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.

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.

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.

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.

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.

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.

A New Approach to Characterizing the Partitioning of Volatile Organic Compounds to Cotton Fabric.

Chemical partitioning to surfaces can influence human exposure by various pathways, resulting in adverse health consequences. Clothing can act as a source, a barrier, or a transient reservoir for chemicals that can affect dermal and inhalation exposure rates. A few clothing-mediated exposure studies have characterized the accumulation of a select number of semi-volatile organic compounds (SVOCs), but systematic studies on the partitioning behavior for classes of volatile organic compounds (VOCs) and SVOCs are lacking. Here, the cloth-air equilibrium partition ratios (KCA) for carbonyl, carboxylic acid, and aromatic VOC homologous series were characterized for cellulose-based cotton fabric, using timed exposures in a real indoor setting followed by online thermal desorption and nontargeted mass spectrometric analysis. The analyzed VOCs exhibit rapid equilibration within a day. Homologous series generally show linear correlations of the logarithm of KCA with carbon number and the logarithms of the VOC vapor pressure and octanol-air equilibrium partition ratio (KOA). When expressed as a volume-normalized partition ratio, log KCA_V values are in a range of 5-8, similar to the values for previously measured SVOCs which have lower volatility. When expressed as surface area-normalized adsorption constants, KCA_S values suggest that equilibration corresponds to a saturated surface coverage of adsorbed species. Aqueous solvation may occur for the most water-soluble species such as formic and acetic acids. Overall, this new experimental approach facilitates VOC partitioning studies relevant to environmental exposure.

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.

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.

Global Historical Production, Use, In-Use Stocks, and Emissions of Short-, Medium-, and Long-Chain Chlorinated Paraffins.

The last few decades have seen ubiquitous and increasing contamination of chlorinated paraffins (CPs) worldwide. Here, we develop the first global inventories of production, use, in-use stocks, and emissions of total CPs, including the short-, medium- and long-chain components (SCCPs, MCCPs, and LCCPs) during 1930-2020 using a dynamic substance flow analysis model named Chemical in Products Comprehensive Anthroposhpheric Fate Estimation. The model estimates that a total of ∼33 million metric tons of CPs have been produced and used globally, ∼40% of which still resided in in-use products by 2020 and is available for long-term emissions in the next decades. Global cumulative emissions of CPs have increased to ∼5.2 million metric tons by 2020, with SCCPs, MCCPs, and LCCPs accounting for ∼30, 40, and 30%, respectively. While the production, use, and emissions of CPs started declining in regions such as Western Europe, they remain high in China. The model also suggests that homologues with 10, 14, and 22-23 carbons were predominant in the cumulatively produced and emitted SCCPs, MCCPs, and LCCPs, respectively. The emission estimates were evaluated by generating environmental concentrations that are comparable to literature-reported environmental monitoring data. Our estimates provide opportunities to link the environmental fate and occurrence of CPs to emission sources and lay the basis for future risk-reduction strategies of CPs around the world.

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).

Clarifying Temporal Trend Variability in Human Biomonitoring of Polybrominated Diphenyl Ethers through Mechanistic Modeling.

Human biomonitoring data collected from individuals of the same age sampled in different years provide within-age temporal trends, which are often employed to evaluate the effectiveness of chemical regulatory policies. For polybrominated diphenyl ethers (PBDEs), this within-age temporal trend has been observed to vary between congeners and age groups. We systematically explore the mechanisms responsible for such variability through simulating human exposure via multiple exposure pathways to PBDEs released from multiple lifecycle stages. Our simulation indicates that, after new use of PBDEs is banned, emissions to the outdoor environment from use and waste disposal outlast those to the indoor environment from the indoor use phase, leading to slower decline rates in the contamination of food items sourced from the outdoor environment than that from indoors. Compared with indoor exposure pathways, the consumption of contaminated food contributes more to the exposure (i) to more hydrophobic, recalcitrant congeners, and (ii) of adults than children, which results in slower rates of decline in the within-age temporal trend of those congeners and in adults. The within-age temporal trend is influenced to a lesser extent by the elimination of PBDEs from the human body, e.g., differences in biotransformation potential of congeners, growth dilution, and pre- and postnatal exposures by children.

Isotopic Characterization of Atmospheric Gaseous Elemental Mercury by Passive Air Sampling.

Tracing emission sources and transformations of atmospheric mercury with Hg stable isotopes depends on the ability to collect amounts sufficient for reliable quantification. Commonly employed active sampling methods require power and long pumping times, which limits the ability to deploy in remote locations and at high spatial resolution and can lead to compromised traps. In order to overcome these limitations, we conducted field and laboratory experiments to assess the preservation of isotopic composition during sampling of gaseous elemental mercury (GEM) with a passive air sampler (PAS) that uses a sulfur-impregnated carbon sorbent and a diffusive barrier. Whereas no mass independent fractionation (MIF) was observed during sampling, the mass dependent fractionation (MDF, δ202Hg) of GEM taken up by the PAS was lower than that of actively pumped samples by 1.14 ± 0.24‰ (2SD). Because the MDF offset was consistent across field studies and laboratory experiments conducted at 5, 20, and 30 °C, the PAS can be used for reliable isotopic characterization of GEM (±0.3‰ for MDF, ±0.05‰ for MIF, 2SD). The MDF offset occurred more during the sorption of GEM rather than during diffusion. PAS field deployments confirm the ability to record differences in the isotopic composition of GEM (i) with distance from point sources and (ii) sampled at different background locations globally.

How are Humans Exposed to Organic Chemicals Released to Indoor Air?

Humans are exposed to organic chemicals released to indoor air through near-field exposure routes such as air inhalation and nondietary dust ingestion as well as far-field exposure routes such as consumption of food. Here, we explore the relative importance of near- and far-field exposure routes and its variability between chemicals, age groups, and subpopulations, by modeling aggregate human exposure to indoor-released chemicals with diverse partitioning behavior and degradability. Our model results indicate that if chemicals are assumed to be perfectly persistent, dietary and nondietary ingestion dominates human exposure to hydrophobic chemicals of relatively low volatility (with an octanol-air partition coefficient KOA > 106.5 and an octanol-water partition coefficient KOW < 1011), whereas inhalation of indoor air dominates human exposure to volatile chemicals. Other exposure routes, for example, dermal absorption and drinking water, make a relatively small contribution to human exposure. Reduced chemical persistence in environmental media and biota lowers the contribution of dietary ingestion. For most chemicals other than those with a KOA between 109 and 1012 and a KOW between 106 and 109 (e.g., polybrominated diphenyl ethers), the relative importance of near- and far-field exposure routes is primarily governed by chemical partitioning and degradability rather than age- and population-dependent human exposure factors.

Development and Evaluation of a Combined Bioenergetics and Organic Chemical Mass-Balance Bioaccumulation Model for Fish.

This study describes the development and evaluation of a new bioenergetically balanced bioaccumulation (3B) model for organic chemicals in fish. The 3B model is developed from a large database of routine metabolic (oxygen consumption) rates composed of a range of species, body mass, and temperatures. The chemical uptake and elimination rates of the 3B model are compared against those from three existing bioaccumulation models. A time-variant version of the 3B model is evaluated against measured concentrations of five polychlorinated biphenyls in different-size fish depurated over the course of a year, during which water temperature changed by 22 °C. The "generic" species 3B model predicts fish concentrations to within a factor of 3 of the measured data for the majority of observations ( n = 438) and outperforms a previously published "species-specific" bioenergetics model. Bioenergetics aspects of the 3B model are further evaluated by comparing predicted feeding rates and growth rates to measured rates obtained from diverse laboratory conditions ( n 572). While bioenergetics performance is acceptable, the 3B model seems to generally perform better when ingestion rates are calculated from growth rates rather than vice versa. For field applications, parametrization of the activity multiplier remains a key uncertainty underlying the bioenergetics calculations.

Trans-Himalayan Transport of Organochlorine Compounds: Three-Year Observations and Model-Based Flux Estimation.

High mountains can trap semivolatile chemicals, such as persistent organic pollutants (POPs), and hinder their dispersion. However, both deep convection and mountain valleys can facilitate POPs' transport over mountains, which have not been investigated before. In this study, a three-year sampling campaign along a south-north altitudinal transect (100-5200m) across the central Himalayas, coupled with a multicompartment contaminant fate model, was conducted for describing the transport processes of POPs. The results show that POPs emitted in the lowlands of the Himalayas can be transported to high altitudes and further to the inner part of the Tibetan Plateau. Modeling suggests that more than 90% of POPs are trapped along the way due to gaseous deposition to soil/foliage and rainfall scavenging; while 2 × 10-3 to 1 × 10-1 Giga-grams/year of POPs are transported across the Himalayas. The transport flux along valleys is 2-3 times higher than that across the mountain ridge. However, due to the limited spatial coverage of mountain valleys, the amount of POPs transported through valleys only accounts for a small part of the total transport. This study shows that POPs can overcome the blocking effect of the Himalayas, and high altitude transport across the mountain ridge is the dominant transport pathway.

Elucidating the Variability in the Hexabromocyclododecane Diastereomer Profile in the Global Environment.

Hexabromocyclododecane (HBCDD) is a hazardous flame retardant subject to international regulation. Whereas γ-HBCDD is a dominant component in the technical HBCDD mixture, the diastereomer profile in environmental samples shows substantial temporal and spatial variations, ranging from γ- to α-HBCDD-dominant. To explain such variability, we simulate the global emissions and fate of HBCDD diastereomers, using a dynamic substance flow analysis model (CiP-CAFE) coupled to a multimedia environmental fate model (BETR-Global). Our modeling results indicate that, as of 2015, 340-1000 tonnes of HBCDD have been emitted globally, with slightly more γ-HBCDD (50%-65%) than α-HBCDD (30%-50%). Emissions of γ-HBCDD primarily originate from production and other industrial processes, whereas those of α-HBCDD are mainly associated with the use and end-of-life disposal of HBCDD-containing products. Presently, α-HBCDD dominates the contamination in the air of populated areas, while γ-HBCDD is more abundant in remote background areas and in regions with HCBDD production and processing facilities. Globally, the relative abundance of α-HBCDD is anticipated to increase after production of HBCDD is banned. Due to isomerization, α-HBCDD accumulates to a larger extent than γ-HBCDD in Arctic surface media. Since α-HBCDD is more persistent and bioaccumulative than other diastereomers, isomerization has bearing on the potential environmental and health impacts on a global scale.

Occurrence of Single- and Double-Peaked Emission Profiles of Synthetic Chemicals.

This work aims to elucidate the circumstances that can lead to two peaks in the temporal emission profile of synthetic chemicals. Using a simplified substance flow model, we explore how emission factors, product lifespan, and degradation half-life in waste stock influence the (i) relative importance of emissions from three lifecycle stages (industrial processes, use phase, and waste disposal), and (ii) the resulting composite emission profile. A double-peaked emission profile occurs if the lifespan of products containing the chemical is longer than its production history, and the gross emission factor from waste disposal exceeds that from the use phase. Since most chemicals fail to meet these two conditions, it is reasonable to use single-peaked emission profile as the default in environmental studies. On the basis of their emission profiles and contributions from individual lifecycle stages, we can categorize chemicals into "simple single-peakers", "composite single-peakers", and "double-peakers". Our simplified model derived emission profiles for five real chemicals that agree well with earlier, more sophisticated calculations, indicating the model's ability to capture the essential features of actual emissions. It is hoped that the model and conclusions in this work will benefit both environmental modelers and decision makers.