A detailed field-based evaluation of naphthenic acid mobility in groundwater

An anaerobic plume of process-affected groundwater was characterized in a shallow sand aquifer adjacent to an oil sands tailings impoundment. Based on biological oxygen demand measurements, the reductive capacity of the plume is considered minimal. Major dissolved components associated with the plume include HCO₃, Na, Cl, SO₄, and naphthenic acids (NAs). Quantitative and qualitative NA analyses were performed on groundwater samples to investigate NA fate and transport in the subsurface. Despite subsurface residence times exceeding 20 years, significant attenuation of NAs by biodegradation was not observed based on screening techniques developed at the time of the investigation. Relative to conservative tracers (i.e., Cl), overall NA attenuation in the subsurface is limited, which is consistent with batch sorption and microcosm studies performed by other authors. Insignificant biological oxygen demand and low concentrations of dissolved As (< 10 µg L^− 1) in the plume suggest that the potential for secondary trace metal release, specifically As, via reductive dissolution reactions driven by ingress of process-affected water is minimal. It is also possible that readily leachable As is not present in significant quantities within the sediments of the study area. Thus, for similar plumes of process-affected groundwater in shallow sand aquifers which may occur as oil sands mining expands, a reasonable expectation is for NA persistence, but minimal trace metal mobilization.     

Sorption of alkylphenols on Ebro River sediments: comparing isotherms with field observations in river water and sediments

This study reports sorption isotherms of the endocrine disruptors nonylphenol (NP) and octylphenol (OP) in three sediment samples from the Ebro River basin (NE Spain), with organic carbon fractions (f_OC) ranging from 0.0035 to 0.082 g_OC g⁻¹. All isotherms were fitted to the Freundlich model with slightly nonlinear exponents ranging from 0.80 to 0.94. The solubility of the compounds as well as the organic carbon (OC) content had the strongest influences on the sorption behavior of these compounds. Comparison of the laboratory-spiked samples with the native contamination of NP of 45 water and concurrent sediment samples resulted in reasonable matches between both data sets, even though the lowest concentrations in the field were not completely reached in laboratory tests. This good agreement indicates that sorption laboratory data can be extrapolated to environmental levels and therefore the distribution of nonylphenol between sediments and water can be predicted with a precision of one order of magnitude. Furthermore, laboratory experiments with simultaneous loading of NP and OP revealed negligible competition for sorption sites at low concentrations.     

Age-dating Diesel Fuel Spills: Using the European Empirical Time-based Model in the U.S.A.

In 1993, a paper was published by Christensen and Larsen that offered a method for determining the age of diesel oil spills in soil (Christensen and Larsen, 1993 Ground Water Mount. R . Fall , 142-149). It presented an empirical time-based model of the degradation of diesel fuel in soils using chemical data gathered at petroleum release sites in Denmark and the Netherlands. Now, evaluation of the validity of the application of this work to subsurface petroleum releases in other countries remains. In the U.S.A., investigations assessing date(s) of release of diesel fuel in soils, e.g. age dating of subsurface petroleum contamination, have considerable interest. Litigation-driven scientific investigations with accompanying expert testimony in a court of law are underway. The number of instances where application of the Christensen and Larsen empirical time-based model to petroleum-contaminated properties is growing in the U.S.A. This paper presents two case studies which evaluate the applicability of the Christensen and Larsen empirical time-based model to petroleum-contaminated properties in general. It illustrates the approach using gas chromatographic data from two recently-completed projects evaluating the applicability of the Christensen and Larsen model to a No. 2 fuel oil/diesel fuel surface spill in the U.S.A. Results showed that the application of the model to petroleum-contaminated soils was scientifically valid, provided its applicability was evaluated using hypothesis testing for specific changes in the characteristics of the petroleum hydrocarbon distribution in a number of soil samples collected over time at one site. The paper offers observations on the application of the Christensen and Larsen model to petroleum found in the light non-aqueous phase liquid (LNAPL) phase and groundwater.     

Round Robin Study--Oil Spill Identification

As part of the ongoing work to develop new guidelines for oil spill identification for the European Committee for Standardization (CEN), a Round Robin test was arranged by SINTEF in co-operation with the Norwegian General Standardizing Body (NAS). Twelve laboratories from ten countries participated in the Round Robin study. They include: Denmark, Finland, France, Germany, the Netherlands, Norway, Scotland, Sweden, Wales, and the U.S.A. The analytical methodology used for the Round Robin testing is a result of the ongoing project "Revision of the Nordtest Methodology for Oil Spill Identification". The analytical methodology is described in the AMOP proceedings 2002. Seven oil samples (two artificially weathered "spill" samples and five possible sources) were analyzed following the recommended analytical protocols. The Round Robin study was a "difficult case", because the two spill samples and three of the suspected sources were highly correlated to one another. These samples were from the same oil field in the North Sea, but from different production wells. The present paper summarizes the Round Robin study, and demonstrates the potential of this methodology as a strong technically defensible tool in oil spill identification due to its ability to distinguish qualitatively similar oils from a spill and any available candidate source.     

Compositional Changes of Aromatic Steroid Hydrocarbons in Naturally Weathered Oil Residues in the Egyptian Western Desert

Naturally weathered oil residues from an arid dumpsite in Al-Alamein, Egypt were analyzed for monoaromatic and triaromatic steranes to demonstrate the utility of biomarker compounds in assessing the chemical composition changes during the degradation of the released oil residues in a terrestrial environment. The characterizations of individual aromatic compounds were based on gas chromatography/mass spectrometry (GC/MS) analyses. The results showed that triaromatic sterane distributions were similar in the oil residues of varying weathering degradation extents and correlated with a fresh crude oil sample of the Western Desert-sourced oil. Molecular ratios of triaromatic sterane compounds (ratios of C 28 20R /C 28 20S , C 27 20R /C 28 20R , and C 28 20S /[C 26 20R + C 27 20S ]) were proved to be suitable for source identification. Major changes in chemical compositions during weathering of the oil residues were the depletion of short chain mono- and tri-aromatic steranes in samples that had undergone extensive degradation. The results of triaromatic sterane distribution are in good agreement with weathering classification based on the analyses of saturate and aromatic hydrocarbons and the ratios of n -alkanes, PAHs and saturate biomarker compounds.     

Oil Identification Based on a Goodness-of-Fit Metric Applied to Hydrocarbon Analysis Results

Assessment of environmental damage following accidental oil spills requires reliable oil identification methods. Results from hydrocarbon analyses of environmental samples are often difficult to interpret, because of the changes in oil composition (or weathering) that follows release into the environment, and because of confounding by hydrocarbons from other sources. To a first-order approximation, weathering proceeds according to simple first-order loss-rate (FOLR) kinetics for polycyclic aromatic hydrocarbons (PAH) based on molecular size. This relationship between relative weathering rate and molecular size can be exploited to infer the initial PAH composition of spilled oils, and this information can be combined with results for weathering-invariant analytes to substantially increase the precision and accuracy of hydrocarbon source recognition methods. The approach presented here evaluates a goodness-of-fit metric between the measured hydrocarbon composition of an environmental sample and a suspected source, after correcting for PAR weathering losses based on FOLR kinetics. Variability from analytical and sampling error may thus be accounted for, and source identifications can be expressed as objective probability statements. This approach is illustrated by application to four independent case studies.     

Chlorinated solvents in a petrochemical wastewater treatment plant: an assessment of their removal using self-organising maps

The self-organising map approach was used to assess the efficiency of chlorinated solvent removal from petrochemical wastewater in a refinery wastewater treatment plant. Chlorinated solvents and inorganic anions (11 variables) were determined in 72 wastewater samples, collected from three different purification streams. The classification of variables identified technical solvents, brine from oil desalting and runoff sulphates as pollution sources in the refinery, affecting the quality of wastewater treatment plant influent. The classification of samples revealed the formation of five clusters: the first three clusters contained samples collected from the drainage water, process water and oiled rainwater treatment streams. The fourth cluster consisted mainly of samples collected after biological treatment, and the fifth one of samples collected after an unusual event. SOM analysis showed that the biological treatment step significantly reduced concentrations of chlorinated solvents in wastewater.     

Chromium speciation in river sediment pore water contaminated by tannery effluent

Cr(VI) is far more soluble and toxic than Cr(III). Sediment pore water was investigated in a river adjacent to the property of a large former tannery, into which Cr-contaminated effluent was discharged over a 55-year period, and where extremely high Cr concentrations have been found in the sediments. Dialysis cells, or peepers, were used to generate depth profiles of Cr concentration in sediment pore water. Samples were analyzed for total Cr using inductively coupled plasma-mass spectrometry (ICP-MS) and for Cr species using high performance liquid chromatography (HPLC)-ICP-MS. The results show an absence of Cr(VI) in all samples. Furthermore, incomplete recovery of Cr(VI) added to the samples collected at the locations with highest sediment Cr concentrations indicate strong reducing conditions at those locations, which are not conducive to the presence of Cr(VI).     

Identification of priority pharmaceuticals in the water environment of China

In recent years, increasing attention has been paid to the trace-level contamination of pharmaceuticals in the water environment all over the world. Considering a large number of pharmaceuticals used, it is crucial to establish a priority list of pharmaceuticals that should be monitored and/or treated first. In the present study, we developed a ranking system based on the pharmaceutical consumption, removal performance in the wastewater treatment plants (WWTPs) and potential ecological effects, and applied to the situation of China. 39 pharmaceuticals, which had available consumption data and also been reported previously in the WWTPs of China, were selected as candidate pharmaceuticals. Among them, seventeen pharmaceuticals were considered as priority pharmaceuticals, out of which, erythromycin, diclofenac acid and ibuprofen, had the high priority. Compared with other literatures, we found that some pharmaceuticals given concerns to globally should also be included in the priority list in China; while some pharmaceuticals, not mentioned in other literatures, such as cefalexin, ketoconazole, should be also given prior consideration in China. Among all the therapeutic classes, antibiotics, which were grossly abused in China, contributed the most to the priority pharmaceuticals. However, priority antibiotics accounted for only 32% of candidate antibiotics, while 71% and 100% of the candidate anti-inflammatory and antilipidemic respectively were identified as the priority pharmaceuticals, indicating that antibiotics might be overanxiously considered in the previous studies on their behaviors in the WWTPs of China.     

Antimicrobial activity of metal oxide nanoparticles supported onto natural clinoptilolite

The antimicrobial activity of Cu₂O, ZnO and NiO nanoparticles supported onto natural clinoptilolite was investigated in the secondary effluent under dark conditions. After 24 h of contact the Cu₂O and ZnO nanoparticles reduced the numbers of viable bacterial cells of Escherichia coli and Staphylococcus aureus in pure culture for four to six orders of magnitude and showed consistent 100% of antibacterial activity against native E. coli after 1 h of contact during 48 exposures. The antibacterial activity of NiO nanoparticles was less efficient. The Cu₂O and NiO nanoparticles showed 100% of antiprotozoan activity against Paramecium caudatum and Euplotes affinis after 1 h of contact, while ZnO nanoparticles were less efficient. The morphology and crystallinity of the nanoparticles were not affected by microorganisms. The metal oxide nanoparticles could find a novel application in the disinfection of secondary effluent and removal of pathogenic microorganisms in the tertiary stage of wastewater treatment.