Heterogeneity of chlorinated hydrocarbon sorption properties in a sandy aquifer

Hydraulic conductivity and sorption coefficients for chlorinated hydrocarbons (chloroform, carbon tetrachloride and tetrachloroethylene) were evaluated for 216 sediment samples collected across a 15 m transect and a 21 m depth interval in a contaminated aquifer near Schoolcraft, Michigan. Relationships between hydraulic conductivity, linear sorption partition coefficients, grain size classes, and spatial location were investigated using linear regression analysis and geostatistical techniques. Clear evidence of layering was found in sorption properties, hydraulic conductivity and grain sizes. Conductivity correlated well with grain size, as expected, but sorption varied inversely with grain size, contrary to some previous reports. No significant correlation was found between sorption properties and hydraulic conductivity. This is likely due to the unexpected presence of small amounts of highly sorptive coal-like solids, which dominate the sorption behavior but have little effect on conductivity. The results demonstrate that recent findings regarding the high sorption capacity of coal materials found in soils can exert a controlling influence on contaminant transport. Designers of in situ remediation systems should be cautioned that 1) it is not reasonable to assume that sorption capacity and hydraulic conductivity are related, 2) sorption capacity and hydraulic conductivity are critical measurements for contaminant site characterization and subsequent transport modeling, 3) estimating sorption capacity from organic carbon measurement may lead to greater errors than performing sorption isotherms, and 4) it is more important to characterize vertical heterogeneity rather than horizontal heterogeneity because both sorption and hydraulic conductivity are correlated across longer distances in the horizontal plane.     

The chemical and biogenotoxic characterization of organic xenobiotics in aquatic sediment materials 1. The application and comparison of chemically non-specific and biogenotoxic methods

The aim of this work was to evaluate the Ames assay and mixed function oxidase (MFO)-Induct Test used in parallel with chemical group tests (ECD fingerprint and PAH estimation) for the characterization of the organic pollution of water sediment materials. Sediment materials were collected from “clean” and relatively heavily polluted locations in the Middle Adriatic Sea, and from some locations in continental Croatia polluted with wastewaters from different enterprises. Characterization of the organic extracts of the sediment materials investigated was performed chemically using UV spectrofluorometry for the determination polyaromatic hydrocarbons (PAH) and gas chromatography for the determination of volatile EC detector sensitive materials. Genotoxic analysis of the extracts was performed using the MFO-Induct Test and mutagenicity testing using the Standard Plate Incorporation Test as described by Maron and Ames with Salmonella typhimurium TA 98. Measurement of the BaPMO enzyme activity in the livers of carp treated i.p. with total extracts of the sediment investigated confirmed that the methanol extracts generally contained more inducing matter than the petroleum ether extracts. Ames assay showed that for all the samples following the elimination of the sulfur, there was an increase in the number of revertants in comparison to the control number, which indicates that the samples contained mutagenic substances. The larger doses of extracts generally demonstrated cytotoxicity, as evidenced by a reduced number of spontaneous revertants in the Salmonella/Microsome Test. Investigation of the correlation of the chemical parameters with the biological parameter showed that the induction of BaPMO exhibited a statistically significant correlation with the level of the ECD fingerprint of the petroleum ether sediment extract.     

The velocity of DNAPL fingering in water-saturated porous media: laboratory experiments and a mobile–immobile–zone model

Dense nonaqueous phase liquids (DNAPLs) are immiscible with water and can give rise to highly fingered fluid distributions when infiltrating through water-saturated porous media. In this paper, a conceptual mobile–immobile–zone (MIZ) model is presented to describe the structure of a DNAPL finger in water-saturated porous media and the velocity of finger propagation. A finger is composed of a finger body and a tip. The finger body has a mobile core and an immobile sheath. All the DNAPL within the tip of a finger is mobile. Lab experiments utilizing image analyses of a DNAPL (PCE) penetrating into water-saturated homogeneous glass beads were carried out in a two-dimensional transparent chamber. The results show that the fingers elongated almost linearly with time. The fingers did not grow laterally after the tip of the finger had passed. The average finger diameters were between 3.9 and 5.4 mm for PCE propagation in water-saturated glass bead porous media with mean particle diameters from 0.32 to 1.36 mm. The estimated mobile core diameters were 51–60% of the average finger diameters.     

Free ‐ living animals as indicators of environmental pollution by chlorinated hydrocarbons

As some species of game and free‐living animals promptly respond to ecosystem damage by a reaction that is easy to interpret, they are important ecological indicators in assessing the total contamination of the environment. Consumers of the highest order like predators, predatory and fish‐eating birds are among the most important bioindicators of environmental contamination by chlorinated hydrocarbons and PCB.

Data on chlorinated hydrocarbons and PCB levels were collected throughout 1988–1992 and obtained from 16 species of free‐living animals from 9 protected areas of Slovakia. Muscle tissue, liver, kidney and egg samples were examined for HCB, HCH isomers, DDT and its analogues, and PCB.

Levels of organic chlorinated contaminants reveal a decreasing tendency and thus cease to be a toxicologically important risk factor in game, with the exception of predatory birds, as significant values have been recorded in their eggs and reproductive organs.     

A History of Dry Cleaners and Sources of Solvent Releases from Dry Cleaning Equipment

Approximately 25, 000-35, 000 dry cleaning facilities currently operate in the U.S. The release of perchloroethylene and other solvents from these establishments represents a major source of soil and groundwater contamination. The manner in which dry cleaning solvents escape from dry cleaning plants is, for all practical purposes, identical for chlorinated and petroleum hydrocarbon solvents and is related to one of the following events: the catastrophic failure of a component of the dry cleaning system, the improper installation, operation or maintenance of the dry cleaning equipment or a combination of all of these causes. Acceptable customs, codes and regulations can also dictate what is authorized for operation of a dry cleaning facility in a particular community, geographic area during a particular time frame. Environmental litigation dealing with the origin of a solvent release from dry cleaners tends to focus on the design and manufacture of dry cleaning industry machines such as washers, washer extractors, tumblers, solvent filters, water separators, stills and spotting boards. A thorough analysis of the daily operations of dry cleaners often reveals that poor maintenance, failure to follow the manufacturer's instructions and the actions of the operator are the most likely causes of soil and groundwater pollution. In order to forensically evaluate the most probable origins of a solvent release and to examine issues regarding liability, a thorough understanding of the history of dry cleaning and a detailed analysis of the operation and maintenance of the dry cleaning equipment are necessary. The discovery of solvent plumes in the vicinity of dry cleaning plants may suggest that the solvent source is the dry cleaning plant; however, the presence of these plumes does not necessarily indicate that the dry cleaning equipment was defectively designed or manufactured. A thorough review of the type of equipment used over the life of the dry cleaning plant and verifiable solvent mileage records frequently indicates that operators of the plant have disposed of solvent and contaminated solids into the municipal sewer or on ground surfaces.     

Was Contamination of Southern California Groundwater By Chlorinated Solvents Foreseen?

The historical record does not support the argument that the cause of widespread groundwater contamination by chlorinated solvents in southern California was an inability to anticipate or detect the problem. The propensity of industrial wastes, including chlorinated solvents, to contaminate groundwater was understood by the 1940s in southern California. This understanding was not limited to a small group of specialists, but extended to regulators, industry, and the interested public. Industrial waste disposal was deregulated in 1949 as a result of lobbying by industry, despite a warning from the director of the State Health Department that such action would create "a backlog of water pollution over the State that will constitute a plague comparable to the air pollution in Los Angeles". Regulators warned specifically about the danger that groundwater pollution in the San Fernando and San Gabriel valleys would result from improper disposals of industrial chemicals, and solvents were identified as major contaminants in the scientific literature. Analytical methods to detect chlorinated solvents in groundwater at the concentrations found near the DNAPL (dense non-aqueous phase liquids) source zones have been well known since at least 1950, and a method with a detection limit of 10 w g/L was published as early as 1953.     

Assessment of aquatic experimental versus predicted and extrapolated chronic toxicity data of four structural analogues

The present study was developed to assess the chronic toxicity predictions and extrapolations for a set of chlorinated anilines (aniline (AN), 4-chloroaniline (CA), 3,5-dichloroaniline (DCA) and 2,3,4-trichloroaniline (TCA)). Daphnia magna 21 d chronic experimental data was compared to the chronic toxicity predictions made by the US EPA ECOSAR QSAR tools and to acute-to-chronic extrapolations. Additionally, Species Sensitivity Distributions (SSDs) were constructed to assess the chronic toxicity variability among different species and to investigate the acute versus chronic toxicity in a multi-species context.Since chlorinated anilines are structural analogues with a designated polar narcotic mode of action, similar toxicity responses were assumed. However, rather large interchemical and interspecies differences in toxicity were observed. Compared to the other three test compounds, TCA exposure had a significantly larger impact on growth and reproduction of D. magna. Furthermore, this study illustrated that QSARs or a fixed ACR are not able to account for these interchemical and interspecies differences. Consequently, ECOSAR was found to be inadequate to predict the chronic toxicity of the anilines and the use of a fixed ACR (of 10) led to under of certain species. The experimental ACRs determined in D. magna were substantially different among the four aromatic amines (ACR of 32 for AN, 16.9 for CA, 5.7 for DCA and 60.8 for TCA). Furthermore, the SSDs illustrated that Danio rerio was rather insensitive to AN in comparison to another fish species, Phimphales promelas. It was therefore suggested that available toxicity data should be used in an integrative multi-species way, rather than using individual-based toxicity extrapolations. In this way, a relevant overview of the differences in species sensitivity is given, which in turn can serve as the basis for acute to chronic extrapolations.     

Determination of chlorinated paraffins in sediments from the Firth of Clyde by gas chromatography with electron capture negative ionisation mass spectrometry and carbon skeleton analysis by gas chromatography with flame ionisation detection

Short chain chlorinated paraffins (SCCPs) are a group of persistent organic pollutants (POPs) of increasing concern, but are to date not widely investigated in the environment, largely due to the challenges involved in their quantification. Here, SCCPs were quantified in marine sediments from the Firth of Clyde, Scotland, by gas chromatography with electron capture negative ionisation mass spectrometry (GC-ECNIMS) and through carbon skeleton analysis by gas chromatography with flame ionisation detection (GC-FID), and the analytical challenges encountered are discussed. Concentrations in the sediments ranged from 0.4 to 69 μg kg⁻¹ when determined by GC-ECNIMS, and from 5.6 to 379 μg kg⁻¹ when determined by GC-FID. For 8 out of 11 samples, analysis by GC-FID gave higher results than analysis by GC-ECNIMS. Unexpected aspects of the analysis, such as the presence of high concentrations of longer chain chlorinated paraffins in the samples, are also presented.     

The polymorphism of the human serum paraoxonase †

The activity of paraoxonase, the enzyme which hydrolyses paraoxon, 0,0‐diethyl‐0–4‐nitrophenylphosphate, in human serum shows a genetically determined polymorphism with strong interethnic differences. The serum paraoxonase genotype has a significant influence on the paraoxon clearance. Individuals with high serum paraoxonase activity may be better protected against the toxic effects of parathion (0,0‐diethyl‐0–4‐nitrophenylthiophosphate).

In Caucasians the polymorphism is governed by two alleles. The first allele has a gene frequency p _low of 0.67 to 0.78, and is manifested in both the form of a first homozygotic group with low activities and a second heterozygotic group with medium activities. About 50% of all Europeans belong to the low activity group. The second allele with a gene frequency q _high of 0.22 to 0.33 is manifested in the second heterozygotic and a third homozygotic group with medium resp. high activities. The Hardy‐Weinberg rule for a two allele model is valid for the distribution.

The percentage of the low activity group decreases as one moves from Europe to Africa and Asia. In most of the Mongoloids and Negroids only 5 to 20% of the population can be included in the low activity group, which is not even demonstrable in Aborigines, Maoris, Tonga and some African and Indian (Central America) tribes. The validity of the Hardy‐Weinberg rule for a two‐ or three‐allele model must be rejected in non‐Caucasians.     

Microbial responses to combined oxidation and catalysis treatment of 1,4-dioxane and co-contaminants in groundwater and soil

Post-treatment impacts of a novel combined hydrogen peroxide (H₂O₂) oxidation and WO_x/ZrO₂ catalysis used for the removal of 1,4-dioxane and chlorinated volatile organic compound (CVOC) contaminants were investigated in soil and groundwater microbial community. This treatment train removed ~90% 1,4-dioxane regardless of initial concentrations of 1,4-dioxane and CVOCs. The Illumina Miseq platform and bioinformatics were used to study the changes to microbial community structure. This approach determined that dynamic shifts of microbiomes were associated with conditions specific to treatments as well as 1,4-dioxane and CVOCs mixtures. The biodiversity was observed to decrease only after oxidation under conditions that included high levels of 1,4-dioxane and CVOCs, but increased when 1,4-dioxane was present without CVOCs. WO_x/ZrO₂ catalysis reduced biodiversity across all conditions. Taxonomic classification demonstrated oxidative tolerance for members of the genera Massilia and Rhodococcus, while catalyst tolerance was observed for members of the genera Sphingomonas and Devosia. Linear discriminant analysis effect size was a useful statistical tool to highlight representative microbes, while the multidimensional analysis elucidated the separation of microbiomes under the low 1,4-dioxane-only condition from all other conditions containing CVOCs, as well as the differences of microbial population among original, post-oxidation, and post-catalysis states. The results of this study enhance our understanding of microbial community responses to a promising chemical treatment train, and the metagenomic analysis will help practitioners predict the microbial community status during the post-treatment period, which may have consequences for long-term management strategies that include additional biodegradation treatment or natural attenuation.

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