Determination of time-dependent partition coefficients for several pesticides using diffusion theory

Diffusion-retarded partitioning of pesticides with aggregated soils results in a time-dependent partition coefficient (Kd') which is different at equilibrium from the partition coefficient derived from conventional 24-h batch studies (Kd) measured on dispersed soil. An experiment was undertaken to determine the importance of Kd' for the prediction of pesticide concentrations in solutions bathing artificial soil aggregates and to determine whether diffusion theory could accurately predict the concentrations. Two clay soils were mixed with polyacrylamide to create artificial aggregates of 0.8, 1.4 and 1.7 cm diameter when dry. After saturation, the aggregates were immersed in solutions containing isoproturon or a mixture of isoproturon, chlorotoluron and triasulfuron. The decline with time of the pesticide concentrations in the bathing solution was monitored and the results were compared with predictions from a diffusion-based model. The effective diffusion coefficients of the compounds were obtained by either fitting the non-linear diffusion model to the data (D(ef)) or by independent calculations based on the properties of the compounds and of the aggregates (D(ec)). The diffusion model was able to predict the temporal variation in pesticide concentrations in the bathing solution reasonably well whether D(ef) or D(ec) values were used. However, equilibrium concentrations in solution were sometimes overestimated due to increased sorption with time at the particle scale. Overall, the ratio between D(ef) and D(ec) ranged from 0.23 to 0.95 which was a reasonable variation when compared to the range of aggregate sizes used in the experiments and of the Kd values of the compounds.     

A study into the parameters affecting selected reaction monitoring of 2,3,7,8-TCDD

The use of high resolution (10,000 resolving power) coupled gas chromatography - mass spectrometry is a well established technique in the analysis of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) but in the case of heavily contaminated stack samples interferences can still occur. A complementary technique that offers high specificity is selected reaction monitoring (SRM).A study has been made into the effects that affect the metastable dissociation of 2,3,7,8-TCDD in the first field free region (FFR1) of a magnetic sector mass spectrometer, and monitored using SRM.Monatomic, diatomic and polyatomic gases have been investigated in the collision chamber of the mass spectrometer, as have the effects of electron energy, source temperature and trap current on the dissociation, and optima conditions determined for them.     

Assessing the human health effects of PCBs

Toxic effects can be induced in experimental animals by high doses of pure PCBs, and in man by PCDF-contaminated PCB. In order to assess the effects of ordinary, uncontaminated PCB on man, a group of capacitor workers who had direct occupational exposure to Aroclors 1254, 1242, and 1016 during the period 1946 to 1977 has been under medical surveillance since 1976. This group presented some indications of non-AhR-mediated microsomal enzyme induction during the period of direct exposure, but no chloracne or increased cancer mortality. Multiple regression studies revealed no significant associations between lipid PCB levels and clinical indicators of hepatotoxicity, hypertension, or pulmonary impairment.     

Earthworms and radionuclides, with experimental investigations on the uptake and exchangeability of radiocaesium

The potential influence of earthworm activity on the mobility of radionuclides in soils and their subsequent availability for uptake by plants and transfer to higher trophic levels is briefly reviewed. The accumulation of caesium by the earthworm Aporrectodea longa from soil and from plant litter was investigated in laboratory experiments, as was the effect of reworking (through burrowing and ingestion) soil and soil with added organic material, on the extractability of caesium (ammonium acetate extraction). Soil was spiked with (134)Cs, organic matter with (137)Cs. In soil-fed worms, most of the radioactivity measured was eliminated with the gut contents; 5-25% of the ingested radioactivity was retained or assimilated. Loss of caesium from soil-fed worms followed a two component curve, with an initial rapid loss due to gut clearance (half-life of loss (Tb1/2) of about 0.2-0.6 days) and a slower loss of assimilated caesium (Tb1/2 of 15-26 days). Loss rates of assimilated caesium from worms fed on fragmented apple leaves were found to have half-lives of 18-54 days. Assimilation of caesium from apple leaves was higher than from soil, ranging from 55-100% of the activity measured before gut clearance. Dry weight transfer factors (concentration in worm tissue/concentration in substrate) for worms cleared of their gut contents were similar for the two substrates 0.04 and 0.04 for two loss experiments with worms fed on radioactive soil, and 0.03 and 0.05 for worms fed on apple leaves. After three months of reworking soil and soil/organic mixtures, A. longa was found to have no measurable effect on the extractable fraction of caesium. If earthworms have any subtle effects they were masked by changes in availability that occurred when the spiked soil and organic substrates were mixed together. Only about half of the extractable fraction in soil was recovered when soil was mixed with organic material suggesting that some of the labile fraction in soil had become complexed with organic material. This exchange occurred in substrate mixtures with and without worms. The limitation of chemical extraction procedures is discussed and suggestions for further work are presented.     

Issues and challenges for forest-based carbon-offset projects: A case study of the Noel Kempff climate action project in Bolivia

The Noel Kempff Climate Action Project in Bolivia, nowin its third year, is breaking ground to establishcredible and verifiable methods to quantify greenhousegas (GHG) benefits of land-use change and forestry (LUCF)projects. Developed under the United Nations FrameworkConvention Climate Change (FCCC) Activities ImplementedJointly pilot phase, the project conserves naturalforests that would otherwise have been subjected tocontinued logging and future agricultural conversion.Carbon (C) monitoring began with a C inventory of theproject area in 1997. The total amount of C in theproject area was 118 Tg (Tg = 10¹²g) ± 4%(95% confidence interval). Periodic monitoring ofrelevant C pools (occurring in 1999 and every 5 yrthereafter) occurs over the 30-year life of theproject to establish the difference between thewith-project and projected without-project scenarios. Permanent sample plots were established both insidethe project area to monitor changes in C pools overtime and in a proxy logging concession near theproject area to determine changes in C pools inforests that have been impacted by logging. Ground-based monitoring is complemented by datacollection on forest industry trends and land-usechange patterns. Remote sensing was used to developa vegetation stratification map of the area, and workis ongoing to investigate the potential application ofdual-camera aerial videography to improve theefficiency of monitoring over time.     

Water quality induced corrosion of stainless steel valves during long-term service in a reverse osmosis system

The current study analyzes the contribution of 10 water quality parameters (including pH, turbidity, conductivity, total dissolved solids (TDS), hardness, total organic carbon (TOC), alkalinity, calcium ions, chlorides and sulfates) to corrosion extent of stainless steel valves taken from different locations in a reverse osmosis system of a reclaimed water plant. The valves were in service for 5 years. Raman spectroscopy and X-ray photoelectron spectroscopy analyses are conducted to quantify corrosion products on different valves under various water quality conditions. On that basis, bivariate and multivariate regression analyses between the 10 water quality parameters and the corrosion extent of valve specimens (represented by metal loss percentage (MLP) values) are carried out to check the contribution of those water quality parameters to MLP. The results indicate that the proportions of metal oxides as corrosion products vary according to the corrosion extent of the valves. Although no linear correlation is found, all 10 water quality parameters except for pH show a significant positive correlation with the MLP values of the valve specimens. Moreover, results of multivariate regression suggest that the variation of MLP can be explained by turbidity, TDS, TOC and sulfates. A positive contribution of turbidity, TDS and TOC to MLP is observed, whereas the contribution of sulfates is negative. The results from the current work help to identify the reasons for water quality-induced failure of stainless steel equipment in RO systems.     

Mitochondrial DNA analysis of native and selectively inbred Chesapeake Bay oysters,Crassostrea virginica

Mitochondrial DNA (mtDNA) genotypes were examined in 1989 in threeCrassostrea virginica (Gmelin) populations native to Chesapeake Bay, USA, and in one population selectively inbred for rapid growth for ten generations. We wished to determine whether this character would be useful as a genetic marker for distinguishing between the inbred line and the native oysters and to determine whether detectable genetic differences exist among present-day native populations ofC. virginica. Thirty mtDNA haplotypes were identified. The average percentage nucleotide difference between native haplotypes was 1.8%. Inbred oysters were characterized by mtDNA haplotypes distinctly different from ancestral native oysters, indicating a high degree of genetic differentiation between the two groups (average percentage mtDNA nucleotide sequence divergence,=21.8%). The common native haplotype was not present in the selectively inbred sample, and six of the seven haplotypes detected in the inbred oysters were not found in the survey of native oysters. Chi-square tests on haplotype frequencies indicated that the native populations were not significantly different from one another. However, the distribution and relatedness of haplotypes suggest that significant change in the oyster gene pool may have occurred over the past few decades.