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The impact of oscillating redox conditions: Arsenic immobilisation in contaminated calcareous floodplain soils
2013
Parsons, Christopher T. | Couture, Raoul-Marie | Omoregie, Enoma O. | Bardelli, Fabrizio | Greneche, Jean-Marc | Roman-Ross, Gabriela | Charlet, Laurent
Arsenic contamination of floodplain soils is extensive and additional fresh arsenic inputs to the pedosphere from human activities are ongoing.We investigate the cumulative effects of repetitive soil redox cycles, which occur naturally during flooding and draining, on a calcareous fluvisol, the native microbial community and arsenic mobility following a simulated contamination event.We show through bioreactor experiments, spectroscopic techniques and modelling that repetitive redox cycling can decrease arsenic mobility during reducing conditions by up to 45%. Phylogenetic and functional analyses of the microbial community indicate that iron cycling is a key driver of observed changes to solution chemistry. We discuss probable mechanisms responsible for the arsenic immobilisation observed in-situ. The proposed mechanisms include, decreased heterotrophic iron reduction due to the depletion of labile particulate organic matter (POM), increases to the proportion of co-precipitated vs. aqueous or sorbed arsenic with α-FeOOH/Fe(OH)3 and potential precipitation of amorphous ferric arsenate.
Show more [+] Less [-]Micro x-ray absorption spectroscopic analysis of arsenic localization and biotransformation in Chironomus riparius Meigen (Diptera: Chironomidae) and Culex tarsalis Coquillett (Culicidae)
2013
Mogren, Christina L. | Webb, Samuel M. | Walton, William E. | Trumble, John T.
The distribution and speciation of arsenic (As) were analyzed in individuals of various life stages of a midge, Chironomus riparius, and the mosquito Culex tarsalis exposed to 1000 μg/l arsenate. X-ray absorption spectroscopy (XAS) revealed that C. riparius larvae accumulate As in their midgut, with inorganic arsenate [As(V)] being the predominant form, followed by arsenite [As(III)] and an As-thiol. Reduced concentrations of As in pupal and adult stages of C. riparius indicate excretion of As between the larval and pupal stages. In adults, As was limited to the thorax, and the predominant form was an As-thiol. In Cx. tarsalis, As was not found in high enough concentrations to determine As speciation, but the element was distributed throughout the larva. In adults, As was concentrated in the thorax and eyes of adults. These results have implications for understanding the biotransformation of As and its movement from aquatic to terrestrial environments.
Show more [+] Less [-]Novel biospectroscopy sensor technologies towards environmental health monitoring in urban environments
2013
Obinaju, Blessing E. | Martin, Francis L.
Biospectroscopy is an emerging inter-disciplinary field that exploits the application of sensor technologies [e.g., Fourier-transform infrared spectroscopy, Raman spectroscopy] to lend novel insights into biological questions. Methods involved are relatively non-destructive so samples can subsequently be analysed by more conventional approaches, facilitating deeper mechanistic insights. Fingerprint spectra are derived and these consist of wavenumber–absorbance intensities; within a typical biological experiment, a complex dataset is quickly generated. Biological samples range from biofluids to cytology to tissues derived from human or sentinel sources, and analyses can be carried out ex vivo or in situ in living tissue. A reference range of a designated normal state can be derived; anything outside this is potentially atypical and discriminating chemical entities identified. Computational approaches allow one to minimize within-category confounding factors. Because of ease of sample preparation, low-cost and high-throughput capability, biospectroscopy approaches herald a new greener means of environmental health monitoring in urban environments.
Show more [+] Less [-]Investigation of gold nanoparticles uptake and their tissue level distribution in rice plants by laser ablation-inductively coupled-mass spectrometry
2013
Koelmel, Jeremy | Leland, Thomas | Wang, Huanhua | Amarasiriwardena, Dulasiri | Xing, Baoshan
The tissue level uptake and spatial distribution of gold nanoparticles (AuNPs) in rice (Oryza sativa L.) roots and shoots under hydroponic conditions was investigated using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS). Rice plants were hydroponically exposed to positively, neutrally, and negatively charged AuNPs [AuNP1(+), AuNP2(0), AuNP3(−)] with a core diameter of 2 nm. Plants were exposed to AuNPs having 1.6 mg Au/L for 5 days or 0.14 mg Au/L for 3 months to elucidate how the surface charges of the nanoparticles affects their uptake into living plant tissues. The results demonstrate that terminal functional groups greatly affected the AuNP uptake into plant tissues. Au concentration determined by LA-ICP-MS in 5 day treated rice roots followed this order: AuNP1(+) > AuNP2(0) > AuNP3(−) but this order was reversed for rice shoots, indicating preferential translocation of AuNP3(−). Bioimages revealed distributions of mesophyll and vascular AuNP dependent on organ or AuNP concentration.
Show more [+] Less [-]Interactions of tetracycline with Cd (II), Cu (II) and Pb (II) and their cosorption behavior in soils
2013
Zhao, Yanping | Tan, Yinyue | Guo, Yong | Gu, Xueyuan | Wang, Xiaorong | Zhang, Yan
Tetracycline (TC), a common antibiotic, can behave as an efficient ligand with cations, but the effect of its interaction with heavy metal cations on the mobility of both species in soils has not been well evaluated. In this study, the complexation affinities of TC with Cd (II), Cu (II) and Pb (II) were examined using potentiometric titration and spectroscopic methods. The cosorption behavior of TC and metal ions onto three selected Chinese soils was evaluated using batch adsorption experiments. The presence of metal cations promoted TC adsorption through an ion bridging effect in the order Cu (II) > Pb (II) > Cd (II), which is in accordance with their complexation ability with TC. The addition of TC affects metal adsorption differently depending on the solution pH and metal type. Therefore, it is necessary to consider the complexation ability of TC and divalent metal cations when evaluating their mobility in soils.
Show more [+] Less [-]Pb and Zn imaging and in situ speciation at the geogenic/biogenic interface in sentinel earthworms using electron microprobe and synchrotron micro-focus X-ray spectroscopy
2013
Morgan, A.J. | Kille, P. | Bennett, A. | O'Reilly, M. | Fisher, P. | Charnock, J.M.
Using synchrotron- and electron microscope-based X-ray microanalyses, the distribution and speciation of Zn and Pb were examined in situ in two earthworm species (Dendrodrilus rubidus and Lumbricus rubellus) living in heavily-polluted soils. Main findings: (i) Zn spectra in ingested soil and in tissues more closely resembled Zn3(PO4)2 than ZnS; (ii) Zn speciation in tissues gave a best fit for Zn to the inner shell of 4 oxygens at 1.94 Å (or nitrogens at 1.96 Å); (iii) the best fit for Pb in tissue was with a shell of oxygens at 2.18 Å and a shell of sulphurs at 2.67 Å; (iv) a component of the Zn and much of the Pb detectable in gut contents was co-distributed with S; (v) Zn and Pb display ‘soft’ acid affinities in soil, but ‘hard’ acid affinities in tissue. This is the first metal characterisation study conducted on an invertebrate quench-frozen in the field.
Show more [+] Less [-]Arsenic K-edge X-ray absorption near-edge spectroscopy to determine oxidation states of arsenic of a coastal aquifer–aquitard system
2013
Wang, Ya | Jiao, Jiu Jimmy | Zhu, Sanyuan | Li, Yiliang
Determination of oxidation states of solid-phase arsenic in bulk sediments is a valuable step in the evaluation of its bioavailability and environmental fate in deposits, but is difficult when the sediments have low arsenic contents and heterogeneous distribution of arsenic species. As K-edge X-ray absorption near-edge spectroscopy (XANES) was used to determine quantitatively the oxidation states of arsenic in sediments collected from different depths of boreholes in the Pearl River Delta, China, where the highest aquatic arsenic concentration is 161.4 μg/L, but the highest solid arsenic content only 39.6 mg/kg. The results demonstrated that XANES is efficient in determining arsenic oxidation states of the sediments with low arsenic contents and multiple arsenic species. The study on the high-resolution vertical variations of arsenic oxidation states also indicated that these states are influenced strongly by groundwater activities. With the help of geochemical data, solid arsenic speciation, toxicity and availability were further discussed.
Show more [+] Less [-]Biomonitors of urban air pollution: Magnetic studies and SEM observations of corticolous foliose and microfoliose lichens and their suitability for magnetic monitoring
2013
Chaparro, Marcos A.E. | Lavornia, Juan M. | Chaparro, Mauro A.E. | Sinito, Ana M.
This study explored the suitability of available lichen species as air pollution biomonitors and assessed their potential for magnetic monitoring in cities. Several lichens on tree bark were collected in urban and industrial sites from Tandil city, as well as control sites. The results showed that magnetite-like minerals were the main magnetic carriers in all sites and samples. However, the concentration varied between clean and polluted sites. In addition, magnetic-grain size-distribution showed clear differences between sites. Observations by scanning electron microscopy showed different particles in a variety of shapes and grain sizes; moreover, the presence of iron oxides and several toxic elements was detected by energy dispersive spectroscopy analysis. Although eleven lichen species were identified that appeared suitable for use as air-pollution monitors, three of them, Parmotrema pilosum, Punctelia hipoleucites and Dirinaria picta, occurred more frequently in the area, thus constituting appropriate species for future monitoring in the study area.
Show more [+] Less [-]Tracing organic matter removal in polluted coastal waters via floating bed phytoremediation
2013
Huang, Lingfeng | Zhuo, Jianfu | Guo, Weidong | Spencer, Robert G.M. | Zhang, Zhiying | Xu, Jing
Organic matter removal by cultured Sesuvium portulacastrum in constructed floating beds was studied during a 20day greenhouse experiment and an 8month field campaign in the polluted Yundang Lagoon (southeastern China). Experiments were traced via dissolved organic carbon (DOC) concentration, fluorescence excitation–emission matrix and absorption spectroscopy. Two ‘terrestrial’ humic-like, one ‘marine’ humic-like and one protein-like components were identified by parallel factor analysis. The ‘terrestrial’ humic-like and protein-like components, DOC and absorption coefficient (a280) decreased during the greenhouse experiment. The intensities of four fluorescence components were all reduced during the field experiment. These results demonstrate the clear potential of floating bed phytoremediation techniques for reducing organic pollution degree in brackish environments. The rhizosphere may play an important role during phytoremediation. Our results show that spectrophotometric measurements such as fluorescence provide a useful tool for examining the removal of different organic moieties during various bioremediation processes.
Show more [+] Less [-]The measurement of gamma-emitting radionuclides in beach sand cores of coastal regions of Ramsar, Iran using HPGe detectors
2013
Tari, Marziyeh | Moussavi Zarandi, Sayyed Ali | Mohammadi, Kheirollah | Zare, Mohammad Reza
Radionuclides which present in different beach sands are sources of external exposure that contribute to the total radiation exposure of human. 226Ra, 235U, 232Th, 40K and 137Cs analysis has been carried out in sand samples collected at six depth levels, from eight locations of the northern coast of Iran, Ramsar, using high-resolution gamma-ray spectroscopy. The average Specific activities of natural radionuclides viz., 226Ra, 235U, 232Th, 40K and 137Cs, in the 0–36cm depth sand were found as: 19.2±0.04, 2.67±0.17, 17.9±0.06, 337.5±0.61 and 3.35±0.12 Bqkg−1, respectively. The effects of organic matter content and pH value of sand samples on the natural radionuclide levels were also investigated. Finally, the measured radionuclide concentrations in the Ramsar beach were compared with the world average values, as reported by UNSCEAR (2000). None of the studied beaches were considered as a radiological risk.
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