A holistic passive integrative sampling approach for assessing the presence and potential impacts of waterborne environmental contaminants

As an integral part of our continuing research in environmental quality assessment approaches, we have developed a variety of passive integrative sampling devices widely applicable for use in defining the presence and potential impacts of a broad array of contaminants. The semipermeable membrane device has gained widespread use for sampling hydrophobic chemicals from water and air, the polar organic chemical integrative sampler is applicable for sequestering waterborne hydrophilic organic chemicals, the stabilized liquid membrane device is used to integratively sample waterborne ionic metals, and the passive integrative mercury sampler is applicable for sampling vapor phase or dissolved neutral mercury species. This suite of integrative samplers forms the basis for a new passive sampling approach for assessing the presence and potential toxicological significance of a broad spectrum of environmental contaminants. In a proof-of-concept study, three of our four passive integrative samplers were used to assess the presence of a wide variety of contaminants in the waters of a constructed wetland, and to determine the effectiveness of the constructed wetland in removing contaminants. The wetland is used for final polishing of secondary-treatment municipal wastewater and the effluent is used as a source of water for a state wildlife area. Numerous contaminants, including organochlorine pesticides, polycyclic aromatic hydrocarbons, organophosphate pesticides, and pharmaceutical chemicals (e.g., ibuprofen, oxindole, etc.) were detected in the wastewater. Herein we summarize the results of the analysis of the field-deployed samplers and demonstrate the utility of this holistic approach.     

A multi-stage sampling strategy for the delineation of soil pollution in a contaminated brownfield

A multi-stage sampling strategy, based on sequential Gaussian simulation, was presented to optimize the step-wise selection of a small numbers of additional samples to delineate soil pollution. This strategy was applied to a Belgian brownfield of 5.2 ha polluted with lead (Pb). Starting from an initial number of 240 samples in stage 1, additional samples were added, 25 per stage, and the reduction of the uncertainty in the Pb delineation was monitored. Twenty stages were used. Already in stage 6 a local optimum was found based on the median conditional coefficient of variation. An independent validation confirmed that this index was to be preferred over the median conditional variance. So for the brownfield considered our procedure indicated that 365 selected samples would have been sufficient, representing a gain of 70.7% in sampling effort compared to current practice which resulted in a sampling effort of 1245 samples.     

Comparison of sampling collection strategies for assessing airborne trichloramine levels in indoor swimming pools

Environmental Science and Pollution Research - Since 1995, Hery’s trichloramine sampling procedure has been widely used to determine trichloramine exposure in indoor swimming pools. This...     

Co-transport of biochar colloids with organic contaminants in soil column

Environmental Science and Pollution Research - Co-transport of biochar (BC) colloids with coexisting organic contaminants (OCs) in soil involves complex interactions among BC colloids, OCs, and...     

A simplified method for sampling and analysis of high volume surface water for organic contaminants using XAD-2

A simple compressed-gas driven system for field processing and extracting water for subsequent analyses of hydrophobic organic compounds is presented. The pumping device is a pneumatically driven pump and filtration system that can easily clarify at 4 L/min. The extraction device uses compressed gas to drive filtered water through two parallel XAD-2 resin columns, at about 200 mL/min. No batteries or inverters are required for water collection or processing. Solvent extractions were performed directly in the XAD-2 glass columns. Final extracts are cleaned-up on Florisil cartridges without fractionation and contaminants analyzed by GC-MS. Method detection limits (MDLs) and recoveries for dissolved organic contaminants, polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and pesticides are reported along with results of surface water analysis for the San Francisco Bay, CA.     

Small-scale variability of metals in soil and composite sampling

Soil pollution data is also strongly scattering at small scale. Sampling of composite samples, therefore, is recommended for pollution assessment. Different statistical methods are available to provide information about the accuracy of the sampling process. Autocorrelation and variogram analysis can be applied to investigate spatial relationships. Analysis of variance is a useful method for homogeneity testing. The main source of the total measurement uncertainty is the uncertainty arising from sampling. The sample mass required for analysis can also be estimated using an analysis of variance. The number of increments to be taken for a composite sample can be estimated by means of simple statistical formulae. Analytical results of composite samples obtained from different fusion procedures of increments can be compared by means of multiple mean comparison. The applicability of statistical methods and their advantages are demonstrated for a case study investigating metals in soil at a very small spatial scale. The paper describes important statistical tools for the quantitative assessment of the sampling process. Detailed results clearly depend on the purpose of sampling, the spatial scale of the object under investigation and the specific case study, and have to be determined for each particular case.     

Modelling the extraction of soil contaminants with supercritical carbon dioxide

Extractions of volatile organic compounds (VOC’s) in contaminated soil from petroleum site were performed with supercritical carbon dioxide at different temperatures, pressures, extraction times, solvent flow rates, soil moisture contents and soil acidity. Three soil systems were investigated in order to compare the best parameters for extraction. A central composite rotatable design has been used to evaluate the influence of operation conditions on the extraction efficiency to generate model equations representing the types of soil. The results indicate that at least 70-80% of the initial amount of VOC’s can be removed at moderate temperatures even at very high moisture content. Supercritical extraction is best suited to silt type soils which have a low adsorption capacity. VOC’s recoveries from the artificial contaminated soil samples were higher in comparison with real contaminated soils. At moderate temperatures, the extraction efficiency for real soils is low because pollutants bind strongly to the soil.     

Bioavailability of contaminants estimated from uptake rates into soil invertebrates

It is often argued that the concentration of a pollutant inside an organism is a good indicator of its bioavailability, however, we show that the rate of uptake, not the concentration itself, is the superior predictor. In a study on zinc accumulation and toxicity to isopods (Porcellio scaber) the dietary EC(50) for the effect on body growth was rather constant and reproducible, while the internal EC(50) varied depending on the accumulation history of the animals. From the data a critical value for zinc accumulation in P. scaber was estimated as 53 microg/g/wk. We review toxicokinetic models applicable to time-series measurements of concentrations in invertebrates. The initial slope of the uptake curve is proposed as an indicator of bioavailability. To apply the dynamic concept of bioavailability in risk assessment, a set of representative organisms should be chosen and standardized protocols developed for exposure assays by which suspect soils can be evaluated.     

Sorption of polar and nonpolar organic contaminants by oil-contaminated soil

Sorption of nonpolar (phenanthrene and butylate) and polar (atrazine and diuron) organic chemicals to oil-contaminated soil was examined to investigate oil effects on sorption of organic chemicals and to derive oil–water distribution coefficients (K_oil). The resulting oil-contaminated soil–water distribution coefficients (K_d) for phenanthrene demonstrated sorption-enhancing effects at both lower and higher oil concentrations (C_oil) but sorption-reducing (competitive) effects at intermediate C_oil (approximately 1 g kg⁻¹). Rationalization of the different dominant effects was attempted in terms of the relative aliphatic carbon content which determines the accessibility of the aromatic cores to phenanthrene. Little or no competitive effect occurred for butylate because its sorption was dominated by partitioning. For atrazine and diuron, the changes in K_d at C_oil above approximately 1 g kg⁻¹ were negligible, indicating that the presently investigated oil has little or no effect on the two tested compounds even though the polarity of the oil is much less than soil organic matter (SOM). Therefore, specific interactions with the active groups (aromatic and polar domains) are dominantly responsible for the sorption of polar sorbates, and thus their sorption is controlled by available sorption sites. This study showed that the oil has the potential to be a dominant sorptive phase for nonpolar pollutants when compared to SOM, but hardly so for polar compounds. The results may aid in a better understanding of the role of the aliphatic and aromatic domains in sorption of nonpolar and polar organic pollutants.     

Three methods for quantifying proximity of air sampling sites to spatially resolved emissions of semi-volatile organic contaminants

Passive air samplers have made it possible to measure long-term average air concentrations of semi-volatile organic contaminants (SVOCs) at a large number of sampling sites. In order to use the results of such measurement networks in the derivation of empirical measures of long-range transport, a method is required that quantitatively expresses the proximity of air sampling sites to spatially distributed emissions. We propose three increasingly sophisticated tiers for quantifying proximity to emissions. The ‘static’ method assumes that a sampling site is only influenced by emission taking place in the same 1° of latitude by 1° of longitude cell in which it is located. The ‘dispersion’ method additionally accounts for the influence of emissions in neighboring cells by adding the emissions into each cell weighted by the distance between the cell’s center and the center of the cell containing the sampling site. The ‘air-shed’ method quantifies proximity to emissions by combining the emissions in each cell with the probability that air arriving at the sampling site passed through each cell. The probability is calculated for each sampling site by aggregating a large number of air mass back-trajectories. These new proximity gauges were contrasted against the remoteness index RI, which is derived from global atmospheric tracer transport modeling. The four methods were used to quantify the proximity of the sampling sites of the Global Atmospheric Passive Sampling (GAPS) study to global Polycyclic Aromatic Hydrocarbon (PAH) emissions. The proximity gauges produce markedly different results primarily for sites located near steep gradients in population, such as occur in coastal areas or at the feet of mountain ranges. The dispersion method produces quite similar results to the air-shed method using drastically less computational power and input data, but application of the air-shed method may be necessary where winds are strongly directional.     

A strategy for the assessment of continuous and pulsed contaminants in river and estuary ecosystems in the Arctic

A transfer of contaminants from the land through the rivers forms a significant part of the Arctic seas' pollution. A whole ecosystem is the target of this harmful action. The response of the ecosystem can be considered as the measure of the impact. To assess this impact we designed a mathematical approach based on the Liebig-Shelford law of tolerance, the "narrow path" principle and the Shannon index of diversity to evaluate a prosperity function and a comprehensive risk index for a river or estuary ecosystem. To illustrate this general approach we consider the propagation of the pollutant along the river bed after (1) continuous and (2) pulsed release of a pollutant. The results of calculations show good correspondence with the actual behaviour of natural ecosystems. Further studies are necessary to find out the actual values of the parameters for different pollutants.     

Characterisation of a reference site for quantifying uncertainties related to soil sampling

The paper reports a methodology adopted to face problems related to quality assurance in soil sampling. The SOILSAMP project, funded by the Environmental Protection Agency of Italy (APAT), is aimed at (i) establishing protocols for soil sampling in different environments; (ii) assessing uncertainties associated with different soil sampling methods in order to select the "fit-for-purpose" method; (iii) qualifying, in term of trace elements spatial variability, a reference site for national and international inter-comparison exercises. Preliminary results and considerations are illustrated.     

Proposal of new convenient extractant for assessing phytoavailability of heavy metals in contaminated sandy soil

Environmental Science and Pollution Research - The aim of the study was to compare the usefulness of 1 M HCl with aqua regia, EDTA, and CaCl2 for the extraction of phytoavailable forms of...     

Decision support tool for soil sampling of heterogeneous pesticide (chlordecone) pollution

When field pollution is heterogeneous due to localized pesticide application, as is the case of chlordecone (CLD), the mean level of pollution is difficult to assess. Our objective was to design a decision support tool to optimize soil sampling. We analyzed the CLD heterogeneity of soil content at 0–30- and 30–60-cm depth. This was done within and between nine plots (0.4 to 1.8 ha) on andosol and ferralsol. We determined that 20 pooled subsamples per plot were a satisfactory compromise with respect to both cost and accuracy. Globally, CLD content was greater for andosols and the upper soil horizon (0–30 cm). Soil organic carbon cannot account for CLD intra-field variability. Cropping systems and tillage practices influence the CLD content and distribution; that is CLD pollution was higher under intensive banana cropping systems and, while upper soil horizon was more polluted than the lower one with shallow tillage (<40 cm), deeper tillage led to a homogenization and a dilution of the pollution in the soil profile. The decision tool we proposed compiles and organizes these results to better assess CLD soil pollution in terms of sampling depth, distance, and unit at field scale. It accounts for sampling objectives, farming practices (cropping system, tillage), type of soil, and topographical characteristics (slope) to design a relevant sampling plan. This decision support tool is also adaptable to other types of heterogeneous agricultural pollution at field level.     

Cell absorption induced desorption of hydrophobic organic contaminants from digested soil residue

Oral ingestion of contaminated soil is an important pathway of human exposure to hydrophobic organic contaminants (HOCs), particularly for children in developing countries. The mobilization potential of various contaminants from ingested soil is often characterized using an in vitro gastrointestinal model, based on the quantities of contaminants remaining in digestive fluid after digestion and separation. Recently, it was experimentally demonstrated that a large fraction of mobilized contaminants sorbed on the digested residue could be released if the dissolved fraction was removed by intestinal absorption. This hypothesis was further tested in this study. Soil spiked with dichlorodiphenyltrichloroethane and its metabolites (DDXs) and polycyclic aromatic hydrocarbons (PAHs) was digested using an in vitro gastrointestinal model. A human colon carcinoma cell line (Caco-2) was cultured in digestive fluid with or without soil residue (pre-equilibrated with the soil) for 2 h. A large proportion of the contaminants (37-68%) was sorbed on the digested residue. Without this residue, 66 ± 13% of DDXs and 73 ± 14% of PAHs dissolved in the fluid, as means and standard deviations, were absorbed by the cell monolayer after exposure. With both digestive fluid and residue, the sorbed fraction of PAHs and DDXs decreased by 38-92%, while the ratios of the cellular to the dissolved concentrations were 2.7-2.8 times higher than those without the residue. This supported the hypothesis that the cell absorption of dissolved HOCs induces desorption of the sorbed fraction from digestive residue, and the desorbed HOCs can be absorbed as well.     

Evaluation of post-Katrina flooded soils for contaminants and toxicity to the soil invertebrates Eisenia fetida and Caenorhabditis elegans

This research evaluated soil samples from a New Orleans neighborhood in the Chalmette, Saint Bernard Parish, that had been inundated by flooding associated with Hurricane Katrina. The goal was to determine if ecological risks persisted from flood waters that had come in contact with hazardous surface chemicals before inundating this low-lying neighborhood for a prolonged period. Research objectives were to establish the presence or absence of volatile organic and heavy metal contaminants, and then asses the toxicity of this soil to Eisenia fetida in a soil exposure assay and Caenorhabditis elegans in a simulated porewater exposure assay. Soil analysis revealed detectable levels of metals and organics in the surface soil at each location. No contaminant was detected in concentrations above human health screening values. Chromium and mercury were detected at levels in excess of typical ecological risk values. Soil extracts revealed concentrations of nitrate, sulfate, and chloride above those from an unflooded background sample. Toxicity testing resulted in no acute effects to either test species, but did show bioaccumulation of arsenic, cadmium, and lead in E. fetida exposed to several samples. The combination of mercury and sulfate provide the potential for mercury methylation should flooding and prolonged inundation occur again.     

Removal technology for pesticide contaminants in potable water

Abstract

Granular activated carbon adsorption is one of the reliable and effective means of removing organochlorine pesticides from water. Continuous stirred tank and fix bed reactor systems were used for the screening of indigenous granular activated carbons in the removal of organochlorine pesticides from water at low microgram levels in simulated samples. The carbon dose reguired to treat raw water at initial concentrations of 5–10 ug/1 of Y‐HCH, p,p'‐DDT and p,p'‐DDE to <2 ug/1 potable level was computed. Data leads to the development of a tap attachable water treatment unit for pesticides removal for applications on domestic scale.     

Grinding and sieving soil affects the availability of organic contaminants: a kinetic analysis

Field contaminated soils are often homogenized before application in bioassays and chemical assays that estimate the (bio)availability of their contaminants. The homogenization of the soil might affect the availability, and thereby the outcome of a bioassay might not reflect field situations. In this study, uptake kinetics of polycyclic aromatic hydrocarbons (PAH) by a negligible depletive passive sampler exposed to a ground and non-ground field contaminated soil were tested. The measurements illustrate how freely dissolved pore water concentrations of contaminants can be affected by soil treatment. It took more than a month, and over a year to reach steady state in the passive sampler exposed to the ground and non-ground soil, respectively. The uptake rate seemed to be limited by desorption from the soil, even though the fiber only extracted 0.2% of the soil-sorbed PAH at maximum. If these observations are translated to the field situation, where contaminants are not homogeneously distributed and disappear by (bio)degradation or physical transport processes, it is unlikely that pore water concentrations are solely determined by a thermodynamic equilibrium. Hence, exposure of organisms in these soils cannot always be estimated by sorption studies and an equilibrium partitioning approach.     

Evaluation of the optimal strategy for ex situ bioremediation of diesel oil-contaminated soil

Purpose  

Bioaugmentation and biostimulation have been widely applied in the remediation of oil contamination. However, ambiguous results have been reported. It is important to reveal the controlling factors on the field for optimal selection of remediation strategy. In this study, an integrated field landfarming technique was carried out to assess the relative effectiveness of five biological approaches on diesel degradation. The limiting factors during the degradation process were discussed.