Are We Justified in Modeling Human Exposure to Chlorinated Paraffin Mixtures Using the Average Properties of Congeners and Homologues?

Concern over human exposure to chlorinated paraffin (CP) mixtures keeps increasing. The absence of a comprehensive understanding of how human exposure varies with the physicochemical properties of CP constituents has hindered the ability to determine at what level of aggregation exposure to CPs should be assessed. We answer this question by comparing exposure predicted with either a "complex" method that utilizes isomer-specific properties or "simplified" methods that rely on median properties of congener, homologue, or short-/medium-/long-chain CP groups. Our results demonstrate the wide range of physicochemical properties across CP mixtures and their dependence on molecular structures. Assuming unit emissions in the environment, these variances translate into an extensive disparity in whole-body concentrations predicted for different isomers, spanning ∼11 orders of magnitude. CPs with 13-19 carbons and 6-10 chlorines exhibit the highest human exposure potential, primarily owing to moderate to high hydrophobicity and slow environmental degradation and biotransformation. Far-field exposure is dominant for most CP constituents. Our study underscores that using average properties of congener, homologue, or S/M/LCCP groups yields results that are consistent with those derived from isomer-based modeling, thus offering an efficient and practical framework for future risk assessments and human exposure studies of CPs and other complex chemical mixtures.

When Does Multiphase Chemistry Influence Indoor Chemical Fate?

Human chemical exposure often occurs indoors, where large variability in contaminant concentrations and indoor chemical dynamics make assessments of these exposures challenging. A major source of uncertainty lies in the rates of chemical transformations which, due to high surface-to-volume ratios and rapid air change rates relative to rates of gas-phase reactions indoors, are largely gas-surface multiphase processes. It remains unclear how important such chemistry is in controlling indoor chemical lifetimes and, therefore, human exposure to both parent compounds and transformation products. We present a multimedia steady-state fugacity-based model to assess the importance of multiphase chemistry relative to cleaning and mass transfer losses, examine how the physicochemical properties of compounds and features of the indoor environment affect these processes, and investigate uncertainties pertaining to indoor multiphase chemistry and chemical lifetimes. We find that multiphase reactions can play an important role in chemical fate indoors for reactive compounds with low volatility, i.e., octanol-air equilibrium partitioning ratios (Koa) above 108, with the impact of this chemistry dependent on chemical identity, oxidant type and concentration, and other parameters. This work highlights the need for further research into indoor chemical dynamics and multiphase chemistry to constrain human exposure to chemicals in the built environment.

Modelling PCB-153 in northern ecosystems across time, space, and species using the nested exposure model.

There is concern over possible effects on ecosystems and humans from exposure to persistent organic pollutants (POPs) and chemicals with similar properties. The main objective of this study was to develop, evaluate, and apply the Nested Exposure Model (NEM) designed to simulate the link between global emissions and resulting ecosystem exposure while accounting for variation in time and space. NEM, using environmental and biological data, global emissions, and physicochemical properties as input, was used to estimate PCB-153 concentrations in seawater and biota of the Norwegian marine environment from 1930 to 2020. These concentrations were compared to measured concentrations in (i) seawater, (ii) an Arctic marine food web comprising zooplankton, fish and marine mammals, and (iii) Atlantic herring (Clupea harengus) and Atlantic cod (Gadus morhua) from large baseline studies and monitoring programs. NEM reproduced PCB-153 concentrations in seawater, the Arctic food web, and Norwegian fish within a factor of 0.1-31, 0.14-3.1, and 0.09-21, respectively. The model also successfully reproduced measured trophic magnification factors for PCB-153 at Svalbard as well as geographical variations in PCB-153 burden in Atlantic cod between the Skagerrak, North Sea, Norwegian Sea, and Barents Sea, but estimated a steeper decline in PCB-153 concentration in herring and cod during the last decades than observed. Using the evaluated model with various emission scenarios showed the important contribution of European and global primary emissions for the PCB-153 load in fish from Norwegian marine offshore areas.

Prioritizing molecular formulae identified by non-target analysis through high-throughput modelling: application to identify compounds with high human accumulation potential from house dust.

Because it is typically not possible to pursue compound identification efforts for all chemical features detected during non-target analysis (NTA), the need for prioritization arises. Here we propose a strategy that ranks chemical features detected in environmental samples based on a model-derived metric that quantifies a feature's attribute that makes it desirable to elucidate its structure, e.g., a high potential for bioaccumulation in humans or wildlife. The procedure involves the identification of isomers that could plausibly represent the molecular formulae assigned to NTA-detected chemical features. For each isomer, the prioritization metric is calculated using properties predicted with high-throughput methods. After the molecular formulae are ranked based on the average values of the prioritization metric calculated for all isomers assigned to a formula, the highest ranked molecular formulae are prioritized for structure elucidation. We applied this workflow to features identified in house dust, using the ratio of chemical intake through dust ingestion to chemical concentration in blood (dose-to-concentration ratio, DCR) as the prioritization metric. Collections of isomers for the molecular formulae were assembled from the PubChem database and DCR was estimated using partitioning and biotransformation properties predicted for each isomer using quantitative structure property relationships. The ten top-ranked molecular formulae with notably lower average DCR-values represented mostly compounds already known to be indoor pollutants of concern, such as two polybrominated diphenyl ethers, bis(2-ethylhexyl) tetrabromophthalate, tetrabromobisphenol A, tris(1,3-dichloroisopropyl)phosphate and the azo dye disperse blue 373.

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.

Characterization of atmospheric mercury from mercury-added product manufacturing using passive air samplers.

Although alternatives to mercury (Hg) are available in most products and industrial activities, Hg continues to be an ingredient in some products, including fluorescent lamps and electrical and electronic equipment (EEE). In this work, low-cost passive air samplers (PASs) were used to investigate the atmospheric Hg pollution in Zhongshan, a large industrial city and major hub of mercury-added product manufacturing in South China. The GEM concentrations in the atmosphere were measured for two weeks during the summer of 2019 at a total of 144 sites across Zhongshan. Comparison with the results of active sampling confirmed that the PASs yielded accurate and reliable gaseous elemental mercury (GEM) concentrations and were thus well-suited for multi-site field monitoring. The mean GEM concentrations in the areas with mercury-added product manufacturing activities (5.1 ± 0.4 ng m-3) were significantly higher than those in other parts of Zhongshan (1.5 ± 0.4 ng m-3), indicating that local releases, rather than regional transport, were responsible for the atmospheric Hg pollution. Elevated GEM concentrations (up to 11.4 ng m-3) were found in the vicinity of fluorescent lamp and EEE factories and workshops, indicating significant Hg vapor emissions, presumably from the outdated production technologies and non-standard operation by under-trained workers. The Hg emissions from mercury-added product manufacturing were estimated to be 0.06 and 7.8 t yr-1 for Zhongshan and China, respectively, based on the scales of fluorescent lamp and EEE production. The non-carcinogenic health risk of Zhongshan residents from inhalation and ingestion was judged acceptable, whereby the inhalation exposure in Hg-polluted areas exceeded that of dietary ingestion. These findings demonstrate that mercury-added product manufacturing still contributes notably to anthropogenic gaseous Hg releases in the industrial areas with intense mercury-added product manufacturing activities.

Use of atmospheric concentrations and passive samplers to assess surface-atmosphere exchange of gaseous mercury in forests.

Direct measurements of gaseous elemental mercury (GEM) exchanges over global ecosystems are challenging and require extensive and costly measurement systems. Here, we explore the use of atmospheric GEM concentration variability and passive samplers to assess underlying ecosystem GEM exchanges at two rural temperate forests in the northeastern United States. We find strong temporal alignments between atmospheric GEM concentration declines and ecosystem GEM deposition in spring at both forests, which followed patterns of CO2 and suggests that ambient air GEM concentration monitoring provides a proxy measurement to assess forest GEM sinks. In fall, we observe GEM concentration increases and reversal of GEM fluxes to emissions, but with poor temporal alignments. Diel GEM concentration variability did not correspond to diel patterns of ecosystem GEM fluxes, which is driven by boundary layer dynamics with different atmospheric mixing depths during day- and nighttime. Passive samplers (PASs) deployed to measure vertical GEM gradients across six heights throughout one of the forest canopies showed excellent agreements with active measurements in detecting seasonal concentration patterns at all deployment heights. We find frequent qualitative agreement between the direction of active and PAS derived concentration gradients, but small concentration differences over small (1.3 and 4.9 m) distances prevent a quantitative comparison of methods. Furthermore, time-averaged GEM concentration gradient measurements are always biased towards stable nighttime periods, while ecosystem GEM fluxes are dominated by daytime exchanges, which results in the inability of integrated measurements such as PAS to correctly quantify forest GEM exchanges. We conclude that concentration measurements both via active and passive sampling can serve as proxies to assess underlying ecosystem GEM sinks and sources, but that the use of passive samplers to quantify GEM exchange via gradient measurements is limited due their strong nighttime biases.

Gaseous elemental mercury emissions from informal E-Waste recycling facilities in Pakistan.

Detrimental effects of mercury (Hg) on ecosystems and human health have been well-documented. Whereas emissions of gaseous elemental mercury (GEM) from e-waste recycling have been reported in developed countries, much less is known about the situation in the Global South. Using a total of 132 passive air samplers, seasonally resolved concentrations of GEM in air were measured continuously at 32 informal e-waste recycling facilities and background location in Pakistan for a period of one year between September 2020 and December 2021. Annual average GEM concentrations at the studied locations ranged from 1.8 to 92 ng m-3. Among the studied cities, higher concentrations were measured in Karachi (mean ± s.d: 17 ± 22, range: 4.2-92 ng m-3), Lahore (16 ± 4.2, 8.2-22 ng m-3) and Peshawar (15 ± 17, 4.9-80 ng m-3), while lower levels were measured in Hyderabad (6.9 ± 6.2, 3.1-25 ng m-3), consistent with a higher rate of informal recycling activities in metropolitan areas. Seasonally, higher GEM levels occurred during autumn (15 ± 16: 3.3-92 ng m-3) and summer (13 ± 8.7: 1.8-80 ng m-3) than in winter (12 ± 8.4: 2.5-49 ng m-3) and spring (9.2 ± 7.3: 1.8-80 ng m-3), possibly reflecting enhanced volatilization at higher temperatures and/or varying magnitude of recycling operations in different seasons. Policies and strict regulations related to e-waste management should be developed and implemented urgently in the country.

Cross-Species Evaluation of Bioaccumulation Thresholds for Air-Breathing Animals.

In air-breathing organisms, an organic chemical's susceptibility to elimination via urinary excretion and respiratory exhalation can be judged on the basis of the octanol-water partition ratio (KOW) and the octanol-air partition ratio (KOA), respectively. Current regulations specify that chemicals with KOW values of <102 and KOA values of <105 may be screened as non-bioaccumulative in air breathers. Here we used a model-based approach to evaluate whether these thresholds are consistent with a biomagnification factor of 1 for 141 different mammals, birds, and reptiles. Animals with lower rates of respiration (e.g., manatees and sloths) and those ingesting high-lipid diets (e.g., polar bears and carnivorous birds) were predicted to be able to biomagnify persistent chemicals with KOA values of <105. This was also observed for several temperate reptiles due to their lower respiration rates and internal temperatures. Protective KOA thresholds were determined to be <104.85 for mammals, <104.60 for birds, <104.60 for reptiles at >25 °C, and <103.95 for reptiles at ≤25 °C. For all animals, urination alone was not efficient to prevent the biomagnification of any organic chemical. For chemicals with KOW values of <101, we found that biomagnification of persistent chemicals was constrained by the water-air partition ratio (KWA) rather than KOA. Differences in physiology may need to be considered in bioaccumulation assessments of air-breathing species.

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.

Mixture effect assessment applying in vitro bioassays to in-tissue silicone extracts of traditional foods prepared from beluga whale blubber.

We complement an earlier study on the nutrient and environmental contaminant levels in Arctic beluga whale traditional foods by mixture effect assessment using in vitro bioassays. Mixtures were extracted by in-tissue sampling of raw blubber and several traditional food preparations including Muktuk and Uqsuq using silicone (polydimethylsiloxane, PDMS) as sampler. PDMS extracts persistent and degradable neutral organic chemicals of a wide range of hydrophobicity with defined lipid-PDMS partition ratios. The solvent extracts of PDMS were dosed in various reporter gene assays based on human cell lines. Cytotoxicity was consistent across all cell lines and was a good indicator of overall chemical burden. No hormone-like effects on the estrogen receptor, the progesterone receptor and the glucocorticoid receptor were observed but a few samples activated the androgen receptor, albeit with low potency. The peroxisome-proliferator activated receptor (PPARγ) was the most sensitive endpoint followed by activation of oxidative stress response and activation of the arylhydrocarbon (AhR) receptor. The detected pollutants only explained a small fraction of the experimental mixture effects, indicating additional bioactive pollutants. The effect levels of the extracted mixtures were higher than those observed in blubber extracts of dugongs living off the shore of Australia. Roasting over an open fire or food preparation near a smokehouse led to increased PAH levels that were reflected in increased oxidative stress response and activation of the AhR. So far in vitro assays have only been used to quantify persistent dioxin-like chemicals in food and feed but this pilot study demonstrates a much broader potential for food safety evaluations complementing chemical analytical monitoring.

An amended in vitro-in vivo extrapolation model that accounts for first pass clearance effects on chemical bioaccumulation in fish.

Measured rates of in vitro intrinsic clearance for fish may be extrapolated to the whole animal as a means of estimating a whole-body biotransformation rate constant (kB; d-1). This estimate of kB can then be used as an input to existing bioaccumulation prediction models. Most in vitro-in vivo extrapolation/bioaccumulation (IVIVE/B) modeling efforts to date have focused on predicting the chemical bioconcentration in fish (aqueous only exposure), with less attention paid to dietary exposures. Following dietary uptake, biotransformation in the gut lumen, intestinal epithelia, and liver can reduce chemical accumulation; however, current IVIVE/B models do not consider these first pass clearance effects on dietary uptake. Here we present an amended IVIVE/B model that accounts for first pass clearance. The model is then used to examine how biotransformation in the liver and intestinal epithelia (alone or combined) may impact chemical accumulation that occurs during dietary exposure. First pass clearance by the liver can greatly reduce dietary uptake of contaminants, but these effects are only apparent at rapid rates of in vitro biotransformation (first order depletion rate constant kDEP ≥ 10 h-1). The impact of first pass clearance becomes more pronounced when biotransformation in the intestinal epithelia is included in the model. Modelled results suggest that biotransformation in the liver and intestinal epithelia cannot entirely explain reduced dietary uptake reported in several in vivo bioaccumulation tests. This unexplained reduction in dietary uptake is attributed to chemical degradation in the gut lumen. These findings underscore the need for research to directly investigate luminal biotransformation in fish.

A multi-pathway exposure assessment for polycyclic aromatic hydrocarbons among residents in the Athabasca oil sands region, Canada.

Due to increasing emissions from ongoing development of the oil sands in Northern Alberta, Canada, there is concern that local residents and organisms are experiencing elevated exposures to hazardous contaminants. We modified an existing human bioaccumulation model (ACC-Human) to represent the local food chain in the Athabasca oil sands region (AOSR), the focus of oil sands development in Alberta. We used the model to assess the potential exposure to three polycyclic aromatic hydrocarbons (PAHs) among local residents that have a high intake of locally sourced traditional foods. To place these estimates into context, we complemented them with estimated PAH intake through market foods and smoking. Our approach was able to produce realistic body burdens of the PAHs in aquatic and terrestrial wildlife and in humans, both in magnitude and with respect to the relative difference between smokers and non-smokers. Over the model simulation period (1967-2009), market food was the dominant dietary exposure route for phenanthrene and pyrene, while local food, and in particular local fish, dominated the intake of benzo[a]pyrene. Exposure to benzo[a]pyrene therefore was also predicted to increase over time in concert with expanding oil sands operations. Those smoking at the average rate of Northern Albertans take in an additional amount of all three PAHs that is at least as large as dietary intake. Estimated daily intake rates are below toxicological reference thresholds for all three PAHs. However, daily intake of BaP in adults is only ∼20 fold below those thresholds and is predicted to increase. Key uncertainties in the assessment included the effect of food preparation on the PAH content in food (e.g., smoking of fish), the limited availability of market food contamination data specific to Canada, and the PAH content of the vapor phase of first-hand cigarette smoke. Considering the satisfactory model evaluation, ACC-Human AOSR should be suited to making predictions of future contaminant exposure based on development scenarios in the AOSR or in response to potential emission reduction efforts. It should also be applicable to other organic contaminants of concern released by oil sands operations.

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.

A Flow-through Passive Sampler for Microplastics in Air.

Microplastics (MP) in air have attracted increasing attention because of their ubiquitous presence. Accurate atmospheric concentrations of MP are essential for evaluating their capacity for long-range transport and for assessing human inhalation risk. In order to sample airborne MP in locations with limited power supply, we adapted a flow-through passive sampler by placing a glass fiber filter in the inner sampling tube. To test the new sampler's performance under field conditions, two sizes of the flow-through sampler (with diameters of 20 and 10 cm) and a conventionally pumped high-volume air sampler were co-deployed on the Lhasa campus of the Institute of Tibetan Plateau Research. Accurate sampling volumes could be estimated from a relationship between wind speeds recorded outside and inside of the flow-through sampler. Atmospheric concentrations and compositions of MP that compared favorably with those obtained by active sampling indicate that the larger version of the flow-through passive sampler can provide reproducible and quantitative information on atmospheric MP at sites with limited or unreliable power supply. This capability should be useful in large-scale and high-temporal resolution air monitoring networks for MP.

Lichen transplants as indicators of gaseous elemental mercury concentrations.

Lichens play an important role in the biogeochemical cycling of mercury (Hg) and are commonly used as indicators of Hg enrichment in remote and anthropogenically impacted environments. To assess their capacity for Hg uptake and accumulation, we determined the concentration of gaseous elemental mercury (GEM) in air and the concentration of total Hg (THg) in transplanted thalli of two lichen species. Lichen transplants and passive air samplers (PASs) were concurrently deployed, side by side, at 10 sites within an abandoned mining area, characterized by large gradients in atmospheric Hg contamination. Highly variable time-weighted GEM concentrations determined by the PASs, ranging from 17 to 4,200 ng/m3, were mirrored by generally high Hg concentrations in transplanted thalli of both Xanthoria parietina (174-8,800 ng/g) and Evernia prunastri (143-5,500 ng/g). Hg concentrations in the two species co-varied linearly indicating about 60% greater Hg accumulation in X. parietina than in E. prunastri. Whereas Hg uptake in the fruticose E. prunastri increased linearly with GEM, a power law equation with a fractional exponent described the uptake in the foliose X. parietina. Extrapolating the relationships observed here to higher GEM levels yielded concentrations in lichen that agree very well with those measured in an earlier fumigation experiment performed under laboratory-controlled conditions. The uptake model of X. parietina was further verified by correctly estimating GEM concentrations from the THg measured in autochthonous thalli collected from the urban area adjacent to the mine site. Passive sampling can effectively provide time-weighted data of suitable spatial resolution to quantitatively describe GEM assimilation by lichens. Therefore, the combined use of passive sampling and lichen transplants can contribute to a more comprehensive understanding of the role of lichens, and potentially also of other cryptogams, in the deposition of atmospheric Hg to terrestrial ecosystems.

The Emissions Fractions Approach to Assessing the Long-Range Transport Potential of Organic Chemicals.

The assessment of long-range transport potential (LRTP) is enshrined in several frameworks for chemical regulation such as the Stockholm Convention. Screening for LRTP is commonly done with the OECD Pov and LRTP Screening Tool employing two metrics, characteristic travel distance (CTD) and transfer efficiency (TE). Here we introduce a set of three alternative metrics and implement them in the Tool's model. Each metric is expressed as a fraction of the emissions in a source region. The three metrics quantify the extent to which the chemical (i) reaches a remote region (dispersion, ϕ1), (ii) is transferred to surface media in the remote region (transfer, ϕ2), and (iii) accumulates in these surface media (accumulation, ϕ3). In contrast to CTD and TE, the emissions fractions metrics can integrate transport via water and air, enabling comprehensive LRTP assessment. Furthermore, since there is a coherent relationship between the three metrics, the new approach provides quantitative mechanistic insight into different phenomena determining LRTP. Finally, the accumulation metric, ϕ3, allows assessment of LRTP in the context of the Stockholm Convention, where the ability of a chemical to elicit adverse effects in surface media is decisive. We conclude that the emission fractions approach has the potential to reduce the risk of false positives/negatives in LRTP assessments.