Soil-air Partitioning Research Articles

Effects of temperature, relative humidity and soil organic carbon content on soil-air partitioning coefficients of volatile PFAS

Soil-air partitioning coefficient (KSA) values are often used to assess the environmental fate of organic contaminants in soil. Till now, sufficient KSA values have not yet been measured for many compounds of interest, including some emerging pollutants such as volatile PFAS. Moreover, the effects of environmental factors such as temperature, relative humidity and soil organic carbon content on KSA of volatile PFAS are also unclear. In this study, the KSA values of target volatile PFAS were measured under various temperature (20–40 °C), relative humidity (30–100 %) and soil organic carbon content (2.1 %–8.0 %) using a modified solid-phase fugacity meter. The results showed that higher temperatures, higher relative humidity and lower organic carbon content in soil may accelerate the diffusion of target volatile PFAS. Furthermore, the KSA measurements were used to derive a multiple linear regression model to depict the relationship between logKSA and temperature, relative humidity, soil organic carbon content and PFAS-specific logKOA. When compared with the predictions obtained from semi-empirical model, we argued that the multiple linear regression model is more robust and easier to implement for target volatile PFAS or other emerging volatile PFAS than the semi-empirical approach to help depict the diffusion process at target volatile PFAS contaminated sites.

Environmental factors influencing the soil-air partitioning of semi-volatile petroleum hydrocarbons: Laboratory measurements and optimization model

The soil-air partition coefficient (KSA) values are commonly utilized to examine the fate of organic contaminants in soils; however, their measurement has been lacking for semi-volatile petroleum hydrocarbons within soil contaminated by crude oil. This research utilized a solid-phase fugacity meter to determine the KSA values of n-alkanes and polycyclic aromatic hydrocarbons (PAHs) under crucial environmental conditions. The results showed a notable increase in KSA values with the extent of crude oil contamination in soil. Specifically, in the 3 % crude oil treatment, the KSA values for n-alkanes and PAHs increased by 1.16 and 0.66 times, respectively, compared to the 1 % crude oil treatment. However, the KSA values decreased with changes in temperature, water content, and particle size within the specified experimental range. Among these factors, temperature played a significant role. The KSA values for n-alkanes and PAHs decreased by 0.27–0.89 and 0.61–0.83 times, respectively, with a temperature increase from 5 °C to 35 °C. Moreover, the research identified that the molecular weight of n-alkanes and PAHs contributed to variations in KSA values under identical environmental factors. With an increase in temperature from 5 °C to 35 °C, the range of n-alkanes present in the air phase expanded from C11 to C34, and PAHs showed elevated levels of acenaphthene (ACE) and benzo (b) fluoranthene (BbFA). Furthermore, heightened water content and particle size were observed to facilitate the volatilization of low molecular weight petroleum hydrocarbons. The effect of environmental variables on soil-air partitioning was evaluated using the Box-Behnken design (BBD) model, resulting in the attainment of the lowest log KSA values. These results illustrate that soil-air partitioning is a complex process influenced by various factors. In conclusion, this study improves our comprehension and predictive capabilities concerning the behavior and fate of n-alkanes and PAHs within soil-air systems.

Phthalate pollution and migration in soil-air-vegetable systems in typical plastic agricultural greenhouses in northwestern China

Phthalate pollution in plastic greenhouses (PGs) has aroused concerns. However, mechanisms and factors of vegetables planted in PGs (VPGs) accumulating phthalates from soil and air are unclear. To fill the gap, 19 PGs in Shaanxi, the largest vegetable production province in northwestern China, were selected to probe this issue. 35 soil samples, 48 air samples, and 26 VPG samples were collected in winter and summer. Medians of sum of 7 phthalate concentrations (∑7 PAEs) in PG soil, air, and VPGs were 73.9 μg kg−1, 5300 ng m−3, and 1053 μg kg−1 dry weight, respectively. ∑7 PAE concentrations in PG environmental media in winter were higher than summer, with the significant difference in VPGs. Sum concentrations of bis (2-ethylhexyl) phthalate (DEHP) and di-n-butyl phthalate (DnBP) accounted for 76.8% and 82.3% of the ∑7 PAEs in soil and VPGs. DnBP and DEHP concentrations in VPGs were significantly correlated to those in air and soil, with correlation coefficients (R) of 0.89 and 0.96 to air and 0.68 and 0.59 to soil. Log-transformed soil-air partition coefficient (log KSA) and fugacity fraction (log ff) of DnBP decreased while log KSA and log ff of DEHP increased from winter to summer, though DnBP in soil volatilized to air while DEHP in air sank to soil within the year. These issues were caused by air temperature changes and the application of plastic films. Furthermore, DnBP concentrations in VPGs were positively correlated to KSA values of DnBP (R = 0.87) while those of DEHP were negative (R = −0.82). Therefore, VPGs could uptake more phthalates from air than from soil, especially for edible parts of leafy and solanaceous VPGs. Applying phthalates free agricultural films and precision management such as adjusting air temperature in PGs could be considered to ensure VPG safeties.

Soil-air partitioning of semivolatile organic compounds in the Lesser Himalaya region: Influence of soil organic matter, atmospheric transport processes and secondary emissions

After decades of imposed regulations about reducing the primary emissions of persistent organic pollutants (POPs), these pollutants are still present in the environment. Soils are important repositories of such persistent semivolatile organic contaminants (SVOCs), and it is assumed that SVOCs sequestered in these reservoirs are being re-mobilized due to anthropogenic influence. In this study, concentrations of organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), and polybrominated diphenyl ethers (PBDEs) in soil and air, their fugacities, fluxes and the soil-air partition coefficient (KSA) were determined for three different land cover types (glacial, remote/mountainous and urban) of the Lesser Himalayan Region (LHR). The concentrations of OCPs, PCBs and PBDEs in soils and air ranged between 0.01 and 2.8, 0.81–4.8, 0.089–0.75 ng g−1; 0.2–106, 0.027–182, and 0.011–7.26 pg m−3, respectively. The levels of SVOCs in the soil were correlated with soil organic matter (SOM) indicating that SOM is a substrate for the organic pollutants in soils. The Clausius-Clapeyron plots between ln P and inverse of temperature (1000/T) suggested that long range atmospheric transport was the major input source of PBDEs and higher chlorinated PCBs over the LHR. The uneven and wide distribution of local sources in LHR and up-slope enrichment of SVOCs explained the spatial variability and altitudinal patterns. The soils near mountain and urban lakes act as local sinks of SVOCs such as β-HCH, pp΄-DDT, CB-28, -118, −153, BDE-47, -99, and −154, with soil-air exchange fluxes tending more toward deposition. However, the soils near glacial lakes acted as local sources of more volatile congeners of α-HCH, γ-HCH, op′-DDT, pp′-DDE and lower to medium chlorinated PCBs such as CB-18, -28, −53, −42 and BDE-47, -99, with soil-air exchange tending more toward volatilization flux.

Nitrated- and oxygenated-polycyclic aromatic hydrocarbon in urban soil from Nepal: Source assessment, air-soil exchange, and soil-air partitioning

In contrast to more frequently investigated priority pollutants, such as polycyclic aromatic hydrocarbons (PAHs), only little is known about the fate and distribution of nitrated- and oxygenated-PAHs (NPAHs and OPAHs) in urban soils, particularly in Indian sub-continent. Moreover, experimental data on air-soil exchange and soil-air partitioning are also lacking, which is critical in assessing the partitioning, fugacity coefficient, and secondary emission of PAH-derivatives. Hence, this article provides an insight into the fate, sources, air-soil exchange, and soil-air partitioning of PAH-derivatives on a molecular basis. Prospective health risk due to their exposure has also been discussed. The result showed that PAH-derivatives had significantly polluted all four Nepalese cities. Ʃ15NPAHs and Ʃ2OPAHs in soil were 4 and 20 times lower than their parent-PAHs, and ranged 396–2530 ng/g (median 458 ng/g) and 91.9–199 ng/g (median 94.9 ng/g), respectively. Ʃ15NPAHs was higher than a few global studies, while Ʃ2OPAHs was lower than some of the less urbanized/remote areas worldwide. The 6-Nitobenzo[a]pyrene (6-NBaP) was most abundant in soil, and accounted for 10–12% of Ʃ15NPAHs, while Benzanthrone (BZONE) exceeded among OPAHs, and represented 71–76% of Ʃ2OPAHs, respectively. Source identification study indicated that direct emissions from domestic/residential cooking and heating and secondary formations are the essential sources of derivative chemicals in soil. Fugacity fraction ratio (fratio) indicated volatilization from the soil. The soil-air partitioning study showed sorption by soil organic matter/black carbon has little role in soil-air partitioning of PAH-derivatives in Nepal's urban soil. The toxicity equivalency quotients (TEQs) of NPAHs (314 ± 102 ng/g) was estimated slightly higher than their parent-PAHs (294 ± 121 ng/g) suggesting a relatively higher risk of soil toxicity in Nepal.

Soil-Air Partition Coefficients of Persistent Organic Pollutants Decline from Climate Warming: a Case Study in Yantai County, Shandong Province, China

Recognizing the kinetics of the soil-air partition coefficients (Ksoil-air) of persistent organic pollutants (POPs) under distinct scenarios of changing climate conditions is crucial for well understanding the response of POPs exchange process across the air-soil interface to climate warming. Taking Yantai County, Shandong Province, China, as a case study, the Ksoil-air values of HCH, DDE, DDD, and DDT in cropland soil under two levels of soil organic matter (SOM) (0.5% and 1.7%) were projected under future climate scenarios by employing representative concentration pathway (RCP) climate scenarios and a multiple linear model of the Ksoil-air of POPs. Compared to baseline conditions, future climate conditions would shift substantially, and daily Ksoil-air values of HCH, DDE, DDD, and DDT under future climate scenarios would decline by approximately 23–91 (× 105), 5,542–21,703 (× 105), 78–309 (× 105), and 18,986–74,133 (× 105), respectively, under future climate scenarios than under baseline conditions when the SOM content was 0.5% or by approximately 9,167–360,45 (× 105), 128,533–508,592 (× 105), 31,513–123,038 (× 105), and 444,513–1738,367 (× 105), respectively, when the SOM level was 1.7%, or by approximately 2–13% under two levels of SOM. Annual Ksoil-air values of HCH, DDE, DDD, and DDT would decline by approximately 3.51–7.54 (× 105), 842.06–1,806.46 (× 105), 11.83–25.66 (× 105), and 2,840.13–6,153.16 (× 105), respectively, when the SOM content was 0.5%, or by approximately 1,397.47–2,997.98 (× 105), 19,739.82–42,347.56 (× 105), 4,713.44–10,211.70 (× 105), and 66,579.06–144,244.10 (× 105), respectively, when the SOM content was 1.7%, or by approximately 8–18% under two levels of SOM. Moreover, Ksoil-air showed daily, monthly, and seasonal temporal changes within whole years and high temporal yearly fluctuation. Daily and annual Ksoil-air values were lower under 0.5% SOM content than under 1.7% SOM content. The results suggested that the adsorbing capacity of soil to POPs would decrease, and many more POPs in the soil would volatilize to the atmosphere from climate warming.

Influence of Adjuvants on Pesticide Soil–Air Partition Coefficients: Laboratory Measurements and Predicted Effects on Volatilization

A solid-phase fugacity meter was used to measure the soil-air partition coefficients of three semivolatile pesticides (chlorpyrifos, pyrimethanil, and trifluralin) in the absence of additional adjuvants (Ksoil-air,AI), as part of commercial formulations (Ksoil-air,formulation), and as formulation mixtures with an additional spray adjuvant added (Ksoil-air,formulation+sprayadjuvant). Chlorpyrifos Ksoil-air,formulation values were also measured over 15-30 °C, allowing for the change in internal energy of the phase transfer reaction (Δsoil-airU) to be calculated and compared to the Δsoil-airU for Ksoil-air,AI from the literature. Measured Ksoil-air values were then used as input parameters in a pesticide volatilization model to understand how their variability affects pesticide volatilization rates under different conditions. Initial experiments conducted at ∼24 °C indicated that all pesticides volatilized more readily in the presence of adjuvants than in their absence and that the additional spray adjuvant had minimal impact. The Δsoil-airU values were 328 and 90 kJ/mol for chlorpyrifos in the absence and presence of formulation adjuvants, respectively, suggesting that adjuvants may weaken or disrupt intermolecular attractions between pesticide molecules and soil. At temperatures below 24.5 °C, modeled chlorpyrifos volatilization rates were higher in the presence of adjuvants than in their absence; however, the opposite occurred at temperatures above 24.5 °C.

Inclusion of molecular descriptors in predictive models improves pesticide soil-air partitioning estimates

The soil-air exchange of pesticides is one potential fate and exposure pathways, and this process is generally thought to be governed by soil properties and environmental conditions. The experimental determination of soil-air partitioning coefficient (Ksa) is laborious and costly and typically, Ksa’s are predicted from a semiempirical or a simple linear regression approach with soil and environmental variables. Here we developed a model that combined linear regression of soil, environmental and molecular parameters with the quantitative structural-property relationship (QSPR) to predict Ksa for pesticides. The values of theoretical descriptors of pesticides were calculated and the best descriptors selected using the Boruta Algorithm. Seventy-six experimental logKsa values for 17 pesticides were used in model development. Multiple linear regression (MLR) with a soil (organic carbon fraction), physicochemical (octanol-air partitioning coefficient), environmental (temperature and humidity) and molecular descriptor (Gmin, a 2D E-state molecular parameter), called as MLR-QSPR combined model exhibited better predictability (adj. r2 = 0.95) of logKsa compared to MLR (adj. r2 = 0.87) or QSPR (adj. r2 = 0.82) itself. MLR-QSPR also showed the best performance in five-fold cross-validation (adj. r2 = 0.94) and test set verification (adj. r2 = 0.96). The developed model was validated and characterized by the applicability domain. Results showed that the proposed MLR-QSPR approach is highly predictive and statistically robust with >95% of predictions within ±0.5 log unit of the measured Ksa. Therefore, this approach can be used in estimating the soil-air partitioning of pesticides to better predict it’s fate and transport in environments.

Soil–air partitioning of volatile organic compounds into soils with high water content

Environmental contextAssessing environmental and human health impacts of chemical spills relies on information about how chemicals move across multiple environments. We measured volatile contaminants in the air above soil saturated with water to provide estimates of air concentrations of selected chemicals released to soil from an oil refinery in Texas during Hurricane Harvey. Estimated concentrations were below recommended exposure limits, even in a worst-case scenario. AbstractThe emission of volatile organic compounds (VOCs) from soil into air is affected by soil moisture dynamics, soil temperature, solar irradiance and carbon availability. The high amount of water in soil can modify its properties, which changes how VOCs interact. We conducted a comprehensive measurement of the soil–air partition coefficient (KSA) of VOCs into water-saturated soil with both low and high water contents for polar, weakly polar and nonpolar VOCs into a mineral soil (S-clay) and soil containing a high amount of organic matter (S-om) under a water-saturated condition. Partitioning of non-polar substituted aromatics (1,2-dichlorobenzene and toluene) was sensitive to the organic matter content in water-saturated soil. 1,2-Dichlorobenzene and toluene had higher affinities to S-om than to S-clay at all investigated water contents because of their strong interaction with the organic matter in soil. KSA decreased with elevated water content only for non-polar substituted aromatic VOCs. Less hydrophobic VOCs (benzene and trichloroethylene) exhibited similar partitioning into both soils by sorbing onto the air-water interface and dissolving in soil water, while the organic matter did not affect partitioning. The weakly polar and polar VOCs (methyl tert-butyl ether and 1-butanol) showed similar partitioning into both soils by dissolving in soil water while sorption to the organic matter was significant only at high soil water contents. KSA of VOCs on soil with high organic matter content correlated strongly with psat and Koa, but not on mineral soil. Estimates of the air concentrations for a subset of VOCs released from one refinery during Hurricane Harvey in 2017 in Harris County, Texas were lower than the recommended exposure limits, even under a worst-case scenario.

Congener-specific composition of polychlorinated biphenyls (PCBs) in soil-air partitioning and the associated health risks

The recent changes in the compositions of polychlorinated biphenyls (PCBs) after their restriction for 40 years may have various effects on human health. In order to characterize the congener-specific compositions of PCBs in the soil-air process and assess the associated human health risks, soil and air samples were simultaneously collected in winter and summer at two different functional locations. Homologue patterns suggest that long-range atmospheric transport might be the major source of soil and air residues of PCBs. The net deposition from air to soil was overwhelming for most PCB congeners. Variations in the occurrence and the homologue patterns of PCBs between the soil and air interface depended on chemical volatility, soil organic matter (OM) content, ambient temperature, topographical condition and atmospheric transport. Dioxin-like PCBs accounted for 11.0–70.3% and 2.31–54.8% of total PCB residues in soil and air, respectively. Non-carcinogenic and carcinogenic risks associated with exposure to soil and air PCBs were also estimated. Different PCB congeners showed different health effects, with the highest contribution from PCB-26. Additionally, the non-carcinogenic risk levels of PCBs were enhanced, while the carcinogenic risk levels decreased during the soil-air exchange process of PCBs with time. Our results highlight the soil-air interaction of PCBs in predicting their potential human exposure health risks.

Characterization of Tibetan Soil As a Source or Sink of Atmospheric Persistent Organic Pollutants: Seasonal Shift and Impact of Global Warming.

Background soils are reservoirs of persistent organic pollutants (POPs). After decades of reduced primary emissions, it is now possible that the POPs contained in these reservoirs are being remobilized because of climate warming. However, a comprehensive investigation into the remobilization of POPs from background soil on the largest and highest plateau on Earth, the Tibetan Plateau (TP), is lacking. In this study, a sampling campaign was carried out on the TP at three background sites with different land cover types (forest, meadow and desert). Field measurements of the air-soil exchange of POPs showed that previous prediction using empirical models overestimated the values of the soil-air partitioning coefficient ( KSA), especially for chemicals with KOA > 9. The direction of exchange for γ-HCH, HCB, and PCB-28 overlapped with the air-soil equilibrium range, but with a tendency for volatilization. Their emission fluxes were 720, 2935, and 538 pg m-2 day-1, respectively, and were similar in extent to those observed for background Arctic soil in Norway. Nam Co and Ngari are also permafrost regions, and most chemicals at these two sites exhibited volatilization. This is the first result showing that permafrost can also emit POPs. Seasonally, we found that chemicals tended to be re-emitted from soils to the atmosphere in winter and deposited from the air to the soil in summer. This finding is opposite to most previous results, possibly because of the higher air-soil concentration gradient caused by the prevailing transport of POPs in summer. Climate warming exerts a strong influence on air-soil exchange, with an increase of 1 °C in ambient temperature likely leading to an increase of Tibetan atmospheric inventories of POPs by 60-400%.

Environmental concentration and atmospheric deposition of halogenated flame retardants in soil from Nepal: Source apportionment and soil-air partitioning.

While various investigations have been driven on polybrominated diphenyl ethers (PBDEs) and other flame retardants (FRs) in different framework around the world, information about contamination and fate of PBDEs and other FRs in developing countries especially in the Indian subcontinent is uncommon. Nepal being located in the Indian subcontinent, very little is known about contamination level of semi-volatile organic pollutants discharged into the environment. This motivated us to investigate the environmental fate of halogenated flame retardant (HFRs) in Nepalese condition. In this study, we investigated the concentration, fate, and sources of 9 PBDEs, 2 dechlorane plus isomers (DPs), and 6 novel brominated flame retardants (NBFRs). Moreover, air-soil exchange and soil-air partitioning were also evaluated to characterize the pattern of air-soil exchange and environmental fate. In general, the concentrations of NBFRs in soil were more prevalent than PBDEs and DPs, and accounted 95% of ∑HFRs. By and large, the concentrations of NBFRs and DPs were measured high in Kathmandu, while PBDEs level exceeded in Pokhara. Principal component analysis (PCA) study suggested contributions from commercial penta-, octa-, and deca-BDEs products and de-bromination of highly brominated PBDEs as the significant source of PBDEs. Likewise, low fanti ratio suggested DPs in soil might have originated from long-range atmospheric transport from remote areas, while high levels of decabromodiphenyl ethane (DBDPE) in soil were linked with the use of wide varieties of consumer products. The estimated fugacity fraction (ff) for individual HFR was quite lower (<0.05) than equilibrium value, suggesting that deposition and net transport from air to the soil is overwhelming. Soil-air partitioning study revealed neither octanol-air partition coefficient (KOA) nor black carbon partition coefficient (KBC-A) is an appropriate surrogate for soil organic matter (SOM), subsequently, absorption by SOM has no or little role in the partitioning of HFRs.

Higher atmospheric levels and contribution of black carbon in soil-air partitioning of organochlorines in Lesser Himalaya

Due to influence of wind patterns (monsoon and westerlies) and anthropogenic activities, lower stretch of Himalaya is at direct exposure to persistent organic pollutants (POPs). Current study was designed to monitor atmospheric concentrations of long lived organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) using polyurethane passive air sampling in the Lesser Himalayan Region (LHR) of Pakistan. Levels of ∑HCHs, ∑DDTs and ∑PCBs were observed in a range between 3 and 210 pg m−3, 0.75–67.1 pg m−3 and 8.49–458 pg m−3, respectively. Though, air mass trajectories over LHR indicated long range transport as atmospheric source input which was further explained by Clausius–Clapeyron plots between ln P and inverse of temperature (1000/T; K) where all OCPs and most of the PCBs have shown insignificant relationship (r2 = 5E-06–0.41; p-value = 0.06–0.995). However, local source emissions and valley transport may also implicate based on spatial distribution and altitudinal patterns. Additionally, soil-air partitioning of organochlorines was assessed using octanol-air partition (KOA) and black carbon-air partition (KBC) based models. Regression results indicated combined influence of both organic matter (r2 = 0.298–0.85) and black carbon (r2 = 0.31–0.86) via absorption and adsorption, respectively in soil-air partitioning of OCs in LHR. This paper sheds light on the atmospheric concentrations of OCs and help in better understanding of the processes involved in fate and transport of organic pollutants in Himalayan region. Further investigations are required to understand the role of carbon moieties in fate and transport of other groups of organic pollutants at higher altitudes of Himalayan region.

Polychlorinated biphenyls in Nepalese surface soils: Spatial distribution, air-soil exchange, and soil-air partitioning

Regardless of the ban on the polychlorinated biphenyls (PCBs) decade ago, significant measures of PCBs are still transmitted from essential sources in cities and are all inclusive ecological contaminants around the world. In this study, the concentrations of PCBs in soil, the air-soil exchange of PCBs, and the soil-air partitioning coefficient (KSA) of PCBs were investigated in four noteworthy urban areas in Nepal. Overall, the concentrations of ∑30PCBs ranged from 10 to 59.4ng/g dry weight; dw (mean 12.2ng/g ±11.2ng/g dw). The hexa-CBs (22–31%) was most dominant among several PCB-homologues, followed by tetra-CBs (20–29%), hepta-CBs (12–21%), penta-CBs (15–17%) and tri-CBs (9–19%). The sources of elevated level of PCBs discharge in Nepalese soil was identified as emission from transformer oil, lubricants, breaker oil, cutting oil and paints, and cable insulation. Slightly strong correlation of PCBs with TOC than BC demonstrated that amorphous organic matter (AOM) assumes a more critical part in holding of PCBs than BC in Nepalese soil. The fugacity fraction (ff) results indicated the soil being the source of PCB in air through volatilization and net transport from soil to air. The soil-air partitioning coefficient study suggests the absorption by soil organic matter control soil-air partitioning of PCBs. Slightly weak but positive correlation of measured Log KSA with Log KOA (R2 = 0.483) and Log KBC-A (R2 = 0.438) suggests that both Log KOA and Log KBC-A can predict soil-air partitioning to lesser extent for PCBs.

Assessing soil-air partitioning of PAHs and PCBs with a new fugacity passive sampler

Soil-air fluxes of polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) were determined using a novel application of passive samplers to measure air and soil air, which is air in close proximity and in equilibrium with soil. Existing methods to measure flux of semi-volatile compounds between soil and air require collecting samples from the top soil layer. Yet, the top soil layer is hard to define and oversampling may misrepresent the exchangeable fraction. Alternatively, modified active samplers can measure soil air in situ, but require electricity while deployed. We present a new method to measure time-weighted averages of soil air concentrations in situ using passive sampling and requiring no electricity: a box is placed over low-density polyethylene passive samplers deployed 1cm above the soil. Passive air samplers were also co-deployed 1.5m above the soil to measure ambient air concentrations in three U.S. locations: near a former PCB manufacturing facility in Anniston, Alabama; on a former creosoting and the current Wyckoff/Eagle Superfund site near Seattle, Washington; and near the site of a recent oil-train derailment and fire in Mosier, Oregon. Following n-hexane extraction, sampler extracts were analyzed for PAHs with gas chromatography-tandem mass spectrometry and PCBs with dual gas chromatography-electron capture detectors. PAHs were generally depositing at Anniston and Mosier sites, but volatilizing from soil in Wyckoff, the site with historically-contaminated soil. PCBs were detected most frequently at the Anniston site, although levels were lower than previous reports. Variability in concentration measurements was greater among soil air samplers than air samplers, likely due to soil heterogeneity. Environmental conditions under the novel soil air box did not substantially change soil-air partitioning behavior. This method of measuring soil air in situ will allow for understanding of source-sink dynamics at sites with recent and historical contamination, and where conventional sampling is challenging.

The Abandoned E-Waste Recycling Site Continued to Act As a Significant Source of Polychlorinated Biphenyls: An in Situ Assessment Using Fugacity Samplers.

The recycling of e-waste has attracted significant attention due to emissions of polychlorinated biphenyls (PCBs) and other contaminants into the environment. We measured PCB concentrations in surface soils, air equilibrated with the soil, and air at 1.5-m height using a fugacity sampler in an abandoned electronic waste (e-waste) recycling site in South China. The total concentrations of PCBs in the soils were 39.8-940 ng/g, whereas the concentrations in air equilibrated with the soil and air at 1.5 m height were 487-8280 pg/m(3) and 287-7380 pg/m(3), respectively. The PCB concentrations displayed seasonal variation; they were higher in winter in the soils and higher in summer in the air, indicating that the emission of PCBs from the soil was enhanced during hot seasons for the relatively high temperature or additional sources, especially for low-chlorinated PCBs. We compared two methods (traditional fugacity model and fugacity sampler) for assessing the soil-air partition coefficients (Ksa) and the fugacity fractions of PCBs. The results suggested that the fugacity sampler provided more instructive and practical estimation on Ksa values and trends in air-soil exchange, especially for low-chlorinated PCBs. The abandoned e-waste burning site still acted as a significant source of PCBs many years after the prohibition on open burning.

Partitioning of Dichloro-diphenyl-trichloroethane and Its Metabolites Between Artificial Solid Media and Air

Soil–air partitioning is an important diffusive process affecting the environmental fate of organic compounds. In this study, the soil–air partition coefficients (KSA) for dichloro-diphenyl-trichloroethane and its metabolites (designated as DDTs, the sum of p, p′- and o, p′-isomers of DDT, DDD, and DDE) over a temperature range from 5 to 50 °C in artificial solid media were determined by a solid–fugacity meter. The results showed that log KSA gradually increased with soil organic carbon content (fOC). A reversed relationship was observed between log KSA values and the environmental temperatures (T). The enthalpy changes (ΔHSA) indicated that o, p′-isomers required more energy to release from artificial solid media to the gas phase. Moreover, with increasing temperature, the slope of the regression line of log KSA vs. log KOA (octanol–air partition coefficient) was approaching to 1. Based on factors influencing soil–air partitioning and the experimental data, a multiple parameter (T, fOC, and KOA) model was used to predict the KSA values for DDTs.

Diurnal Variations of Air-Soil Exchange of Semivolatile Organic Compounds (PAHs, PCBs, OCPs, and PBDEs) in a Central European Receptor Area.

Concentrations of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs), and polybrominated diphenyl ethers (PBDEs) in air and soil, their fugacities, and the experimental soil-air partitioning coefficient (KSA) were determined at two background sites in the Gt. Hungarian Plain in August 2013. The concentrations of the semivolatile organic compounds (SOCs) in the soil were not correlated with the organic carbon content but with two indirect parameters of mineralization and aromaticity, suggesting that soil organic matter quality is an important parameter affecting the sorption of SOCs onto soils. Predictions based on the assumption that absorption is the dominant process were in good agreement with the measurements for PAHs, OCPs, and the low chlorinated PCBs. In general, soils were found to be a source of PAHs, high chlorinated PCBs, the majority of OCPs and PBDEs, and a sink for the low chlorinated PCBs and γ-hexachlorocyclohexane. Diurnal variations in the direction of the soil-air exchange were found for two compounds (i.e., pentachlorobenzene and p,p'-dichlorodiphenyldichloroethane), with volatilization during the day and deposition in the night. The concentrations of most SOCs in the near-ground atmosphere were dominated by revolatilization from the soil.

Tracking the fingerprints and combined TOC–black carbon mediated soil–air partitioning of polychlorinated naphthalenes (PCNs) in the Indus River Basin of Pakistan

This study reports the first investigation of polychlorinated naphthalenes (PCNs) in air and soil samples from ecologically important sites of the Indus River Basin, Pakistan. The concentrations of ∑39-PCNs in air and soil were found in a range between 1–1588 pg m−3 and 0.02–23 ng g−1 while the mean TEQ values were calculated to be 5.4E−04 pg TEQ m−3 and 1.6E+01 pg TEQ g−1, respectively. Spatially, air and soil PCN concentrations were found to be high at Rahim Yar Khan (agricultural region). Lower-medium chlorinated PCNs (sum of tri-, tetra- and penta-CNs) predominated in both air and soil, altogether constituting 87 and 86% of total PCNs in the two environmental matrices, respectively. According to the data, soil–air partitioning of PCNs was interpreted to be similarly controlled by the combined effect of black carbon and organic matter in the Indus River Basin, with no preferential implication of the recalcitrant organic form.

Influence of Temperature, Relative Humidity, and Soil Properties on the Soil-Air Partitioning of Semivolatile Pesticides: Laboratory Measurements and Predictive Models.

Soil-air partition coefficient (Ksoil-air) values are often employed to investigate the fate of organic contaminants in soils; however, these values have not been measured for many compounds of interest, including semivolatile current-use pesticides. Moreover, predictive equations for estimating Ksoil-air values for pesticides (other than the organochlorine pesticides) have not been robustly developed, due to a lack of measured data. In this work, a solid-phase fugacity meter was used to measure the Ksoil-air values of 22 semivolatile current- and historic-use pesticides and their degradation products. Ksoil-air values were determined for two soils (semiarid and volcanic) under a range of environmentally relevant temperature (10-30 °C) and relative humidity (30-100%) conditions, such that 943 Ksoil-air measurements were made. Measured values were used to derive a predictive equation for pesticide Ksoil-air values based on temperature, relative humidity, soil organic carbon content, and pesticide-specific octanol-air partition coefficients. Pesticide volatilization losses from soil, calculated with the newly derived Ksoil-air predictive equation and a previously described pesticide volatilization model, were compared to previous results and showed that the choice of Ksoil-air predictive equation mainly affected the more-volatile pesticides and that the way in which relative humidity was accounted for was the most critical difference.