Effective elution of RDX and TNT from particles of Comp B in surface soil

During live fire training exercises, large amounts of explosives are consumed. Low order detonations of high explosive payloads result in the patchy dispersal of particles of high explosive formulations over large areas of firing range soils. Dissolution of explosives from explosive formulation particles into soil pore water is a controlling factor for transport, fate, and effects of explosive compounds. We developed an empirical method to evaluate soils based on functionally defined effective dissolution rates. An automated Accelerated Solvent Extractor was used to determine the effective elution rates under controlled conditions of RDX and TNT from soil columns containing particles of Comp B. Contrived soils containing selected soil geosorbants and reactive surfaces were used to quantitatively determine the importance of these materials. Natural soils from training ranges of various soil types were also evaluated. The effects of geosorbants on effective elution rates were compound- and sorbent-specific. TNT elution was less than that of RDX and was greatly slowed by humic acid. Iron and iron-bearing clays reduced the effective elution rates of both RDX and TNT. This empirical method is a useful tool for directly generating data on the potential for explosives to leach from firing range soils, to identify general bulk soil characteristics that can be used to predict the potential, and to identify means to engineer soil treatments to mitigate potential transport.     

Determination of toxic cyclic heptapeptides by liquid chromatography with detection using ultra-violet, protein phosphatase assay and tandem mass spectrometry

Microcystins, toxic cyclic heptapeptides and nodularin-R, a toxic cyclic pentapeptide, were determined using liquid chromatography (LC) with detection using photo-diode array ultra-violet (PDA-UV) and protein phosphatase (PP) assay. Positive fractions were analysed for toxins using collision-induced dissociation (CID) and tandem MS/MS experiments which were carried out simultaneously using electrospray ion-trap instrumentation. Reversed-phase liquid chromatography (LC) using an acetonitrile/water gradient was used for the LC-MS(2) determination of six microcystins standards and nodularin. The molecular related ion species, [M+H](+)([M+2H](2+) in the case of MC-RR), were used as the precursor ions for MS(2) experiments. Optimum calibration and reproducibility data were obtained for MC-LR using LC-MS(2); 0.1-5.0 microg/ml, r2 = 0.992 (n = 3); % RSD < or =7.3 at 0.25 microg MC-LR/ml (n = 3). The detection limit (S/N = 3) was better than 0.1 ng. Water samples for microcystin analysis were first screened using protein phosphatase (PP) assays and positives were concentrated using C-18 solid-phase extraction. The developed method was applied to examine a lake in Ireland contaminated by Microcystis sp. and MC-LR and MC-LA were identified.     

Bioavailability of hydrophobic organic contaminants and quality of organic carbon

U.S. laws require that contaminant bioaccumulation potential be evaluated before dredged material can be recycled. Simple fugacity models, e.g. organic contaminant aqueous partition coefficient (K _oc)-derived theoretical bioaccumulation potential, are commonly used to estimate the partitioning of hydrophobic organic contaminants between sediment organic matter and organism lipid. K _oc-derived models, with or without the addition of a soot carbon term, did not accurately or consistently predict total polycyclic aromatic hydrocarbons (PAHs) and polychlorobiphenyls partitioning of eight sediments from ongoing dredging operations onto C₁₈-coated filter paper. These models also failed to predict the partitioning of individual PAHs from these eight sediments. These data underscore the trade-offs between the ease of using simple models and the uncertainty of predicted partitioning values.     

Species-specific variation in cuttlebone δ13C and δ18O for three species of Mediterranean cuttlefish

Stable carbon (δ¹³C) and oxygen (δ¹⁸O) isotopes in cuttlebones of three species of Mediterranean cuttlefish (Sepia elegans, S. officinalis, and S. orbignyana) with different life histories were contrasted. Cuttlebone δ¹³C and δ¹⁸O were quantified at both the core and edge (representing early life and recent deposition, respectively) for all three species sampled from the southern Adriatic Sea in 2010 (n = 28). For S. officinalis, cuttlebone δ¹³C and δ¹⁸O values were both lower relative to S. elegans and S. orbignyana at the core by approximately 1.0–2.0 and 3.0 ‰, respectively. Differences between core and edge in cuttlebone δ¹³C and δ¹⁸O were also observed for S. officinalis with observed values at the cuttlebone edge (recent) exceeding core (early life) values by 2.5 ‰ for δ¹³C and 1.4 ‰ for δ¹⁸O. Differences in isotopic composition across S. officinalis cuttlebones are possibly reflective of ontogenetic migrations from nearshore nurseries (lower seawater δ¹³C and δ¹⁸O values) to offshore overwintering habitats (higher seawater δ¹³C and δ¹⁸O values). Overall, results from this study suggest that cuttlebone δ¹³C and δ¹⁸O hold promise as natural tags for determining the degree of spatial connectivity between nearshore and offshore environments used by cuttlefish.