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    ABSTRACT: Carbon stable isotope ((13)C) fractionation in chlorofluorocarbon (CFC) compounds arising from abiotic (chemical) degradation using zero-valent iron (ZVI) and biotic (landfill gas attenuation) processes is investigated. Batch tests (at 25 °C) for CFC-113 and CFC-11 using ZVI show quantitative degradation of CFC-113 to HCFC-123a and CFC-1113 following pseudo-first-order kinetics corresponding to a half-life (τ(1/2)) of 20.5 h, and a ZVI surface-area normalized rate constant (k(SA)) of -(9.8 ± 0.5) × 10(-5) L m(-2) h(-1). CFC-11 degraded to trace HCFC-21 and HCFC-31 following pseudo-first-order kinetics corresponding to τ(1/2) = 17.3 h and k(SA) = -(1.2 ± 0.5) × 10(-4) L m(-2) h(-1). Significant kinetic isotope effects of ε(‰) = -5.0 ± 0.3 (CFC-113) and -17.8 ± 4.8 (CFC-11) were observed. Compound-specific carbon isotope analyses also have been used here to characterize source signatures of CFC gases (HCFC-22, CFC-12, HFC-134a, HCFC-142b, CFC-114, CFC-11, CFC-113) for urban (UAA), rural/remote (RAA), and landfill (LAA) ambient air samples, as well as in situ surface flux chamber (FLUX; NO FLUX) and landfill gas (LFG) samples at the Dargan Road site, Northern Ireland. The latter values reflect biotic degradation and isotopic fractionation in LFG production, and local atmospheric impact of landfill emissions through the cover. Isotopic fractionations of Δ(13)C ∼ -13‰ (HCFC-22), Δ(13)C ∼ -35‰ (CFC-12) and Δ(13)C ∼ -15‰ (CFC-11) were observed for LFG in comparison to characteristic solvent source signatures, with the magnitude of the isotopic effect for CFC-11 apparently similar to the kinetic isotope effect for (abiotic) ZVI degradation. See ACS ActiveView PDF at http://pubs.acs.org/doi/full/10.1021/es203386a N.B. in Table 1 the stated HCFC-22 solvent source signature (Ertl, 1997) should read -56‰ and not in the range -48 to -45‰. The ACS site gives link also to the cited Supporting Information. Here is a link to my article,"Carbon Isotopic Fractionation of CFCs during Abiotic and Biotic Degradation...." You can view the full text of this article at http://pubs.acs.org/articlesonrequest/AOR-WzvgYy37T88bDJ24uysI
    Environmental Science & Technology 12/2011; 46(3):1764-73.
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    ABSTRACT: The Monkstown zero-valent iron permeable reactive barrier (ZVI PRB), Europe's oldest commercially-installed ZVI PRB, had been treating trichloroethene (TCE) contaminated groundwater for about 10 years on the Nortel Network site in Northern Ireland when cores from the reactive zone were collected in December, 2006. Groundwater data from 2001-2006 indicated that TCE is still being remediated to below detection limits as the contaminated groundwater flows through the PRB. Ca and Fe carbonates, crystalline and amorphous Fe sulfides, and Fe (hydr)oxides have precipitated in the granular ZVI material in the PRB. The greatest variety of minerals is associated with a approximately 1-2 cm thick, slightly cemented crust on top (up-gradient influent entrance) of the ZVI section of the PRB and also with the discontinuous cemented ZVI material ( approximately 23 cm thick) directly below it. The greatest presence of microbial communities also occurred in the up-gradient influent portion of the PRB compared to its down-gradient effluent section, with the latter possibly due to less favorable conditions (i.e., high pH, low oxygen) for microbial growth. The ZVI filings in the down-gradient effluent section of the PRB have a projected life span of >10 years compared with ZVI filings from the continuous to discontinuous cemented up-gradient ZVI section (upper approximately 25 cm) of the PRB, which may have a life span of only approximately 2-5 more years. Supporting Information from applied, multi-tracer testing indicated that restricted groundwater flow is occurring in the upper approximately 25 cm of the ZVI section and preferential pathways have also formed in this PRB over its 10 years of operation. See ACS ActiveView PDF at http://pubs.acs.org/doi/abs/10.1021/es902737t Here is a link to my article,"Ten Year Performance Evaluation of a Field-Scale Zero-Valent Iron Permeable Reactive Barrier In...." You can view the full text of this article at http://pubs.acs.org/articlesonrequest/AOR-DEiRPJhhAacIu2jvjRNF
    Environmental Science and Technology 05/2010; 44(10):3861-9.
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    ABSTRACT: Architectural paints are commonly found as trace evidence at scenes of crime. Currently the most widely used technique for the analysis of architectural paints is Fourier Transformed Infra-Red Spectroscopy (FTIR). There are, however, limitations to the forensic analysis of white paints, and the ability to discriminate between samples. Isotope ratio mass spectrometry (IRMS) has been investigated as a potential tool for the analysis of architectural white paints, where no preparation of samples prior to analysis is required. When stable isotope profiles (SIPs) are compared, there appears to be no relationship between paints from the same manufacturer, or between paints of the same type. Unlike existing techniques, IRMS does not differentiate resin samples solely on the basis of modifier or oil-type, but exploits additional factors linked to samples such as geo-location where oils added to alkyd formulations were grown. In combination with the use of likelihood ratios, IRMS shows potential, with a false positive rate of 2.6% from a total of 1275 comparisons.
    Science & Justice 07/2009; 49(2):114-9.
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    ABSTRACT: Uranium-containing precipitates have been observed in a dolomitic gravel fill near the Department of Energy (DOE) S-3 Ponds former waste disposal site as a result of exposure to acidic (pH 3.4) groundwater contaminated with U (33 mg L(-1)), Al3+ (900 mg L(-1)), and NO3- (14 000 mg L(-1)). The U containing precipitates fluoresce a bright green under ultraviolet (UV) short-wave light which identify U-rich coatings on the gravel. Scanning electron microscopy (SEM) microprobe analysis show U concentration ranges from 1.6-19.8% (average of 7%) within the coatings with higher concentrations at the interface of the dolomite fragments. X-ray absorption near edge structure spectroscopy (XANES) indicate that the U is hexavalent and extended X-ray absorption fine structure spectroscopy (EXAFS) shows that the uranyl is coordinated by carbonate. The exact nature of the uranyl carbonates are difficult to determine, but some are best described by a split K(+)-like shell similar to grimselite [K4Na(UO2)(CO3)3 x H2O] and other regions are better described by a single Ca(2+)-like shell similar to liebigite [Ca2(UO2)(CO3)3 x 11(H2O)] or andersonite [Na2CaUO2(CO3)3 x 6H2O]. The U precipitates are found in the form of white to light yellow cracked-formations as coatings on the dolomite gravel and as detached individual precipitates, and are associated with amorphous basalumnite [Al4(SO4)(OH)10 x 4H2O].
    Environmental Science and Technology 11/2008; 42(19):7104-10.
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    ABSTRACT: The relationship between diet, geographic location and isotopic composition of human tissue has been successfully exploited in archaeological and palaeodietary studies, i.e. on ancient man, but cases in which this approach has been applied to present-day people e.g. to aid identification of mutilated or deteriorated bodies are far and few between. Stable isotope data are presented here from a case where for the first time stable isotope based intelligence aided victim identification by DNA analysis and subsequent apprehension of the perpetrators thus demonstrating that it is possible in principal for stable isotope data of present-day people to be useful for human provenancing, i.e. to yield valuable information about a person's life history and geographic origin.
    Science & Justice 10/2008; 48(3):153-9.
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    ABSTRACT: The in situ characterisation of thermocouple sensors is a challenging problem. Recently the authors introduced a novel blind characterisation technique based on the cross-relation method of blind identification that allows in situ characterisation of temperature measurement probes consisting of two-thermocouple sensors with differing time constants. While the technique has a number of advantages over competing methods, including low estimation variance and no need for a priori estimation of the time constant ratio, it was found to be positively biased and becomes unstable at high noise levels. In this paper the origin of the stability issues and bias are analysed. It is shown that an alternative normalised cost function formulation, which eliminates the stability problem, results in negatively biased time constant estimates at high noise levels. Further, it is demonstrated that this bias is less significant when temperature variations are broadband. All results are verified using Monte-Carlo simulations.
    17th IFAC World Congress; 07/2008
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    ABSTRACT: When submitting samples for analysis, maintaining sample integrity is essential. Appropriate packaging must be used to prevent damage, contamination or loss of sample. This is particularly important for stable isotope analysis by isotope ratio mass spectrometry as this technique is capable of detecting subtle differences in isotopic composition with great precision. In a novel study, scalp hair and fingernail samples were placed in five different types of packaging, routinely used in forensic laboratories and stored for 6 weeks and 6 months. Samples were subsequently cleaned and submitted for (13)C/(12)C, (15)N/(14)N, (2)H/(1)H and (18)O/(16)O analysis. Results from (13)C analysis indicate that type of packaging can cause slight changes in (13)C abundance over time. Differences were noted in the (15)N isotope signatures of both hair and nail samples after 6-week storage, but not after 6 months. This apparent discrepancy could be a result of the packaging not being properly sealed in the 6 weeks study. Fewer differences were noted when analyzing samples for (2)H and (18)O abundance.
    Journal of Forensic Sciences 02/2008; 53(1):95-9.
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    ABSTRACT: Synthetic resins are shown to be effective in removing uranium from contaminated groundwater. Batch and field column tests showed that strong-base anion-exchange resins were more effective in removing uranium from both near-neutral-pH (6.5)- and high-pH (8)-low-nitrate-containing groundwaters, than metal-chelating resins, which removed more uranium from acidic-pH (5)-high-nitrate-containing groundwater from the Oak Ridge Reservation (ORR) Y-12 S-3 Ponds area in Tennessee, USA. Dowex 1-X8 and Purolite A-520E anion-exchange resins removed more uranium from high-pH (8)-low-nitrate-containing synthetic groundwater in batch tests than metal-chelating resins. The Dowex 21K anion-exchange resin achieved a cumulative loading capacity of 49.8 mg g(-1) before breakthrough in a field column test using near-neutral-pH (6.5)-low-nitrate-containing groundwater. However, in an acidic-pH (5)-high-nitrate-containing groundwater, metal-chelating resins Diphonix and Chelex-100 removed more uranium than anion-exchange resins. In 15 m L of acidic-pH (5)-high-nitrate-containing groundwater spiked with 20 mg L(-1) uranium, the uranium concentrations ranged from 0.95 mg L(-1) at 1-h equilibrium to 0.08 mg L(-1) at 24-h equilibrium for Diphonix and 0.17 mg L(-1) at 1-h equilibrium to 0.03 mg L(-1) at 24-h equilibrium for Chelex-100. Chelex-100 removed more uranium in the first 10 min in the 100mL of acidic-(pH 5)-high-nitrate-containing groundwater ( approximately 5 mg L(-1) uranium); however, after 10 min, Diphonix equaled or out-performed Chelex-100. This study presents an improved understanding of the selectivity and sorption kenetics of a range of ion-exchange resins that remove uranium from both low- and high-nitrate-containing groundwaters with varying pHs.
    Water Research 02/2008; 42(1-2):260-8.
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    ABSTRACT: This paper presents a novel approach based on the use of evolutionary agents for epipolar geometry estimation. In contrast to conventional nonlinear optimization methods, the proposed technique employs each agent to denote a minimal subset to compute the fundamental matrix, and considers the data set of correspondences as a 1D cellular environment, in which the agents inhabit and evolve. The agents execute some evolutionary behavior, and evolve autonomously in a vast solution space to reach the optimal (or near optima) result. Then three different techniques are proposed in order to improve the searching ability and computational efficiency of the original agents. Subset template enables agents to collaborate more efficiently with each other, and inherit accurate information from the whole agent set. Competitive evolutionary agent (CEA) and finite multiple evolutionary agent (FMEA) apply a better evolutionary strategy or decision rule, and focus on different aspects of the evolutionary process. Experimental results with both synthetic data and real images show that the proposed agent-based approaches perform better than other typical methods in terms of accuracy and speed, and are more robust to noise and outliers.
    Pattern Recognition 01/2008;
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    ABSTRACT: Chemical analysis and scanning electron microscopy (SEM) microanalysis were carried out on cores of contaminated geological material collected around four closed waste disposal ponds to examine the extent of nitric acid extractable U (U(NA)) association with P, S, and extractable Fe, Al, and Mn oxides within deeply weathered fractured shale. The solid phase in many regimes on the site has been exposed to highly buffered acidic (< 3.5) groundwater and has been aggressively weathered. Higher correlations occur between U(NA) and total P and S (r2 = 0.76, 0.69, respectively), citrate bicarbonate dithionite extractable Fe (Fed) and Al (Ald) (r2 = 0.87, 0.80, respectively), and acid oxalate extractable or amorphous/poorly crystalline Fe (Feo) (r2 = 0.63) in core material from a field plot known as Area 1 compared to core material from another field plot known as Area 3. In Area 3 core material, linear regression analysis of U(NA) and total P and S, and Fed, Ald and Feo gave r2 values of 0.67, 0.4, 0.06, 0.24, and 0.45, respectively. These results showed similar relationships with SEM-wavelength dispersive spectroscopy (WDS) mapping of this material. It is noteworthy that Area 1 geological material has not been as aggressively weathered as Area 3 material due to its physical location from the waste source. In all of the cores, most of the Fe and Al oxides were crystalline, while most of the Mn oxides were amorphous. The greater adsorption and/or fixation of anion complexes of P-U (uranium phosphate) and S onto Fe and Al oxides from Area 1 cores compared to Area 3 core material is probably due to a higher amount of crystalline Fe and Al oxides compared to amorphous Fe and Al oxides and higher Al substitution in Fe oxides in Area 1. This unique study illustrates the relationships between U(NA), total P and S, and Al, Fe and Mn oxides in fractured shale under field conditions which can be used in planning remediation of this site and other similar sites.
    Environmental Science and Technology 12/2007; 41(22):7653-60.
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