Analysis of BTEX and other substituted benzenes in water using headspace SPME-GC-FID: method validation

The analysis of BTEX and other substituted benzenes in water samples using solid phase microextraction (SPME) and quantification by gas chromatography with flame ionization detection (GC-FID) was validated. The best analytical conditions were obtained using PDMS/DVB/CAR fibre using headspace extraction (HS-SPME) at 50 [degree]C for 20 min without stirring. The linear range for each compound by HS-SPME with GC/FID was defined. The detection limits for these compounds obtained with PDMS/DVB/CAR fibre and GC/FID were: benzene (15 ng L(-1)), toluene (160 ng L(-1)), monochlorobenzene (54 ng L(-1)), ethylbenzene (32 ng L(-1)), m-xylene (56 ng L(-1)), p-xylene (69 ng L(-1)), styrene (35 ng L(-1)), o-xylene (42 ng L(-1)), m-dichlorobenzene (180 ng L(-1)), p-dichlorobenzene (230 ng L(-1)), o-dichlorobenzene (250 ng L(-1)) and trichlorobenzene (260 ng L(-1)). This headspace SPME-GC-FID method was compared with a previously validated method of analysis using closed-loop-stripping analysis (CLSA). The headspace SPME-GC-FID method is suitable for monitoring the production and distribution of potable water and was used, in field trials, for the analysis of samples from main intakes of water (surface or underground) and from the water supply system of a large area (Lisbon and neighbouring municipalities).     

Trace Element Concentrations and Bioindicator Responses in Tree Swallows from Northwestern Minnesota

Extremely high concentrations of cadmium (3.5 μg/g dry wgt.) and elevated concentrations of chromium (>10 μg/g dry wgt.) and mercury (1.6 μg/g dry wgt.) were reported in waterbird tissues at Agassiz National Wildlife Refuge in northwestern Minnesota in 1994. Tree swallows (Tachycineta bicolor) were studied during 1998–2001 at three drainages into the Refuge, two pools on the Refuge, and at a nearby reference location to document whether high levels of contaminants were still present, and if so to quantify the source and severity of the contamination. Trace elements were measured in tree swallow eggs, livers, and diet. Reproductive success and bioindicator responses were monitored. In 2000, water was drawn down on Agassiz Pool, one of the main pools on the Refuge. This presented an opportunity to evaluate the response of trace element concentrations in the diet and tissues of tree swallows after reflooding. High concentrations of trace elements were not detected in swallow tissues, nor were there differences among locations. Less than 20% of swallow samples had detectable concentrations of cadmium or chromium. Mercury concentrations were low and averaged <0.25 μg/g dry wgt. in swallow tissues. Trace elements, including mercury, did not increase in tree swallows following the 2000 drawdown at Agassiz Pool. Hatching success and survival of nestlings to 12 days-of-age for tree swallows on the Refuge were similar to the national average and consistent with background trace element concentrations. Bioindicator measurements were within the normal ranges as well.     

Influence of soil properties and aging on the toxicity of copper on compost worm and barley

Influence of soil properties and aging on Cu partitioning and toxicity was assessed on 10 artificial soils constituted using a statistical design considering pH (5.5 and 7.5), organic matter (1-30% [w/w]), and clay content (5-35% [w/w]). Total Cu as well as water-, CaCl2-, and diethylene triamine pentaacetic acid (DTPA)-extracted Cu fractions were determined for each soil mixture. Ecotoxic effect was assessed by determining growth inhibition of barley (Hordeum vulgare L.) and compost worm (Eisenia fetida) mortality. Analyses were repeated after a 16-wk aging period of the soils at pH 7.5 (8 x 2-wk wetting and drying cycle). Results indicated that pH was the main factor controlling Cu partitioning, ahead of organic matter and clay content. Calcium chloride (0.5 M)-extracted Cu fractions showed the best correlation with toxic responses (r = 0.55-0.66; p < 0.05), while total and DTPA-extracted Cu concentrations could not explain differences in toxicity. Direct regressions between toxicity and soil properties (pH, organic matter, and clay content) provided better explanation of variance: r2= 0.50 (p = 0.00006) for compost worm mortality, r2= 0.77 (p < 0.00001) for barley shoot inhibition, and r2= 0.92 (p < 0.00001) for barley root inhibition. Copper toxicity was mainly influenced by pH and, to a lesser extent, by organic matter and clay content. Aging in organic soils revealed a slight reduction in ecotoxicity while an increase was observed in soils with low organic matter content. Further investigation using longer aging periods would be necessary to assess the significance of this observation.     

Phosphorus fractions in manure from growing pigs receiving diets containing micronized peas and supplemental enzymes

Different livestock feeds manipulations have been reported to reduce the total P concentration in manure. Information on the influence of these dietary manipulation strategies on the forms of P in manure is, however, limited. This study was, therefore, conducted to investigate the effect of diet manipulation through feed micronization and enzyme supplementation on the forms of P in swine manure. Eight growing pigs were fed four diets: barley-raw pea (BRP), barley-micronized pea (BMP), barley-raw pea with enzyme (BRPE), and barley-micronized pea with enzyme (BMPE) in a 4 x 4 Latin square design. Because we are interested in the effect of enzyme cocktail and pea micronization on manure P, we did not reduce the non-phytate P with enzyme addition in this study. The fecal material and urine were collected and analyzed for total P. Fecal material was fractionated to determine the total P in H2O-, NaHCO3-, NaOH-, and HCl-extractable fractions. The total P in the residual fractions was also determined. About 98% of the total P excreted by the pigs was found in the fecal material. Inclusion of micronized pea in pig diet did not have any significant effect (p > 0.1) on either the total P or the different P fractions in the manure. The labile P (the sum of H2O-P and NaHCO3-P) was significantly reduced (p < 0.05) by the addition of enzyme to swine diets. Pigs fed the BRPE and BMPE had 14 and 18% lower labile P, respectively, compared with pigs fed the BRP. Enzyme addition to pig diets reduced not only the total P in manure, but also the labile P fraction, which is of great environmental concern. Thus, the potential of P loss to runoff and the subsequent eutrophication can be reduced by enzyme addition to pig diets.     

Field reconnaissance and estimation of petroleum hydrocarbon and heavy metal contents of soils affected by the Ebocha-8 oil spillage in Niger Delta, Nigeria

Field reconnaissance of the Ebocha-8 oil spill-affected site at Obiobi/Obrikom in the Niger Delta region of Nigeria was carried out to assess the extent of damage to the terrestrial ecosystem and delimit the epicenter of oil spillage. Following three successive reconnaissance surveys, the area to be sampled was delimited (200 x 200 m2), and soil samples were collected using the grid method from three replicate quadrats at two depths, surface (0-15 cm) and subsurface (15-30 cm). A geographically similar area located 50 m adjacent to the oil-polluted area was used as a reference (control) site. Total hydrocarbon content (THC) and heavy metal concentrations were later determined in the laboratory by extraction and spetrophotemetric techniques. Generally, the THC of soils at surface and subsurface depths of the oil-polluted plots was 2.06 x 10(4) +/- 4.97 x 10(3) mg/kg and 1.67 x 10(3) +/- 3.61 x 10(2) mg/kg soil, respectively, (no overlap in standard errors at 95% confidence limit) while concentrations of heavy metals(Pb, Cd, V, Cu and Ni) were enhanced, especially at the surface. The high levels of THC and heavy metals may predispose the site, which hitherto served as arable agricultural land, to impaired fertility and possible conflagration. When concentrations of heavy metals reach the levels obtained in this study, they may become toxic to plants or possibly bio-accumulate, thus leading to toxic reactions along the food chain. While the spilled-oil may have contributed to the enhanced levels of the metals in the affected soils, physico-chemical properties of the soils, mobility of metals, and the intense rainfall and flooding that preceded the period of study may have also contributed in part to their enhanced concentrations. The presence of high hydrocarbon content may cause oxygen deprivation, which may result in the death of soil fauna by asphyxiation. There is, therefore, an urgent need to clear the affected site of these excess hydrocarbon deposits so as to enhance the rehabilitation process of the affected mat layer of soils. Other appropriate mitigating measures, such as subsequent monitoring of hydrocarbon levels at suitable intervals after the clean up activities, are also recommended, with reference to the findings of this study, for effective management of the affected area.     

Step-up multiple regression model to compute Chlorophyll a in the coastal waters off Cochin, southwest coast of India

The interaction effects of abiotic processes in the production of phytoplankton in a coastal marine region off Cochin are evaluated using multiple regression models. The study shows that chlorophyll production is not limited by nutrients, but their physiological regulations (responses to nutrients, pH, temperature and salinity) are mainly responsible for the increased biological production. The model explaining 77% of variability for chlorophyll a production is indicative of preconditioning of the coastal waters. The phytoplankton production is found to be sensitive to the environment, which varies seasonally. Further, the study suggests that supply of organic matter and grazing of zooplankton (not included) would improve the model efficiency. Despite this, the good agreement in the computed and measured chlorophyll a values shows that step-up multiple regression model is a useful tool to understand the influence of environmental variables on the production of phytoplankton in these coastal waters.     

Origin and characterisation of microparticles in an ice core from the Central Dronning Maud Land, East Antarctica

The scanning electron microscopy-energy dispersive spectroscopic (SEM-EDS) study of selected samples from an ice core collected from Central Dronning Maud Land (CDML), East Antarctica, revealed several microparticles. They are mainly siliceous and carbonaceous particles and have distinct variations in their shape and composition. The morphology and major element chemistry of the particles suggest their origin from either volcanic eruptions or continental dust. The EDS analysis revealed that the volcanic particles are enriched in silica (average SiO2 62%), compared to the continental dust particle (average SiO2 56%). We found that the tephra relating to Agung (1963) and Karkatau (1883) volcanic eruptions, as recorded, in the ice core harbored microbial cells (both coocoid and rods). The occurrence of organic and inorganic particles which bear relation to volcanic eruption and continental dust implies significant environmental changes in the recent past.