Determination of organochlorine and organophosphorus pesticide residues in low moisture,nonfatty products using a solid phase extraction cleanup and gas chromatography

Abstract

A multiresidue solid‐phase extraction (SPE) method for the isolation and subsequent gas Chromatographie determination of organochlorine and organophosphorus pesticide residues in low‐moisture, nonfatty products is described. Residues are extracted from samples with an acetonitrile/water mixture. Cleanup of the extract is performed using graphitized carbon black and anion exchange SPE columns, and analysis is performed by gas chromatography with Hall electrolytic conductivity and flame photometric detection. Recovery data was obtained by fortifying corn, oats and wheat with pesticides. The average recoveries were 79–123% for eight organochlorine and 51–122% for 28 organophosphorus pesticide residues. The limit of quantitation for chlorpyriphos was 0.05 ppm using the Hall electrolytic conductivity detector and <0.005 ppm using the flame photometric detector.     

Effect of modified montmorillonites on the biodegradation and adsorption of biomarkers such as hopanes, steranes and diasteranes

The effect of modified montmorillonites on the biodegradation and adsorption of selected steranes, diasteranes and hopanes was investigated in aqueous clay/oil microcosm experiments with a hydrocarbon degrading microorganism community. The unmodified montmorillonite was treated with didecyldimethylammonium bromide, hydrochloric acid and the relevant metallic chloride to produce organomontmorillonite, acid activated montmorillonite and homoionic montmorillonite respectively which were used in this study. The study indicated that organomontmorillonite, acid activated montmorillonite and potassium montmorillonite did not support the biodegradation of the selected steranes, diasteranes and hopanes as alteration of the biomarkers via biodegradation varied from a paltry 2–6 %. The adsorption of the selected biomarkers on acid activated montmorillonite and organomontmorillonite was also poor. However, adsorption of the biomarkers on potassium montmorillonite was relatively high. Sodium montmorillonite and unmodified montmorillonite appear to stimulate the biodegradation of the selected biomarkers moderately (30–35 %) with adsorption occurring at low level. Calcium montmorillonite and ferric montmorillonite effected significant biodegradation (51–60 %) of the selected biomarkers.     

Dietary exposure to technical hexabromocyclododecane (HBCD) alters courtship, incubation and parental behaviors in American kestrels (Falco sparverius)

Hexabromocyclododecane (HBCD) is a high production volume brominated flame retardant that has been detected in the environment and wildlife at increasing concentrations. This study was designed to determine potential effects of dietary exposure to environmentally relevant levels of HBCD on behavior during reproduction in captive American kestrels. Twenty kestrel pairs were exposed to 0.51 μg technical HBCD g⁻¹ kestrel d⁻¹ from 4 weeks prior to pairing until chicks hatched (∼75 d). Ten pairs of controls received the safflower oil vehicle only and were used for comparison. During the courtship period the chitter-calls were reduced in both sexes (p = 0.038) and females performed fewer bonding displays (p = 0.053). Both sexes showed a propensity to be less active than controls during courtship. The reduction in male courtship behavior was correlated with reduced courtship behaviors of females (p ? 0.008) as well as reduced egg mass (p = 0.019). During incubation, nest temperatures of treatment pairs were lower at mid-incubation (p = 0.038). HBCD-exposed males performed fewer key parental behaviors when rearing nestlings, including entering the nest-box, pair-bonding displays and food-retrievals. HBCD-exposed females appeared to compensate for the reduced parental behavior of their mates by performing these same behaviors more frequently than controls (p = 0.004, p = 0.027, p = 0.025, respectively). This study demonstrates that HBCD affects breeding behavior in American kestrels throughout the reproductive season and behavioral alterations were linked to reproductive changes (egg size). This is the first study to report HBCD effects on reproductive behavior in any animal model.     

Spring-harvested game birds in the Western James Bay region of Northern Ontario, Canada: the amount of organochlorines in matched samples of breast muscle, skin, and abdominal fat

We examined matched-tissue samples (the right pectoral muscle plus the associated skin and fat was considered a breast portion) of 81 spring-harvested waterfowl and 19 summer-harvested godwits (Limosa spp.) to assess the potential of these water birds contributing to the body burden of PCBs and DDT noted in First Nation people of the western James Bay region, northern Ontario, Canada. In general, the dabbling ducks (mallard duck, Anas platyrhynchos; and northern pintail, A. acuta) had significantly lower percent lipid (gravimetrically determined) values in skin tissue, fat tissue, and breast muscle compared to the goose species (Canada goose, Branta canadensis; lesser snow goose, Chen caerulescens); godwits had percent lipid values not significantly different than ducks and geese. Also, the percent lipid values in skin for all species of birds examined approached those found in fat tissue. Organochlorine data were expressed as the amount (microg) of each contaminant per breast portion to show contaminant consumption in terms of typical and easily recognizable dietary portions; direct comparisons were made to acceptable daily intake (ADI) or tolerable daily intake (TDI) values as recommended by Health Canada. Significant differences in the amount of organochlorines between bird species for skin, fat tissue, and breast muscle samples were found. In general, breast portions from snow geese contained the least amount of organochlorines, followed by godwits (except for mirex) and then Canada geese; the dabbling ducks had the greatest amount of organochlorines on a breast portion basis. However, on average, no 60 kg person would exceed the calculated organochlorine ADI/TDI values consuming one breast portion (i.e., breast + associated skin and fat), but the maximum value of SigmaPCBs for skin tissue alone in male mallards (47 microg) was more than twice the ADI/TDI (18 microg/day); while, that in fat tissue alone (17 microg) approached the ADI/TDI. Thus, the consumption of dabbling ducks by children is an issue that should be explored further, if tissue other than breast muscle is eaten. Lastly, the consumption of waterfowl was a source of PCBs for people of Fort Albany and Kashechewan, but not DDT, as this organochlorine was infrequently detected.     

Quantifying nickel in soils and plants in an ultramafic area in Philippines

In this study, concentrations of nickel (Ni) were quantified in the soils and plants in the agricultural areas of Salcedo watershed in Eastern Samar Island, Philippines. The quantity of total Ni in soils (TS-Ni) was significantly high with a mean of 1,409 mg kg^?1, while the soil available Ni (SA-Ni) was low with a mean of 8.66 mg kg^?1. As the levels of TS-Ni in the Salcedo watershed greatly exceeded the maximum allowable concentrations for agricultural soils, the site is not suitable for agricultural purposes. Despite significant TS-Ni levels, SA-Ni levels were very low due to tight binding between Ni and soil components. Consequently, all plants investigated did not meet the criterion for a Ni hyperaccumulator plant with low Ni contents (mean TP-Ni of 14.7 mg kg^?1). Comparison of Ni levels between food plants and its recommended daily intake (RDI) suggests that consumption of food-plants grown in the study area is unlikely to pose health risks. However, caution must be taken against combined consumption of food plants with high Ni levels or their prolonged consumption, as it can induce accumulation of Ni above RDI.     

Chronic and episodic acidification of Adirondack streams from acid rain in 2003-2005

Limited information is available on streams in the Adirondack region of New York, although streams are more prone to acidification than the more studied Adirondack lakes. A stream assessment was therefore undertaken in the Oswegatchie and Black River drainages; an area of 4585 km(2) in the western part of the Adirondack region. Acidification was evaluated with the newly developed base-cation surplus (BCS) and the conventional acid-neutralizing capacity by Gran titration (ANC(G)). During the survey when stream water was most acidic (March 2004), 105 of 188 streams (56%) were acidified based on the criterion of BCS < 0 microeq L(-1), whereas 29% were acidified based on an ANC(G) value < 0 microeq L(-1). During the survey when stream water was least acidic (August 2003), 15 of 129 streams (12%) were acidified based on the criterion of BCS < 0 microeq L(-1), whereas 5% were acidified based on ANC(G) value < 0 microeq L(-1). The contribution of acidic deposition to stream acidification was greater than that of strongly acidic organic acids in each of the surveys by factors ranging from approximately 2 to 5, but was greatest during spring snowmelt and least during elevated base flow in August. During snowmelt, the percentage attributable to acidic deposition was 81%, whereas during the October 2003 survey, when dissolved organic carbon (DOC) concentrations were highest, this percentage was 66%. The total length of stream reaches estimated to be prone to acidification was 718 km out of a total of 1237 km of stream reaches that were assessed.     

Optimal spatial resolution for collection of ground data and multi-sensor image mapping of a soil erosion cover factor

Military training activities disturb ground and vegetation cover of landscapes and increases potential soil erosion. To monitor the dynamics of soil erosion, there is an important need for an optimal sampling design in which determining the optimal spatial resolutions in terms of size of sample plots used for the collection of ground data and the size of pixels for mapping. Given a sample size, an optimal spatial resolution should be cost-efficient in both sampling costs and map accuracy. This study presents a spatial variability-based method for that purpose and compared it with the traditional methods in a study area in which a soil erosion cover factor was sampled and mapped with multiple plot sizes and multi-sensor images. The results showed that the optimal spatial resolutions obtained using the spatial variability-based method were 12 and 20m for years 1999 and 2000, respectively, and were consistent with those using the traditional methods. Moreover, the most appropriate spatial resolutions using the high-resolution images were also consistent with those using ground sample data, which provides a potential to use the high-resolution images instead of ground data to determine the optimal spatial resolutions before sampling. The most appropriate spatial resolutions above were then verified in terms of cost-efficiency which was defined as the product of sampling cost and map error using ordinary kriging without images and sequential Gaussian co-simulation with images to generate maps.     

Raptors and Red Grouse: Conservation Conflicts and Management Solutions

Abstract: Recovering predator populations may present problems for conservationists if their prey are of economic or conservation value. We address this issue by examining the conflict between raptor conservation and management of Red Grouse (   Lagopus l. scoticus ) in Britain. Heather moorland is a distinctive habitat that supports an important assemblage of breeding birds. Large areas of moorland are managed by private landowners for shooting grouse. Although grouse shooting benefits conservation by retaining heather moorland, it is currently unclear whether grouse management directly benefits other upland birds. Human persecution has greatly restricted the range and abundance of most raptor species in Britain. Following the introduction of bird protection laws, the decline in gamekeeping, and the restriction of organochlorine pesticides, raptor populations have started to recover. Persecution of raptors on grouse moors is widespread and limits the range and abundance of Hen Harriers (  Circus cyaneus ), Peregrine Falcons (   Falco peregrinus ), and Golden Eagles ( Aquila chrysaetos ). In some circumstances, raptor predation can reduce both the breeding density and productivity of Red Grouse. Limitation of grouse populations through raptor predation is most likely to occur where raptors are at high density because of the abundance of alternative prey, and grouse are at low density either because of poor management or the cyclic nature of some grouse populations. In the long term, habitat management may reduce densities of alternative prey, leading to reductions in raptor densities and their predation on grouse. More active intervention may be required, however, if grouse moors are to remain viable in the short-term. Current research is focused on manipulating harrier diet through diversionary feeding. Complementary research is needed to investigate methods to reduce raptor numbers locally while ensuring their national status.     

Impact of growth conditions on transport behavior of E. coli

The aim of this investigation is to determine the effect that growth solution has on the cell surface properties and transport behavior of eleven Escherichia coli isolates through saturated porous media. The two growth solutions used were a standard laboratory growth medium (LB) and a dairy manure extract solution. In general, cells grown in manure extract were more hydrophobic, had a more negative zeta potential, had lower amounts of surface macromolecules, and had lower attachment efficiencies than isolates grown in LB. An inverse relationship between the natural log of zeta potential and the attachment efficiency of the isolates for the cells grown in LB media was the only statistically significant correlation observed between transport behavior and cell characteristics of the isolates. This study shows the need to consider growth conditions when studying bacteria to better mimic the environmental stresses that bacteria undergo in the natural environment. This approach could lead to a better understanding of the behavior of manure-derived bacteria in aquatic and terrestrial environments.