Contaminant Biomagnification in Polar Bears: Interindividual Differences, Dietary Intake Rate, and the Gut Microbiome.

Some persistent hydrophobic pollutants biomagnify, i.e., achieve higher contaminant levels in a predator than in its prey (Cpredator/Cprey > 1). This ratio is called the biomagnification factor (BMF) and is traditionally determined using tissues from carcasses or biopsies. Using a noninvasive method that relies on equilibrium sampling in silicone-film-coated vessels and chemical analysis of paired diet and feces, we determined on three occasions the thermodynamic biomagnification limit (BMFlim) and feces-based biomagnification factor (BMFF) for three zoo-housed polar bears who experience seasonal periods of hyperphagia and hypophagia. All bears had high biomagnification capabilities (BMFlim was up to 200) owing to very efficient lipid assimilation (up to 99.5%). The bears differed up to a factor of 3 in their BMFlim. BMFlim and BMFF of a bear increased by up to a factor of 4 during the hypophagic period, when the ingestion rate was greatly reduced. Much of that variability can be explained by differences in the lipid assimilation efficiency, even though this efficiency ranged only from 98.1 to 99.5%. A high BMFlim was associated with a high abundance of Bacteroidales and Lachnospirales in the gut microbiome. Biomagnification varies to a surprisingly large extent between individuals and within the same individual over time. Future work should investigate whether this can be attributed to the influence of the gut microbiome on lipid assimilation by studying more individual bears at different key physiological stages.

Field Calibration and PAS-SIM Model Evaluation of the XAD-Based Passive Air Sampler for Semi-Volatile Organic Compounds.

The use of passive air samplers (PAS) for semi-volatile organic compounds (SVOCs) continues to expand. To advance quantitative understanding of uptake kinetics, we calibrated the XAD-PAS, using a styrene-divinylbenzene sorbent, through a year-long side-by-side deployment with an active sampler. Twelve XAD-PASs, deployed in June 2020, were retrieved at 4-week intervals, while gas phase SVOCs were quantified in 48 consecutive week-long active samples taken from June 2020 to May 2021. Consistent with XAD's high uptake capacity, even relatively volatile SVOCs, such as hexachlorobutadiene, displayed linear uptake throughout the entire deployment. Sampling rates (SRs) range between 0.1 and 0.6 m3 day-1 for 26 SVOCs, including brominated flame retardants, organophosphate esters, and halogenated methoxylated benzenes. SRs are compared with experimental SRs reported previously. The ability of the existing mechanistic uptake model PAS-SIM to reproduce the observed uptake and SRs was evaluated. Agreement between simulated and measured uptake curves was reasonable but varied with compound volatility and the assumed stagnant air layer boundary thickness. Even though PAS-SIM succeeds in predicting the SR range for the studied SVOCs, it fails to capture the volatility dependence of the SR by underestimating the length of the linear uptake period and by failing to consider the kinetics of sorption.

Probing the Thermodynamics of Biomagnification in Zoo-Housed Polar Bears by Equilibrium Sampling of Dietary and Fecal Samples.

In a proof-of-concept study, we recently used equilibrium sampling with silicone films to noninvasively derive the thermodynamic limit to a canine's gastrointestinal biomagnification capability (BMFlim) by determining the ratio of the products of the volume (V) and fugacity capacity (Z) of food and feces. In that earlier study, low contaminant levels prevented the determination of contaminant fugacities (f) in food and feces. For zoo-housed polar bears, fed on a lipid-rich diet of fish and seal oil, we were now able to measure the increase in f of nine native polychlorinated biphenyls (PCBs) upon digestion, providing incontestable proof of the process of gastrointestinal biomagnification. A high average BMFlim value of ∼171 for the bears was caused mostly by a remarkable reduction in fugacity capacity driven by a high lipid assimilation capacity. Lipid-rich diets increase the uptake of biomagnifying contaminants in two ways: because they tend to have higher contaminant concentrations and because they lead to a high Z value drop during digestion. We also confirmed that equilibrium sampling yielded similar Z values for PCBs originally present in food and feces and for isotopically labeled PCBs spiked onto those samples, which makes the method suitable for investigating the biomagnification capability of organisms, even if native contaminant concentrations in their diet and feces are low.

Quantifying the Biomagnification Capability of Arctic Wolf and Domestic Dog by Equilibrium Sampling.

The mechanism underlying contaminant biomagnification is a decrease in the volume (V) and the fugacity capacity (Z) of food during digestion in the gastrointestinal tract. Traditionally, biomagnification is quantified by measuring contaminant concentrations in animal tissues. Here, we present a proof-of-concept study to noninvasively derive the thermodynamic limit to an organism's biomagnification capability (biomagnification limit -BMFlim) by determining the ratio of the V·Z-products of undigested and digested food. We quantify Z-values by equilibrating food and feces samples, which have been homogenized and spiked with polychlorinated biphenyls (PCBs), with silicone films of variable thickness coated on the inside of glass vials. We demonstrate the feasibility of this method for wolf (Canis lupus hudsonicus) and domestic dog (Canis lupus familiaris). For an adult wolf eating a relatively lean meat diet, a BMFlim (averaged over several PCB congeners) of approximately 41 was observed, whereas the BMFlim reached 81 for an adult domestic dog eating a lipid-rich diet. Besides the dietary lipid content that strongly affects the Z-value of the diet, the capability of an animal to digest its diet also influences the BMFlim by controlling the Z-values of their feces and the volume reduction of the food in the gastrointestinal tract. Less efficient digestion leads to a lower BMFlim in a juvenile dog (approximately 35) compared to its older self, even though their diets had similar lipid contents. The effect of the volume reduction (VD/VF ranging from 4 to 15) was comparable to the effect of the Z-value reduction (ZD/ZF from 3 to 20).

Investigating the Sources and Transport of Benzotriazole UV Stabilizers during Rainfall and Snowmelt across an Urbanization Gradient.

Benzotriazole UV stabilizers (BT-UVs) have attracted increasing attention due to their bioaccumulative nature and ubiquitous presence in surface waters. We apply high-frequency sampling in paired watersheds to describe, for the first time, the behavior of BT-UVs in stream channels during snowmelt and rainfall. Relative to a largely agricultural watershed, concentrations of BT-UVs in an urban watershed were 4-90 times greater during rainfall and 3-21 times greater during snowmelt. During rainfall, a decrease in BT-UV concentrations on particles with increasing suspended sediments and streamflow occurred at all urban sites due to input of relatively clean sediments, while both decreases and increases were observed at rural sites. Where increases occurred in the rural watershed, road sediments were consistently suggested as the source. Contrasts between the urban and rural sites were also observed during snowmelt. While BT-UV concentrations on particles peaked with peak suspended sediment levels at urban stream sites, the opposite was true at rural stream sites. This appeared to be driven partially by different snowpack melt rates in the two watersheds, with earlier melt and presumably higher streamflow facilitating suspension or erosion of more contaminated sediment in the urban stream. In general, it appears that relatively high, consistent emissions in the form of informal (plastic) debris disposal by consumers or industrial releases have likely led to more homogeneous BT-UV profiles and temporal behavior in the urban watershed. In the rural watershed, low emissions instead entail that emissions variability is more likely to translate to variability in chemical profiles and temporal behavior.

Assessing the Source-to-Stream Transport of Benzotriazoles during Rainfall and Snowmelt in Urban and Agricultural Watersheds.

While benzotriazoles (BTs) are ubiquitous in urban waters, their sources and transport remain poorly characterized. We aimed to elucidate the origin and hydrological pathways of BTs in Toronto, Canada, by quantifying three BTs, electrical conductivity, and δ18O in high-frequency streamwater samples taken during two rainfall and one snowmelt event in two watersheds with contrasting levels of urbanization. Average concentrations of total BTs (∑BT) were 1.3 to 110 times higher in the more urbanized Mimico Creek watershed relative to the primarily agricultural and suburban Little Rouge Creek. Strong correlations between upstream density of major roads and total BT concentrations or BT composition within all events implicate vehicle fluids as the key source of BTs in both watersheds. Sustained historical releases of BTs within the Mimico Creek watershed have likely led to elevated ∑BT in groundwater, with elevated concentrations observed during baseflow that are diluted by rainfall and surface runoff. In contrast, relatively constant concentrations, caused by mixing of equally contaminated baseflow and rainfall/surface runoff, are observed in the Little Rouge Creek throughout storm hydrographs, with an occasional first flush occurring at a subsite draining suburban land. During snowmelt, buildup of BTs in roadside snowpiles and preferential partitioning of BTs to the liquid phase of a melting snowpack leads to early peaks in ∑BT in both streams, except the sites in the Little Rouge Creek with low levels of vehicle traffic. Overall, a history of BT release and land use associated with urbanization have led to higher levels of BTs in urban areas and provide a glimpse into future BT dynamics in mixed use, (sub)urbanizing areas.

Effect of Sodium Sulfate, Ammonium Chloride, Ammonium Nitrate, and Salt Mixtures on Aqueous Phase Partitioning of Organic Compounds.

Dissolved inorganic salts influence the partitioning of organic compounds into the aqueous phase. This influence is especially significant in atmospheric aerosol, which usually contains large amounts of ions, including sodium, ammonium, chloride, sulfate, and nitrate. However, empirical data on this salt effect are very sparse. Here, the partitioning of numerous organic compounds into solutions of Na2SO4, NH4Cl, and NH4NO3 was measured and compared with existing data for NaCl and (NH4)2SO4. Salt mixtures were also tested to establish whether the salt effect is additive. In general, the salt effect showed a decreasing trend of Na2SO4 > (NH)2SO4 > NaCl > NH4Cl > NH4NO3 for the studied organic compounds, implying the following relative strength of the salt effect of individual anions: SO42- > Cl- > NO3- and of cations: Na+ > NH4+. The salt effect of different salts is moderately correlated. Predictive models for the salt effect were developed based on the experimental data. The experimental data indicate that the salt effect of mixtures may not be entirely additive. However, the deviation from additivity, if it exists, is small. Data of very high quality are required to establish whether the effect of constituent ions or salts is additive or not.

Calculating Equilibrium Phase Distribution during the Formation of Secondary Organic Aerosol Using COSMOtherm.

Challenges in the parametrization of compound distribution between the gas and particle phase contribute significantly to the uncertainty in the prediction of secondary organic aerosol (SOA) formation and are rooted in the complexity and variability of atmospheric condensed matter, which includes water, salts, and a multitude of organic oxidation products, often in two separated phases. Here, we explore the use of the commercial quantum-chemistry-based software COSMOtherm to predict equilibrium partitioning and Setchenow coefficients of a suite of oxidation products of α-pinene ozonolysis in an aerosol that is assumed to separate into an organic-enriched phase and an electrolyte-enriched aqueous phase. The predicted coefficients are used to estimate the phase distribution of the organic compounds, water and ammonium sulfate, the resulting phase composition, and the SOA yield. Four scenarios that differ in terms of organic loading, liquid water content, and chemical aging are compared. The organic compounds partition preferentially to the organic phase rather than the aqueous phase for the studied aerosol scenarios, partially due to the salting-out effect. Extremely low volatile organic compounds are predicted to be the dominant species in the organic aerosols at low loadings and an important component at higher loadings. The highest concentration of oxidation products in the condensed phase is predicted for a scenario assuming the presence of non-phase-separated cloud droplets. Partitioning into an organic aerosol phase composed of the oxidation products is predicted to be similar to partitioning into a phase composed of a single organic surrogate molecule, suggesting that the calculation procedure can be simplified without major loss of accuracy. COSMOtherm is shown to produce results that are comparable to those obtained using group contribution methods. COSMOtherm is likely to have a much larger application domain than those group contribution methods because it is based on fundamental principles with little calibration.

Measuring and modeling the salting-out effect in ammonium sulfate solutions.

The presence of inorganic salts significantly influences the partitioning behavior of organic compounds between environmentally relevant aqueous phases, such as seawater or aqueous aerosol, and other, nonaqueous phases (gas phase, organic phase, etc.). In this study, salting-out coefficients (or Setschenow constants) (KS [M(-1)]) for 38 diverse neutral compounds in ammonium sulfate ((NH4)2SO4) solutions were measured using a shared headspace passive dosing method and a negligible depletion solid phase microextraction technique. The measured KS were all positive, varied from 0.216 to 0.729, and had standard errors in the range of 0.006-0.060. Compared to KS for sodium chloride (NaCl) in the literature, KS values for (NH4)2SO4 are always higher for the same compound, suggesting a higher salting-out effect of (NH4)2SO4. A polyparameter linear free energy relationship (pp-LFER) for predicting KS in (NH4)2SO4 solutions was generated using the experimental data for calibration. pp-LFER predicted KS agreed well with measured KS reported in the literature. KS for (NH4)2SO4 was also predicted using the quantum-chemical COSMOtherm software and the thermodynamic model AIOMFAC. While COSMOtherm generally overpredicted the experimental KS, predicted and experimental values were correlated. Therefore, a fitting factor needs to be applied when using the current version of COSMOtherm to predict KS. AIOMFAC tends to underpredict the measured KS((NH4)2SO4) but always overpredicts KS(NaCl). The prediction error is generally larger for KS(NaCl) than for KS((NH4)2SO4). AIOMFAC also predicted a dependence of KS on the salt concentrations, which is not observed in the experimental data. In order to demonstrate that the models developed and calibrated in this study can be applied to estimate Setschenow coefficients for atmospherically relevant compounds involved in secondary organic aerosol formation based on chemical structure alone, we predicted and compared KS for selected α-pinene oxidation products.

A Decade of Global Atmospheric Monitoring Delivers Mixed Report Card on the Stockholm Convention.

Time trends in atmospheric concentrations serve to evaluate how effective the Stockholm Convention is in reducing or eliminating environmental releases of persistent organic pollutants (POPs). Twelve years (2005-2016) of continuous monitoring with a global network of 20 sampling sites reveals that concentrations of the pesticide endosulfan began to drop coincident with its listing as POP in 2011. Concentrations of other POPs started to decrease prior to listing and during the sampling period declined very slowly or not at all. Concentrations of some unintentionally produced POPs (hexachlorobenzene, hexachlorobutadiene) increased to become the most abundant and most widely dispersed POPs in the global atmosphere. Their formation processes and release locations need to be identified to facilitate the Convention's goal of curbing releases from unintentional production.

Mountain cold-trapping increases transfer of persistent organic pollutants from atmosphere to cows' milk.

Concentrations of long-lived organic contaminants in snow, soil, lake water, and vegetation have been observed to increase with altitude along mountain slopes. Such enrichment, called "mountain cold-trapping", is attributed to a transition from the atmospheric gas phase to particles, rain droplets, snowflakes, and Earth's surface at the lower temperatures prevailing at higher elevations. Milk sampled repeatedly from cows that had grazed at three different altitudes in Switzerland during one summer was analyzed for a range of persistent organic pollutants. Mountain cold-trapping significantly increased air-to-milk transfer factors of most analytes. As a result, the milk of cows grazing at higher altitudes was more contaminated with substances that have regionally uniform air concentrations (hexachlorobenzene, α-hexachlorocyclohexane, endosulfan sulfate). For substances that have sources, and therefore higher air concentrations, at lower altitudes (polychlorinated biphenyls, γ-hexachlorocyclohexane), alpine milk has lower concentrations, but not as low as would be expected without mountain cold-trapping. Differences in the elevational gradients in soil concentrations and air-to-milk transfer factors highlight that cold-trapping of POPs in pastures is mostly due to increased gas-phase deposition as a result of lower temperatures causing higher uptake capacity of plant foliage, whereas cold-trapping in soils more strongly depends on wet and dry particle deposition. Climatic influences on air-to-milk transfer of POPs needs to be accounted for when using contamination of milk lipids to infer contamination of the atmosphere.

Seasonal and latitudinal variability in the atmospheric concentrations of cyclic volatile methyl siloxanes in the Northern Hemisphere.

Field data from two latitudinal transects in Europe and Canada were gathered to better characterize the atmospheric fate of three cyclic methylsiloxanes (cVMSs), i.e., octamethyl-cyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6). During a year-long, seasonally resolved outdoor air sampling campaign, passive samplers with an ultra-clean sorbent were deployed at 15 sampling sites covering latitudes ranging from the source regions (43.7-50.7 °N) to the Arctic (79-82.5 °N). For each site, one of two passive samplers and one of two field blanks were separately extracted and analyzed for the cVMSs at two different laboratories using gas-chromatography-mass spectrometry. Whereas the use of a particular batch of sorbent and the applied cleaning procedure to a large extent controlled the levels of cVMS in field blanks, and therefore also the method detection and quantification limits, minor site-specific differences in field blank contamination were apparent. Excellent agreement between duplicates was obtained, with 95% of the concentrations reported by the two laboratories falling within a factor of 1.6 of each other. Nearly all data show a monotonic relationship between the concentration and distance from the major source regions. Concentrations in source regions were comparatively constant throughout the year, while the concentration gradient towards remote regions became steeper during summer when removal via OH radicals is at its maximum. Concentrations of the different cVMS oligomers were highly correlated within a given transect. Changes in relative abundance of cVMS oligomers along the transect were in agreement with relative atmospheric degradation rates via OH radicals.

Sources and environmental fate of halomethoxybenzenes.

Halomethoxybenzenes are pervasive in the atmosphere at concentration levels that exceed, often by an order of magnitude, those of the persistent organic pollutants with which they share the attributes of persistence and potential for long-range transport, bioaccumulation, and toxic effects. Long ignored by environmental chemists because of their predominantly natural origin-namely, synthesis by terrestrial wood-rotting fungi, marine algae, and invertebrates-knowledge of their environmental pathways remains limited. Through measuring the spatial and seasonal variability of four halomethoxybenzenes in air and precipitation and performing complementary environmental fate simulations, we present evidence that these compounds undergo continental-scale transport in the atmosphere, which they enter largely by evaporation from water. This also applies to halomethoxybenzenes originating in terrestrial environments, such as drosophilin A methyl ether, which reach aquatic environments with runoff, possibly in the form of their phenolic precursors. Our findings contribute substantially to the comprehension of sources and fate of halomethoxybenzenes, illuminating their widespread atmospheric dispersal.

Field evaluation of a flow-through sampler for measuring pesticides and brominated flame retardants in the arctic atmosphere.

A flow-through sampler (FTS) was codeployed with a super high volume active sampler (SHV) between October 2007 and November 2008 to evaluate its ability to determine the ambient concentrations of pesticides and brominated flame retardants in the Canadian High Arctic atmosphere. Nine pesticides and eight flame retardants, including three polybrominated diphenyl ether (PBDE) replacement chemicals, were frequently detected. Atmospheric concentrations determined by the two systems showed good agreement when compared on monthly and annually integrated time scales. Pesticide concentrations were normally within a factor of 3 of each other. The FTS tended to generate higher PBDE concentrations than the SHV presumably because of the entrainment of blowing snow/ice crystals or large particles. Taking into account uncertainties in analytical bias, sample volume, and breakthrough estimations, the FTS is shown to be a reliable and cost-effective method, which derives seasonally variable concentrations of semivolatile organic trace compounds at extremely remote locations that are comparable to those obtained by conventional high volume air sampling. Moreover, the large sampling volumes captured by the FTS make it suitable for the screening of new and emerging chemicals in the remote atmosphere where concentrations are usually low.

Identifying organic chemicals not subject to bioaccumulation in air-breathing organisms using predicted partitioning and biotransformation properties.

Because the respiration processes contributing to the elimination of organic chemicals deviate between air- and water-breathing organisms, existing and widely used procedures for identifying chemicals not subject to bioaccumulation in aquatic organisms based on the octanol-water partition ratio KOW need to be complemented with similar procedures for organisms respiring air. Here, we propose such a procedure that relies on the comparison of a compound's predicted KOW , octanol-air partition ratio KOA , and biotransformation half-life HLB with three threshold values, below which elimination is judged to be sufficiently rapid to prevent bioaccumulation. The method allows for the consideration of the effect of dissociation on the efficiency of urinary and respiratory elimination. Explicit application of different types of the prediction error, such as the 95% prediction interval or the standard error, allows for variable tolerance for false-negative decisions, that is, the potential to judge a chemical as not bioaccumulative even though it is. A test with a set of more than 1000 diverse organic chemicals confirms the applicability of the prediction methods for a wide range of compounds and the procedure's ability to categorize approximately four-fifth of compounds as being of no bioaccumulation concern, suggesting its usefulness to screen large numbers of commercial chemicals to identify those worthy of further scrutiny. The test also demonstrates that a screening based solely on KOW and KOA would be far less effective because the fraction of chemicals that can be judged as sufficiently volatile and/or sufficiently water soluble for rapid respiratory and urinary elimination based on the partitioning properties predicted for their neutral form is relatively small. Future improvements of the proposed procedure depend largely on the development of prediction methods for the biotransformation kinetics in air-breathing organisms and for the potential for renal reabsorption. Integr Environ Assess Manag 2022;18:1297-1312. © 2021 The Authors. Integrated Environmental Assessment and Management published by Wiley Periodicals LLC on behalf of Society of Environmental Toxicology & Chemistry (SETAC).

Laboratory studies on the fate of perfluoroalkyl carboxylates and sulfonates during snowmelt.

Perfluoroalkyl acids (PFAAs) are anthropogenic chemicals that occur in snow from both remote and source regions. Experiments were conducted to determine how PFAAs are released from a melting snowpack. Different PFAAs eluted from the snowpack at different times, those with short chains eluting early, those with long chains eluting late. The concentrations in the meltwater of PFAAs with medium chain lengths of 6 to 9 perfluorinated carbon atoms first increased and then decreased during the melt period. Such a peak elution had not been previously observed for any other chemicals. The specific snow surface area (SSA) influenced this elution type, with peak concentrations occurring earlier in a snowpack with lower SSA. Model simulations suggested that the snow surface decrease during the melt alone was insufficient to explain the observations. It was ruled out that the calcium concentration affected PFAA sorption to the snow surface in a similar way as sorption to sediments. Adsorption coefficients of PFAAs to the snow surface were estimated by fitting the measured and modeled elution profiles.

Reliable Prediction of the Octanol-Air Partition Ratio.

The octanol-air equilibrium partition ratio (KOA ) is frequently used to describe the volatility of organic chemicals, whereby n-octanol serves as a substitute for a variety of organic phases ranging from organic matter in atmospheric particles and soils, to biological tissues such as plant foliage, fat, blood, and milk, and to polymeric sorbents. Because measured KOA values exist for just over 500 compounds, most of which are nonpolar halogenated aromatics, there is a need for tools that can reliably predict this parameter for a wide range of organic molecules, ideally at different temperatures. The ability of five techniques, specifically polyparameter linear free energy relationships (ppLFERs) with either experimental or predicted solute descriptors, EPISuite's KOAWIN, COSMOtherm, and OPERA, to predict the KOA of organic substances, either at 25 °C or at any temperature, was assessed by comparison with all KOA values measured to date. In addition, three different ppLFER equations for KOA were evaluated, and a new modified equation is proposed. A technique's performance was quantified with the mean absolute error (MAE), the root mean square error (RMSE), and the estimated uncertainty of future predicted values, that is, the prediction interval. We also considered each model's applicability domain and accessibility. With an RMSE of 0.37 and a MAE of 0.23 for predictions of log KOA at 25 °C and RMSE of 0.32 and MAE of 0.21 for predictions made at any temperature, the ppLFER equation using experimental solute descriptors predicted the KOA the best. Even if solute descriptors must be predicted in the absence of experimental values, ppLFERs are the preferred method, also because they are easy to use and freely available. Environ Toxicol Chem 2021;40:3166-3180. © 2021 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Phase partitioning, transport and sources of Benzotriazole Ultraviolet Stabilizers during a runoff event.

Benzotriazole Ultraviolet Stabilizers (BT-UVs) are ubiquitous in the environment, given their wide use as additives in consumer products. Their bio-accumulative and toxic properties are increasingly being scrutinised, evinced by the recent proposition to add UV328 to the Stockholm Convention on Persistent Organic Pollutants. Here, we measured concentrations of six BT-UVs in the dissolved and particulate phases of stream water collected from an urban and rural stream during a runoff event. Under baseflow conditions, the less hydrophobic BT-UVs were present at low concentrations in the dissolved phase, while much higher loads of particulate BT-UVs occurred during stormflow, especially in the urban creek. Time-weighted average BT-UV concentrations were up to 4 times higher in the urban than in the rural creek. BT-UVs were found to be prevalent in water obtained from laundering textiles, which plausibly constitutes a major portion of domestic wastewater, and can serve as a BT-UV source to aquatic waterways. However, the observed dilution of a sewage tracer during the run-off event suggests that unregulated wastewater seepage is not responsible for the high BT-UV loads in storm water. High levels of UV328 and UV234 were detected in a select few plastic debris items collected from the urban watershed and in artificial turf grass, respectively. Whereas this may allow for the leaching of those BT-UVs into the creek, most plastic debris is more likely a sink than a source of BT-UVs. The observed input of particle-bound BT-UVs at the onset of the rain event indicates that most of the BT-UVs reach the creek with contaminated particles that had built up on surfaces during the antecedent dry period. UV328 was the dominant BT-UV in those particles. If such particle build-up occurs on road surfaces, it may suggest that the use of UV328 in automotive applications contributes to their presence in urban storm water.

Development, characterization, and testing of a personal passive sampler for measuring inhalation exposure to gaseous elemental mercury.

Inhalation of gaseous elemental mercury (GEM) is an occupational exposure concern for workers handling elemental mercury or mercury-containing waste. GEM is also often present near historically mercury-contaminated sites, potentially resulting in low-level, chronic exposure of the wider population. Here we introduce a passive sampler for personal GEM monitoring which combines a radial porous diffusive barrier with an activated carbon sorbent. A total mercury analyzer is used to quantify GEM sorbed to the carbon by thermal decomposition, amalgamation, and atomic absorption spectroscopy. A sampling rate of 0.070 m3/day was determined by calibrating the sampler at low and high concentrations. Deployments lasting 8 h result in limits of quantification well below 200 ng/m3. The sampler has a measurement range of at least four orders of magnitude. Derived air concentrations were not statistically significantly different from those obtained by active air sampling but were more precise than those obtained using a personal pump. If properly stored, the sampler maintains low blank levels in high GEM environments. Affordability, sturdiness, simplicity, and the wide availability of total mercury analyzers make this sampler highly suited for monitoring GEM inhalation exposure, including in developing countries.