liquid thermal conductivity of linear siloxanes: Octamethyltrisiloxane (MDM) and Hexamethyldisiloxane (MM)

In this work, the thermal conductivity data of Octamethyltrisiloxane (MDM) and Hexamethyldisiloxane (MM) were measured by the transient hot wire method, in the temperature range of 263.15 K to 353.15 K and the pressures ranging from 0.1 MPa to 7.0 MPa, with an uncertainty of 3.5 % for MDM and 3.8 % for MM. Then a comparison between the present data and previously reported thermal conductivities was made, indicating a good agreement. Additionally, a thermal conductivity model based on the modified Enskog theory was used to represent the experimental data. This study provides a necessary basis for the calculation and analysis of the heat transfer of typical linear siloxanes for the organic Rankine cycle.

Removal of linear siloxanes and dimethyl sulfone from water using hierarchical zeolite porous carbon adsorbents

Low molecular weight linear siloxanes are problematic compounds known to occur in water bodies, especially in water reclaimed from closed volumes. Remediation was attempted using a hierarchical porous composite adsorbent containing a Faujasite zeolite imprinted in activated carbon, namely CFAU. Although CFAU was prepared using procedures reported elsewhere, it was modified also to include extra-framework Ag+ cations. The composites long-range, textural, and compositional characteristics were verified via XRD, nitrogen porosimetry, water contact angle, zeta potential, TGA, and ICP elemental analyses. Furthermore, the composites were tested for the adsorption of siloxanes (i.e., monomethylsilanetriol, dimethylsilanediol, and trimethylsilanol (TMS)) as well as dimethyl sulfone (DMSO2) from water (mg L−1 level) in single and multicomponent fashion at ambient temperature and neutral pH. DMSO2 is highly ubiquitous in reclaimed waters where these siloxanes occur. Ag+-CFAU was the superior adsorbent, with siloxane and DMSO2 loadings of up to 20 and 87 mg cm−3 (or 17 and 72 mg g−1), respectively. These are at least an order of magnitude larger than commercial alternatives like carbon and resins. FTIR data suggest that the adsorption interaction with siloxanes is of Van der Waals type, whereas interactions between Ag+-CFAU and DMSO2 plausibly involve complexation. Moreover, multicomponent adsorption tests showed that Ag+-CFAU excels probably because of the complexation with DMSO2 and a TMS-driven siloxane co-adsorption.

Influence of wastewater effluents on the bioaccumulation of volatile methylsiloxanes in the St. Lawrence River

The bioaccumulation of cyclic volatile methylsiloxanes (D3 to D6) as well as linear siloxanes (L3 to L5) was studied in a food web in the St. Lawrence River downstream of the effluent of the municipal wastewater treatment plant in Montreal, Canada. For most species, differences in δ15N in fish and prey showed a clear separation of individual fish feeding in food webs influenced by the wastewater plume from those feeding outside the plume. Cyclic siloxanes were detected in all biotic samples from the individuals identified as feeding in the effluent plume. Siloxane D5 accounted for more than 80% of the total siloxanes. Linear siloxane L5 was also abundant in walleye and gull eggs. Total siloxane concentrations in suspended sediments were 17.3 times higher than in surface sediments in the region of the river in the effluent plume. Caged freshwater mussels (Elliptio sp.), placed in the effluent plume, bioaccumulated 43 times more total siloxanes than PBDEs in 30 days, demonstrating how readily siloxanes are taken up in biota and what a significant component of the contaminant body burden they can account for. The sediment-biota accumulation factors (BSAF) for total siloxanes (∑ D3 to D6 and L3 to L5) showed values of 65.4, 27.8, 9.9 and 6.4 for walleye, northern pike, yellow perch and round goby respectively.

Silanes and Siloxanes Thermal Conductivity in the Liquid Phase: A Critical Review and an Improved Prediction Method

The thermal conductivity λ of the silanes and siloxanes families in the liquid phase at atmospheric pressure or along the saturation line is investigated as function of the reduced temperature. Because of the large scarcity or even of the lack of accurate experimental λ data an empirical equation is proposed as a generalization based on investigations presented in previous works [1, 2]. The families of silanes and siloxanes (21 chlorosilanes, 5 cyclosiloxanes, 10 linear siloxanes, 10 silanes and 19 other silanes) are taken into consideration using a large database [3] in order to extend the use of a general formula valid for organic compounds (alcohols, alkanes, ketones,….) and to improve preceeding results obtained in the case of the cited silanes and siloxanes, for which experimental thermal conductivity data at atmospheric pressure or along the saturation line in the liquid phase are available in very few cases. The equation is proposed as acceptable for engineering purposes and comparable with the existing prediction methods [3]. The database DIPPR [3] in the version 2020 containing a linear correlation with various parameters is taken into account, also considering the results of 7 other prediction methods existing in the technical and scientific literature. An extensive and critical comparison points out that the method proposed in this work can be considered valid with absolute errors usually not greater than 5%.

Tissue-specific distribution and bioaccumulation of cyclic and linear siloxanes in South Korean crucian carp (carassius carassius)

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

Analytical pyrolysis of poly(dimethylsiloxane) and poly(oxyethylene) siloxane copolymers. Application to the analysis of sewage sludges

Dimethicone (poly(dimethylsiloxane), PDMS) and its copolymers bearing a poly(ethylene glycol) (PEG) side chain (PEG-12 dimethicone and PEG-8 dimethicone) are utilised as ingredients in personal care products. These materials along with bis-PEG-18 methyl ether dimethyl silane were analysed by Py-GC–MS. The pyrolysates of dimethicone was dominated by cyclic dimethyl siloxanes from D3 to over D10. Besides Dn, the pyrolysates of PEG-dimethicone were featured by the presence of linear dimethyl siloxanes Ln. Hydroxylated siloxanes were also tentatively identified. Pyrograms were also characterised by PEG oligomers with different terminal groups (hydroxyl, ethyl, ethenyl). The molecular structure of pyrolysis products from the combined structural units of PDMS and PEG could not be assigned. Internal standard calibration protocols using pyrolysis products of PEG-12 dimethicone (L6, L8, L9, and triethyleneglycol monoethyl ether) exhibited satisfactory linearity (R2 > 0.992) in the 0.75−58 μg range and repeatability (RSD < 15 %). Three samples of dried sewage sludge from a municipal water treatment plant were extracted with tetrahydrofuran and the extracts analysed by Py-GC–MS. The pyrograms were characterised by intense signals due to the lipid matrix (hydrocarbons, fatty acids, steranes, sterenes, sterols). Dn and Ln were identified indicative for the presence of siloxanes at levels around 60−290 μg gdw−1, while pyrolytic markers of PEG were not revealed. The recovery of PEG-12 dimethicone (17 μg) in spiked sample was 76 %. Galaxolide, galaxolide lactone and triclosan were identified in the pyrograms. The results of this study evidenced the potential of Py-GC–MS as a screening tool for the determination of cosmetic ingredients in sewage sludge.

Development of a New Passive Sampling Method for the Measurement of Atmospheric Linear and Cyclic Volatile Methyl Siloxanes.

A new passive sampling method was developed and characterized to measure atmospheric volatile methyl siloxanes (VMS). The infrastructure of a commercial passive air sampler (PAS) was used along with XAD-2 resin as the adsorbent. Experimental sampling rates (SR) determined using collocated active and passive samplers ranged between 0.0363 (L5) and 0.0561 (D3) m3/day and agreed well with the theoretical ones. VMS uptake was highly linear for eight weeks. The precision of the method was very good (<10%). Compared to the other PASs used for VMS, the new method has several advantages (i.e., the sampler is much smaller, it has commercially available components, and the solvent requirement, equipment needed for extraction, and steps for sample preparation are minimal) while achieving similar or lower method detection limits. The developed method was applied to investigate the spatial distribution and possible sources of atmospheric VMS in the Izmir region. Field sampling covered 42 sites representing different source and land use areas. ΣVMS concentrations ranged between 41.4 and 981 ng/m3. The dominant VMS was D5 followed by D3 and D4. Spatial distributions indicated that the main VMS sources in the area were urban areas, wastewater treatment plants, and landfills where the VMS-containing products are used and disposed.