Evaluation and modelling of polycyclic aromatic hydrocarbon (PAH) bioavailability in soils affected by coal tar asphalt.

There are large masses of coal tar asphalt present in old roads, containing high concentrations of polycyclic aromatic hydrocarbons (PAHs). Uncertainty surrounding the risk they pose causes problems during road reconstruction and for the reuse of the asphalt present. To help elucidate potential risks, a parsimonious linear equilibrium partitioning model for the bioavailability of PAHs in soils contaminated by tar asphalt particles was developed. Furthermore, a set of partitioning coefficients for PAHs between sampled coal tar binders and water were determined experimentally, as well as measurements of freely dissolved concentrations using polyoxymethylene samplers in batch tests and column recirculation experiments with various mixtures of different soils (peat and sandy loam) and tar asphalts. The model predictions of freely dissolved concentrations were conservative and within an order of magnitude of measurements in both batch and column tests. The model presented here only relies on soil organic carbon content and the fraction coal tar binder in the soil to model PAH partitioning. This model could be used for more realistic. Low tier risk assessments towards rational prioritization of sensitive areas for risk reduction efforts.

Identifying persistent, mobile and toxic (PMT) organic compounds detected in shale gas wastewater.

Shale gas exploitation is a water-intensive process, generating flowback and produced water (FPW) with complex chemical compositions. Reuse, disposal and treatment of FPW are of increasing concern, because of the potential risk of FPW contamination to the surrounding aquatic environment and drinking water sources when emitted. Among numerous organic substances present in FPW, of particular concern are those that are persistent, mobile and toxic (PMT) and very persistent and very mobile (vPvM). PMT and vPvM substances have the greatest potential to spread in groundwater and are the hardest to remediate. This study presents the outcome of a literature review to identify organic compounds that were previously detected in FPW. The 162 target compounds identified from this review were assessed to see if they can be considered PMT/vPvM substances based on their substance properties. Our results indicated that most FPW substances are "not PMT", accounting for 108 (66.7 %) compouds. In total 22 FPW substances can be considered PMT/vPvM or very likely to meet this criteria if more data were available. Examples of PMT substances in FPW include anthracene, 1,4-dioxane and 1,4-dichlorobenzene. PMT/vPvM compounds identified in FPW should be prioritized for risk management measures and monitoring in order to protect regional water resources.

The Fate and Transport of Chlorinated Polyfluorinated Ether Sulfonates and Other PFAS through Industrial Wastewater Treatment Facilities in China.

Wastewater from certain industrial processes can be primary emission sources of per- and polyfluoroalkyl substances (PFAS) and fluorinated alternatives like chlorinated polyfluorinated ether sulfonates (Cl-PFESA). Two such industrial processes are electroplating and textile printing and dyeing (PD). This study focused on the fate of Cl-PFESA in wastewater from these two industrial processes, in comparison to other PFAS, as they went through different wastewater treatment plants located in southeast China. The total target PFAS concentrations were 520 ± 30 and 4200 ± 270 ng/L at the effluents of the PD WWTP and electroplating WWTP, respectively. Specifically, 6:2 Cl-PFESA (18%) and 8:2 Cl-PFESA (0.7%) were abundant in electroplating-wastewater. Cl-PFESA were also detected in PD wastewater but at trace concentrations and were likely present due to diffuse emissions. The dissolved-phase Cl-PFESA and PFAS mass flows through the WWTPs were fairly constant throughout both facilities. The majority of Cl-PFESA was captured by sludge sedimentation. However, there were individual treatment processes that could cause the wastewater concentrations to fluctuate, and also could lead to relative enrichment of specific Cl-PFESAs as indicated by the 6:2/8:2 Cl-PFESA ratios. Cl-PFESA and perfluoroalkyl sulfonic acids were more influenced by the investigated treatment processes than perfluorocarboxylic acids.

Effects of leachates from UV-weathered microplastic on the microalgae Scenedesmus vacuolatus.

Plastics undergo successive fragmentation and chemical leaching steps in the environment due to weathering processes such as photo-oxidation. Here, we report the effects of leachates from UV-irradiated microplastics towards the chlorophyte Scenedesmus vacuolatus. The microplastics tested were derived from an additive-containing electronic waste (EW) and a computer keyboard (KB) as well as commercial virgin polymers with low additive content, including polyethylene (PE), polyethylene terephthalate (PET), polypropylene (PP), and polystyrene (PS). Whereas leachates from additive-containing EW and KB induced severe effects, the leachates from virgin PET, PP, and PS did not show substantial adverse effects in our autotrophic test system. Leachates from PE reduced algae biomass, cell growth, and photosynthetic activity. Experimental data were consistent with predicted effect concentrations based on the ionization-corrected liposome/water distribution ratios (Dlip/w) of polymer degradation products of PE (mono- and dicarboxylic acids), indicating that leachates from weathering PE were mainly baseline toxic. This study provides insight into algae toxicity elicited by leachates from UV-weathered microplastics of different origin, complementing the current particle- vs. chemical-focused research towards the toxicity of plastics and their leachates.

Effects of Leachates from UV-Weathered Microplastic in Cell-Based Bioassays.

Standard ecotoxicological testing of microplastic does not provide insight into the influence that environmental weathering by, e.g., UV light has on related effects. In this study, we leached chemicals from plastic into artificial seawater during simulated UV-induced weathering. We tested largely additive-free preproduction polyethylene, polyethylene terephthalate, polypropylene, and polystyrene and two types of plastic obtained from electronic equipment as positive controls. Leachates were concentrated by solid-phase extraction and dosed into cell-based bioassays that cover (i) cytotoxicity; (ii) activation of metabolic enzymes via binding to the arylhydrocarbon receptor (AhR) and the peroxisome proliferator-activated receptor (PPARγ); (iii) specific, receptor-mediated effects (estrogenicity, ERα); and (iv) adaptive response to oxidative stress (AREc32). LC-HRMS analysis was used to identify possible chain-scission products of polymer degradation, which were then tested in AREc32 and PPARγ. Explicit activation of all assays by the positive controls provided proof-of-concept of the experimental setup to demonstrate effects of chemicals liberated during weathering. All plastic leachates activated the oxidative stress response, in most cases with increased induction by UV-treated samples compared to dark controls. For PPARγ, polyethylene-specific effects were partially explained by the detected dicarboxylic acids. Since the preproduction plastic showed low effects often in the range of the blanks future studies should investigate implications of weathering on end consumer products containing additives.

Combining in Silico Tools with Multicriteria Analysis for Alternatives Assessment of Hazardous Chemicals: A Case Study of Decabromodiphenyl Ether Alternatives.

Alternatives assessment is applied for minimizing the risk of unintentionally replacing a hazardous chemical with another hazardous chemical. Central challenges are the diversity of properties to consider and the lack of high-quality experimental data. To address this, a novel alternatives assessment procedure was developed based on in silico data and multicriteria decision analysis (MCDA) methods. As a case study, 16 alternatives to the flame retardant decabromodiphenyl ether were considered. The hazard properties included persistence (P), bioaccumulation potential (B), toxicities (T), and mobility in water (M). Databases were consulted and 2866 experimental data points were collected for the target chemicals; however, these were mostly replicate data points for some hazard criteria for a subset of alternatives. Therefore, in silico data and three MCDA strategies were tested including heat mapping, multiattribute utility theory (MAUT), and Elimination Et Choix Traduisant la REalité (ELECTRE III). The heat map clearly showed that none of the target chemicals are hazard-free, whereas MAUT and ELECTRE III agreed on ranking the "least worst" choices. This study identified several challenges and the complexity in the alternatives assessment processes motivating more case studies combining in silico and MCDA approaches.

The degradation behaviour of nine diverse contaminants in urban surface water and wastewater prior to water treatment.

An increasing diversity of emerging contaminants are entering urban surface water and wastewater, posing unknown risks for the environment. One of the main contemporary challenges in ensuring water quality is to design efficient strategies for minimizing such risks. As a first step in such strategies, it is important to establish the fate and degradation behavior of contaminants prior to any engineered secondary water treatment. Such information is relevant for assessing treatment solutions by simple storage, or to assess the impacts of contaminant spreading in the absence of water treatment, such as during times of flooding or in areas of poor infrastructure. Therefore in this study we examined the degradation behavior of a broad array of water contaminants in actual urban surface water and wastewater, in the presence and absence of naturally occurring bacteria and at two temperatures. The chemicals included caffeine, sulfamethoxazole, carbamazepine, atrazine, 17ß-estradiol, ethinylestradiol, diclofenac, desethylatrazine and norethindrone. Little information on the degradation behavior of these pollutants in actual influent wastewater exist, nor in general in water for desethylatrazine (a transformation product of atrazine) and the synthetic hormone norethindrone. Investigations were done in aerobic conditions, in the absence of sunlight. The results suggest that all chemicals except estradiol are stable in urban surface water, and in waste water neither abiotic nor biological degradation in the absence of sunlight contribute significantly to the disappearance of desethylatrazine, atrazine, carbamazepine and diclofenac. Biological degradation in wastewater was effective at transforming norethindrone, 17ß-estradiol, ethinylestradiol, caffeine and sulfamethoxazole, with measured degradation rate constants k and half-lives ranging respectively from 0.0082-0.52 d(-1) and 1.3-85 days. The obtained degradation data generally followed a pseudo-first-order-kinetic model. This information can be used to model degradation prior to water treatment.

Native oxy-PAHs, N-PACs, and PAHs in historically contaminated soils from Sweden, Belgium, and France: their soil-porewater partitioning behavior, bioaccumulation in Enchytraeus crypticus, and bioavailability.

Soil quality standards are based on partitioning and toxicity data for laboratory-spiked reference soils, instead of real world, historically contaminated soils, which would be more representative. Here 21 diverse historically contaminated soils from Sweden, Belgium, and France were obtained, and the soil-porewater partitioning along with the bioaccumulation in exposed worms (Enchytraeus crypticus) of native polycyclic aromatic compounds (PACs) were quantified. The native PACs investigated were polycyclic aromatic hydrocarbons (PAHs) and, for the first time to be included in such a study, oxygenated-PAHs (oxy-PAHs) and nitrogen containing heterocyclic PACs (N-PACs). The passive sampler polyoxymethylene (POM) was used to measure the equilibrium freely dissolved porewater concentration, Cpw, of all PACs. The obtained organic carbon normalized partitioning coefficients, KTOC, show that sorption of these native PACs is much stronger than observed in laboratory-spiked soils (typically by factors 10 to 100), which has been reported previously for PAHs but here for the first time for oxy-PAHs and N-PACs. A recently developed KTOC model for historically contaminated sediments predicted the 597 unique, native KTOC values in this study within a factor 30 for 100% of the data and a factor 3 for 58% of the data, without calibration. This model assumes that TOC in pyrogenic-impacted areas sorbs similarly to coal tar, rather than octanol as typically assumed. Black carbon (BC) inclusive partitioning models exhibited substantially poorer performance. Regarding bioaccumulation, Cpw combined with liposome-water partition coefficients corresponded better with measured worm lipid concentrations, Clipid (within a factor 10 for 85% of all PACs and soils), than Cpw combined with octanol-water partition coefficients (within a factor 10 for 76% of all PACs and soils). E. crypticus mortality and reproducibility were also quantified. No enhanced mortality was observed in the 21 historically contaminated soils despite expectations from PAH spiked reference soils. Worm reproducibility weakly correlated to Clipid of PACs, though the contributing influence of metal concentrations and soil texture could not be taken into account. The good agreement of POM-derived Cpw with independent soil and lipid partitioning models further supports that soil risk assessments would improve by accounting for bioavailability. Strategies for including bioavailability in soil risk assessment are presented.

Sewage sludge biochar influence upon rice (Oryza sativa L) yield, metal bioaccumulation and greenhouse gas emissions from acidic paddy soil.

Biochar addition to soil has been proposed to improve plant growth by increasing soil fertility, minimizing bioaccumulation of toxic metal(liod)s and mitigating climate change. Sewage sludge (SS) is an attractive, though potentially problematic, feedstock of biochar. It is attractive because of its large abundance; however, it contains elevated concentrations of metal(loid)s and other contaminants. The pyrolysis of SS to biochar (SSBC) may be a way to reduce the availability of these contaminants to the soil and plants. Using rice plant pot experiments, we investigated the influence of SSBC upon biomass yield, bioaccumulation of nutrients, and metal(loid)s, and green housegas (GHG) emissions. SSBC amendments increased soil pH, total nitrogen, soil organic carbon and available nutrients and decreased bioavailable As, Cr, Co, Ni, and Pb (but not Cd, Cu, and Zn). Regarding rice plant properties, SSBC amendments significantly (P ≤ 0.01) increased shoot biomass (71.3-92.2%), grain yield (148.8-175.1%), and the bioaccumulation of phosphorus and sodium, though decreased the bioaccumulation of nitrogen (except in grain) and potassium. Amendments of SSBC significantly (P ≤ 0.05) reduced the bioaccumulation of As, Cr, Co, Cu, Ni, and Pb, but increased that of Cd and Zn, though not above limits set by Chinese regulations. Finally regarding GHG emissions, SSBC significantly (P < 0.01) reduced N2O emissions and stimulated the uptake/oxidation of CH4 enough to make both the cultivated and uncultivated paddy soil a CH4 sink. SSBC can be beneficial in rice paddy soil but the actual associated benefits will depend on site-specific conditions and source of SS; long-term effects remain a further unknown.

Sorption of pure N2O to biochars and other organic and inorganic materials under anhydrous conditions.

Suppression of nitrous oxide (N2O) emissions from soil is commonly observed after amendment with biochar. The mechanisms accounting for this suppression are not yet understood. One possible contributing mechanism is N2O sorption to biochar. The sorption of N2O and carbon dioxide (CO2) to four biochars was measured in an anhydrous system with pure N2O. The biochar data were compared to those for two activated carbons and other components potentially present in soils-uncharred pine wood and peat-and five inorganic metal oxides with variable surface areas. Langmuir maximum sorption capacities (Qmax) for N2O on the pine wood biochars (generated between 250 and 500 °C) and activated carbons were 17-73 cm(3) g(-1) at 20 °C (median 51 cm(3) g(-1)), with Langmuir affinities (b) of 2-5 atm(-1) (median 3.4 atm(-1)). Both Qmax and b of the charred materials were substantially higher than those for peat, uncharred wood, and metal oxides [Qmax 1-34 cm(3) g(-1) (median 7 cm(3) g(-1)); b 0.4-1.7 atm(-1) (median 0.7 atm(-1))]. This indicates that biochar can bind N2O more strongly than both mineral and organic soil materials. Qmax and b for CO2 were comparable to those for N2O. Modeled sorption coefficients obtained with an independent polyparameter-linear free-energy relationship matched measured data within a factor 2 for mineral surfaces but underestimated by a factor of 5-24 for biochar and carbonaceous surfaces. Isosteric enthalpies of sorption of N2O were mostly between -20 and -30 kJ mol(-1), slightly more exothermic than enthalpies of condensation (-16.1 kJ mol(-1)). Qmax of N2O on biochar (50000-130000 µg g(-1) biochar at 20 °C) exceeded the N2O emission suppressions observed in the literature (range 0.5-960 µg g(-1) biochar; median 16 µg g(-1)) by several orders of magnitude. Thus, the hypothesis could not be falsified that sorption of N2O to biochar is a mechanism of N2O emission suppression.

The effects of biochars from rice residue on the formation of iron plaque and the accumulation of Cd, Zn, Pb, As in rice (Oryza sativa L.) seedlings.

A historically multi-metal contaminated soil was amended with biochars produced from different parts of rice plants (straw, husk and bran) to investigate how biochar can influence the mobility of Cd, Zn, Pb and As in rice seedlings (Oryza sativa L.). Rice shoot concentrations of Cd, Zn and Pb decreased by up to 98%, 83% and 72%, respectively, due to biochar amendment, though that of As increased by up to 327%. Biochar amendments significantly decreased pore water concentrations (C(pw)) of Cd and Zn and increased that of As. For Pb it depended on the amendment. Porewater pH, dissolved organic carbon, dissolved phosphorus, silicon in pore water and iron plaque formation on root surfaces all increased significantly after the amendments. The proportions of Cd and Pb in iron plaque increased by factors 1.8-5.7 and 1.4-2.8, respectively; no increase was observed for As and Zn. Straw-char application significantly and noticeably decreased the plant transfer coefficients of Cd and Pb. This study, the first to investigate changes in metal mobility and iron plaque formation in rice plants due to amending a historically contaminated soil with biochar, indicates that biochar has a potential to decrease Cd, Zn and Pb accumulations in rice shoot but increase that of As. The main cause is likely biochar decreasing the C(pw) of Cd and Zn, increasing the C(pw) of As, and increasing the iron plaque blocking capacity for Cd and Pb.

Equilibrium partition coefficients of diverse polar and nonpolar organic compounds to polyoxymethylene (POM) passive sampling devices.

Equilibrium passive samplers (EPS) based on polyoxymethylene (POM) are increasingly used for determining freely dissolved water and pore water concentrations of hydrophobic organic compounds in the environment. Unlike other polymeric materials commonly used as EPS, namely poly(dimethylsiloxane) (PDMS) and low-density polyethylene (PE), POM is a polar polymer, containing repeating H-bond accepting ether units. Thus, POM is expected to be a more sensitive EPS than PDMS and PE for polar, H-bond donating compounds, such as many hormones, pharmaceuticals, and biocides. To better characterize the sorption capacity of POM for diverse polar and apolar compounds, equilibrium POM-water partition coefficients, K(POM/w), were measured for 56 compounds, including several classes of polar compounds and organochlorine pesticides. Using this data set and literature data, various POM-partitioning models were calibrated and validated for their ability to predict K(POM/w). The best performing models tested were an Abraham descriptor based polyparameter linear free energy relationship (PP-LFER) (SD = 0.24 log units) and COSMOthermX (SD = 0.37 log units). The performance of SPARC (SD = 0.61 log units) and log-log correlations with K(ow) (SD = 0.49 log units) were lower. A comparison with PDMS and PE confirmed expectations that POM exhibits a higher sensitivity for H-bond donating polar compounds than PDMS and PE do for these compounds. These findings expand the domain of chemicals for which POM can be used as an EPS sampler, and demonstrate that POM is as suitable a passive sampler for many polar organic compounds as it is for hydrophobic organic compounds.

Improving predictability of sediment-porewater partitioning models using trends observed with PCB-contaminated field sediments.

More than 1900 sediment-water partitioning coefficients were measured for 58 polychlorinated biphenyl (PCB) congeners in 53 historically contaminated sediments collected from 10 urban and rural waterways in the United States and Canada. Freely dissolved porewater concentrations were determined using passive sampling with polyoxymethylene. Measured total organic carbon (TOC)/water partitioning coefficients, K(TOC), ranged from one to nearly three orders-of-magnitude higher than typical literature values based on spiking experiments and model predictions. Although total PCB concentrations ranged from 0.08 to 194 mg/kg, the more highly contaminated sediments showed only slightly lower K(TOC) values than less-contaminated sediments. No correlation was observed between log K(TOC) values and sediment TOC, black carbon (BC), or BC/TOC fractions (r(2) typically <0.1). Utilizing a two-carbon model incorporating anthropogenic BC did not improve predictions over a one-carbon TOC model. A comparison of models recently validated for field data showed that a coal-tar poly parameter linear-free energy relationship (PP-LFER) and a Raoult's Law model were successful at predicting average log K(TOC) values, without the need for any calibration or fitting (within a factor of 10 more than 90% of the time, and within a factor of 30 more than 99% of the time). Predictions were further improved by the introduction of a Weathering Factor (WF) that accounts for the relative depletion of lower molecular weight congeners due to weathering. Highly weathered sediments (with a WF near 1) tended to follow the coal-tar PP-LFER and Raoult's Law model the closest. Less-weathered sediments (with WF ≪ 1) sorbed less than predicted by these models. Noncalibrated WF inclusive coal-tar PP-LFER and Raoult's Law models performed as well or better than a quantitative-structure activity relationship (QSAR) model calibrated specifically to the data. These recommended partitioning models here can readily be used for all 209-PCB congeners.

Partitioning of organochlorine pesticides from water to polyethylene passive samplers.

The mass transfer rates and equilibrium partitioning behaviour of 14 diverse organochlorine pesticides (OCP) between water and polyethylene (PE) passive samplers, cut from custom made PE sheets and commercial polyethylene plastic bags, were quantified. Overall mass transfer coefficients, k(O), estimated PE membrane diffusion coefficients, D(PE), and PE-water partitioning coefficients, K(PE-water,) are reported. In addition, the partitioning of three polycyclic aromatic hydrocarbons (PAHs) from water to PE is quantified and compared with literature values. K(PE-water) values agreed mostly within a factor of two for both passive samplers and also with literature values for the reference PAHs. As PE is expected to exhibit similar sorption behaviour to long-chain alkanes, PE-water partitioning coefficients were compared to hexadecane-water partitioning coefficients estimated with the SPARC online calculator, COSMOtherm and a polyparameter linear free energy relationship based on the Abraham approach. The best correlation for all compounds tested was with COSMOtherm estimated hexadecane-water partitioning coefficients.

Gas/particle partitioning behavior of perfluorocarboxylic acids with terrestrial aerosols.

Experimentally determined gas/particle partitioning constants, K(ip), using inverse gas chromatography (IGC) are presented for perfluorocarboxylic acids (PFCAs), covering a diverse set of terrestrial aerosols over an ambient range of relative humidity (RH) and temperature. The results are compared to estimated K(ip) values using a recently developed model that has been validated for diverse neutral and ionizable organic compounds. The modeling results consistently underestimate the experimental results. This is likely due to additional partition mechanisms unique for surfactants not being accounted for in the model, namely aggregate formation and water surface adsorption. These processes likely also biased the IGC K(ip) measurements compared to ambient PFCA concentrations. Nevertheless, both the experimental and modeling results indicate that partitioning to terrestrial particles in ambient atmospheres is negligible, though sorption to condensed water can be substantial. This favors rain sequestration as a more important atmospheric removal mechanism than dry particle sequestration. PFCAs found on particle filters during ambient sampling are thus accountable to vapor-phase PFCAs or aqueous-phase PFCAs sorbing directly to the filters, or the trapping of perfluorocarboxylate-salt particles. Further work on understanding the partitioning and speciation of PFCAs in atmospheric water droplets is needed to further quantify and understand their atmospheric behavior. To aid in this, a general RH dependent K(ip) model for surfactants is presented.

Estimating the in situ sediment-porewater distribution of PAHs and chlorinated aromatic hydrocarbons in anthropogenic impacted sediments.

It has become increasingly apparent that the in situ sediment-porewater distribution behavior of organic compounds within anthropogenic impacted sediments is quite diverse, and challenging to generalize. Traditional models based on octanol-water partitioning generally overestimate native porewater concentrations, and modern approaches accounting for multiple carbon fractions, including black carbon, appear sediment specific. To assess the diversity of this sorption behavior, we collected all peer-reviewed total organic carbon (TOC)-normalized in situ sediment-porewater distribution coefficients, K(TOC), for impacted sediments. This entailed several hundreds of data for PAHs, PCBs, PCDD/Fs, and chlorinated benzenes, covering a large variety of sediments, locations, and experimental methods. Compound-specific K(TOC) could range up to over 3 orders of magnitude. Output from various predictive models for individual carbonaceous phases found in impacted sediments, based on peer-reviewed polyparameter linear free energy relationships (PP-LFERs), Raoult's Law, and the SPARC online-calculator, were tested to see if any of the models could consistently predict literature K(TOC) values within a factor of 30 (i.e., approximately 1.5 orders of magnitude, or half the range of K(TOC) values). The Raoults Law model and coal tar PP-LFER achieved the sought-after accuracy for all tested compound classes, and are recommended for general, regional-scale modeling purposes. As impacted sediment-porewater distribution models are unlikely to get more accurate than this, this review underpins that the only way to accurately obtain accurate porewater concentrations is to measure them directly, and not infer them from sediment concentrations.

Ambient gas/particle partitioning. 3. Estimating partition coefficients of apolar, polar, and ionizable organic compounds by their molecular structure.

Equilibrium gas/particle partitioning coefficients of terrestrial aerosols, Kip, are dependent on various intermolecular interactions that can be quantified by experimentally determined compound-specific descriptors. For many compounds of environmental interest, such as emerging contaminants and atmospheric phototransformation products, these compound-specific descriptors are unknown or immeasurable. Often, only the molecular structure is known. Here we present the ability of two computer programs to predict equilibrium partitioning to terrestrial aerosols solely on the basis of molecular structure: COSMOtherm and SPARC. The greatest hurdle with designing such an approach is to identify suitable molecular surrogates to represent the dominating sorbing phases, which for ambient terrestrial aerosols are the water insoluble organic matter (WIOM) phase and the mixed-aqueous phase. For the WI0M phase, hypothetical urban secondary organic aerosol structural units from Kalberer et al. Science 2004, 303, 1659-1662 were investigated as input surrogates, and for the mixed-aqueous phase mildly acidic water was used as a surrogate. Using a validation data set of more than 1400 experimentally determined Kip values for polar, apolar, and ionic compounds ranging over 9 orders of magnitude (including semivolatile compounds such as PCDD/Fs, pesticides, and PBDEs), SPARC and COSMOtherm were generally able to predict Kip values well within an order of magnitude over an ambient range of temperature and relative humidity. This is remarkable as these two models were not fitted or calibrated to any experimental data. As these models can be used for potentially any organic molecule, they are particularly recommended for environmental screening purposes and for use when experimental compound descriptor data are not available.

Ambient gas/particle partitioning. 2: The influence of particle source and temperature on sorption to dry terrestrial aerosols.

In a companion paper we reported that, for apolar and most polar compounds, the dominating sorption mechanism governing ambient gas/particle partitioning under dry conditions is absorption into a water-insoluble organic matter (WIOM) phase, whereas under moist conditions, polar and ionized compounds can partition additionally into a mixed-aqueous phase. In order to understand how sorption into the WIOM varies for particles from diverse terrestrial locations, we looked at over 500 equilibrium gas/particle partitioning constants, Kip, measured at a specific temperature and relative humidity (15 degrees C, 50% RH), covering aerosol samples from all seasons and various locations. The data indicate that for every sample the WIOM exhibits similar intermolecular interactions with gas-phase organic compounds. For a given compound, the Kip values usually vary within a factor 3 for different aerosol samples, though they could vary by up to an order of magnitude. This is most likely due to variations in the WIOM weight fraction. Fitted poly parameter linear free energy relationships (PP-LFERs) were validated by giving good predictions of Kip values for many SVOCs in the literature, including n-alkanes, organochlorines, PCBs, though not PAHs as much of the particle-bound PAHs are likely nonexchangeable with the air phase. This study also investigated the influence of temperature on partitioning to WIOM, and found thatthe temperature dependence of Kip values can be reasonably predicted using the pure compound's enthalpy of vaporization.

Ambient gas/particle partitioning. 1. Sorption mechanisms of apolar, polar, and ionizable organic compounds.

There remain several ambiguities in the literature regarding the dominating sorption mechanisms involved in gas/particle partitioning, particularly for polar and ionizable compounds. The various hypothetical mechanisms would depend differently on relative humidity (RH) and the presence of various aerosol components. Thus, in order to resolve these ambiguities, here we measured the RH-dependency of gas/particle partitioning constants, K(ip), for four diverse aerosol samples and a large set of chemicals covering apolar, polar, and ionizable organic compounds. In addition, we also removed the water-soluble components from two ambient particle samples to study how their presence influences sorption behavior. The measured K(ip) values collectively indicate that a dual-phase sorption mechanism is occurring, in which organic compounds partition into a RH-independent water-insoluble organic matter phase and additionally into a RH-dependent mixed-aqueous phase. All K(ip) values could be successfully fitted to a RH-dependent dual-phase sorption model. The trends in K(ip) data further support findings that the sorption behavior of ambient aerosol samples is different from raw mineral surfaces and soot.