Silicone Rubber Passive Samplers Research Articles

Time integrative sampling properties of Speedisk and silicone rubber passive samplers determined by chemical analysis and in vitro bioassay testing

Compared to grab samples, passive samplers have the advantage that they sample over a longer time period and can detect lower compound concentrations in water quality monitoring campaigns. To allow the determination of time-weighted average concentrations, however, sampler uptake should remain linear in time over the entire sampling period. Therefore, the time integrative or linear uptake properties of adsorption-based Speedisks and partitioning-based silicone rubber samplers were assessed with respect to chemically analyzed single compounds and measured bioactivity in in vitro bioassays. Both sampler types were deployed in consecutive and overlapping time series in a WTTP effluent and in the river Meuse up to 105 days. Extracts were chemically analyzed for PCBs, PAHs and pesticides and tested in the Aliivibrio fischeri and DR-LUC bioassays. Speedisks showed time integrative sampling for the detected pesticides as well as for bioassay responses at both sampling locations for the entire sampling period. The silicone rubber samplers showed poor linear uptake in time for the unknown compounds causing bioassay responses. The bioassay results indicate that conversion of a bioassay response to a passive sampler extract into a time-weighted average bioactivity per liter water seems justified for Speedisks, confirming that concentrations in the samplers correspond to a single volume of sampled water for all compounds. The bioassay results also indicate that a similar conversion for silicone rubber extracts should be interpreted with caution. In principle, it is actually impossible, because the concentration of each compound contributing to the bioassay response corresponds to a different sampled water volume.

Passive Samplers vs Sentinel Organisms: One-Year Monitoring of Priority and Emerging Contaminants in Coastal Waters

Temporal monitoring of pollutants in aquatic systems impacted by human activities is mandatory for a correct assessment on their environmental impact and later management. The aim of this work was to study the suitability of using silicone rubber passive samplers and caged organisms (Ruditapes philippinarum), simultaneously, to examine the spatial and temporal variability of priority and emerging contaminants in a coastal environment (Cadiz Bay, SW Spain) over the course of an entire year. Seasonal trends were observed for some classes of compounds such as UV filters and fragrances, and attributed to fluctuations in their sources and changes in the hydrodynamic conditions, respectively. Up to 42 out of 48 (in seawater) and 27 out of 37 (in biota) target analytes were detected, the highest concentrations being observed for synthetic fragrances and UV filters in both biota (136.9-159 ng g-1) and the dissolved phase (3322.2-265.7 ng L-1). Conversely, spatiotemporal differences in the concentrations of target contaminants in clam tissues were minimal. Higher field bioaccumulation factors (log BAF > 5) were found for priority substances. Overall, silicone rubber passive samplers proved to be more sensitive than sentinel organisms for monitoring spatiotemporal changes in the dissolved aqueous concentrations of contaminants, whereas the latter allowed for a more realistic evaluation of the potential uptake and bioaccumulation of each compound.

Elevated Concentrations of Semivolatile Organic Compounds in Social Housing Multiunit Residential Building Apartments

Flame retardants and phthalates are commonly used in consumer products and building materials, and as such, are prevalent in indoor air. Polycyclic aromatic hydrocarbons (PAHs) can have both indoor and outdoor sources and can also be found in indoor air. Flame retardants, phthalates, and PAHs were measured in indoor air in 71 units in low-income social housing multi-unit residential buildings (MURBs) using silicone rubber (polydimethylsiloxane or PDMS) passive air samplers deployed for 1 week in Toronto, Canada, in late spring and winter of 2017. Tris(1,3-dichloro-2-propyl) phosphate (TDCiPP), diethyl phthalate (DEP), and phenanthrene were the dominate flame retardant, phthalate, and PAH, with median concentrations of 1640 pg/m3 and 1840 and 79.0 ng/m3, respectively. Flame retardant and phthalate concentrations were 2 to 18 times higher than those in predominantly detached and semi-detached houses in Toronto measured using the same passive samplers. These results indicate higher exposures among residents of low-income social housing (63% with income <$23,400) than those of higher socio-economic status single-family dwellings (67% with income >$100,000).

Partitioning and Bioaccumulation of Legacy and Emerging Hydrophobic Organic Chemicals in Mangrove Ecosystems.

Knowledge regarding partitioning behavior and bioaccumulation potential of environmental contaminants is important for ecological and human health risk assessment. While a range of models are available to describe bioaccumulation potential of hydrophobic organic chemicals (HOCs) in temperate aquatic food webs, their applicability to tropical systems still needs to be validated. The present study involved field investigations to assess the occurrence, partitioning, and bioaccumulation behavior of several legacy and emerging HOCs in mangrove ecosystems in Singapore. Concentrations of synthetic musk fragrance compounds, methyl triclosan (MTCS), polychlorinated biphenyls, organochlorine pesticides, and polycyclic aromatic hydrocarbons were measured in mangrove sediments, clams, and caged mussels. Freely dissolved concentrations of the HOCs in water were determined using silicone rubber passive samplers. Results showed that polycyclic musks and MTCS are present in mangrove ecosystems and can accumulate in the tissues of mollusks. The generated HOC concentration data for mangrove water, sediments, and biota samples was further utilized to evaluate water-sediment partitioning (e.g., Koc values) and bioaccumulation behavior (e.g., BAF and BSAF values). Overall, the empirical models fit reasonably well with the data obtained for this ecosystem, supporting the concept that general models are applicable to predict the behavior of legacy and emerging HOCs in mangrove ecosystems.

An in-situ assessment of low-density polyethylene and silicone rubber passive samplers using methods with and without performance reference compounds in the context of investigation of polychlorinated biphenyl sources in rivers

This study firstly aims to assess the field performances of low density polyethylene (LDPE) and silicone rubber (SR) samplers for the monitoring of polychlorinated biphenyls (PCBs) in water regarding the uptake, the sampling rate (RS) estimated by using performance reference compounds (PRCs) and the time-weighted average (TWA) concentrations. The second aim is to evaluate the efficiency of these samplers to investigate PCB sources (localization and imputation steps) using methods with and without PRCs to correct for the impact of water velocity on the uptake. Samplers spiked with PRCs were deployed in the outfalls of two PCB sources and at 8 river sites situated upstream and downstream of the outfalls. After 6weeks, the uptake of PCBs in the linear phase was equivalent in LDPE and SR but 5 times lower in LDPE for PCBs approaching equilibrium. PRC-based RS and water velocity (0.08 to 1.21ms−1) were well correlated in river (LDPE: R2=0.91, SR: R2=0.96) but not in outfalls (higher turbulences and potential release of PRCs to air). TWA concentrations obtained with SR were slightly higher than those obtained with LDPE (factor 1.4 to 2.6 in river) likely because of uncertainty in sampler-water partition coefficient values. Concentrations obtained through filtration and extraction of water samples (203L) were 1.6 and 5.1 times higher than TWA concentrations obtained with SR and LDPE samplers, respectively. PCB sources could efficiently be localized when PRCs were used (increases of PCB loads in river) but the impact of high differences of water velocity was overcorrected (leading sometimes to false positives and negatives). Increases of PCB loads in the river could not be entirely imputed to the investigated sources (underestimation of PCBs contributing to the load increases). A method without PRCs (relationship between uptake and water velocity) appeared to be a good complementary method for LDPE.

Determination of silicone rubber and low-density polyethylene diffusion and polymer/water partition coefficients for emerging contaminants.

There is a growing interest in assessing the concentration and distribution of new nonregulated organic compounds (emerging contaminants) in the environment. The measurement of freely dissolved concentrations using conventional approaches is challenging because of the low concentrations that may be encountered and their temporally variable emissions. Absorption-based passive sampling enables the estimation of freely dissolved concentrations of hydrophobic contaminants of emerging concern in water. In the present study, calibration was undertaken for 2 polymers, low-density polyethylene (LDPE) and silicone rubber for 11 fragrances, 5 endocrine-disrupting compounds, 7 ultraviolet (UV) filters, and 8 organophosphate flame retardant compounds. Batch experiments were performed to estimate contaminant diffusion coefficients in the polymers (Dp ), which in general decreased with increasing molecular weight. The values for fragrances, endocrine-disrupting compounds, and UV filters were in ranges similar to those previously reported for polycyclic aromatic hydrocarbons, but were 1 order of magnitude lower for organophosphate flame retardant compounds. Silicone rubber had higher Dp values than LDPE and was therefore selected for further experiments to calculate polymer/water partition coefficients (KPW ). The authors observed a positive correlation between log KPW and log octanol/water partition coefficient values. Field testing of silicone rubber passive samplers was undertaken though exposure in the River Alna (Norway) for an exposure time of 21 d to estimate freely dissolved concentration. Some fragrances and UV filters were predominant over other emerging and regulated contaminants, at levels up to 1600 ng L(-1) for galaxolide and 448 ng L(-1) for octocrylene. Environ Toxicol Chem 2016;35:2162-2172. © 2016 SETAC.

Determination of Dissolved Concentrations of Polycyclic Aromatic Hydrocarbons in River

This study shows the sensitivity of using silicone rubber passive sampler(SR-PS) andgas chromatography with mass spectrometer (GC-MS) detection for monitoring and identification of polycyclic aromatic hydrocarbons in surface water systems. The analysis was performed for eighteen PAHs compounds after pre-concentration using Soxhlet extraction method. By comparison, a total of 13 PAHs were detected in the spot water samples, of which none was quantifiable. The freely dissolved PAH concentrations were found to range from 0.17 ng/L to 0.76 ng/L at Ugieriver. The use of fluorine d10 as Performance reference compound(PRC) gives a sampling rates of 8.14 (L/day) for silicone rubber passive samplers. Analysis of PAHs concentrations suggest the contaminants are mainly from pyrolytic sources. Overall it can be concluded that SR-PS are viable alternatives in the environmental monitoring of PAHs.

Determination of Dissolved Concentrations of Polycyclic Aromatic Hydrocarbons in River

This study shows the sensitivity of using silicone rubber passive sampler(SR-PS) andgas chromatography with mass spectrometer (GC-MS) detection for monitoring and identification of polycyclic aromatic hydrocarbons in surface water systems. The analysis was performed for eighteen PAHs compounds after pre-concentration using Soxhlet extraction method. By comparison, a total of 13 PAHs were detected in the spot water samples, of which none was quantifiable. The freely dissolved PAH concentrations were found to range from 0.17 ng/L to 0.76 ng/L at Ugieriver. The use of fluorine d10 as Performance reference compound(PRC) gives a sampling rates of 8.14 (L/day) for silicone rubber passive samplers. Analysis of PAHs concentrations suggest the contaminants are mainly from pyrolytic sources. Overall it can be concluded that SR-PS are viable alternatives in the environmental monitoring of PAHs.

Quantifying the effects of temperature and salinity on partitioning of hydrophobic organic chemicals to silicone rubber passive samplers.

Nowadays, passive sampling is a widely applied technique to determine freely dissolved aqueous concentrations of hydrophobic organic chemicals (HOCs), such as polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs). Crucial to the measurements are sampler-water partition coefficients, which are generally determined in the laboratory under "standard conditions" (in freshwater at 20 °C). Theoretically, however, the coefficients are dependent on environmental conditions, such as temperature and salinity. Yet, there are insufficient experimental data in the scientific literature to prove this for different polymers. Several polymers are already being applied during field monitoring, however, and neglecting any effects may lead to imprecise results. In the present study, we therefore quantified the effects of temperature and salinity on the sampler-water partition coefficients of PAHs and PCBs for silicone rubber, a material used in Dutch passive sampling monitoring campaigns. The results demonstrated a chemical-specific and hydrophobicity-dependent temperature effect, being independent of salinity, and a chemical- and temperature-independent salinity effect. Based on the obtained data, location-specific silicone rubber-water partition coefficients (Ksr-w; adjusted for temperature and salinity) can be calculated. The impact of applying such location-specific values was demonstrated using the Dutch passive sampling field monitoring database, covering ten years of PAH and PCB data for several locations. Adjusting the Ksr-w values resulted in aqueous concentrations that were lowered by a factor of 1.6 on average. The reduction was rather constant because of the manner of sampling (under nonequilibrium conditions and using performance reference compounds) and calculating. When sampling under equilibrium conditions in seawater at temperatures at about freezing, and/or applying different calculation approaches, the adjustment effect can potentially increase up to a factor of about 5-6 for the more hydrophobic PAHs and PCBs. Although this study exclusively focused on silicone rubber, qualitatively the results will also apply to other passive sampling materials.

Pressurized liquid extraction of polycyclic aromatic hydrocarbons from silicone rubber passive samplers

Silicone rubber passive samplers effectively concentrate organic contaminants from water and are simple-to-use and robust. However, during the extraction of analytes from the samplers with organic solvents, oligomers associated with the rubber are inevitably extracted and this creates analytic challenges. Additionally, extraction methods that use Soxhlet or shaking are time-consuming and use large volumes of solvent. We evaluated a new method for the extraction of polycyclic aromatic hydrocarbons from silicone rubber passive samplers that uses pressurized liquid extraction with gel permeation chromatography. Extraction with dichloromethane at 100°C provided better recoveries compared to that of 50°C. The recoveries of 14 individual PAHs ranged from 81% to 102% and the mean recovery was 93% (standard deviation=7). Relative to comparable methods in which Soxhlet or shaking were used for the extraction, this method uses considerably less solvent and time.

Silicone rubber passive samplers for measuring pore water and exchangeable concentrations of polycyclic aromatic hydrocarbons concentrations in sediments

The use of a silicone rubber passive sampler for the assessment of the availability of lipophilic organic contaminants in sediments is described. The passive sampler accumulated polycyclic aromatic hydrocarbons (PAHs) from sediments with an equilibration time of 20days for most PAHs. The method was used to measure the free dissolved concentrations in pore water of 30 PAHs (parent and alkylated), their water exchangeable concentrations and sediment–water partition coefficients in field sediments from a Scottish sea loch that supports fish farming. Fluoranthene and pyrene dominated the PAH concentration composition in the pore waters. The water exchangeable concentration reflected the pyrogenic pollution pattern found in the sediments and indicated that a proportion of the PAHs were not available for exchange with the aqueous phase. Strong linear relationships between organic carbon normalised sediment–water partition coefficients (logKoc) and corresponding octanol–water partition coefficients of PAHs were obtained. The logKoc values obtained are on average, 0.6log units higher than literature values commonly used in sediment risk assessments, consequently direct measurements of logKoc in field sediments should be used to improve the reliability of risk assessments.

Application of a silicone rubber passive sampling technique for monitoring PAHs and PCBs at three Belgian coastal harbours

A 4-year monitoring was performed to study the freely dissolved water concentrations of PAHs and PCBs in three coastal harbours and at an offshore station in the North Sea. The results are part of a more extensive study to provide information on occurrence, distribution and effects of pollutants in the Belgian coastal zone. Several methods for the estimation of freely dissolved water concentrations are reported in the literature. In the present study silicone rubber passive samplers were used. The non-linear least-square (NLS) method proved to be suitable for estimating sampling rates when using the following performance reference compounds: fluorene-d10, phenanthrene-d10, fluoranthene-d10, benzo(e)pyrene-d12, coronene-d12, CB10, CB14, CB50, CB104, CB145 and CB204. The application of two NLS methods for estimating the sampling rate (Rs) resulted in significant differences for freely dissolved concentrations for individual compounds of up to 30% between the two methods. A model that takes into account the decrease of sampling rate for compounds with higher molecular weight should give a more accurate Rs and was the preferred estimation method. Rs varied from 0.9 to 34.8Ld−1 for the different target compounds, while estimated freely dissolved concentrations for sum 15 PAHs varied between 3.9 and 170ngL−1 and for sum 14 PCBs between 0.030 and 3.1ngL−1. The stations located within marinas showed the highest level of contamination, while the offshore station (5 mile from coastline) exhibited the lowest level. The implications of the use of passive samplers for monitoring programs are discussed.

Levels and distribution of dissolved hydrophobic organic contaminants in the Morava river in Zlín district, Czech Republic as derived from their accumulation in silicone rubber passive samplers

Dissolved waterborne polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) were assessed over a period of one year at five sampling sites in a model industrial region in the Czech Republic using silicone rubber passive samplers. The spatial variability of POPs in the studied region in water was small and diffusive pollution sources predominate. Concentrations of the most volatile PAHs decreased with increasing water temperature in the whole region, which reflects the seasonality in atmospheric deposition. The dissolved concentrations of more hydrophobic PAHs, PCBs and OCPs in and downstream the industrial zone are related to desorption from suspended particles. Upstream the industrial area, a positive correlation of dissolved and particle-bound contamination was observed only for DDT metabolites and hexachlorobenzene. Calculated fugacities in water and bottom sediment indicated a fair degree of equilibrium between these compartments for OCPs and PCBs, whereas sediment represented a potential source of PAHs.

Application of silicone rubber passive samplers to investigate the bioaccumulation of PAHs by Nereis virens from marine sediments

The availability of polycyclic aromatic hydrocarbons (PAHs) from marine sediments to the ragworm ( Nereis virens) was studied. Concentrations of PAHs in pore waters were determined using silicone rubber passive samplers. Calculated bioconcentration factors confirmed that partitioning of PAHs between the lipid phase of the polychaetes and pore water is a passive process. Low biota-sediment accumulation factors (BSAF) calculated using total sediment concentration suggested a fraction of the total PAH burden in the sediment may be strongly sorbed to organic carbon and not available to the polychaete. Organic carbon normalised concentrations of the potentially exchangeable fractions of contaminants and freely dissolved concentrations (measured using silicone rubber samplers) provide a better description of the observed bioaccumulation by the ragworms. These data indicate that the concept of availability should be included in environmental risk assessments based upon equilibrium partitioning models, and that silicone rubber samplers can provide the necessary information for these models.

Using silicone passive samplers to detect polycyclic aromatic hydrocarbons from wildfires in streams and potential acute effects for invertebrate communities

Silicone rubber passive samplers spiked with 4 deuterated performance reference compounds were deployed for 29–33 days to estimate the concentrations of 16 polycyclic aromatic hydrocarbons (PAHs) in 9 streams in Victoria, Australia, following a wildfire. Silicone rubber strips of 2 thicknesses were used to obtain information on the status of uptake of the chemicals of interest at retrieval. In addition, we monitored the stream macroinvertebrate community for potential effects of PAHs or other fire organics. All selected PAHs were detected in the passive samplers and the sampling rates ranged from 0.5 to 50 L/day significantly varying between sites but not compounds, presumably due to differences in current velocity. The estimated water concentrations were 0.1–10 ng/L for total PAHs with phenanthrene, pyrene and fluoranthene accounting for 91% of the total concentration. All PAHs were a factor of 1000 or more below the reported 48-h median lethal concentrations (48-h LC50) for Daphnia magna. Two sites located closest to the fires exhibited elevated concentrations compared to the other sites and the passive samplers in these sites remained in the integrative uptake regime for all compounds, suggesting precipitation-associated PAH input. No acute toxic effects of PAHs or other fire organics on the invertebrate community were detected using a biotic index for organic toxicants (SPEAR), whereas a non-specific biotic index (SIGNAL) decreased in two sites indicating impacts from changes in other environmental parameters. We conclude (1) that silicone-based passive samplers with two different area-to-volume ratios represent a promising tool for determining organic toxicants and (2) that PAHs from wildfires are unlikely to be a common main cause for fire-related ecological effects in streams adjacent to burnt regions.

Calibration of Silicone Rubber Passive Samplers: Experimental and Modeled Relations between Sampling Rate and Compound Properties

Sampling rates (Rs) for silicone rubber (SR) passive samplers were measured under two different hydrodynamic conditions. Concentrations were maintained in the aqueous phase by continuous equilibration with SR sheets of a large total surface area which had been spiked with polycyclic aromatic hydrocarbons and/or polychlorinated biphenyls. Test sheets made of the same SR but of much smaller surface area were used to measure the uptake rate. Measured Rs values decreased with increasing passive sampler-water partition coefficient (Kpw) according to Rs approximately Kpw(-0.08) under both hydrodynamic conditions. This decrease is not significantly different from modeled values if the uncertainty of the diffusion coefficients in water is included. Modeling also confirmed that uptake of the test compounds under the experimental conditions was entirely controlled by diffusion in the water phase. A model using Rs approximately M(-0.47) is suggested for extrapolation of Rs estimated from the dissipation of performance reference compounds to target compounds in a higher hydrophobicity range.