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.

Metal concentrations in schoolyard soils from New Orleans, Louisiana before and after Hurricanes Katrina and Rita.

The long-term environmental impact and potential human health hazards resulting from Hurricanes Katrina and Rita throughout much of the United States Gulf Coast, particularly in the New Orleans, Louisiana, USA area are still being assessed and realized after more than four years. Numerous government agencies and private entities have collected environmental samples from throughout New Orleans and found concentrations of contaminants exceeding human health screening values as established by the United States Environmental Protection Agency (USEPA) for air, soil, and water. To further assess risks of exposure to toxic concentrations of soil contaminants for citizens, particularly children, returning to live in New Orleans following the storms, soils collected from schoolyards prior to Hurricane Katrina and after Hurricane Rita were screened for 26 metals. Concentrations exceeding USEPA Regional Screening Levels (USEPA-RSL), total exposure, non-cancer endpoints, for residential soils for arsenic (As), iron (Fe), lead (Pb), and thallium (Tl) were detected in soil samples collected from schoolyards both prior to Hurricane Katrina and after Hurricane Rita. Approximately 43% (9/21) of schoolyard soils collected prior to Hurricane Katrina contained Pb concentrations greater than 400mgkg(-1), and samples from four schoolyards collected after Hurricane Rita contained detectable Pb concentrations, with two exceeding 1700mgkg(-1). Thallium concentrations exceeded USEPA-RSL in samples collected from five schoolyards after Hurricane Rita. Based upon these findings and the known increased susceptibility of children to the effects of Pb exposure, a more extensive assessment of the soils in schoolyards, public parks and other residential areas of New Orleans for metal contaminants is warranted.

Spatial distribution of lead concentrations in urban surface soils of New Orleans, Louisiana USA.

Immediately following hurricane Katrina concern was raised over the environmental impact of floodwaters on the city of New Orleans, especially in regard to human health. Several studies were conducted to determine the actual contaminant distribution throughout the city and surrounding wetlands by analyzing soil, sediment, and water for a variety of contaminants including organics, inorganics, and biologics. Preliminary investigations by The Institute of Environmental and Human Health at Texas Tech University concluded that soils and sediments contained pesticides, semi-volatiles, and metals, specifically arsenic, iron, and lead, at concentrations that could pose a significant risk to human health. Additional studies on New Orleans floodwaters revealed similar constituents as well as compounds commonly found in gasoline. More recently, it has been revealed that lead (Pb), arsenic, and vanadium are found intermittently throughout the city at concentrations greater than the human health soil screening levels (HHSSLs) of 400, 22 (non-cancer endpoint) and 390 µg/g, respectively. Of these, Pb appears to present the greatest exposure hazard to humans as a result of its extensive distribution in city soils. In this study, we spatially evaluated Pb concentrations across greater New Orleans surface soils. We established 128 sampling sites throughout New Orleans at approximately half-mile intervals. A soil sample was collected at each site and analyzed for Pb by ICP-AES. Soils from 19 (15%) of the sites had Pb concentrations exceeding the HHSSL threshold of 400 µg/g. It was determined that the highest concentrations of Pb were found in the south and west portions of the city. Pb concentrations found throughout New Orleans in this study were then incorporated into a geographic information system to create a spatial distribution model that can be further used to predict Pb exposure to humans in the city.

Assessment of organochlorine pesticides and metals in ring-tailed lemurs (Lemur catta) at Beza Mahafaly Special Reserve, Madagascar.

Like most of Madagascar's endemic primates, ring-tailed lemurs (Lemur catta) face a number of threats to their survival. Although habitat loss is of greatest concern, other anthropogenic factors including environmental contamination may also affect lemur health and survival. In this study, we examined ring-tailed lemurs from the Beza Mahafaly Special Reserve (BMSR), southern Madagascar for exposure to organochlorine (OC) pesticides and metals and examined differences in contaminant concentrations between sexes and among age groups, troops, and habitats. A total of 14 pesticides and 13 metals was detected in lemur blood (24 individuals) and hair (65 individuals) samples, respectively. p,p'-DDT, heptachlor, aldrin, heptachlor epoxide, endrin aldehyde, and endrin were among the most prevalent pesticides detected. Surprisingly, the persistent metabolite of p,p'-DDT, p,p'-DDE, was not detected. The most commonly detected metals were aluminum, zinc, boron, phosphorus, silicon, and copper, whereas metals considered more hazardous to wildlife (e.g. arsenic, cadmium, lead, selenium, vanadium) were not found above detection limits. Overall, concentrations of OC pesticides and metals were low and similar to those considered to be background concentrations in other studies examining the ecotoxicology of wild mammals. Few inter-sex, -age, -troop, and -habitat differences in contaminant concentrations were observed, suggesting a uniform distribution of contaminants within the reserve. Several statistically significant relationships between lemur body size and contaminant concentrations were observed, but owing to the lack of supportive data regarding contaminant exposure in wild primates, the biological significance of these findings remains uncertain. Results of this study document exposure of ring-tailed lemurs at BMSR to multiple OC pesticides and metals and provide essential baseline data for future health and toxicological evaluations of lemurs and other wild primates, especially those in regions with expanding agricultural and mining operations.

Spatial and temporal evaluation of metal concentrations in soils and sediments from New Orleans, Louisiana, USA, following hurricanes Katrina and Rita.

During January 2006, soil and sediment samples from 75 sites in the New Orleans (LA, USA) area were collected and tested for 26 inorganic elements. The study design was intended to provide a spatial pattern of metal concentrations within the city following hurricanes Katrina and Rita. The sampling design included four transects that traversed the city in a north-south direction and three transects that traversed the city in an east-west direction. Contaminant concentrations were determined at multiple sites within each transect and compared to U.S. Environmental Protection Agency soil screening criteria pertaining to human health. Concentrations of Pb and As exceeded the criteria indiscriminately throughout the city. Of the 75 sites, 14 (19%) exceeded the soil screening criteria for Pb, and 73 (97%) exceeded the criteria for As. Forty-three of the 75 sites coincided with a previous sampling event in October 2005. Metal concentrations were evaluated for temporal comparisons using a pair sampled t test. Arsenic concentrations differed significantly over time, but Pb concentrations did not.