Detection and Classification of Ignitable Liquid Residues in the Presence of Matrix Interferences by Using Direct Analysis in Real Time Mass Spectrometry.

Conventional Gas Chromatography-Mass Spectrometry (GC-MS) methods for the analysis of ignitable liquids (ILs) are usually time-consuming, and the data produced are difficult to interpret. A fast IL screening method using direct analysis in real time mass spectrometry (DART-MS) is proposed in this study. GC-MS, QuickStrip DART-MS, and thermal desorption DART-MS methods were used to analyze neat ILs and thermal desorption DART-MS without extraction was used to analyze ILs on five substrates (e.g., carpet, wood, cloth, sand, and paper). Compared to GC-MS, DART-MS methods generated different spectral profiles for neat ILs with more peaks in the higher mass range and also provided better detection of less volatile compounds. ILs on substrates were successfully classified (98 ± 1%) using partial least squares discriminant analysis (PLS-DA) models based on thermal desorption DART-MS data. This study shows that DART-MS has great potential for the high-throughput screening of ILs on substrates.

A Watershed Analysis of Seasonal Concentration- and Loading-based Results for Escherichia coli in Inland Waters.

Fecal indicator bacteria, such as Escherichia coli, are frequently monitored in recreational waterbodies as indicators of potential fecal pathogen presence and exposure. The present watershed analysis investigated the influence of season on E. coli concentration (MPN/100 mL) and loading (MPN/day) measurements for inland waters at baseflow conditions. The master dataset collected during 2007-2012 for three watersheds included 896 E. coli (Colilert) samples with simultaneous flow taken for a subset (39 %) of samples. The outcomes for grouped watersheds were reflected in most cases for individual watersheds. Concentration- and loading-based results were highest in summer and spring, and lowest in the winter and fall, respectively. The comparison of these two measurement techniques (concentration and loading) highlight the impact of flow data during baseflow conditions for inland waters and reveal that caution should be used when inferring one method's results from another.

Effects of Maternally-Transferred Methylmercury on Stress Physiology in Northern Water Snake (Nerodia sipedon) Neonates.

Biomagnification of methylmercury in aquatic systems can cause elevated tissue mercury (Hg) and physiological stress in top predators. Mercury is known to affect stress hormone levels in mammals, birds and fish. In this study, the effects of maternally-transferred methylmercury on the stress physiology of Northern Water Snake (Nerodia sipedon) neonates were tested. Gravid females were dosed via force-fed capsules during late gestation with 0, 0.01, or 10 µg methylmercury per gram of body mass. Plasma corticosterone levels and leukocyte differentials were analyzed in baseline and confinement-stressed neonates from all dose levels. Neither Hg nor confinement stress had a significant effect on leukocyte differentials nor was Hg related to corticosterone levels. However, stress group neonates showed lower heterophil/lymphocyte ratios and this study was the first to show that neonate N. sipedon can upregulate CORT in response to stress. These results indicate that N. sipedon may be somewhat tolerant to Hg contamination.

The use of tetragnathid spiders as bioindicators of metal exposure at a coal ash spill site.

On 22 December 2008, a dike containing coal fly ash from the Tennessee Valley Authority Kingston Fossil Fuel Plant (TN, USA) failed, resulting in the largest coal ash spill in US history. The present study was designed to determine sediment metal concentrations at multiple site locations and to determine whether site-specific bioaccumulation of metals existed in tetragnathid spiders. Selenium and nickel were the only 2 metals to exceed the US Environmental Protection Agency sediment screening levels. Selenium concentrations in spiders were significantly higher at ash-affected sites than in those from reference sites. The ratio of methylmercury to total mercury in spiders was found to be similar to that in other organisms (65-75%), which highlights the potential use of tetragnathid spiders as an indicator species for tracing contaminant transfer between the aquatic and terrestrial ecosystems.

Trophic status and metal bioaccumulation differences in multiple fish species exposed to coal ash-associated metals.

On December 22, 2008 a dike containing coal fly ash from the Tennessee Valley Authority Kingston Fossil Plant near Kingston Tennessee USA failed and resulted in the largest coal ash spill in U.S. history. Coal ash, a by-product of coal combustion, is known to contain multiple contaminants of concern, including arsenic and selenium. The purpose of this study was to investigate species differences in the bioaccumulation of arsenic and selenium and potential factors contributing to these differences (i.e., trophic dynamics and gut pH) in the vicinity of the Kingston coal ash spill. Elevated levels of arsenic and selenium were observed in various tissues of largemouth bass, white crappie, bluegill and redear sunfish from sites associated with the Kingston coal ash spill. Highest concentrations of selenium were found in redear sunfish with liver concentrations as high as 24.83mg/kg dry weight and ovary concentrations up to 10.40mg/kg dry weight at coal ash-associated sites. Investigations into the gut pH and trophic dynamics of redear sunfish and bluegill demonstrated a large difference in the gut physiology between these two species. Redear sunfish stomach and intestinal pH was found to be 1.1 and 0.16 pH units higher than in bluegill, respectively. In addition, fish from coal ash-associated sites showed enrichment differences ((15)N and (13)C) compared to no ash sites, indicating differences in food web dynamics between sites. These results imply the incorporation of coal ash-associated compounds into local food webs and/or a shift in diet at ash sites compared to the no ash reference sites. Based on these results, further investigation into a broader food web at ash-associated sites is warranted.

Effects of silver nanoparticles on zebrafish (Danio rerio) and Escherichia coli (ATCC 25922): a comparison of toxicity based on total surface area versus mass concentration of particles in a model eukaryotic and prokaryotic system.

Silver nanoparticles (Ag NPs) have been classified as the most abundant NP found in commercial products. In the present study, zebrafish (Danio rerio) and bacteria (Escherichia coli; ATCC 25922) were used to test the size-dependent toxicological effects of Ag NPs, the effects of ionic silver versus Ag NPs, and Ag NP effects on mortality using mass concentration (mg/L) compared with total surface area (nm(2) /L). Several diameters of Ag NPs (20, 50, 110 nm) as well as AgNO(3) were chosen as experimental treatments. Treated zebrafish embryos exhibited anomalies of the heart, namely, slower heart rates and pericardial edema. A size-dependent response was not observed in zebrafish when viewing mortality across all Ag NP treatments, although 20 nm elicited the highest incidence of abnormal motility and induced slower development. An Ag NP dose- and size-dependent response was observed in treated bacteria using mass concentration, with 20-nm Ag NP producing the highest mortality rate. In both zebrafish and bacteria, AgNO(3) was shown to be more toxic than Ag NPs at equivalent concentrations. When total surface area of Ag NPs was used to gauge bacterial mortality, a total surface area-dependent, but not size-dependent, response was observed for all three Ag NPs used in the present study, with nearly 100% mortality observed once a total surface area of approximately 1E + 18 nm(2) /L was reached. This trend was not apparent, however, when measuring total surface area for zebrafish mortality.

Mercury speciation and biomagnification in the food web of Caddo Lake, Texas and Louisiana, USA, a subtropical freshwater ecosystem.

We studied the biomagnification of total mercury and methylmercury in a subtropical freshwater lake, Caddo Lake, Texas and Louisiana, USA. The present study is unique in that it not only included invertebrates (seven species) and fish (six species) but also an amphibian (one species), reptiles (three species), and mammals (three species). Nonfish vertebrates such as those included in the present study are often not included in assessments of trophic transfer of Hg. Mean trophic position (determined using stable isotopes of nitrogen) ranged from 2.0 (indicative of a primary consumer) to 3.8 (indicative of a tertiary consumer). Mean total Hg concentrations ranged from 36 to 3,292 ng/g dry weight in muscle and whole body and from 150 to 30,171 ng/g dry weight in liver. Most of the Hg in muscle and whole-body tissue was found as methylmercury, and at least 50% of the Hg found in liver was in the inorganic form (with the exception of largemouth bass, Micropterus salmoides). Mercury concentrations were positively correlated with trophic position, indicating that biomagnification occurs in the food web of Caddo Lake. The food web magnification factors (FWMFs; slope of the relationship between mean Hg concentration and trophic position) for both total Hg and methylmercury were similar to those observed in other studies. Because most of the total Hg in consumers was methylmercury, the FWMF for methylmercury was not significantly different from the FWMF for total Hg. Some vertebrates examined in the present study had low Hg concentrations in their tissues similar to those observed in invertebrates, whereas others had concentrations of Hg in their tissues that in previous studies have been associated with negative health consequences in fish.

Asparagine362 is essential for zinc binding and catalysis in the peptidase reaction of Saccharomyces cerevisiae leukotriene A4 hydrolase.

Zinc metallopeptidases are ubiquitous enzymes with diverse cellular functions that can be found in most organisms. Leukotriene A4 hydrolase (LTA4H; E.C. 3.3.2.6) is an unusual zinc metallopeptidase of the M1 family that also possesses an epoxide hydrolase activity; however, the role of its peptidase activity remains unknown. To further characterize the peptidase activity of LTA4H and other closely related metallopeptidases, a multiple sequence alignment and predicted structure were used to target three amino acid residues of yeast LTA4H for mutagenesis: Asn362, Trp365, and Asp399. Although mutating Trp365 and Asp399 had little effect on catalysis, altering Asn362 had varying effects on catalysis, depending on the replacement residue. Mutation of Asn362 to glutamine (N362Q) caused minor catalytic defects, while mutation to leucine (N362L) or glutamate (N362E) caused large reductions in activity. Both N362L and N362E also exhibited an altered pH dependence of catalysis, reduced chloride activation, and reduced zinc affinity and content, indicating that Asn362 may interact with the nearby zinc coordinating residue His344, and possibly with Glu363 as well, to polarize and/or orient these residues.