Energy-dispersive X-ray fluorescence systems as analytical tool for assessment of contaminated soils

To determine the heavy metal content in soil samples at contaminated locations, a static and time consuming procedure is used in most cases. Soil samples are collected and analyzed in the laboratory at high quality and high analytical costs. The demand by government and consultants for a more dynamic approach and by customers requiring performances in which analyses are performed in the field with immediate feedback of the analytical results, is growing. Especially during the follow-up of remediation projects or during the determination of the sampling strategy, field analyses are advisable. For this purpose four types of ED-XRF systems, ranging from portable up to high performance laboratory systems, have been evaluated. The evaluation criteria are based on the performance characteristics for all the ED-XRF systems such as limit of detection, accuracy and the measurement uncertainty on one hand, and also the influence of the sample pretreatment on the obtained results on the other hand. The study proved that the field portable system and the bench top system, placed in a mobile van, can be applied as field techniques, resulting in semi-quantitative analytical results. A limited homogenization of the analyzed sample significantly increases the representativeness of the soil sample. The ED-XRF systems can be differentiated by their limits of detection which are a factor of 10 to 20 higher for the portable system. The accuracy of the results and the measurement uncertainty also improved using the bench top system. Therefore, the selection criteria for applicability of both field systems are based on the required detection level and also the required accuracy of the results.     

A combination of micro-porous membrane liquid-gas extraction and solid-phase trapping for ultra trace determination of benzene in urine

A method was developed for the determination of benzene in urine. The sample was pumped through the donor channel of a membrane extraction unit with a micro-porous membrane, separating the donor channel from an identical acceptor channel purged with nitrogen. The analyte reached the acceptor channel by diffusion through the membrane and was then swept by the carrier to a solid sorbent tube, where it was trapped. The analyte was subsequently thermally desorbed and analyzed by gas chromatography (GC) with mass selective detection (MS). After optimization, the recovery was close to quantitative, or 95%. Purging the membrane unit with pure water in between the samples eliminated any memory effects. The linearity was good in the concentration range examined (20-4000 ng l(-1)), with a correlation coefficient of 0.9996. The repeatability at 50 ng l(-1) and 400 ng l(-1) was 1.4% and 1.2%, respectively. The limit of detection was 12 ng l(-1) and the limit of quantification 35 ng l(-1). This enables assessment of benzene exposures of occupationally exposed subjects, of smokers and the majority of the general population. The developed method can be easily automated.     

Concentrations and profiles of polychlorinated biphenyls, -dibenzo-p-dioxins and -dibenzofurans in livers of mink from South Carolina and Louisiana,U.S.A

In South Carolina, U.S.A., mink have been reintroduced from two apparently healthy populations to areas where populations haveexisted in the past but have been extirpated. High mortality wasobserved during transport of mink from the source populations. Inorder to elucidate the potential effects of dioxin-like compoundson the survival and reproduction of mink, concentrations of totalpolychlorinated biphenyls (PCBs), p,p-DDE, dioxin-likePCBs, polychlorinated dibenzo-p-dioxins (PCDDs), anddibenzofurans (PCDFs) were measured in livers of mink collectedfrom the source populations in South Carolina and Louisiana. Concentrations of total 2,3,7,8-tetrachlorodibenzo-p-dioxinequivalents (TEQs) for the South Carolina and Louisiana mink were21 and 14 pg g^-1, wet wt., respectively. PCB and TEQ concentrations were close to the threshold values that can, under laboratory conditions, elicit toxic effects in ranchmink. Therefore, any additional exposures of these populations toTEQs might adversely affect their populations.     

Competitive Retention of Lead and Cadmium on an Agricultural Soil

Lead and cadmium contamination of an agricultural soil has been studied using batch and column experiments. Thermodynamics of theretention phenomena may be represented by a Langmuir isotherm foran aqueous metal concentration up to 100 mg L^-1. First order kinetics with respect to the solid phase yield good predictabilityfor both batch and column experiments. Kinetics and thermodynamics of lead retention predominate over those ofcadmium. As a consequence, lead is preferentially retainedand can even displace sorbed cadmium. In the event of anspill involving both metals, cadmium would move further inthe soil and its aqueous concentration downstream could beeven higher than that of the influent solution, increasingpotential risks. A two-region model has been used to fit all the experimental results. Satisfactory predictions for column experiments are obtained with parameters which are consistent with those obtained for the batch experiments, for which sorption is described by a Langmuir isotherm including competitive retention.     

Fly-ash-induced oxidative stress and tolerance in Prosopis juliflora L. grown on different amended substrates

Field experiments were conducted to study the impact of metal accumulation on malondialdehyde (MDA), cysteine and non-protein thiol (NPSH) contents in the plants of Prosopis juliflora grown on the fly ash (FA) amended with soil, blue green algae (BGA) biofertilizer, farm yard manure, press mud and Rhizobium inoculation. The analysis of data revealed that the level of MDA, cysteine and NPSH was higher in the roots of the plant than leaves, which was found positively correlated with metal accumulation. An increase of 361.14, 64.25 and 305.62% in MDA, cysteine and NPSH contents, respectively was observed after 45 days in the roots of the plants grown in 100% FA as compared to 100% garden soil (GS). The level of MDA, cysteine and NPSH was found less in the plants grown on various amendments of FA showing ameliorating effect on the toxicity induced due to the accumulation of metals. The decrease in MDA, cysteine and NPSH contents was higher in Rhizobium-inoculated plants as compared to uninoculated plants grown on 100% FA. The results showed a high tolerance potential of the plant, which is further increased by inoculating the plant with FA-tolerant Rhizobium showing feasibility of using P. juliflora in environmental monitoring of FA landfills.     

Extractive Spectrofluorometric Determination of Quinalphos Using Fluorescein in Environmental Samples

A simple, sensitive, convenient and low cost spectrofluorometric technique for determination of quinalphos is described. Quinalphos is decomposed with sodium ethoxide. Resultant sodium diethyl thiophosphate (Na-DETP) is extracted with a cationic fluorescein as ion pair complex into 1-chloro-2-nitrobenzene. The fluorescence of the ion pair, fluorescein-DETP is measured at 530 nm after excitation at 490 nm. This technique is applicable for the determination of quinalphos in water, food grains and vegetable samples up to ng level with Amberlite XAD-4.     

Determination of pollution trends in an abandoned mining site by application of a multivariate statistical analysis to heavy metals fractionation using SM&T-SES

The mobility, availability and persistence of Heavy Metals (HMs), As, Cd, Cu, Ni, Pb and Zn, in contaminated soils of a former abandoned mining area were evaluated by means of a sequential extraction scheme (SES) and applying a multivariate statistical analysis to the obtained data. Chemical partitioning of HMs in each sample was determined in four fractions (acid-soluble, reducible, oxidable and residual) following the Standard Measurements and Testing (SM&T) SES, formerly BCR-SES. Statistical evaluation of results by pattern recognition techniques allowed identification of groups of samples with similar characteristics and observations of correlations between variables, determining the pollution trends and distribution of HMs within the studied area. Typical metal-fraction association and metal availability characteristics of heavy metals have been depicted. The obtained results indicate an urgent need to attenuate the hazard in that area posed by high concentrations of toxic metals, which exceed the limits specified by different European legislations on soil reclamation.     

One-year monitoring survey of organic compounds (PAHs, PCBs, TBT), heavy metals and biomarkers in blue mussels from the Arcachon Bay, France

Marine mussels Mytilus sp. were transplanted on a monthly basis in cages over one year to oyster farms and harbours in the Arcachon Bay (France) in order to assess the water quality of the bay. Contaminant levels (organotin compounds, trace metals, PCBs and PAHs) were measured in tissues of transplanted mussels and mussels from a reference station, along with physiological parameters of the mussels (condition indexes, lipid content and dry weight). Four biomarkers (AChE: acetylcholinesterase activity, GST: gluthathione S-transferase activity, CAT: catalase activity and TBARS: thiobarbituric acid-reactive substance content) were also monitored. The remote stations monitored (oyster parks) exhibited no accumulation pattern of pollutants. Their respective concentrations therefore constitute a background level of the contamination in the bay ([TBT]= 30 ng Sn g(-1) dw, [SigmaHAPs]= 100 ng g(-1) dw, [SigmaPCBs]= 35 ng g(-1) dw). The elevated chemical contamination of the largest harbour of the bay, the Arcachon harbour, can be interpreted in terms of persistence of organotin compounds ([SigmaOTs]= 1500-2000 ng Sn g(-1) dw) and PAHs ([SigmaHAPs]= 4500-5000 ng g(-1) dw) in sediments and, to a lesser extent, of direct inputs of copper ([Cu]= 20 microg g(-1) dw in harbours versus 7 in oyster parks) and petrogenic PAHs ([methylphenanthrenes]= 1600 ng g(-1) dw in the dockyard versus 170 at the gas stations), related to the use of copper-based antifouling paints and to dockyard activity, respectively. However, the Arcachon Bay presents a low contamination level by PCBs and metals, including harbour stations. Furthermore, higher levels of other PAHs (particularly alkyl PAHs such as methylphenanthrenes/1600 ng g(-1) dw) not included in the 16 PAHs from the EPA priority list (usually studied in biomonitoring programmes/1500 ng g(-1) dw) in the Arcachon harbour underline the need to integrate these compounds in biomonitoring of highly PAH-polluted areas such as harbours in order to avoid misinterpretation of the biological responses observed. Biomarker responses were not able to discriminate the different chemical contamination levels recorded in the Arcachon Bay and rather reflected changes in environmental factors. Furthermore, the strong intraspecies variability of biological responses could be due to genetic differences of mussels from the Arcachon Bay. It is the first time that such an integrated monitoring is performed in the Arcachon Bay, also taking into account seasonal variations of chemical contents and biomarkers levels in mussel tissues.     

Exposure and inhalation risk assessment in an aluminium cast-house

To date the exposure, absorption and respiratory health effects of cast-house workers have not been described since most studies performed in the aluminium industry are focused on exposure and health effects of potroom personnel. In the present study, we assessed the external exposure and the absorbed dose of metals in personnel from the aluminium cast house. This was combined with an evaluation of respiratory complaints and the lung function of the personnel. 30 workers from an aluminium casting plant participated and 17 individuals of the packaging and distribution departments were selected as controls. The exposure was assessed by the quantification of total inhalable fume with metal fraction and by the determination of urinary aluminium, chromium, beryllium, manganese and lead concentration. Carbon monoxide (CO), carbon dioxide (CO2), aldehydes and polyaromatic hydrocarbons and man-made mineral fibres concentration were assessed as well. In order to evaluate their respiratory status each participant filled out a questionnaire and their lung function was tested by forced spirometry. Total inhalable fume exposure was maximum 4.37 mg m(-3). Exposure to the combustion gases, man-made mineral fibres and metal fume was well below the exposure limits. Beryllium could not be detected in the urine. The values of aluminium, manganese and lead in the urine were all under the respective reference value. One individual had a urinary chromium excretion above the ACGIH defined biological exposure index (BEI) of 30 microg g(-1) creatinine. There was no significant difference in any of the categories of the respiratory questionnaire and in the results of the spirometry between cast house personnel and referents (Chi-square, all p > 0.05). Exposure in cast houses seem to be acceptable under these conditions. However, peak exposure to fumes cannot be excluded and the potential risk of chromium and beryllium exposure due to the recycling of aluminium requires further attention.     

A framework for assessment and monitoring of arthropods in a lowland tropical forest

By applying principles of adaptive management, and by using the valuable information that arthropods provide from assessment and monitoring programs, managers can identify and reduce possible impacts on biodiversity in development projects. In 1996, the Smithsonian Institution's Monitoring and Assessment of Biodiversity program worked together with Shell Prospecting and Development Peru to establish an adaptive management program to protect biodiversity in a natural gas exploration project in a Peruvian rainforest. In this paper, we outlined the conceptual steps involved in establishing an assessment and monitoring program for arthropods, including setting objectives, evaluating the results and making decisions. We also present the results of the assessment using some of groups of arthropods, and summarize the steps taken to identify appropriate groups for monitoring.