Environmental Fate Of Organic Contaminants Research Articles

Potential interaction mechanisms between PAHs and glomalin related-soil protein (GRSP)

Glomalin-related soil protein (GRSP) has gained widespread attention because of its benefits to carbon sequestration, improving soil quality and fixing heavy metals. However, studies on how GRSP affects the environmental fate of organic contaminants are scarce. In this study, different types of GRSPs were isolated from forest soils and characterized to study the binding of GRSPs and PAHs under different environmental conditions. The results indicated that GRSPs contain abundant functional groups (such as –NH, –COOH, and CO) and material composition, like humic acid, proteins, and lipids. For the tested GRSPs, EE-GRSP has lower DOC, SUVA260 and SUVA280 values, as well as higher E2/E3 values, indicating that EE-GRSP has lower hydrophobicity and molecular weight. These properties can lead to strong interactions between GRSP and PAHs, especially with benzopyrene, which has a high Kow and Ksw and a large molecular size, with binding constants ranging from 16,119 to 163,697 L·kg−1. Furthermore, low pH (pH = 3) and temperature (15 °C) could increase GRSP's aggregation, enhance the GRSP binding ability with PAHs, whose binding constants were 11,595 and 5067.3 L·kg−1. Therefore, the binding between GRSP and PAHs may lead to changes in the fate of PAHs in the soil and affect the environmental risk of PAHs. The results presented here will deepen our understanding of the environmental function of GRSPs and provide a theoretical basis to further elucidate the mechanisms of GRSPs and organic pollutants.

Effect of Cu2+ on the Laccase-Inducted Formation of Non-Extractable Residues of Tetrabromobisphenol A in Humic Acids.

We used 14C-radiolabelling to study the non-extractable residues (NERs) formation of tetrabromobisphenol A (TBBPA) in a humic acid (HA) suspension under catalysis of laccase in the presence of copper. When entering the suspension after TBBPA adsorbing to HA supramolecular associates, Cu2+ at low concentrations (even without toxicity to laccase) significantly reduced the amount and first-order kinetic constant of the NER formation, while Cu2+ had no significant effect on the formation after it was complexed with HA. The inhibition effect of Cu2+ on the NER formation is explained to be attributed to the prevention of laccase-induced oxidation of TBBPA in the voids of HA associates by complexation of Cu2+ with periphery molecules of the associates. The results provide insights into varying effects of heavy metals on the environmental fate of organic contaminants and suggest that co-existing heavy metals could increase their environmental risk by reducing their NER formation.

Enhanced phototransformation of atorvastatin by polystyrene microplastics: Critical role of aging

Reactive oxygen species (ROS) generated from light irradiation of microplastics (MPs) can potentially affect the environmental fate of organic contaminants when they coexist in the same environment. This study investigated the effect of polystyrene (PS) MPs with different aging degrees on the phototransformation of atorvastatin (ATV) under simulated sunlight. Results showed that the presence of PS MPs facilitated the phototransformation of ATV, and the degradation rate was linearly correlated with the aging degree (i.e., carbonyl index) of MPs. The enhanced effects mainly depended on the contents of oxygen-containing functional groups of PS MPs, which increased the absorption of light energy and the generation of ROS (e.g., singlet oxygen (1O2) and triplet-excited state PS (3PS*)). Quenching experiments indicated that 1O2 generated from photosensitization of PS was the major contributor to the increased phototransformation of ATV. Additionally, the role of 3PS* became more important in the photodegradation mediated by higher degree aged MPs because much more 1O2 was generated from the 3PS* . PS MPs also increased the types and yields of degradation products, especially for higher degree aged MPs, despite the low effect on leachate toxicity. The findings provide a novel insight into the critical role of MPs in the fate of organic contaminants in aquatic environments.

Sequential solvent extraction as a tool for evaluating hydrocarbons speciation in soil after electrochemical treatment

Soluble and total extractable concentrations used for predicting contaminants' environmental fate may lead to uncertainties due to the lack of understanding of soil-contaminants interactions. The present study focuses on the influence of a controlled electric field on the distribution of polycyclic aromatic hydrocarbons in soil samples evaluated through a speciation scheme. Soil samples were spiked with 25,000 mg (hexadecane, phenanthrene, and pyrene 100:1:1 w/w) per kg of soil, and speciation of hydrocarbons was determined by employing a novel Sequential Solvent Extraction procedure, resulting in five fractions: soluble, pseudosoluble, desorbable, extractable, and sequestered. The distribution of hydrocarbons was then changed through the application of an electric field (72 h, 0.708 mA cm−2, 2.95 ± 0.13 V cm−1), which modified the interactions in the soil-water interface. The electrochemical treatment significantly increased the pyrene soluble, desorbable and sequestered fractions by 340, 1.3 and 19-fold (p < 0.05); the hexadecane soluble fraction increased in 6-fold (p < 0.05) and the phenanthrene desorbable fraction increased in 1.3-fold (p < 0.05). The use of the speciation scheme proposed in this study provides a wider view of hydrocarbons distribution in soils, rather than using water-soluble or total extractable concentrations. Finally, this speciation scheme is proposed as a tool to evaluate the environmental fate of organic contaminants in soils.

Enhanced Cu(II)-mediated fenton-like oxidation of antimicrobials in bicarbonate aqueous solution: Kinetics, mechanism and toxicity evaluation

Increasing attention has been attracted in developing new technologies to remove chlorofene (CF) and dichlorofene (DCF), which were active agents in antimicrobials for general cleaning and disinfecting. This study investigated the significant influences of bicarbonate (HCO3−) on the degradation of CF and DCF in the Cu(II)-mediated Fenton-like system Cu2+/H2O2. Our results indicate that HCO3− may play a dual role to act 1) as a ligand to stabilize Cu(II), forming soluble [CuII(HCO3−)(S)]+ species to catalyze H2O2 producing hydroxyl radical (OH) and superoxide ion (O2−) and 2) as a OH scavenger. Furthermore, the reaction kinetics, mechanisms, and intermediates of CF and DCF were assessed. The apparent rate constants of CF and DCF were enhanced by a factor of 8.5 and 5.5, respectively, in the presence of HCO3− at the optimized concentration of 4 mM. Based on the intermediate identification and frontier electron densities (FEDs) calculations, the associated reaction pathways were tentatively proposed, including C–C scission, single or multiple hydroxylation, and coupling reaction. In addition, significant reduction in the aquatic toxicity of CF and DCF was observed after treatment with Cu2+/H2O2–HCO3- system, evaluated by Ecological Structure Activity Relationships (ECOSAR) program. These findings provide new insights into Cu(II)-mediated reactions to better understand the environmental fate of organic contaminants in carbonate-rich waters.

Hot foam for weed control—Do alkyl polyglucoside surfactants used as foaming agents affect the mobility of organic contaminants in soil?

Use of alkyl polyglucosides (APGs) as a foaming agent during hot water weed control may influence the environmental fate of organic contaminants in soil. We studied the effects of the APG-based foaming agent NCC Spuma (C8-C10) on leaching of diuron, glyphosate, and polycyclic aromatic hydrocarbons (PAHs) in sand columns. We also examined how APG concentration affected the apparent water solubility and adsorption of the herbicides and of the PAHs acenaphthene, acenaphthylene and fluorene. Application of APGs at the recommended concentration of 0.3% did not significantly affect leaching of any of the compounds studied. However, at a concentration of 1.5%, leaching of both diuron and glyphosate was significantly increased. The increased leaching corresponded to an increase in apparent water solubility of diuron and a decrease in glyphosate adsorption to the sand. However, APG addition did not significantly affect the mobility of PAHs even though their apparent water solubility was increased. These results suggest that application of APG-based foam during hot water weed control does not significantly affect the mobility of organic contaminants in soil if used according to recommendations. Moreover, they suggest that APGs could be useful for soil bioremediation purposes if higher concentrations are used.

A large-scale model for simulating the fate &amp; transport of organic contaminants in river basins

We present STREAM-EU (Spatially and Temporally Resolved Exposure Assessment Model for EUropean basins), a novel dynamic mass balance model for predicting the environmental fate of organic contaminants in river basins. STREAM-EU goes beyond the current state-of-the-science in that it can simulate spatially and temporally-resolved contaminant concentrations in all relevant environmental media (surface water, groundwater, snow, soil and sediments) at the river basin scale. The model can currently be applied to multiple organic contaminants in any river basin in Europe, but the model framework is adaptable to any river basin in any continent. We simulate the environmental fate of perfluoroctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) in the Danube River basin and compare model predictions to recent monitoring data. The model predicts PFOS and PFOA concentrations that agree well with measured concentrations for large stretches of the river. Disagreements between the model predictions and measurements in some river sections are shown to be useful indicators of unknown contamination sources to the river basin.

SORPTION AND DESORPTION BEHAVIORS OF METHYLENE BLUE IN SOILS AMENDED WITH RICE-STRAW-DERIVED ASH AND BIOCHAR

The ash (Ash) and biochar (BC) derived from the partial combustion of rice-straw are ubiquitous in soils and sediments and can potentially affect the environmental fate of organic contaminants. In this study, the effects of Ash and BC on the sorption and desorption behaviors of methylene blue (MB) were investigated. Ash was obtained from the direct burning of the rice-straw, and BC was separated from Ash by HCl treatment. SEM, BET, FT-IR, and pore size distribution analyses were used to characterize the Ash and BC prepared. Sorption capacities of MB on Ash-amended soil (AS) and BC-amended soil (BS) increased significantly with increasing contents of Ash and BC in soils. Sorption isotherms of soil amended with various amounts of Ash or BC fitted better to the Langmuir equation. The significant increase of apparent desorption hysteresis could be observed with increasing content of Ash or BC in the soils, especially in the case of BC, presumably due to the presence of micropores, hydroxyl groups and relatively higher specific surface area. It is believed that the presence of small amounts of BC produced from the rice-straw-derived ash in soil can have a marked effect on the transfer behavior of dye contaminations.

Measurement of loss rates of organic compounds in snow using in situ experiments and isotopically labelled compounds

Organic molecular marker compounds are widely used to identify emissions from anthropogenic and biogenic air pollution sources in atmospheric samples and in deposition. Specific organic compounds have been detected in polar regions, but their fate after deposition to snow is poorly characterized. Within this context, a series of exposure experiments were carried out to observe the post-depositional processing of organic compounds under real-world conditions in snow on the surface of the Greenland Ice Sheet, at the Summit research station. Snow was prepared from water spiked with isotopically labelled organic compounds, representative of typical molecular marker compounds emitted from anthropogenic activities. Reaction rate constants and reaction order were determined based on a decrease in concentration to a stable, non-zero, threshold concentration. Fluoranthene- d 10 , docosane- d 46 , hexadecanoic acid- d 31 , docosanoic acid- d 43 and azelaic acid- d 14 were estimated to have first order loss rates within surface snow with reaction rate constants of 0.068, 0.040, 0.070, 0.067 and 0.047 h -1 , respectively. No loss of heptadecane- d 36 was observed. Overall, these results suggest that organic contaminants are archived in polar snow, although significant post-depositional losses of specific organic compounds occur. This has implications for the environmental fate of organic contaminants, as well as for ice-core studies that seek to use organic molecular markers to infer past atmospheric loadings, and source emissions. Keywords: Snow; photochemistry; air pollution; Greenland; Arctic To access the supplementary material to this article: 'Supplementary Figures & Table' and 'Supplementary File', please see Supplementary files in the column to the right (under Article Tools). (Published: 26 July 2012) Citation: Polar Research 2012, 31 , 11597, http://dx.doi.org/10.3402/polar.v31i0.11597

The Application of Fugacity and Activity to Simulating the Environmental Fate of Organic Contaminants

The concept of fugacity, which is widely used in chemical processing calculations, has also been successfully applied to a variety of environmental simulations of the fate and transport of organic contaminants. The challenges of estimating fugacities in environmental phases are discussed, especially for ill-defined phases such as soils, sediments, and biota for which activity coefficients and molar volumes cannot be measured. It is shown that by lumping these quantities and a reference fugacity in a single parameter, empirical partition coefficient data can be used to deduce fugacities and thus the relative equilibrium status between phases and directions of diffusive transport. For assessments of substances that display narcosis, chemical activities, which can be readily deduced from fugacities, can provide valuable estimates of the proximity of calculated or measured environmental concentrations to potentially toxic levels. Five illustrations are presented to demonstrate the value of applying the fugacity concept in environmental contexts, namely, the equilibrium distribution of diverse substances, the evaluation of air−water exchange processes, bioconcentration and bioaccumulation in fish, comprehensive risk assessment of regional chemical fate and exposure, and demonstrating the global distribution of chemicals by atmospheric and oceanic transport.

Illustrating Sensitivity and Uncertainty in Environmental Fate Models Using Partitioning Maps

Variations of model predictions of the environmental fate of organic contaminants are usually analyzed for only one or at most a few selected chemicals, even though parameter sensitivity and contribution to uncertainty are widely different for different chemicals. A graphical method is introduced that allows for the comprehensive investigation of model sensitivity and uncertainty for all persistent organic nonelectrolytes at the same time. This is achieved by defining a two-dimensional hypothetical "chemical space" as a function of the equilibrium partition coefficients between air, water, and octanol (KOW, KAW, KOA), and plotting sensitivity and/or uncertainty of a specific model result to each input parameter as a function of this chemical space. The approach is illustrated for the bulk phase concentrations in air, water, soil, and sediment calculated by a level III model. Colored contour maps facilitate the identification of those input parameters that cause a high output variation of hypothetical and real chemicals. They also allow for the easy categorization of chemicals in terms of common parameter sensitivities, and thus comparable environmental behavior. Sensitivity varies with the mode of emission and the degradability of the chemicals, making it necessary to develop multiple sets of contour maps. Comparison of these sets of maps in turn allows the investigation of how parameter sensitivities change as a result of changes in mode of emission and persistence. The presented method can be used for investigating the sensitivity of any prediction obtained with any linear fate model that characterizes the partitioning behavior of organic chemicals with KAW, KoW, and KOA. Once the sensitivity maps have been constructed for a given environmental scenario, it is possible to perform a sensitivity analysis for a specific chemical by simple. placement of the substances' partitioning combinations within the chemical space. The maps can further contribute to the mechanistic understanding of a model's behavior, can aid in explaining observations of divergent environmental behavior of related substances, and can provide a rationale for grouping chemicals with similar model behavior, or for selecting representative example chemicals for a model investigation. They can also help in deciding when accurate and precise knowledge of physical chemical property data is crucial and when approximate numbers suffice to conduct a model investigation.

Enhanced pesticide sorption by soils containing particulate matter from crop residue burns.

Lack of proper techniques to isolate black carbon (BC) from soils has hindered the understanding of their roles in the sorption and environmental fate of organic contaminants in soils and sediments. The burning of crop residues may be the primary source of BC in agricultural soils. In this study, wheat (Triticum aestivum L.) and rice (Oryza sativa L.) residues were burned, and the resulting particulate matter (ashes) along with a soil were used to sorb diuron from water. Calculations indicated that the burning of crop residues may result in an appreciable level of ashes in soils. The diuron sorption isotherms on ashes were curvilinear Langmuir type, suggestive of surface adsorption and similar to that with activated carbon. Ashes were 400-2500 times more effective than soil in sorbing diuron over the concentration range of 0-6 mg/L. Sorption by wheat ash-amended soils and the degree of isotherm nonlinearity increased with increasing ash content from 0% to 1% (weight), indicating the significant contribution of wheat ash to the sorption. Calculations show that wheat ash and soil independently contributed to the sorption. Above the wheat ash content of 0.05%, the sorption was largely controlled by the ash. Density-based fractionation and repeated HCI-HF washing of wheat ash yielded carbon-enriched fractions and enhanced diuron sorption by these fractions. BC appeared primarily responsible for the high adsorptivity of ashes. Ashes arising from the burning of crop residues may be an important determinant of pesticide immobilization and environmental fate in soils.

Screening the environmental fate of organic contaminants in sewage sludge applied to agricultural soils: II. The potential for transfers to plants and grazing animals

This is the second of two papers which screen the environmental fate of sludge or sludge organic contaminants when applied to agricultural land. A simple screening model has been developed to assess the likelihood of organic contaminants accumulating into the food-chain following the application of sludge onto arable and pasture land. The purpose of this exercise is to highlight those compounds that have the potential to accumulate into plants and animal tissues using data on physico-chemical properties of the compounds of interest. Over 300 organic compounds or groups of compounds which have been identified as potential pollutants in sludge have been screened for their potential to transfer from sludge-amended soils to plants via retention by root surfaces, root uptake and translocation, foliar uptake and animal intake via soil and herbage ingestion. Various organic contaminants have been identified as having a high potential to transfer into the food-chain through plant and animal accumulation. Two priority lists have been produced to include (a) those compounds which are shown as being of sufficient or suspected importance, but for which further sludge concentration data and fate studies would be necessary to check on their status, and (b) those compounds which have been highlighted in the screening processes as having a high potential to accumulate up the food-chain. This screening approach can be adapted to other chemicals as information on new chemicals and their physico-chemical properties becomes available.

Screening the environmental fate of organic contaminants in sewage sludges applied to agricultural soils: 1. The potential for downward movement to groundwaters

The potential for organic contaminants present in sewage sludge to leach and cause groundwater contamination following sludge application to agricultural land has been assessed. Models used to predict compound mobility in soil on the basis of physico-chemical parameters were applied to a range of contaminants prioritised and/or detected in sludge and a provisional list of potential ‘leachers’ compiled. In addition, theoretical soil water concentrations following sludge application were calculated using mean reported sludge contaminat concentrations and soil/water partition coefficients. These estimated aqueous phase concentrations were compared with Dutch groundwater quality standards in the absence of appropriate UK standards to identify those compounds which could be present in groundwater at levels of concern. The two prioritised lists were used to identify compounds in sludge which could pose a possible threat to groundwater. Appropriate experimental data were not available to qualify model results. However, the screening exercise indicated that under routine operational practice with typical sludge application rates, and the usual range of compound concentrations detected in sludge, groundwater quality standards were unlikely to be exceeded. However, data variability, reliability and scarcity limited the usefulness of this screening approach.