Equilibrium Partitioning Research Articles

Passive sampling of polycyclic aromatic hydrocarbons with low-density polyethylene: Equilibration limitations in aqueous suspensions

Polyethylene (PE) and other polymers are widely and successfully used as passive samplers for organic pollutants in the environment. This study provides high-resolution experimental data from batch shaking tests on the uptake, reversibility, and linear equilibrium partitioning of polycyclic aromatic hydrocarbons (PAHs) using two different PE sheets of 30 µm and 80 µm thickness. Kinetics for phenanthrene are well described by a mechanistic first-order model with mass transfer limited by an aqueous boundary layer (with a mean thickness of 170 µm). Equilibration in laboratory batch systems during uptake and desorption is very rapid with characteristic times of 1–2 h but this depends on the boundary condition, e.g., the ratio of PE mass to water volume. Therefore, equilibration of PE in other setups, e.g., in soil slurries or sediment suspensions, may take orders of magnitude longer because the boundary condition for PE changes from finite to infinite bath conditions (soil or sediment particles may keep the concentration in water almost constant). Solid precipitates for high molecular weight PAHs explain partition coefficients below expected values because of kinetic limitations in such a system. Nevertheless, passive sampling can be employed safely if such limitations are considered; furthermore, partition coefficients can be estimated accurately by empirical relationships (e.g., within 0.1 log unit) based on molecular weight, octanol/water partition coefficients, or subcooled liquid solubilities.

Assessment of toxicity potential of freely dissolved PAHs using passive sampler in Kentucky Lake and Ohio River

Polycyclic aromatic hydrocarbons (PAHs) are characterized with high KOW values, which lead to their recalcitrant nature, bioaccumulation, and biotoxicity, adversely affects the environment. Passive samplers (PS) have proven effective in measuring bioavailable PAH concentrations for toxicity assessments. In this study, we used low-density polyethylene (LDPE) to measure freely dissolved PAH concentrations (Cfree) in Kentucky Lake (KL) and Ohio River (OH), USA. PAHs toxicity potential in sediment was assessed using equilibrium partitioning sediment benchmarks toxic units (ESBTUs) and the interstitial water toxic units (IWTUs) that were derived from OC-normalized concentration (COC) and Cfree, respectively. The Cfree in April and June were 127 and 97 times higher in OH than in KL, respectively. Moreover, ESBTUs were higher in both the KL and OH compared to the IWTUs, suggesting that ESBTUs overestimate the toxicity potential to organisms. These results indicate that PS provides a reliable method for assessing the toxicity potential in sediments.

Biodegradable Acid-Based Fe2MnO4 Nanoparticles for Water Remediation.

This study demonstrated the synthesis of Fe2MnO4 modified by citric acid, a biodegradable acid, using a simple co-precipitation method. Characterization was performed using qualitative analysis techniques such as Fourier-transformed infrared spectroscopy, scanning electron microscopy equipped with energy-dispersive X-ray spectroscopy, X-ray diffraction, selected-area electron diffraction, N2 adsorption-desorption, and zero-point charge. The prepared nanoparticles had a rough and porous surface, and contained oxygenous (-OH, -COOH, etc.) functional groups. The specific surface area and average pore size distribution were 83 m2/g and 5.17 nm, respectively. Net zero charge on the surface of the prepared nanoparticles was observed at pH 7.5. The prepared nanoparticles were used as an adsorbent to remove methylene blue dye from water under various conditions. Using small amounts of the adsorbent (2.0 g/L), even a high concentration of MB dye (60 mg/L) could be reduced by about ~58%. Exothermic, spontaneous, feasible, and monolayer adsorption was identified based on thermodynamics and isotherm analysis. Reusability testing verified the stability of the adsorbent and found that the reused adsorbent performed well for up to three thermal cycles. Comparative analysis revealed that the modified adsorbent outperformed previously reported adsorbents and unmodified Fe2MnO4 in terms of its partition coefficient and equilibrium adsorption capacity under different experimental conditions.

Legacy and novel brominated flame retardants in outdoor settled dusts and pine needles in a megacity of Eastern China: Interpretation of plant uptake

Brominated flame retardants, considered emerging contaminants, are widespread and persist in the environment. This study investigated the contamination of legacy and novel brominated flame retardants in paired outdoor settled dusts and pine needles sampled from a megacity in the Eastern China. The measured total concentrations of PBDEs (∑27PBDEs) in outdoor settled dusts and pine needles were in the range of 77.4–345.2 ng/g dw and 20.7–120.0 ng/g dw, respectively, and equivalent ranges for novel brominated flame retardants (∑11NBFRs) were 25.7–1917.2 ng/g dw and 9.4–38.7 ng/g dw, respectively. BDE-209 and DBDPE dominated PBDEs and NBFRs profiles, respectively, in both dusts and pine needles. Outdoor settled dusts exhibited greater potentials to accumulate high-brominated PBDE homologues and EH-TBB while pine needles tended to accumulate low-brominated PBDE homologues, BTBPE and TBC. The plant uptake of BFRs was interpreted by McLachlan's framework on the assumption that the levels of BFRs in outdoor settled dusts and particle phase of air were positively correlated. The accumulation of PBDEs in pine needles was dominated by equilibrium partitioning between the vegetation and the gas phase when log KOA values <10 and by particle-bound deposition when log KOA values >13. However, NBFRs exhibited more complicated accumulation behavior. The predicted 50th percentile of the estimated daily intakes of ∑27PBDEs via outdoor settled dusts exposure for adults and children were 3.5 × 10−2 and 1.4 × 10−1 ng/kg body weight (bw)/day, respectively, and equivalent values for ∑11NBFRs were 1.6 × 10−2 ng/kg bw/day and 6.3 × 10−2 ng/kg bw/day, respectively. The calculated hazard index (HI) values were far <1, indicating exposure of BFRs via outdoor settled dust intake would not pose potential non-carcinogenic health risks to both adults and children.

Gas/particle partitioning of PCDD/Fs: Distributions and implications for available models

Polychlorinated dibenzo-p-dioxins/furans (PCDD/Fs) are semi-volatile organic compounds (SVOCs) existing in the atmosphere in the gas and particulate phase, remain persistent for a long time and pose a high risk to the environment and human health. In this study, PCDD/F measurements were made in an urban area between June 2022 and April 2023. In order to understand the fate of PCDD/Fs, the gas/particle (G/P) partitioning was studied. Although various models have been developed to determine the G/P partitioning of SVOCs, only logKp-logPL0, Junge-Pankow and Harner-Bidleman models are generally used for PCDD/Fs. In this study, nine different models (Junge-Pankow, Harner-Bidleman, Dachs-Eisenreich, Li-Ma-Yang, pp-LFER, mp-pp-LFER, QSPR, logKp-logPL0, logKp-logKOA) were employed to determine the G/P partitioning. To the best of our knowledge, pp-LFER, mp-pp-LFER and QSPR models were evaluated for PCDD/Fs for the first time in this study. In addition, the performance of the models within the equilibrium (EQ), non-equilibrium (NE) and maximum partitioning (MP) domain was investigated for PCDD/Fs for the first time in this study. Accordingly, models based on absorption in the EQ domain, adsorption in the NE domain and adsorption and absorption mechanisms in the MP domain were found to be effective in explaining the G/P transitions. It was determined that there is no equilibrium situation in the G/P partitioning. The Junge-Pankow, pp-LFER, Li-Ma-Yang and QSPR models under-predicted the particle fraction values while the other models showed a high prediction profile. The Li-Ma-Yang model showed the closest results to the measured particle fraction values, and it determined that deposition mechanisms are of non-negligible importance in the G/P partitioning of PCDD/Fs. One of the new models, the pp-LFER model, has shown remarkable success at high logKOA values. The mp-pp-LFER model, which overestimated the contribution of the adsorption mechanism, showed a very high prediction profile compared to the measured values.

Contribution of the Moon-forming Impactor to the Volatile Inventory in the Bulk Silicate Earth

The timing and mechanism by which the present-day inventory of life-essential volatiles hydrogen–carbon–nitrogen–sulfur (H–C–N–S) in the bulk silicate Earth (BSE) was established are debated. In this study we have modeled the equilibrium partitioning of H–C–N–S between core, magma ocean (MO), and atmosphere to determine whether the Moon-forming impactor (MFI) was the primary source of volatiles in the BSE. Our findings suggest that the MFI’s core and MO-degassed atmosphere were its primary H–C–N–S reservoirs. Since the MFI likely lost its MO-degassed atmosphere before the giant impact, most of the BSE’s volatiles must come from the small fraction of the MFI’s core which reequilibrated with Earth’s post-impact MO. This implies a high H–C–N–S inventory in the MFI (up to 50% of volatile-rich carbonaceous chondrites) to establish the BSE’s volatile budget. Although isotopic compositions of nonvolatile elements do not rule out the possibility of substantial volatile-rich, carbonaceous material accretion, MFI’s collisional growth from thermally metamorphosed/differentiated planetesimals makes it improbable that it contained ∼50% carbonaceous chondrite equivalent of H–C–N during its differentiation. Therefore, the MFI was unlikely the primary source of volatiles in the BSE. A significant portion of the BSE’s volatile inventory (especially H and C) likely predates the Moon-forming event. To prevent loss to space and segregation into Earth’s core, volatile-bearing materials must be delivered during the final accretion event(s) preceding the Moon-forming event. The substantial size of the proto-Earth at this stage, combined with limited metal–silicate equilibration during the Moon-forming event, facilitated the retention of these volatiles within the BSE.

Moment analysis method for determination of rate constants of solute permeation across interface of spherical molecular aggregates by means of high-performance liquid chromatography

A moment analysis method was developed for the study of solute permeation at the interface of spherical molecular aggregates. At first, new moment equations were developed for determining the partition equilibrium constant (Kp) and permeation rate constants (kin and kout) of solutes from the first absolute (μ1A) and second central (μ2C) moments of elution peaks measured by using high-performance liquid chromatography (HPLC). Then, the method was applied to the analysis of mass transfer phenomena of three solutes, i.e., hydroquinone, resorcinol, and catechol, at the interface of sodium dodecylsulfate (SDS) micelles. HPLC data were measured by using an ODS column and an aqueous phosphate buffer solution (pH = 7.0) as the mobile phase solvent. Pulse response experiments were conducted while changing SDS concentration (5 - 20 mmol dm−3) in the mobile phase under the conditions that the surface of ODS stationary phase was dynamically coated by SDS monomers. In order to demonstrate the effectiveness of the moment analysis method using HPLC, the values of Kp, kin, and kout were determined for the three solutes as 35 - 69, 2.4 × 10−8 - 1.4 × 10−6 m s−1, and 7.0 × 10−10 - 2.1 × 10−8 m s−1, respectively. Their values increase with an increase in the hydrophobicity of the solutes. The method has some advantages for the study of interfacial solute permeation of molecular aggregates. For example, neither immobilization nor chemical modification of both solute molecules and molecular aggregates is required when elution peaks are measured by using HPLC. Interfacial solute permeation takes place in the mobile phase without any chemical reaction or physical action on molecular aggregates. The values of Kp, kin, and kout were analytically determined from those of μ1A and μ2C by using the moment equations. The results of this study must contribute to the dissemination of an opportunity for studying the interfacial solute permeation of molecular aggregates to many researchers because of extremely high versatility of HPLC.

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.

Sequential thin film microextraction and overcoated thin film microextraction devices for characterization of sparkling wine aroma profiles and partitioning equilibria

Solid Phase Microextraction (SPME) is a commonly used, robust method for characterization of aroma profiles in food matrices. However, challenges such as saturation, swelling, and competition can occur when sampling such complex matrices, resulting in decreased accuracy in the quantitation of polar compounds. In this study, sequential thin film micro-extraction (TFME) was employed to study the aroma profile of sparkling wine, with a focus to evaluate the displacement of polar analytes at extraction times longer than their corresponding equilibrium time. This investigation also describes advancements in the production of TFME devices, specifically the overcoating of hydrophilic-lipophilic balance/polydimethylsiloxane (HLB/PDMS) thin films to increase their matrix compatibility. Sequential thin film micro-extraction and overcoated HLB/PDMS thin films were evaluated for characterization of sparkling wine samples. The results were encouraging, showing that these advancements can decrease competition phenomena and increase the calibration linearity range compared to traditional micro-extraction approaches more commonly used for the characterization of such samples. In addition, multiphase equilibria investigation involving micellar systems enabled by the microextraction technology provides better understanding between wine aroma and its composition.

Community-level risk assessments on organophosphate esters in the sediments from the Bohai Sea of China based on multimodal species sensitivity distributions coupled with the equilibrium partitioning method

Organophosphate esters (OPEs), increasingly used as alternatives to brominated flame retardants, are ubiquitous in the global aquatic environment. Despite their potential toxicological impact on ecosystems, community-level risk assessments for OPEs in sediments remain scarce. This study investigated OPE occurrences and composition characteristics in the Bohai Sea's sediments and appraised both individual and joint ecological risks posed by characteristic OPE homologs using ten commonly used species sensitivity distribution (SSD) models, integrating acute-to-chronic conversion and phase equilibrium partitioning. OPEs were detected across all sediment samples, with total concentrations ranging from 0.213 ng/g dry weight (dw) to 91.1 ng/g dw. The predominant congeners included tri-n-butyl phosphate (TnBP), triisobutyl phosphate (TiBP), tri(2-ethylhexyl) phosphate, tris(2-chloroethyl) phosphate (TCEP), tris(1-chloro-2-propyl) phosphate (TCPP), tris(1, 3-dichloro-2-propyl) phosphate (TDCIPP), and triphenylphosphine oxide. Best-fit SSD models varied among TnBP, TiBP, TCEP, TCPP, and TDCIPP, demonstrating Sigmoid, Burr III, Sigmoid, Burr III, and Burr III, respectively. The same parametric model demonstrated variability in the fitting process for different OPE congeners, which also happened to the fitting results of ten parametric models for the same specific characteristic congener, underscoring the necessity of employing multiple models for precise community-level risk assessments. Hazard concentrations for a 5% cumulative probability were 0.116 mg/L, 2.88 mg/L, 1.30 mg/L, 1.44 mg/L, and 1.85 mg/L for each respective congener. The resulting risk quotients (RQ) and overall hazard index (HI) were selected as criteria to assess the individual and joint ecological risks of OPEs in sediments from the Bohai Sea, respectively. RQ and HI were both below 0.1, indicating a low risk to the local ecosystems. Multi-model SSD analysis could provide refined data for community-level risk evaluation, offering valuable insights for the development of evidence-based environmental standards and pollution control strategies.

Potential Hazards of Polycyclic Aromatic Hydrocarbons in Great Lakes Tributaries Using Water Column and Porewater Passive Samplers and Sediment Equilibrium Partitioning.

The potential for polycyclic aromatic hydrocarbon (PAH)-related effects in benthic organisms is commonly estimated from organic carbon-normalized sediment concentrations based on equilibrium partitioning (EqP). Although this approach is useful for screening purposes, it may overestimate PAH bioavailability by orders of magnitude in some sediments, leading to inflated exposure estimates and potentially unnecessary remediation costs. Recently, passive samplers have been shown to provide an accurate assessment of the freely dissolved concentrations of PAHs, and thus their bioavailability and possible biological effects, in sediment porewater and overlying surface water. We used polyethylene passive sampling devices (PEDs) to measure freely dissolved porewater and water column PAH concentrations at 55 Great Lakes (USA/Canada) tributary locations. The potential for PAH-related biological effects using PED concentrations were estimated with multiple approaches by applying EqP, water quality guidelines, and pathway-based biological activity based on in vitro bioassay results from ToxCast. Results based on the PED-based exposure estimates were compared with EqP-derived exposure estimates for concurrently collected sediment samples. The results indicate a potential overestimation of bioavailable PAH concentrations by up to 960-fold using the EqP-based method compared with measurements using PEDs. Even so, PED-based exposure estimates indicate a high potential for PAH-related biological effects at 14 locations. Our findings provide an updated, weight-of-evidence-based site prioritization to help guide possible future monitoring and mitigation efforts. Environ Toxicol Chem 2024;43:1509-1523. © 2024 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

A kinetic partitioning method for simulating the condensation mass flux of organic vapors in a wide volatility range

Organic aerosols are ubiquitous, playing important roles in various atmospheric physicochemical processes such as the formation of cloud droplets and haze. Condensation of organic vapors, as a net effect of association with particles and dissociation from the condensed phase, is a fundamental process that drives the formation of organic aerosols. Kinetic models are often used to simulate the condensation fluxes of low-volatility organic vapors and aerosol growth. However, the widely used kinetic growth models usually calculate the evaporation of a certain species based on previous particulate compositions, without including the co-condensation of other species. Here we present a new kinetic partitioning method for calculating the condensation fluxes of organic vapors in a wide volatility range with low computational cost. In this method, the organic vapors are assumed to be in a quasi-steady state, but never reach real association-dissociation equilibrium during the simultaneous condensation of multiple species. We show a good consistency between the kinetic partitioning method and kinetic models in simulating particle mass fractions and condensation fluxes. Under relevant atmospheric conditions, we reveal that the kinetic partitioning method also reproduce the trend that low-volatility species are almost non-volatile while volatile organic compounds almost reach association-dissociation equilibrium, while there is a transition regime between them. This transition regime varies with atmospheric conditions, such as temperature and vapor concentrations. Compared with previous studies combining kinetic growth methods with equilibrium partitioning theories to simplify the condensation flux calculation, this method helps to improve accuracy without a significant expense of computation cost, and it can be applied in a wider range of atmospheric conditions such as in extremely cold atmospheres and polluted exhaust plumes.

Secondary organic aerosols derived from intermediate-volatility n-alkanes adopt low-viscous phase state

Abstract. Secondary organic aerosol (SOA) derived from n-alkanes, as emitted from vehicles and volatile chemical products, is a major component of anthropogenic particulate matter, yet the chemical composition and phase state are poorly understood and thus poorly constrained in aerosol models. Here we provide a comprehensive analysis of n-alkane SOA by explicit gas-phase chemistry modeling, machine learning, and laboratory experiments to show that n-alkane SOA adopts low-viscous semi-solid or liquid states. Our study underlines the complex interplay of molecular composition and SOA viscosity: n-alkane SOA with a higher carbon number mostly consists of less functionalized first-generation products with lower viscosity, while the SOA with a lower carbon number contains more functionalized multigenerational products with higher viscosity. This study opens up a new avenue for analysis of SOA processes, and the results indicate few kinetic limitations of mass accommodation in SOA formation, supporting the application of equilibrium partitioning for simulating n-alkane SOA formation in large-scale atmospheric models.

Highly sensitive passive sampling of new pollutants in urban reclaimed water using hydrophilic-lipophilic balance sorbent-embedded cellulose acetate membrane

Urban reclaimed water is important water resource in China, while the residual new pollutants in the water largely challenge their safety for further use. China's action program for the management of new pollutants (also known as emerging contaminants) requires effective method for monitoring diverse new pollutants in water. This work proposed a highly sensitive passive sampling method for monitoring diverse new pollutants in urban reclaimed water. Hydrophilic–lipophilic balance sorbent-embedded cellulose acetate membranes (HECAMs) were dynamically deployed in self-developed continuous flow integrative sampling device (CFISD) for sampling four types of new pollutants with wide polarity ranges (1.11 < log Kow < 9.49) in a reclaimed water network for landscape irrigation in Beijing, China. The estimated equilibrium partition ratios of most chemicals between HECAM and water were over 104, which would provide low detection limits. In the 7-d high-efficiency deployment, thirty new pollutants were detected, which indicated incompletely removal of various new pollutants in wastewater treatment process. The dynamical accumulation data were successfully fitted by first-order kinetic model and different contaminants reached different accumulation phases in the HECAMs during 7 d. Acceptable and steady uptake rate constants and sampling rates were obtained with the use of CFISD in field sampling. The estimated time-weighted average concentrations for contaminants had wide concentration range and were from 0.03 ng L−1 (pendimethalin) to 3,394 ng L−1 (dibutyl phthalate) and this may lead to environmental risk for further use the reclaimed water. Dynamical deployment results also provided sensitive information of concentration fluctuations and twelve pollutants showed concentration fluctuations during the sampling period. In summary, HECAM showed high sensitivities and credible performance of monitoring diverse new pollutants in the urban reclaimed water.

Equilibrium partitioning approach for metal toxicity assessment in tropical estuarine sediment of Bandon Bay, Thailand

An equilibrium partitioning approach (EqPA) was employed to evaluate the metal toxicity and define sediment quality guidelines (SQGs) for arsenic (As), cadmium (Cd), chromium (Cr), copper (Cu), nickel (Ni), lead (Pb), zinc (Zn), and mercury (Hg) in the cockle cultivated areas located in Bandon Bay, Thailand. An assessment of metal toxicity using the [∑SEM]-[AVS] and [∑SEM]-[AVS]/foc models indicated no adverse effect on benthic organisms. The normalized total metal concentrations in this area were below the established SQG values for As, Cd, Cu, Ni, Pb, Zn, and Hg, namely respectively 21.3, 0.8, 84.6, 36.0, 34.6, 440.9 mg/kg dry weight, and 49.3 μg/kg dry weight on sand and calcium carbonate free with 1 % total organic carbon basis, suggesting low metal toxicity. This study provides locality adapted SQG values for supporting sediment quality management specifically in Bandon Bay, potentially serving as a model for other coastal areas.

Metal directional crystallization: A sustainable green separation method for the purification of bismuth from crude bismuth while enriching lead and silver

In the traditional crude bismuth refining process, the addition of additives to form refining slag and the subsequent removal of impurities via separating the refining slag introduce new impurities while lowering the direct yield of bismuth, thereby restricting the green development of bismuth smelters. In this study, we propose a method that uses directional crystallization of metals to purify crude bismuth and enrich lead and silver. The phase diagram was analyzed using equilibrium partition coefficients, and lead and silver impurities were primarily enriched in the liquid phase during the crystallization of crude bismuth. In addition, we investigated the ground-state structures of the clusters, calculated the average binding energies, and elucidated the tendency of Ag to be enriched with Pb rather than Bi during the directional crystallization of crude bismuth from an atomic perspective. Using small-scale experiments, we determined the optimum process conditions, which were a crystallization separator speed of 4 r/min and a 10° inclination of the crystallization separator toward the horizontal plane. The guided semi-industrial experiments yielded Bi with a purity of 98.08 wt%, bismuth with a direct recovery of 92.49%, and Pb and Ag with removal rates of 95.64% and 90.53%, respectively. The entire process is simple, involves no additives, and effectively avoids the generation of refining slag.

Nitrogen inventory of iron meteorite parent bodies constrained by nitrogen partitioning between Fe-rich solid and liquid alloys

Delivery of nitrogen (N), one of the most important elements for life, to Earth thought to have occurred via both undifferentiated and differentiated bodies, lasting at least 50–100 Ma from the birth of the Solar System. Therefore, to understand how Earth got its N, it is imperative to know the N budget of the earliest formed bodies in our Solar System. The best astromaterials available for providing constraints on N budget of the earliest formed planetesimals are the iron meteorites. However, iron meteorites are crystallized products of a liquid alloy and do not represent the N budget of the bulk cores of various iron meteorite parent bodies (IMPBs). Therefore, to determine how N partitioned between solid alloy (sa) and liquid alloy (la) (DNsa/la) during crystallization of molten metal alloy core, we present a series of equilibrium partitioning experiments at 1–2 GPa and 1150–1550 ℃ for various initial starting compositions having different sulfur (S), nickel (Ni), iron (Fe) and fixed nitrogen (N) concentrations. We observe that N changes from mildly incompatible to mildly compatible with increasing S concentration in the liquid alloy. Furthermore, we observed that N concentration in solid alloy decreases with increasing temperature, while pressure and Ni content showed almost no effect on the partitioning behavior of N. We used a regression model based on the results of our study and a previous study to establish a parameterization for DNsa/la. Using our parameterized DNsa/la, we determine potential siderophile element proxies of N in metallic systems and model the initial N budget of various IMPBs groups pertaining to the inner (Non-Carbonaceous (NC) reservoir) and outer Solar System (Carbonaceous (CC) reservoir). Between two possible end-member styles of IMPB differentiation (IMO – Internal Magma Ocean; EMO – External Magma Ocean), EMOs result in a higher initial N budget with a major fraction getting lost via atmospheric loss. Importantly, our calculations suggest a gradation in the N budget of CC and NC IMPBs with CC IMPBs hosting lesser N than NC IMPBs. Therefore, the early Solar protoplanetary disk likely showed a gradation in N both in its elemental and isotopic composition.

Aquatic and sediment ecotoxicity data of difenoconazole and its potential environmental risks in ponds bordering rice paddies

Difenoconazole has a widespread agricultural use to control fungal diseases in crops, including rice. In edge-of-field surface waters the residues of this lipophilic fungicide may be toxic to both pelagic and benthic organisms. To allow an effect assessment we mined the regulatory and open literature for aquatic toxicity data. Since published sediment toxicity data were scarce we conducted 28 d sediment-spiked toxicity test with 8 species of benthic macroinvertebrates. Ecotoxicological threshold levels for effects were assessed by applying the species sensitivity distribution approach. Based on short-term L(E)C50’s for aquatic organisms from water-only tests an acute Hazardous Concentration to 5% of the species (HC5) of 100 µg difenoconazole/L was obtained, while the HC5 based on chronic NOEC values was a factor of 104 lower (0.96 µg difenoconazole/L). For benthic macroinvertebrates the chronic HC5, based on 28d-L(E)C10 values, was 0.82 mg difenoconazole/kg dry weight sediment. To allow a risk assessment for water- and sediment-dwelling organisms, exposure concentrations were predicted for the water and sediment compartment of an edge-of-field pond bordering rice paddies treated with difenoconazole using the Chinese Top-Rice modelling approach, the Chinese Nanchang exposure scenario and the Equilibrium Partitioning theory. It appeared that in the vast majority of the 20 climate years simulated, potential risks to aquatic and sediment organisms cannot be excluded. Although the HC5 values based on laboratory toxicity data provide one line of evidence only, our evaluation suggests population- and community-level effects on these organisms due to chronic risks in particular.

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.

Pseudo-Second-Order Kinetic Equation for Describing the Effect of Sorbent and Sorbate Concentrations.

The sorbent concentration (Cs) effect and sorbate initial concentration (C0) effect are common phenomena observed in the study of adsorption kinetics at solid-liquid interfaces. That is, adsorption rate constants simulated with classical kinetic equations, such as the pseudo-second-order (PSO) model, for a given system vary with Cs and C0. The classical kinetic equations cannot predict or describe the "Cs-effect" and "C0-effect" (called "C-effects" here). In the current work, the dynamic partition coefficient of sorbate between solid and liquid phases (Kt) was used to describe the adsorption kinetic processes. Based on the surface component activity (SCA) model, which assumes the activity coefficients of the surface components (fs) are not equal to unity but rather a function of Cs and the adsorption capacity (or C0) and referring to the classical PSO model, a new kinetic equation was established, called the "SCA-PSO kinetic model", and its two parameters, the intrinsic equilibrium partition coefficient (Ke0) and the intrinsic rate constant (k20), are independent of Cs and C0. In addition, the new model relates Kt and the rate constant (k2) to Cs and C0 via fs, and can thus describe the C-effects. The fs can be estimated from the change of equilibrium partition coefficient (Ke) with Cs and C0. The new model predicts that with the increase of Cs and C0, Ke decreases while k2 increases. Its rationality was confirmed by the literature-reported adsorption kinetic data of heavy metals on inorganic and biomass sorbents with the C-effects.