Tandem capillary column gas chromatography-mass spectrometric determination of the organophosphonate nerve agent surrogate dimethyl methylphosphonate in gaseous phase.

A procedure based on capillary column gas chromatographic-mass spectrometric (GC-MS) confirmation was developed for the verification of the ubiquitous and versatile chemical and nerve agent simulant, dimethyl methyl phosphonate (DMMP; CAS# 756-79-6), from gaseous samples. This method was developed to verify low nanogram DMMP concentrations during testing of a nerve agent detection system. Standard solutions of 1, 5, 10, 50, 100, 500, and 1000ng/ml DMMP in acetonitrile were employed. Through 15 calibration curves using the 5 lowest concentrations, coefficient of determination (r(2)) values showed a mean of 0.998 (0.992-1.000). An additional 15 calibration curves likewise containing 5 concentrations of DMMP spanning 3 orders of magnitude (1, 50, 100, 500, and 1000ng/ml) yielded a mean r(2) of 0.997 (0.991-1.000). Sixty-five nitrogen diluted gaseous samples varying from 1.0 to 10.0microl in volume were analyzed and concentrations of DMMP ranging from 1 to 1000ng/ml were confirmed. An additional 35 vapor samples in UHP N(2) ranging in DMMP concentration from 5.8microg/m(3) to 1.0mg/m(3) were analyzed by increasing sample volume range to between 10.0 and 100microl. For gaseous samples with volumes>1.0microl, the lowest concentration observed was 5.8microg/m(3). The method detection limit (Appendix B of Title 40 CFR, United States) for 1.0microl autoinjected standards in acetonitrile was determined to be 0.331ng/ml. Method precision for 15 independently analyzed standards of 25ng/ml had a relative standard deviation of 1.168. This method demonstrated high linearity across a wide range of concentrations, as well as excellent sensitivity and repeatability, and proved applicable to other lower alkyl-phosphonates.

Metals and organochlorine pesticides in caudal scutes of crocodiles from Belize and Costa Rica.

Despite high animal diversity in the Neotropics and the largely unregulated use and disposal of pesticides and industrial chemicals in Central America, few data exist regarding accumulation of environmental contaminants in Central American wildlife. In this study we examined accumulation of metals and organochlorine (OC) pesticides in caudal scutes of crocodiles from Belize and Costa Rica. Scutes from Morelet's crocodiles (Crocodylus moreletii) from two sites in northern Belize were analyzed for metals, and scutes from American crocodiles (C. acutus) from one site in Costa Rica were analyzed for metals and OC pesticides. All scutes (n=25; one scute from each of 25 individuals) contained multiple contaminants. Mercury was the predominant metal detected, occurring in all scutes examined from both species. Other metals detected include cadmium, copper, lead, and zinc. American crocodile scutes from Costa Rica contained multiple OC pesticides, including endrin, methoxychlor, p,p'-DDE, and p,p'-DDT, all of which occurred in 100% of scutes analyzed (n=6). Mean metal and OC concentrations varied in relation to those previously reported in crocodilian scutes from other localities in North, Central, and South America. OC concentrations in American crocodile scutes were generally higher than those previously reported for other Costa Rican wildlife. Currently, caudal scutes may serve as general, non-lethal indicators of contaminant accumulation in crocodilians and their areas of occurrence. However, a better understanding of the relationships between pollutant concentrations in scutes, internal tissues, and environmental matrices at sample collection sites are needed to improve the utility of scutes in future ecotoxicological investigations.

Influence of land use on metal concentrations in playa sediments and amphibians in the Southern High Plains.

The Southern High Plains (SHP) is a semi-arid region in which playa wetlands are the focal points of biodiversity. Playas are highly influenced by surrounding land use. Most of the SHP is in agricultural production (primarily cotton) with a history of arsenic-containing herbicide use. Metals influence reproduction and development in amphibians. We analyzed metal residues in playa sediment and whole body tissue of Spea spp. and Bufo cognatus metamorphs from two land uses: cropland and native grassland. Cd and Ni concentrations in B. cognatus tissues differed between land uses. Metal concentrations in Spea spp. tissues did not differ between land uses. Ba was higher in Spea spp. than B. cognatus collected from the same grassland playas, indicating differential habitat use. No correlations between sediment and tissue concentrations were found. Land use appeared to have little influence on metal concentrations and levels were below those known to cause effects in amphibians.

Effects of perchlorate on earthworm (Eisenia fetida) survival and reproductive success.

The effects of perchlorate on earthworm, Eisenia fetida, survival and reproductive success were evaluated using three types of tests: dermal contact (filter paper), sand, and artificial soil. All studies utilized a range of perchlorate concentrations in order to simulate levels that are likely to occur in the environment under different scenarios (typical soil levels vs. spill levels). The OECD filter paper contact test involved exposing earthworms to the test compound on moist filter paper for 14 days to evaluate earthworm survival under a worst-case dermal exposure scenario. A similar test involved exposing the earthworms to perchlorate-contaminated sand, where earthworm survival decreased as concentration of perchlorate increased, with no worms surviving 14 days at the highest treatment concentrations (>2000 microg/g). However, the perchlorate concentrations that affected the survival of E. fetida are likely to occur only under extreme conditions (e.g. spills). The effect of perchlorate on the reproductive success (cocoon production) of E. fetida over a 4-week test period in artificial soil and a 3-week test period in sand was also examined. Production of cocoons was observed in soil containing up to 100 microg/g perchlorate, with no production in the uppermost treatment groups (1000 microg/g). Cocoon production was highest in the control group, although overall cocoon production appeared to be low. In contrast to the acute toxicity tests, perchlorate did affect earthworm reproduction at environmentally relevant soil concentrations. In addition, preliminary data suggest that cocoons produced under perchlorate contamination did not hatch as well as cocoons produced in control soil despite incubation of both sets of cocoons in clean soil or sand.