Passive sampling: partition coefficients for a silicone rubber reference phase

Silicone rubber sheeting can be used as a passive sampling device for hydrophobic organic contaminants in the environment to determine the available concentrations in water and sediments. Reliable sampler-water partition coefficients are required to determine the sampling rates and the dissolved contaminant concentrations in water and in sediment pore water. Log partition coefficients (logK(sr,w)) for silicone rubber-water have been estimated for 32 polycyclic aromatic hydrocarbons (PAHs), 2 deuterated PAH analogues and 32 chlorobiphenyls (CBs) using the cosolvent method, with methanol as cosolvent. Strong linear relationships were found with literature values for the corresponding log octanol-water partition coefficients (logK(ow)) for both CBs and PAHs, confirming that partitioning into the silicone rubber is strongly determined by the hydrophobicity of the compounds, which suggests logK(ow) is a good predictor of logK(sr,w) and that absorption is the main mechanism for accumulation of analytes into the silicone rubber polymer.     

Classification of alluvial soils according to their potential environmental risk: a case study for Belgian catchments

Alluvial soils may represent important sinks of contaminants as a result of the deposition of contaminated sediments along the river by overbank flooding or after dredging. Because of the erosion of alluvial deposits or the release of contaminants from sediments, alluvial soils can also be a source of contamination. In this paper, a risk assessment for contaminated (alluvial) soils is presented. The approach, mainly based on physico-chemical soil characteristics, single extractions and leaching tests, is illustrated by means of a case study from four Belgian catchments. The extractions and leaching tests that were used have been validated by European testing programs and can provide valuable information for classifying the potential environmental risks of soils. Irrespective of the location, pH, organic carbon content and 'mobilisable' metal concentrations were the most important factors explaining 'mobile' metal concentrations in the alluvial soils. Additionally, the data of the physico-chemical soil characterization, extractions and leaching tests were combined with local and regional factors to classify the alluvial soils in different categories according to their actual and potential risk for the environment.     

Colloid-Associated Groundwater Contaminant Transport in Homogeneous Saturated Porous Media: Mathematical and Numerical Modeling

During the past two decades, significant efforts have been made to study contaminant transport in the presence of colloids. Several researchers reported that colloidal particles could enhance the migration of contaminants in groundwater by reducing retardation factor. When the colloidal particles are present in the aquifer, the subsurface system can be considered as a three-phase system with two solid phases and an aqueous phase. The interaction between contaminants, colloids, and solid matrix should be considered in assessing the fate and transport of the contaminant in the groundwater flow system. In this study, a one-dimensional numerical model is developed by employing a fully implicit finite difference method. This model is based on mass balance equations and mass partition mechanisms between the carriers and solid matrix, as well as between the carriers and contaminants in a saturated homogeneous porous medium. This phenomenon is presented by two approaches: equilibrium approach and fully kinetic first-order approach. The formulation of the model can be simplified by employing equilibrium partitioning of particles. However, contaminant transport can be predicted more accurately in realistic situations by kinetic modeling. To test the sensitivity of the model, the effect of the various chemical and physical coefficients on the migration of contaminant was investigated. The results of numerical modeling matched favorably with experimental data reported in the literature.     

Estimating overall persistence and long-range transport potential of persistent organic pollutants: a comparison of seven multimedia mass balance models and atmospheric transport models

Two different approaches to modeling the environmental fate of organic chemicals have been developed in recent years. The first approach is applied in multimedia box models, calculating average concentrations in homogeneous boxes which represent the different environmental media, based on intermedia partitioning, transport, and degradation processes. In the second approach, used in atmospheric transport models, the spatially and temporally variable atmospheric dynamics form the basis for calculating the environmental distribution of chemicals, from which also exchange processes to other environmental media are modeled. The main goal of the present study was to investigate if the multimedia mass balance models CliMoChem, SimpleBox, EVn-BETR, G-CIEMS, OECD Tool and the atmospheric transport models MSCE-POP and ADEPT predict the same rankings of the overall persistence (P(ov)) and long-range transport potential (LRTP) of POPs, and to explain differences and similarities between the rankings by the mass distributions and inter-compartment mass flows. The study was performed for a group of 14 reference chemicals. For P(ov), the models yield consistent results, owing to the large influence of phase partitioning parameters and degradation rate constants, which are used similarly by all models. Concerning LRTP, there are larger differences between the models than for P(ov), due to different LRTP calculation methods and spatial model resolutions. Between atmospheric transport models and multimedia fate models, no large differences in mass distributions and inter-compartment flows can be recognized. Deviations in mass flows are mainly caused by the geometrical design of the models.     

Assessment of spatial distribution of soil loss over the upper basin of Miyun reservoir in China based on RS and GIS techniques

Soil conservation planning often requires estimates of the spatial distribution of soil erosion at a catchment or regional scale. This paper applied the Revised Universal Soil Loss Equation (RUSLE) to investigate the spatial distribution of annual soil loss over the upper basin of Miyun reservoir in China. Among the soil erosion factors, which are rainfall erosivity (R), soil erodibility (K), slope length (L), slope steepness (S), vegetation cover (C), and support practice factor (P), the vegetative cover or C factor, which represents the effects of vegetation canopy and ground covers in reducing soil loss, has been one of the most difficult to estimate over broad geographic areas. In this paper, the C factor was estimated based on back propagation neural network and the results were compared with the values measured in the field. The correlation coefficient (r) obtained was 0.929. Then the C factor and the other factors were used as the input to RUSLE model. By integrating the six factor maps in geographical information system (GIS) through pixel-based computing, the spatial distribution of soil loss over the upper basin of Miyun reservoir was obtained. The results showed that the annual average soil loss for the upper basin of Miyun reservoir was 9.86 t ha(-1) ya(-1) in 2005, and the area of 46.61 km(2) (0.3%) experiences extremely severe erosion risk, which needs suitable conservation measures to be adopted on a priority basis. The spatial distribution of erosion risk classes was 66.9% very low, 21.89% low, 6.18% moderate, 2.89% severe, and 1.84% very severe. Thus, by using RUSLE in a GIS environment, the spatial distribution of water erosion can be obtained and the regions which susceptible to water erosion and need immediate soil conservation planning and application over the upper watershed of Miyun reservoir in China can be identified.     

Global climate change and contaminants--an overview of opportunities and priorities for modelling the potential implications for long-term human exposure to organic compounds in the Arctic

This overview seeks to provide context and insight into the relative importance of different aspects related to global climate change for the exposure of Northern residents to organic contaminants. A key objective is to identify, from the perspective of researchers engaged in contaminant fate, transport and bioaccumulation modelling, the most useful research questions with respect to projecting the long-term trends in human exposure. Monitoring studies, modelling results, the magnitude of projected changes and simplified quantitative approaches are used to inform the discussion. Besides the influence of temperature on contaminant amplification and distribution, accumulation of organic contaminants in the Arctic is expected to be particularly sensitive to the reduction/elimination of sea-ice cover and also changes to the frequency and intensity of precipitation events (most notably for substances that are highly susceptible to precipitation scavenging). Changes to key food-web interactions, in particular the introduction of additional trophic levels, have the potential to exert a relatively high influence on contaminant exposure but the likelihood of such changes is difficult to assess. Similarly, changes in primary productivity and dynamics of organic matter in aquatic systems could be influential for very hydrophobic contaminants, but the magnitude of change that may occur is uncertain. Shifts in the amount and location of chemical use and emissions are key considerations, in particular if substances with relatively low long range transport potential are used in closer proximity to, or even within, the Arctic in the future. Temperature-dependent increases in emissions via (re)volatilization from primary and secondary sources outside the Arctic are also important in this regard. An increased frequency of boreal forest fires has relevance for compounds emitted via biomass burning and revolatilization from soil during/after burns but compound-specific analyses are limited by the availability of reliable emission factors. However, potentially more influential for human exposure than changes to the physical environment are changes in human behaviour. This includes the gradual displacement of traditional food items by imported foods from other regions, driven by prey availability and/or consumer preference, but also the possibility of increased exposure to chemicals used in packaging materials and other consumer products, driven by dietary and lifestyle choices.     

Sensitive Parameters In Predicting Exposure Contaminants Concentration In A Risk Assessment Process

A sensitivity analysis (SA) was conducted on the analytical models considered in the risk-based corrective-action (RBCA) methodology of risk analysis, as developed by the American Society for Testing of Materials (ASTM), to predict a contaminant‘s concentration in the affected medium at the point of human exposure. These models are of interest because evaluations regarding the best approach to contaminated site remediation are shifting toward increased use of risk-based decision, and the ASTM RBCA methodology represents the most effective and internationally widely used standardized guide for risk assessment process. This paper identifies key physical and chemical parameters that need additional precision and accuracy consideration in order to reduce uncertainty in models prediction, thereby saving time, money and engineering effort in the data collection process. SA was performed applying a variance-based method to organic contaminants migration models with reference to soil-to-groundwater leaching ingestion exposure scenario. Results indicate that model output strongly depends on the organic-carbon partition coefficient, organic-carbon content, net infiltration, Darcy velocity, source-receptor distance, and first-order decay constant.     

Impact of intensive agricultural practices on drinking water quality in the EVROS Region (NE GREECE) by GIS analysis

Chemical fertilizers are used extensively in modern agriculture, in order to improve yield and productivity of agricultural products. However, nutrient leaching from agricultural soil into groundwater resources poses a major environmental and public health concern. The Evros region is one of the largest agricultural areas in Northern Greece, extending over 1.5 million acres of cultivated land. Many of its drinking water resources are of groundwater origin and lie within agricultural areas. In order to assess the impact of agricultural fertilizers on drinking water quality in this region, tap-water samples from 64 different locations were collected and analyzed for the presence of nitrates [Formula: see text], nitrites [Formula: see text], ammonium [Formula: see text], sulfate [Formula: see text] and phosphate [Formula: see text]. These chemicals were selected based on the information that ammonium nitrate, ammonium sulfate and inorganic phosphate were the primary fertilizers used in local crop production. [Formula: see text], [Formula: see text] and [Formula: see text] levels exceeding accepted values were recorded in 6.25, 4.70 and 9.38% of all sampling points, respectively. [Formula: see text] and [Formula: see text] concentrations, on the other hand, were inside the permitted range. The data generated were introduced into a geographic information system (GIS) program for computer analysis and projection maps representing afflicted areas were created. Our results indicate a profound geographic correlation in the surface distribution of primary contaminants in areas of intensified agricultural production. Thus, drinking water pollution in these areas can be attributed to excessive fertilizer use from agricultural sources.     

The fate and persistence of polychlorinated biphenyls in soil

The fate and persistence of PCBs 28, 52, 101, 138, and 180 artificially introduced into three soils was studied under a variety of field conditions for up to 415 d following initial contamination. A relationship was detected between ln Koa (octanol/air partition coefficient) and the experimentally observed first-order loss rate constant that was statistically significant at at least the 90% level in all but one instance. In nearly all experiments, PCB persistence was greater in soils of higher organic carbon content. Soil temperature and moisture content were also indicated as important influences on persistence. Significantly longer half-lives were observed in a soil in which initial PCB contamination had occurred ca. 1 year previously. A mass balance showed the most likely mechanism of loss to be volatilisation. Losses attributable to aerobic biodegradation could not be ruled out, but those due to leaching, uptake by biota, and soil erosion were demonstrated to be negligible. First-order rate constants (Kv) were determined for volatilisation of the same congeners from soil under a variety of controlled laboratory scenarios. Multiple linear regression analysis (MLRA) showed the most important influences on kv to be ln Koa (adjusted for soil temperature) and soil organic carbon content. Limited evidence was observed for a relationship between kv and soil moisture content, but not water flux. When tested against field measurements, the MLRA-derived relationship between kv and independent variables predicted to within a factor of 2.5, the persistence of PCBs 28, 52, and 101, However, it did not account for the influence of the age of contaminant association with the soil, soil moisture content or water flux, and failed to function for soils of high organic content, or where ln Koa exceeds ca. 23.     

Estimation of pollutant partition in sandy soils with different water contents

The objectives of this work were: (1) to identify an isotherm model to relate the contaminant contents in the gas phase with those in the solid and non-aqueous liquid phases; (2) to develop a methodology for the estimation of the contaminant distribution in the different phases of the soil; and (3) to evaluate the influence of soil water content on the contaminant distribution in soil. For sandy soils with negligible contents of clay and natural organic matter, contaminated with benzene, toluene, ethylbenzene, xylene, trichloroethylene (TCE), and perchloroethylene (PCE), it was concluded that: (1) Freundlich’s model showed to be adequate to relate the contaminant contents in the gas phase with those in the solid and non-aqueous liquid phases; (2) the distribution of the contaminants in the different phases present in the soil could be estimated with differences lower than 10% for 83% of the cases; and (3) an increase of the soil water content led to a decrease of the amount of contaminant in the solid and non-aqueous liquid phases, increasing the amount in the other phases.     

Partitioning and sources of PAHs in wastewater receiving streams of Tianjin,China

Polycyclic aromatic hydrocarbons (PAHs) partitioning among dissolved phase, suspended particulate matter, pore water, and sediment was studied in one moderately contaminated river (Yongding New River) and two highly contaminated drainage canals (South Drainage Canal and North Drainage Canal) of Tianjin, China. PAHs concentrations in sediment (ranged from 0.2 to 195 μg/g) showed positive relations with both total organic carbon contents (ranged from 0.7% to 31.1%, dw) and black carbon contents (ranged from 0.1% to 2.1%, dw) in the sediments. Moreover, most of the measured organic carbon normalized partition coefficients of PAHs in the three streams were 0.76 to 1.54 log units higher than the predicted values. These indicated that strong and nonlinear sorption of PAHs by carbonaceous geosorbents such as black carbon (BC) existed in the streams, and BC was an important part of the carbonaceous particles controlling the partitioning of PAHs in the sediments of this study. PAH component ratio analyses suggested that PAHs in the three streams, effluent samples from wastewater treatment plants, and soil samples by the riverbank had similar main sources, which is coal/petroleum combustion. We suggested the transportation and transformation of both carbonaceous particles and PAHs during wastewater treatment process, surface runoff, etc, should be studied further in order to make decisions on PAHs controlling measures.     

Development of an integrative passive sampler for the monitoring of organic water pollutants

The development of convenient and competitive devices and methods for monitoring of organic pollutants in the aquatic environment is of increasing interest. An integrative passive sampling system has been developed which consists of a solid poly(dimethylsiloxane) (PDMS) material (tube or rod), acting as hydrophobic organic receiving phase, enclosed in a water-filled or an air-filled low-density polyethylene (LDPE) membrane tubing. These samplers enable the direct analysis of the pollutants accumulated during exposure in the receiving phase by thermodesorption-GC/MS, avoiding expensive sample preparation and cleanups. The capabilities of these sampling devices were studied for the sampling of 20 persistent organic pollutants (chlorobenzenes, hexachlorocyclohexanes, p,p'-DDE, PAHs, and PCBs) in laboratory exposure experiments. For the three sampler designs investigated the uptake of all target analytes was integrative over exposure periods up to 9 days (except PCB 101). The determined sampling rates range from 4 to 1340 microl h(-1) for the water-filled samplers and from 20 to 6360 microl h(-1) for the air-filled ones, respectively. The sampling rate of the analytes is dependent on their molecular weight, partition between water and sampler media (PDMS, polyethylene, water, air) and also of the sampler design. The passive samplers enable the estimation of time-weighted average (TWA) concentration of water pollutants in the lower ng l(-1) to pg l(-1) range.     

Construction of a chemical ranking system of soil pollution substances for screening of priority soil contaminants in Korea

The Korean government recently proposed expanding the number of soil-quality standards to 30 by 2015. The objectives of our study were to construct a reasonable protocol for screening priority soil contaminants for inclusion in the planned soil quality standard expansion. The chemical ranking system of soil pollution substances (CROSS) was first developed to serve as an analytical tool in chemical scoring and ranking of possible soil pollution substances. CROSS incorporates important parameters commonly used in several previous chemical ranking and scoring systems and the new soil pollution parameters. CROSS uses soil-related parameters in its algorithm, including information related to the soil environment, such as soil ecotoxicological data, the soil toxic release inventory (TRI), and soil partitioning coefficients. Soil TRI and monitoring data were incorporated as local specific parameters. In addition, CROSS scores the transportability of chemicals in soil because soil contamination may result in groundwater contamination. Dermal toxicity was used in CROSS only to consider contact with soil. CROSS uses a certainty score to incorporate data uncertainty. CROSS scores the importance of each candidate substance and assigns rankings on the basis of total scores. Cadmium was the most highly ranked. Generally, metals were ranked higher than other substances. Pentachlorophenol, phenol, dieldrin, and methyl tert-butyl ether were ranked the highest among chlorinated compounds, aromatic compounds, pesticides, and others, respectively. The priority substance list generated from CROSS will be used in selecting substances for possible inclusion in the Korean soil quality standard expansion; it will also provide important information for designing a soil-environment management scheme.     

Application of multimedia exposure assessment to drinking water

A potentially important exposure route for humans is the ingestion of chemicals via drinking water. If comprehensive exposure assessments are to be completed for either existing or proposed new chemicals and cost effective control strategies developed, then a quantitative understanding of multimedia transport and fate of specific chemical pollutants must be achieved. Mathematical models provide a powerful framework into which quantitative relationships may be placed to provide guidance in reaching water quality goals. Existing, state-of-the-art media-specific toxic organic transport and fate models for atmospheric (DiDOT), land surface (NPS) and surface water processes (EXAMS) and potable water treatment (WTP) have been linked to demonstrate the technical feasibility of such an approach. Limited application and sensitivity testing of this linked modeling system has shown that the impact of various source loadings and control strategies on drinking water quality can be estimated.     

Estuarine mixing behavior of colloidal organic carbon and colloidal mercury in Galveston Bay, Texas

Mercury (Hg) in estuarine water is distributed among different physical phases (i.e. particulate, colloidal, and truly dissolved). This phase speciation influences the fate and cycling of Hg in estuarine systems. However, limited information exists on the estuarine distribution of colloidal phase Hg, mainly due to the technical difficulties involved in measuring it. In the present study, we determined Hg and organic carbon levels from unfiltered, filtered (<0.45 μm), colloidal (10 kDa-0.45 μm), and truly dissolved (<10 kDa) fractions of Galveston Bay surface water in order to understand the estuarine mixing behavior of Hg species as well as interactions of Hg with colloidal organic matter. For the riverine end-member, the colloidal fraction comprised 43 ± 11% of the total dissolved Hg pool and decreased to 17 ± 8% in brackish water. In the estuarine mixing zone, dissolved Hg and colloidal organic carbon showed non-conservative removal behavior, particularly in the low salinity (<15 ppt) region. This removal may be caused by salt-induced coagulation of colloidal matter and consequent removal of dissolved Hg. The particle-water interaction, K(d) ([particulate Hg (mol kg(-1))]/[dissolved Hg (mol L(-1))]) of Hg decreased as particle concentration increased, while the particle-water partition coefficient based on colloidal Hg and the truly dissolved Hg fraction, K(c) ([colloidal Hg (mol kg(-1))]/[truly dissolved Hg (mol L(-1))]) of Hg remained constant as particle concentration increased. This suggests that the particle concentration effect is associated with the amount of colloidal Hg, increasing in proportion to the amount of suspended particulate matter. This work demonstrates that, colloidal organic matter plays an important role in the transport, particle-water partitioning, and removal of dissolved Hg in estuarine waters.     

Performance of semipermeable membrane devices for sampling of organic contaminants in groundwater

Lipid-filled semipermeable membrane devices (SPMDs) are receiving increasing attention as passive, in situ samplers for the assessment of environmental pollutant exposure. Although SPMDs have been successfully used in a variety of field studies in surface waters, only a few studies have addressed their characteristics as groundwater samplers. In this study, the performance of the SPMDs for monitoring organic contaminants in groundwater was evaluated in a pilot field application in an area severely contaminated by chemical waste, especially by chlorinated hydrocarbons. The spatial distribution of hydrophobic groundwater contaminants was assessed using a combination of passive sampling with SPMDs and non-target semiquantitative GC-MS analysis. More than 100 contaminants were identified and semiquantitatively determined in SPMD samples. Along the 6 field sites under investigation, a large concentration gradient was observed, which confirms a very limited mobility of hydrophobic substances in dissolved form in the aquifer. The in situ extraction potential of the SPMD is limited by groundwater flow, when the exchange volume of well water during an exposure is lower than the SPMD clearance volume for the analytes. This study demonstrates that SPMDs present a useful tool for sampling and analyzing of groundwater polluted with complex mixtures of hydrophobic chemicals and provides guidance for further development of passive sampling technology for groundwater.     

Ecotoxicity monitoring of hydrocarbon-contaminated soil using earthworm (Eisenia foetida)

In order to assess the applicability of an earthworm bioassayas a technique for monitoring the soil flushing process, short-term and long-term toxicity tests were conducted on remediatedsoil using various pore volumes of surfactant solution. Resultsobtained on short-term toxicity testing indicated that biomassincreased as the soil flushing proceeded, and on diesel-contaminated soils this testing showed that the effect of dieselis lethal and that 25 pore volumes of soil surfactant were notsufficient to abrogate the toxic effect of diesel. These short-term tests also showed strong sublethal relationships between the development of biomass, and the concentrations of toxic chemicals in the soil. Although relationships between contaminants and the various bioassay parameters examined werenot significant in long-term testing, an increase in the numberof juveniles was observed over time, which may have been a consequence of a reduction in toxicity associated with the flushing process.     

Simulation of soil loss processes based on rainfall runoff and the time factor of governance in the Jialing River Watershed,China

Jialing River is the largest tributary in the catchment area of Three Gorges Reservoir, and it is also one of the important areas of sediment yield in the upper reaches of the Yangtze River. In recent years, significant changes of water and sediment characteristics have taken place. The "Long Control" Project implemented since 1989 had greatly changed the surface appearance of the Jialing River Watershed (JRW), and it had made the environments of the watershed sediment yield and sediment transport change significantly. In this research, the Revised Universal Soil Loss Equation was selected and used to predict the annual average amount of soil erosion for the special water and sediment environments in the JRW after the implementation of the "Long Control" Project, and then the rainfall–runoff modulus and the time factor of governance were both considered as dynamic factors, the dynamic sediment transport model was built for soil erosion monitoring and forecasting based on the average sediment yield model. According to the dynamic model, the spatial and temporal distribution of soil erosion amount and sediment transport amount of the JRW from 1990 to 2007 was simulated using geographic information system (GIS) technology and space-grid algorithm. Simulation results showed that the average relative error of sediment transport was less than 10% except for the extreme hydrological year. The relationship between water and sediment from 1990 to 2007 showed that sediment interception effects of the soil and water conservation projects were obvious: the annual average sediment discharge reduced from 145.3 to 35 million tons, the decrement of sediment amount was about 111 million tons, and decreasing amplitude was 76%; the sediment concentration was also decreased from 2.01 to 0.578 kg/m³. These data are of great significance for the prediction and estimation of the future changing trends of sediment storage in the Three Gorges Reservoir and the particulate non-point source pollution load carried by sediment transport from watershed surface.     

Estimating aquatic toxicity as determined through laboratory tests of great lakes sediments containing complex mixtures of environmental contaminants

We developed and evaluated a total toxic units modeling approach for predicting mean toxicity as measured in laboratory tests for Great Lakes sediments containing complex mixtures of environmental contaminants (e.g., polychlorinated biphenyls, polycyclic aromatic hydrocarbons, pesticides, chlorinated dioxins, and metals). The approach incorporates equilibrium partitioning and organic carbon control of bioavailability for organic contaminants and acid volatile sulfide (AVS) control for metals, and includes toxic equivalency for planar organic chemicals. A toxic unit is defined as the ratio of the estimated pore-water concentration of a contaminant to the chronic toxicity of that contaminant, as estimated by U.S. Environmental Protection Agency Ambient Water Quality Criteria (AWQC). The toxic unit models we developed assume complete additivity of contaminant effects, are completely mechanistic in form, and were evaluated without any a posteriori modification of either the models or the data from which the models were developed and against which they were tested. A linear relationship between total toxic units, which included toxicity attributable to both iron and un-ionized ammonia, accounted for about 88% of observed variability in mean toxicity; a quadratic relationship accounted for almost 94%. Exclusion of either bioavailability components (i.e., equilibrium partitioning control of organic contaminants and AVS control of metals) or iron from the model substantially decreased its ability to predict mean toxicity. A model based solely on un-ionized ammonia accounted for about 47% of the variability in mean toxicity. We found the toxic unit approach to be a viable method for assessing and ranking the relative potential toxicity of contaminated sediments.The U.S. Government right to retain a non-exclusive royalty free licence in and to any copyright is acknowledged.