A novel sensor for monitoring leakage of petroleum and other liquid hydrocarbons into soil environments

This paper describes the use of a potentially implantable infrared reflectometer for the qualitative detection of petroleum and a number of other hydrocarbon solvents. A rugged, low-power, re-useable sensor was evaluated in the laboratory for its ability to detect petrol in soil. A hydrophobic fluoropolymer was used as the sensing surface due to its high selectivity for petroleum hydrocarbons. The photocurrent reflected by this surface from a near IR source was measured to test for petroleum saturation within the membrane, which in turn was an indicator of petroleum in the surrounding soil. The simplicity in the sensor design enabled a stable, low cost detection method for petroleum and other hydrocarbons, ideal for use in sub-surface applications.     

Transportation and fate of cationic surfactant in river water

The degradation, sorption, transportation and material balance of cationic surfactants discharged from domestic waste into river water was studied. Ion-pair solid-phase extraction behavior showed that the sorption of cationic surfactants as an ion-pair with anionic surfactant onto river sediment was so strong that little cationic surfactant was found in the bulk water. Cationic surfactant was found in river sediment at more than 500 times higher concentration than that in the bulk water. The degradation of the cationic surfactant was very slow in river water and much slower in the sediment. A material balance of cationic surfactant was estimated for a river running through Toyama City by measuring the flow rate and the concentration of cationic surfactant in the water at several points. It was found that more than 30% of cationic surfactant introduced to the river was lost during the river running through ca. 3 km in 3 h. This reduction probably comes from a quick transfer of the cationic surfactant from river water to sediment and water weed by means of adsorption or precipitation with suspending solids.     

Persistent chlorinated pesticides in fish and cattle fat and their implications for human serum concentrations from the Sene-Gambian region

The concentrations of organochlorine pesticides (OCPs) in fish, shrimps, cattle fat and human serum samples from the Sene-Gambian region were measured using validated analytical methodologies. The results obtained were compared with those of other existing African studies and with data from other developing countries. In fish samples, p,p'-dichlorodiphenyldichloroethylene (p,p'-DDE) and HCB were detected with a frequency of 100%, whereas p,p'-dichlorodiphenyltrichloroethane (p,p'-DDT) was detected in eight, heptachlorepoxide in six and endosulfansulfate in five of the nine fish samples. Relatively low concentrations of OCPs were found in cattle and shrimp fat samples. p,p'-DDE and alpha-hexachlorocyclohexane (alpha-HCH) were the most frequently identified. The sum of HCHs ranged from undetected to 13.3 ng g-1 fat, the sum of DDTs from 11.1 to 199.2 ng g-1 fat and the sum of endosulfans from not detected to 49.7 ng g-1 fat in fish and shrimps. In serum samples, alpha-HCH, p,p'-DDE, o,p'-DDT and p,p'-DDT were detected in all 16 pooled serum samples, whereas endosulfansulfate, methoxychlor, mirex, heptachlorepoxide and endrin were detected in 15 samples with most of the concentrations below 10 ng mL-1. The concentrations of OCPs in human serum were given on a serum lipid and whole serum volume basis. The implications for the human diet of these OCP concentrations in serum were investigated by means of biomagnification factors related to the log Kow values of the targeted compounds. The current use of HCH mixtures was suggested to explain the unusually high alpha-HCH concentration. The distribution pattern of these OCPs in humans was also discussed and compared with that in other studies.     

Partitioning of mercury onto suspended sediments in estuaries

Radiochemical partitioning experiments using 203Hg have been undertaken with mixtures of river, seawater and sediment samples taken from three geochemically contrasting UK estuaries: the Plym, Beaulieu and Mersey. Species of dissolved Hg were determined using reversed-phase C18 chelating columns and particulate species were determined by sequential leaching with 1 M NH4OAc and 1 M HCl. Mercury had a high particle reactivity with partition coefficients, KDs, ranging from 10(4) to 5 x 10(5) ml g(-1), depending on salinity, the chemical composition of the end-member waters, and on the physico-chemical characteristics of the sediment. Dissolved organic matter present in the waters (humic substances and/or anthropogenic compounds) was found to be the main factor governing the forms of dissolved Hg and their reactivity. From the spiked 203Hg, up to 95% of the dissolved metal was retained on the C18 columns for the Mersey waters, whereas this fraction was < 60% in the Plym and Beaulieu waters. Quasi-irreversible adsorption of Hg onto particles from each estuary was observed over a time-scale of a few hours and < 20% of total particulate Hg was released by the sequential leach. In this paper, physico-chemical processes are proposed to explain the estuarine behaviour of Hg and the results are discussed in terms of Hg availability in estuarine systems.     

SI-traceable certification of Cu, Cr, Cd and Pb in sediment and fly ash candidate reference materials

Many fields in environmental analytical chemistry deal with very low limits and thresholds as set by governmental legislations or transnational regulations. The need for the accuracy, comparability and traceability of analytical measurements in environmental analytical chemistry has significantly increased and total uncertainties are even asked for by accreditation bodies of environmental laboratories. This paper addresses achieving these goals to guarantee accuracy, quality control, quality assurance or validation of a method by means of certified reference materials. The assessment of analytical results in certified reference materials must be as accurate as possible and every single step has to be fully evaluated. This paper presents the SI-traceable certification of Cu, Cr, Cd and Pb contents in geological and environmentally relevant matrices (three sediments and one fly ash sample). Certification was achieved using isotope dilution (ID) ICPMS as a primary method of measurement. In order to reduce significantly the number of analytical steps and intermediate samples a multiple spiking approach was developed. The full methodology is documented and total uncertainty budgets are calculated for all certified values. A non-element specific sample digestion process was optimised. All wet chemical digestion methods examined resulted in a more or less pronounced amount of precipitate. It is demonstrated that these precipitates originate mainly from secondary formation of fluorides (essentially CaF2) and that their formation takes place after isotopic equilibration. The contribution to the total uncertainty of the final values resulting from the formation of such precipitates was in general < 0.1% for all investigated elements. Other sources of uncertainty scrutinised included the moisture content determination, procedural blank determination, cross-contamination from the different spike materials, correction for spectral interferences, instrumental background and deadtime effects, as well as the use of either certified values or IUPAC data in the IDMS equation. The average elemental content in the sediment samples was 30-130 micrograms g-1 for Pb, 0.5-3 micrograms g-1 for Cd and 50-70 micrograms g-1 for Cu. Cr was measured in one sample and was about 60 micrograms g-1. The concentrations in the fly ash sample were up to 2 orders of magnitude higher. Expanded uncertainty for the investigated elements was about 3% (coverae factor k = 2) except for Cr, (measured by high resolution ICPMS), for which the expanded uncertainty was about 7% (k = 2).     

Using Multiple Antibiotic Resistance and land use characteristics to determine sources of fecal coliform bacterial pollution

Multiple Antibiotic Resistance (MAR) analysis and regression modeling techniques were used to identify surface water areas impacted by fecal pollution from human sources, and to determine the effects of land use on fecal pollution in Murrells Inlet, a small, urbanized, high-salinity estuary located between Myrtle Beach and Georgetown, South Carolina. MAR analysis was performed to identify areas in the estuary that are impacted by human-source fecal pollution. Additionally, regression analysis was performed to determine if an association exists between land use and fecal coliform densities over the ten-year period from 1989 to 1998. Land-use variables were derived using Geographic Information System (GIS) techniques and were used in the regression analysis.MAR analyses were conducted by comparing the frequency and patterns of antibiotic resistance found in Escherichia coli isolates derived from surface water samples and from sewage sources in the Murrells Inlet sewage collection system. The MAR results suggest that the majority of the fecal pollution detected in the Murrells Inlet estuary may be from non-human sources, including fecal coliforms isolated from areas in close proximity to high densities of active septic tanks.A MAR Index, which measures the frequency of antibiotic resistance, was calculated for each of twenty-three water samples and nine sewage samples. The antibiotic resistance pattern comparisons were performed using cluster analysis. Although the MAR indices indicated that several surface water sites had potential human-source contamination, the cluster analysis suggests that only one sampling site had MAR patterns that were similar to those found in the sewage samples. This site was in close proximity to several large pleasure boats as well as a sewage collection system lift station, but was not near areas with active septic tanks. The results of the regression analysis also suggest that sewage sources and rainfall runoff from urbanized areas may contribute to fecal pollution in the estuary.     

IMPACTS OF VISITORS ON SOIL AND VEGETATION OF THE RECREATIONAL AREA “NACIMIENTO DEL RÍO MUNDO” (CASTILLA-LA MANCHA, SPAIN)

This study examines the effects of recreational use on the soil and vegetation at a site of ecological importance (Nacimiento del Río Mundo, Albacete, Spain). The most visited sites showed increased soil compaction of approximately 50%, bare ground increase to 61 ± 10% and a decrease in richness (from 25 ± 2 to 15 ± 2 species), diversity (from 4.0 ± 0.1 to 2.7 ± 0.4) and stratification of plant species (from 80 ± 11 to 21 ± 4%). The most visited sites had 90% less plant species as compared to the least visited. Intense use was associated with the presence of nitrophilous plant and vegetal species with a morphology adapted to heavy trampling. The recreational areas showed a distribution pattern of impact radiating outwards from the most used and degraded point. At the most visited point, Los Chorros (the spring of the river), the impact radiated outwards for about 20 m. A pilot experiment examining the effects of one-year restriction to visitors for access to a formerly impacted area showed a plant cover increase by anthropic and not by native species of 57 percent units.     

Assessment of Metal Contamination in Doñana National Park (Spain) using Crayfish (Procamburus Clarkii)

Water quality assessment in the Aznalcollar area was attempted using multivariate methods based on heavy metal concentrations in red swamp crayfish (Procamburus clarkii). Trace levels of four heavy metals, copper (Cu), zinc (Zn), cadmium (Cd) and lead (Pb), were detected in crayfish from eleven different stations. Principal component analysis (PCA) highlighted a gradient of contamination between the sampling stations. Cluster analysis (CA) distinguished three groups of stations. Discriminant analysis also differentiated three groups. The group centroids of the first discriminant function were used to devise an index that varies according to the source of the crayfish. These standardized values are proposed for use as a water quality index. The ability of this index to successfully predict environmental quality was proved with random samples.     

Responses of Gammarus pulex (Amphipoda, Crustacea) to metalliferous effluents: identification of toxic components and the importance of interpopulation variation

This study was designed to evaluate the ability of an in-situ bioassay to assess the impact of complex effluents on freshwaters and to identify toxic components. Reductions in the feeding rate of Gammarus pulex proved to be a sensitive indicator of the impact of metalliferous effluents on receiving water quality. The effluents contained a mixture of five potentially toxic metals. By combining information on feeding rates with bioaccumulation data, two metals, iron and manganese, were identified as the probable toxic agents. Laboratory experiments validated the conclusions reached from the field study and confirmed that iron was a major toxicant. The sensitivities of Gammarus pulex from a metal-contaminated site and a clean site were compared during both the field and laboratory studies. Interpopulation differences in the response of G. pulex to toxicants were detected in the field study but not in the laboratory experiments. Possible reasons for this are discussed.