Preliminary studies of a fast screening method for polycyclic aromatic hydrocarbons in soil by using solvent microextraction-gas chromatography

Solvent microextraction (SME) was applied to the extraction of polycyclic aromatic hydrocarbons (PAHs) from spiked and real environmental soil samples with different matrices. Soil sample was mixed with 7 mL of acetone and 14 mL of water to allow partitioning of the PAHs from the soil to the liquid phase. A 2 microL octane drop suspended from a microsyringe needle tip was then immersed into the stirred solution-soil mixture for extraction. After an 11 min extraction, the octane drop was withdrawn into the syringe and injected directly into the GC for identification and quantification. The whole analysis procedure took 27 min, with an extraction time of 11 min, and a GC separation time of 16 min. A second extraction could be undertaken whilst the GC is running, hence the GC run time currently limits the sample throughput. In this method, a small amount of organic solvent was used for the extraction process, which produced little waste. The limits of detection for lower molecular weight (< 230) PAHs range from 0.13 to 0.36 mg kg-1, and for higher molecular weight (> 250) PAHs are estimated to be between 0.5 and 1.0 mg kg-1, with RSD values generally under 20%. Due to the small volumes of organic solvent used, the consumable cost per extraction is only US$ 0.12. This is the first report of the application of SME to solid samples, and the first report of the use of SME for the analysis of PAHs.     

Analysis of two-way layout of count data with negative binomial variation

A number of methods has been proposed for dealing with single-factor or factorial experiments when the requirements for performing the normal theory analysis of variance procedure are not satisfied. This paper suggests the use of the likelihood ratio statistic for testing the main effects and the interaction between the factors in two-way layout of count data following negative binomial distributions with a common dispersion parameter. The likelihood ratio statistic for testing the equality of the dispersion parameters of several groups of count data is also derived. The methods is illustrated by an example concerning the study of spatial and temporal variation of bacterial counts.     

Changes in levels of organochlorines in woodcock wings from 1971 to 1975

Wings from woodcock (Philohela minor) were first monitored for organochlorine pesticides and polychlorinated biphenyls (PCBs) in the eastern U.S. in 1971. Regional differences in these compounds were clearly demonstrated and baseline residue levels were obtained for later comparisons. An expanded sampling of wings in 1972 revealed that residues in wings of adult woodcock may differ significantly from those in immatures, and that residues of several important agricultural insecticides and PCBs had declined significantly. More extensive sampling was undertaken in 1975 to determine if changes in residue levels had taken place in the intervening years. PCBs, mirex, and heptachlor epoxide increased significantly between 1972 and 1975 in adult woodcock wings. In immature woodcock wings mirex, dieldrin, and PCBs increased significantly between 1972 and 1975, but DDT residues decreased significantly.     

Soil fauna and soil microflora as possible indicators of soil pollution

Research on biological indicators of soil pollution is hampered by soil variability and temporal and spatial fluctuations of numbers of soil animals. These characters on the other hand promote a high biological diversity in the soil. A high diversity combined with persistent soil pollutants increases the chance to select good indicators. However research on these topics is still limited. Examples of specific indicators are the changed arthropod species patterns due to pesticide influence and the changed soil enzyme activity under the influence of specific heavy metals. Another approach is to look for organisms that give a general indication of soil pollution. In this respect the earthworm species Allolobophora caliginosa proved to be sensitive for different types of manure especially pig manure with copper, for sewage sludge, for municipal waste compost and for fly ash. A third way of indication is by organisms accumulating pollutants. For some heavy metals (Cd, Zn), earthworms are very efficient accumulators. More research is needed especially on the specific relation between biological responses and abiotic soil characteristics.     

Excrement from Heron colonies for environmental assessment of toxic elements

Excrement cast from Great Blue Heron nests was collected during the nesting period of 1978 from four colonies in Washington and Idaho. Cheesecloth strips placed on the ground beneath the nests served as excrement collecting devices. Chemical analysis for lead, mercury and cadmium were performed on dried samples. Lead was the most abundant trace metal found in heron debris. The Idaho colony at Lake Chatcolet had an average concentration of 46 ppm in the beneath-nest samples and 6 ppm in control samples. A heron colony near Tacoma, Washington had beneath-nest samples averaging 28 ppm and control samples averaging 20 ppm. Two colonies located in the interior region of Washington had substantially lower concentrations of lead. The difference observed between colonies was attributed to their associations with a polluted watershed (Chatcolet colony) an interstate highway (Tacoma colony) and an unpopulated largely agricultural area (inland Washington).     

Strontium-90 in Canada goose eggshells and reed canary grass from the Columbia River,Washington

Strontium-90 (⁹⁰SR) released to the ground near the N Reactor at the U.S. Department of Energy's Hanford Site enters the Columbia River through shoreline seeps. The ⁹⁰Sr is then potentially available for uptake by plants and animals. The life history and foraging behavior of nesting Canada geese is such that female geese could ingest ⁹⁰Sr while foraging on shoreline plants. Radichemical analyses showed that goose eggshells taken from an island, downstream from the N Reactor, contained more ⁹⁰Sr than did eggshells collected from other downstream islands. Reed canary grass samples taken from shoreline areas immediately downstream from the N Reactor contained higher concentrations of ⁹⁰Sr than samples from other downstream areas. All goose eggshells did not contain enhanced levels of ⁹⁰Sr, and all reed canary grass samples did not contain enhanced levels of ⁹⁰Sr, but a relationship exists between the releases of ⁹⁰Sr to the Columbia River and the enhanced levels of ⁹⁰Sr in some of the environmental samples analyzed.Pacific Northwest Laboratory is operated by Battelle Memorial Institute for the U.S. Department of Energy under contract DE-ACO6-76RLO 1830.     

Test of a Modelling System for Estimating Nitrogen Leaching – A Pilot Study in a Small Agricultural Catchment

Nitrogen leaching is a world-wide concern for the quality of ground- and surfacewater. Measures to abate this is still limited by a lack of understanding mechanisms behind all factors describing the leaching process, time lags between countermeasures and improvement in waterquality and spatial distribution of nitrogen leaching. The purpose of this study was to do an initial test of the SOILNDB model system which is built on the existing mechanistic SOIL and SOILN models and an automatic parameterization procedure for use of simplified input data. The test was done by simulating nitrogen leaching from each of the 150 fields in a small catchment during a three-year study period. The simulated mean root-zone nitrogen leaching rate from all the fields in the catchment was compared to measurements of nitrogen flow in the stream draining the catchment and showed good agreement in between-year dynamics.     

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.     

Survey of the occurrence of residues of methyl tertiary butyl ether (MTBE) in Dutch drinking water sources and drinking water

An indicative survey has been carried out in The Netherlands investigating the presence of methyl tertiary butyl ether (MTBE) in drinking water and the corresponding sources. In total, 71 different sites used for the preparation of drinking water in The Netherlands were sampled in two successive seasons in 2001 involving the analysis of 156 samples. (ground water (n = 88), surface water (n = 17), bank filtrate water (n = 6) and drinking water (n = 45)). To combine high sample throughput with high selectivity and sensitivity, off-line purge and trap for sampling and gas chromatography mass spectrometry equipped with an automated thermal desorption sampler (TDS-GC-MS) was selected as the preferred analytical methodology. The developed procedure enabled the analysis of at least 40 samples per day and provided a limit of quantification of 2 ng l(-1). In the first period 63 samples of raw water were analyzed. Concentrations ranged between < 10 ng l(-1) and 420 ng l(-1) with a median concentration below 10 ng l(-1). The second period was focused at the re-sampling of positive locations (MTBE > 10 ng l(-1)) and a few additional drinking water utilities of which both the raw and drinking water of the utilities were analyzed. The median concentration of MTBE in the selected set of drinking water samples was 20 ng l(-1) (n = 45). At one location MTBE was found at a level of 2900 ng l(-1) caused by point source contamination of the ground water (11 900 ng l(-1)). Special attention has been paid to the quality of the results by analyzing all samples in duplicate and the analysis of control samples during each series of analyses.