Modelling the fate of organic chemicals in the soil plant environment: Model study of root uptake of pesticides

The fate of organic chemicals in the soil-plant-atmosphere environment and the governing processes were studied with a coupled dynamic soil transport and plant compartment model. Scenarios with applications of pesticides on sand and loam soils with chemical uptake in barley and wheat were used in the model calculations. Root uptake and concentrations in the plant compartments stem, leave and fruit were calculated for the pesticides terbuthylazine, isoproturon and carbofuran.

The effectivity of uptake from soils with different soil sorption coefficients had been shown for sand and loam soils. The processes degradation in plant and volatilization from leaves to atmosphere are especially effective for carbofuran and terbuthylazine. Although the concentrations in corn at harvest are lower than the maximum allowed concentrations, the peak concentrations in the course of the vegetation period are significantly higher (factor ≤ 200).     

An assessment of the environmental fate and exposure of benzene and the chlorobenzenes in Canada

Systematic modelling of the fate of benzene and the chlorobenzenes is presented which follows a four-stage process of chemical classification, quantifying discharge rates and environmental concentrations, evaluative assessment of fate and regional mass balance modelling has been carried out for the southern Ontario region. The EQC model was applied to determine the principal transport and transformation processes experienced by this group of chemicals, which vary considerably in volatility and hydrophobicity. Observed environmental concentrations are in satisfactory agreement with the predictions of the steady state Level III ChemCAN model of chemical fate. A multiple pathway human exposure model which estimates intake of contaminants by residents of southern Ontario has been developed and applied to these chemicals. A novel method of deducing maximum tolerable environmental concentrations is presented. Results suggest that benzene and 1,4-dichlorobenzene are present in the environment at levels sufficient to cause exposures near allowable daily intake (ADI) levels for the general population, but the other substances are present at levels which result in exposure ranging from 1/10 to 1/1000 of the ADI.     

Strategies for including vegetation compartments in multimedia models

The incentives for including vegetation compartments in multimedia Level I, II and III fugacity calculations are discussed and equations and parameters for undertaking the calculations suggested. Model outputs with and without vegetation compartments are compared for 12 non-ionic organic chemicals with a wide variety of physical-chemical properties. Inclusion of vegetation compartments is shown to have a significant effect on two classes of chemicals: (1) those that are taken up by atmospheric deposition and (2) those that are taken up by transpiration through the plant roots. It is suggested that uptake from the atmosphere is important for chemicals with logK(OA) greater than 6 and a logK(AW) of greater than -6. Plant uptake by transpiration is important for chemicals with logK(OW) less than 2.5 and a logK(AW) of less than -1. At logK(OA) > 9 atmospheric uptake is dominated by particle-bound deposition and the importance of partitioning to vegetation is largely dependent on the relative magnitude of the particle deposition velocities to soil and vegetation. These property ranges can be used to determine if a chemical will significantly partition to vegetation. If the chemical falls outside the property ranges of the two classes it will probably be unnecessary to include vegetation in models for assessing environmental fate. The amount of chemical predicted to partition to vegetation compartments in the model is shown to be highly sensitive to certain model assumptions. Further experimental research is recommended to obtain more reliable equations describing equilibrium partitioning and uptake/depuration kinetics.     

BETR North America: a regionally segmented multimedia contaminant fate model for North America

We present the Berkeley-Trent North American contaminant fate model (BETR North America), a regionally segmented multimedia contaminant fate model based on the fugacity concept. The model is built on a framework that links contaminant fate models of individual regions, and is generally applicable to large, spatially heterogeneous areas. The North American environment is modeled as 24 ecological regions, within each region contaminant fate is described using a 7 compartment multimedia fugacity model including a vertically segmented atmosphere, freshwater, freshwater sediment, soil, coastal water and vegetation compartments. Inter-regional transport of contaminants in the atmosphere, freshwater and coastal water is described using a database of hydrological and meteorological data compiled with Geographical Information Systems (GIS) techniques. Steady-state and dynamic solutions to the 168 mass balance equations that make up the linked model for North America are discussed, and an illustrative case study of toxaphene transport from the southern United States to the Great Lakes Basin is presented. Regionally segmented models such as BETR North America can provide a critical link between evaluative models of long-range transport potential and contaminant concentrations observed in remote regions. The continent-scale mass balance calculated by the model provides a sound basis for evaluating long-range transport potential of organic pollutants, and formulation of continent-scale management and regulatory strategies for chemicals.     

Validation of predicted exponential concentration profiles of chemicals in soils

Multimedia mass balance models assume well-mixed homogeneous compartments. Particularly for soils, this does not correspond to reality, which results in potentially large uncertainties in estimates of transport fluxes from soils. A theoretically expected exponential decrease model of chemical concentrations with depth has been proposed, but hardly tested against empirical data. In this paper, we explored the correspondence between theoretically predicted soil concentration profiles and 84 field measured profiles. In most cases, chemical concentrations in soils appear to decline exponentially with depth, and values for the chemical specific soil penetration depth (d(p)) are predicted within one order of magnitude. Over all, the reliability of multimedia models will improve when they account for depth-dependent soil concentrations, so we recommend to take into account the described theoretical exponential decrease model of chemical concentrations with depth in chemical fate studies. In this model the d(p)-values should estimated be either based on local conditions or on a fixed d(p)-value, which we recommend to be 10cm for chemicals with a log K(ow)>3.     

Regression models to predict water-soil heavy metals partition coefficients in risk assessment studies

Risk assessment studies apply fate and transport models to predict the behaviour of chemicals in the environment. The definition of physico-chemical properties is crucial to predict the mobility of pollutants and heavy metals in particular within the environmental compartments. The conservative approach normally adopted at a screening level in attributing a value to the K(d) value, results in an extremely variable mobility in soil. In this paper a regression model to estimate rapidly the K(d) for heavy metals is proposed and applied to Pb, allowing a considerable reduction (3-4 orders of magnitude) of the estimation uncertainty. The application of a stepwise forward multiple regression to literature data provided a pH-dependent regression equation of the soil-water distribution coefficient (K(d)) for Pb: log K(d)=1.99+0.42 pH.     

Calculation of environmental concentration and comparison of output for existing chemicals using regional multimedia modeling

The environmental fate of 40 existing chemicals is discussed using the EUSES multimedia distribution and risk assessment model with site-specific parameter setting in an urban area of Japan including a highly industrial region. There has been a strong need to assess the environmental fate of a huge number of existing chemicals. Data on the emission amounts of chemicals are essential for such prediction, and PRTR surveys may yield this data. The study delivered the following results: (1) Volatile compounds with large amounts of emission showed higher predicted concentrations in air, and the concentrations of several compounds agreed well with averaged monitoring data within an order of magnitude. (2) A close relationship was found between the concentration of water and that of sediment, suggesting that the fate of chemicals in sediment essentially depended on the water environment. (3) A group of volatile solvents had high mass distribution ratio to air. Some compounds having high solubility in water were also included in that group due to the high ratio of air emission. Highly hydrophobic compounds with logK(OW) larger than 6.0 showed a high distribution ratio to soil and sediment. (4) Volatile compounds were mostly taken through air. The exposure through fish is a dominant pathway for highly hydrophobic compounds. (5) Exposure ratio could be gathered from physicochemical properties. The exposure from fish intake was roughly estimated by logK(OW), whereas exposure from air and water intake was difficult to estimate simply by vapor pressure and solubility in water, respectively.     

BETR-World: a geographically explicit model of chemical fate: application to transport of alpha-HCH to the Arctic

The Berkeley-Trent (BETR)-World model, a 25 compartment, geographically explicit fugacity-based model is described and applied to evaluate the transport of chemicals from temperate source regions to receptor regions (such as the Arctic). The model was parameterized using GIS and an array of digital data on weather, oceans, freshwater, vegetation and geo-political boundaries. This version of the BETR model framework includes modification of atmospheric degradation rates by seasonally variable hydroxyl radical concentrations and temperature. Degradation rates in all other compartments vary with seasonally changing temperature. Deposition to the deep ocean has been included as a loss mechanism. A case study was undertaken for alpha-HCH. Dynamic emission scenarios were estimated for each of the 25 regions. Predicted environmental concentrations showed good agreement with measured values for the northern regions in air, and fresh and oceanic water and with the results from a previous model of global chemical fate. Potential for long-range transport and deposition to the Arctic region was assessed using a Transfer Efficiency combined with estimated emissions. European regions and the Orient including China have a high potential to contribute alpha-HCH contamination in the Arctic due to high rates of emission in these regions despite low Transfer Efficiencies. Sensitivity analyses reveal that the performance and reliability of the model is strongly influenced by parameters controlling degradation rates.     

Modelling the fate of persistent organic pollutants in Europe: parameterisation of a gridded distribution model

A regionally segmented multimedia fate model for the European continent is described together with an illustrative steady-state case study examining the fate of gamma-HCH (lindane) based on 1998 emission data. The study builds on the regionally segmented BETR North America model structure and describes the regional segmentation and parameterisation for Europe. The European continent is described by a 5 degrees x5 degrees grid, leading to 50 regions together with four perimetric boxes representing regions buffering the European environment. Each zone comprises seven compartments including; upper and lower atmosphere, soil, vegetation, fresh water and sediment and coastal water. Inter-regions flows of air and water are described, exploiting information originating from GIS databases and other georeferenced data. The model is primarily designed to describe the fate of Persistent Organic Pollutants (POPs) within the European environment by examining chemical partitioning and degradation in each region, and inter-region transport either under steady-state conditions or fully dynamically. A test case scenario is presented which examines the fate of estimated spatially resolved atmospheric emissions of lindane throughout Europe within the lower atmosphere and surface soil compartments. In accordance with the predominant wind direction in Europe, the model predicts high concentrations close to the major sources as well as towards Central and Northeast regions. Elevated soil concentrations in Scandinavian soils provide further evidence of the potential of increased scavenging by forests and subsequent accumulation by organic-rich terrestrial surfaces. Initial model predictions have revealed a factor of 5-10 underestimation of lindane concentrations in the atmosphere. This is explained by an underestimation of source strength and/or an underestimation of European background levels. The model presented can further be used to predict deposition fluxes and chemical inventories, and it can also be adapted to provide characteristic travel distances and overall environmental persistence, which can be compared with other long-range transport prediction methods.     

An environmental fate, exposure and risk assessment of ethylene oxide from diffuse emissions

Ethylene oxide (EO) is mainly used as a chemical intermediate and as a fumigant and sterilizing agent. Through its manufacturing and intended uses, EO may be released into the environment. Therefore, an assessment of the environmental significance of those potential emissions was conducted. Data were collected describing pertinent physical properties, degradation and other loss mechanisms that control the fate of EO in the environment. Available aquatic and terrestrial ecotoxicity data were assembled and used as the basis of calculating critical toxicity values to characterize hazard. Environmental compartment concentrations of EO were calculated using Level III fugacity-based modeling. Six scenarios were developed to account for different climatic conditions in various portions of the US. Finally, potential regional-scale risks to aquatic and terrestrial wildlife were determined. In the conceptual model that was developed in this assessment, EO diffuses into air, partitions between environmental compartments, is transported out of the different compartments via advection, and undergoes abiotic and biological degradation within each compartment. All known emissions within the continental USA were assumed to enter a modeled region roughly the size of the State of Ohio. Organisms (receptors) were assumed to dwell in both terrestrial and aquatic compartments. Receptors were assumed to include small mammals, soil invertebrates, water column (pelagic) organisms, and sediment benthos. The goal of this assessment was to characterize any potential adverse risks to terrestrial and aquatic wildlife populations. Hazard Quotients (HQ) were calculated by dividing predicted concentrations of EO in air, water, sediment, and soil by their critical toxicity values. Maximum calculated HQ values in air were 1.52x10(-7), in water were 1.17x10(-5), in sediment were 2.25x10(-4), and in soil were 1.37x10(-5). The results of this assessment suggest that EO as currently manufactured and used does not pose adverse risks to aquatic or terrestrial wildlife. In all cases, the HQ values were much less than the maximum desired HQ value of 1.0 (4,400-6,600,000 times), indicating that the potential for diffuse emissions of EO to pose adverse environmental risks is quite low.     

Fugacity modelling to predict the distribution of organic contaminants in the soil:oil matrix of constructed biopiles

Level I and II fugacity approaches were used to model the environmental distribution of benzene, anthracene, phenanthrene, 1-methylphenanthrene and benzo[a]pyrene in a four phase biopile system, accounting for air, water, mineral soil and non-aqueous phase liquid (oil) phase. The non-aqueous phase liquid (NAPL) and soil phases were the dominant partition media for the contaminants in each biopile and the contaminants differed markedly in their individual fugacities. Comparison of three soils with different percentage of organic carbon (% org C) showed that the % org C influenced contaminant partitioning behaviour. While benzene showed an aqueous concentration worthy of note for leachate control during biopiling, other organic chemicals showed that insignificant amount of chemicals leached into the water, greatly reducing the potential extent of groundwater contamination. Level II fugacity model showed that degradation was the dominant removal process except for benzene. In all three biopile systems, the rate of degradation of benzo(a)pyrene was low, requiring more than 12 years for soil concentrations from a spill of about 25 kg (100 mol) to be reduced to a concentration of 0.001 microgg(-1). The removal time of 1-methylphenanthrene and either anthracene or phenanthrene was about 1 and 3 years, respectively. In contrast, benzene showed the highest degradation rate and was removed after 136 days in all biopile systems. Overall, this study confirms the association of risk critical contaminants with the residual saturation in treated soils and reinforces the importance of accounting for the partitioning behaviour of both NAPL and soil phases during the risk assessment of oil-contaminated sites.     

Development of continental scale multimedia contaminant fate models: integrating GIS

The incentives and approaches for modelling chemical fate at a continental scale are discussed and reviewed. It is suggested that a multi-media model consisting of some 20-30 regions, each of which contains typically seven environmental compartments represents a reasonable compromise between the issues of the need for detailed resolution, avoidance of excessive data demands and inherent complexity and transparency. Strategies adopted in compiling the Berkley-Trent (BETR) model for North America are discussed and used to illustrate the issues of selecting appropriate number and nature of segments, treatment of air and water flows and the acquisition of environmental data. It is suggested that GIS software can play a valuable role in gathering and processing such data and in the display and interpretation of the results of the model assessment. The BETR model will be a useful tool for describing the nature of persistence and long-range transport of chemicals of concern in the North American environment.     

Hazardous air pollutants in industrial area of Mumbai - India

Hazardous Air Pollutants (HAPs) have a potential to be distributed into different component of environment with varying persistence. In the current study fourteen HAPs have been quantified in the air using TO-17 method in an industrial area of Mumbai. The distribution of these HAPs in different environmental compartments have been calculated using multi media mass balance model, TaPL3, along with long range transport potential and persistence. Results show that most of the target compounds partition mostly in air. Phenol and trifluralin, partition predominantly into soil while ethyl benzene and xylene partition predominantly into vegetation compartment. Naphthalene has the highest persistence followed by ethyl benzene, xylene and 1,1,1 trihloro ethane. Long range transport potential is maximum for 1,1,1 trichloroethane. Assessment of human health risk in terms of non-carcinogenic hazard and carcinogenic risk due to exposure to HAPs. have been estimated for industrial workers and residents in the study area considering all possible exposure routes using the output from TaPL3 model. The overall carcinogenic risk for residents and workers are estimated as high as unity along with very high hazard potential.     

Evaluation of the STP model: comparison of modelled and experimental results for ten polycyclic aromatic hydrocarbons (PAHs)

Screening level risk assessment models are used by many countries to assess the treatability of organic chemicals during the sewage treatment process, especially those that are new to commerce. The performance of one such model, the sewage treatment plant model, is evaluated in the current study by comparing model predictions with actual measurement data collected at various stages of a typical full-scale activated sludge type sewage treatment plant. A suite of ten polycyclic aromatic hydrocarbons (PAHs) with widely varying physico–chemical properties were monitored for the comparison. Model predicted removal efficiencies were in very good agreement with those measured for all ten PAHs. Observed chemical concentrations and their trends at various stages of the sewage treatment process were also well simulated by the model. Results also suggest that a reasonable first approximation estimate of a range for the biodegradation half-life needed for the model may be obtained by dividing reported aqueous biodegradation half-life by scaling factors of 50 and 150.     

Ozonation of a mixture of estrogens and progestins in aqueous solution: Interpretation of experimental results by computational methods

In this paper the results of a thorough evaluation of the environmental fate and effects of azilsartan are presented. Azilsartan medoxomil is administered as a pro-drug for the treatment of patients with essential hypertension. The pro-drug is converted by hydrolysis to the active pharmaceutical ingredient azilsartan. Laboratory tests to evaluate the environmental fate and effects of azilsartan medoxomil were conducted with azilsartan and performed in accordance with OECD test guidelines. The predicted environmental concentration (PEC) in surface water was estimated at 0.32 μg L⁻¹ (above the action limit of 0.01 μg L⁻¹), triggering a Phase II assessment. Azilsartan is not readily biodegradable. Results of the water sediment study demonstrated significant shifting of azilsartan metabolites to sediment. Based on the equilibrium partitioning method, metabolites are unlikely to pose a risk to sediment-dwelling organisms. Ratios of the predicted environmental concentrations (PECs) to the predicted-no-effect concentrations (PNECs) did not exceed the relevant triggers, and the risk to aquatic, sewage treatment plant (STP), groundwater and sediment compartments was concluded acceptable. A terrestrial assessment was not triggered. Azilsartan poses an acceptable risk to the environment.     

Environmental fate of pesticides used in Australian viticulture: Behaviour of dithianon and vinclozolin in the soils of the South Australian Riverland

The red calcareous earth soils of the South Australian Riverland produce more than one-third of the grapes used in Australian winemaking. As part of on-going investigations into pesticide transport in Australian vineyard soils, the movement of the fungicides dithianon and vinclozolin through such strongly alkaline soils was investigated. Small, undisturbed soil cores were extracted from the inter-row topsoil of a vineyard adjacent to the River Murray, approximately 10 km S.W. of Overland Corner, South Australia. The vines were grown in a deep (1 – 4 m) reddish brown, strongly alkaline, sandy loam with a low organic carbon content (1 – 2 %). Surface fluxes of pesticide were applied at the maximum recommended application rates to the surface of the cores, which were then irrigated, and pesticide residues in the leachate determined by HPLC. No leaching of either dithianon or vinclozolin occurred. Dithianon was immobilised in the top 2 cm of the soil. Dithianon concentrations were low ( 0 – 37 % applied dose) suggesting that rapid degradation of this compound occurs in these soils (63 – 100 % degradation in 10 days). Extremely low concentrations of vinclozolin were found throughout the soil core profiles (0.05 – 1.4 % applied dose) suggesting that this fungicide was somewhat mobile, but also that it too was unstable in such alkaline soils (> 98 % degradation in 10 days). These results suggest that the irrigated vineyard soils of this region are unlikely to be prone to leaching of dithianon or vinclozolin, and therefore that groundwater supplies in this area are unlikely to be at any significant risk of contamination through viticultural use of these compounds.     

Comparison of competitive and synergetic adsorption of three phenolic compounds on river sediment

Knowledge of toxic chemical sorption by soil/sediment is critical for environmental risk assessment of toxic chemicals, especially for the multi-sorbate system in river ecosystem. Sorption characteristics of 2, 4-Dichlorophenol, 2, 4-Dinitrophenol and 2, 4-Dimethyphenol on sediment were investigated. Adsorption isotherms in single- and multi-sorbate systems fitted well the Freundlich model. The adsorption effects were different among three selected phenolic compounds in single- and multi-sorbate systems. The synergetic affect that 2, 4-Dinitrophenol and 2, 4-Dimethyphenol bring to 2, 4-Dichlorophenol can be explained by the compression of double electronic layer and the charge neutrality. Adsorption kinetic results showed that pseudo-second-order model can be used to describe the experimental data and the adsorption affinity of phenolic compounds influenced greatly by the adsorption velocity. The present study suggests that the fate and transport of emerging pollutants such as phenolic compounds could be affected in the presence of different hydrophobic pollutants in aquatic systems.     

Distribution of steroid- and dioxin-like activities between sediments, POCIS and SPMD in a French river subject to mixed pressures

The contamination of aquatic systems by endocrine disrupting chemicals (EDCs) is now a widely established fact. Nevertheless, there is still a scarcity of knowledge concerning the source, transport, fate and bioavailability of such active compounds. In the present study we assessed the distribution of estrogenic, (anti-)androgenic, pregnane X receptor-like (PXR) and dioxin-like activities between sediment and water compartments using a polar organic compound integrative sampler (POCIS) and a semi-permeable membrane device (SPMD) passive sampler in a river where sediment has been previously described as highly and multi-contaminated. We first confirmed the contamination pattern of this river sediment between 2004, 2009 and 2010 samples, suggesting that this river is subject to a constant high contamination level. However, we showed a different distribution pattern of these activities between compartments: estrogenic activity was mainly detected in POCIS extracts and to a lesser extent in sediment and SPMD extracts; anti-androgenic activities were mainly detected in SPMD and sediment extracts while no activity was detected in POCIS extracts; PXR-like activity was detected in all three investigated compartments, with POCIS > SPMD > sediment; dioxin-like activity was mainly found in the sediment and the SPMD extracts. Overall, partitioning of the biological activities was in accordance with physicochemical properties (e.g., log K _ow) of typical known active chemicals in each bioassay. Furthermore, in order to establish whether the chemicals involved in these activities were similar between the compartments, we fractionated sediment, POCIS and SPMD extracts using a multi-step fractionation procedure. This highlighted differences in the nature of active chemicals between compartments. Altogether, our results support the need to consider different compartments in order to enhance exposure assessment.