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At least 955 records · Page 53Linked to original sources
PubMed2006

Kinetics and mechanism of the degradation of methyl parathion in aqueous hydrogen sulfide solution: investigation of natural organic matter effects.

The kinetics of the transformation of methyl parathion have been investigated in aqueous solution containing reduced sulfur species and small concentrations of natural organic matter (NOM) from different sources such as soil, river, and peat. It was shown that NOM mediates the degradation of methyl parathion in aqueous solutions containing hydrogen sulfide. After evaluating and quantifying the effect of the NOM concentration on the degradation kinetics of methyl parathion in the presence of hydrogen sulfide, it was found that the observed pseudo-first-order reaction rate constants (k(obs)) were proportional to NOM concentrations. The influence of pH on the degradation of methyl parathion in the aqueous solutions containing hydrogen sulfide and NOM has been studied. The rate of degradation of methyl parathion was strongly pH dependent. The results indicate k(obs) with a commercially available humic acid has a maximum value at approximately pH 8.3. Two main reaction mechanisms are identified to dominate the degradation of methyl parathion in aqueous solution containing hydrogen sulfide and NOM based on the products aminomethyl parathion and desmethyl methyl parathion. The two mechanisms are nitro-group reduction and nucleophilic attack at the methoxy-carbon. The reduction of the nitro-group is only observed in the presence of NOM. The results of this study form an important base for the evaluation and interpretation of transformation processes of methyl parathion in the environment.

Humic Substances↗
PubMed2006

Organic phosphorus sequestration in subtropical treatment wetlands.

Diffuse phosphorus pollution is commonly remediated by diverting runoff through treatment wetlands to sequester phosphorus into soil layers. Much of the sequestered phosphorus occurs in organic forms, yet our understanding of its chemical nature is limited. We used NaOH-EDTA extraction and solution 31P NMR spectroscopy to speciate organic phosphorus sequestered in a large treatment wetland (STA-1W) in Florida, USA. The wetland was constructed on previously farmed peat and was designed to remove phosphorus from agricultural runoff prior to discharge into the Everglades. Unconsolidated benthic floc that had accumulated during the 9-year operation of the wetland was sampled along transects through two connected cells dominated by cattail (Typha dominigensis Pers.) and an additional cell colonized by submerged aquatic vegetation, including southern water nymph (Najas guadalupensis(Spreng.) Magnus) and coontail (Ceratophyllum demersum L.). Organic phosphorus was a greater proportion of the sequestered phosphorus in the cattail marsh compared to the submerged aquatic vegetation wetland, but occurred almost exclusively as phosphate diesters and their alkaline hydrolysis products. Itwas therefore markedly different from the organic phosphorus in mineral soils, which is dominated typically by inositol phosphates. Phosphate diesters are readily degradable in most soils, raising concern about the long-term fate of organic phosphorus in treatment wetlands. Further studies are now necessaryto assess the stability of the sequestered organic phosphorus in response to biogeochemical and hydrological perturbation.

Ecosystem↗
PubMed2006

Investigating the role of mineral-bound humic acid in phenanthrene sorption.

Contaminant-soil interaction studies have indicated that physical conformation of organic matter atthe solid-aqueous interface is important in governing hydrophobic organic compound (HOC) sorption. To testthis, organo-clay complexes were constructed by coating montmorillonite and kaolinite with peat humic acid (PHA) in Na+ or Ca2+ dominated solutions with varying pH and ionic strength values. The solution conditions encouraged the dissolved PHA to adopt a "coiled" or "stretched" conformation prior to interacting with the clay mineral surface. Both kaolinite and montmorillonite organo-clay complexes exhibited higher phenanthrene sorption (Koc values) with decreasing pH, indicating that the coiled configuration provided more favorable sorption conditions. Evidence from 1H high-resolution magic angle spinning (HR-MAS) nuclear magnetic resonance (NMR) indicated that polymethylene groups were prevalent at the surface of the organo-clay complexes and may enhance sorptive interactions. Preferential sorption of polymethylene groups on kaolinite and aromatic compounds on montmorillonite may also contribute to the difference in phenanthrene sorption by PHA associated with these two types of clay. This study demonstrates the importance of solution conditions in the sorption of nonionic, hydrophobic organic contaminants and also provides evidence for the indirect role of clay minerals in sorption of contaminants at the soil-water interface.

Adsorption↗
PubMed2006

Landscape control of stream water aluminum in a boreal catchment during spring flood.

Inorganic aluminum (Al) concentrations are critical for defining the biological effects of acidification. The landscape's role in controlling the spatial variability of Al and its speciation has received only limited attention. We analyzed the speciation of stream Al at 14 sites within a 68 km2 boreal catchment during spring snowmelt, a period of episodic acidity. Three factors that influenced Al at these sites were landscape type (specifically the proportion of wetland areas), stream pH, and dissolved organic carbon (DOC). Forested catchment sites underlain by mineral soils had higher total Al concentrations and greater inorganic Al proportions than catchments with larger wetland areas, despite significantly higher pH. We suggest that this difference results from source limitation of Al in the peat wetlands. The control of Al solubilitywas dominated by organic complexes, with the organic carrying capacity exceeding Al in the majority of samples. When assessing the inorganic phase, only four percent of the samples were oversaturated with regards to commonly forming secondary Al minerals, with no samples showing supersaturation higher than 10 times with respect to any given solid phase. Inorganic Al rarely exceeded biological thresholds, except for short periods during peak flow in forested areas, despite two-thirds of the streams having minimum pH values below 4.9. Streams with a high percentage of wetland area were associated with lower Al:DOC ratios. The Al:DOC ratios were quite stable in each stream before, during, and after snowmelt, with the exception of isolated spikes in the Al:DOC ratio associated with particulate Al at a downstream site during high flow.

Aluminum↗
PubMed2005

Effects of dissolved organic carbon on phosphate retention on two calcareous soils.

To evaluate the effects of dissolved organic carbon (DOC) on phosphate retention (including both sorption and/or precipitation reactions) on soils, experiments were performed by using two typical calcareous soils from southeastern Spain (Calcic Regosol and Luvic Xerosol) and two different types of DOC: (1) extracts from a commercial peat (DOC-PE) and (2) high-purity tannic acid (DOC-TA). The experiments were carried out from a 0.01 M CaCl2 aqueous medium at 25 degrees C. The results obtained show that the presence of both DOC-PE and DOC-TA, over a concentration range of 15 (DOC-15) to 100 (DOC-100) mg L(-1), produces in all cases a decreasing amount of phosphate retained in the soils studied, the decrease observed being higher when DOC-PE is used as source of DOC. The values of the decrease observed when DOC-PE was added ranged between 19.9% (DOC-15) and 15.6% (DOC-100) for the Calcic Regosol and between 17.3% (DOC-70, DOC-100) and 14.6% (DOC-15) for the Luvic Xerosol. The variation observed when DOC-TA was added ranged between 8.5% (DOC-100) and 0.5% (DOC-35) for the Calcic Regosol and between 7.0% (DOC-100) and 1.0% (DOC-15) for the Luvic Xerosol.

Adsorption↗
PubMed2005

Nitrogen isotope relationships between crops and fertilizer: implications for using nitrogen isotope analysis as an indicator of agricultural regime.

The effect of fertilizer type, amount of fertilizer applied, growing medium, and water type on the nitrogen-15 content of carrots, tomatoes, and lettuces has been investigated. Crops grown using synthetic nitrogen fertilizer were isotopically lighter than those grown using pelleted chicken manure. For example, for equivalent amounts of nitrogen applied, carrots grown with ammonium nitrate fertilizer had delta15N values between 3 per thousand and 4 per thousand lower than those grown using pelleted chicken manure. Plants grown in peat-based compost were generally found to be isotopically lighter than those grown in composted bark based compost. Results suggest that nitrate content and the delta15N of the nitrate in irrigation water may also influence crop delta15N. Wider implications of using crop delta15N more generally as an indicator of whether synthetic nitrogen fertilizers have been applied to a crop and the possible application and limitations of using crop delta15N as an indicator of agricultural regime (organic/conventional) are discussed.

Crops, Agricultural↗
PubMed2007

Adaptation of the biobed composition for chlorpyrifos degradation to Southern Europe conditions.

Biobeds developed in Sweden bind and degrade pesticides from point sources. The objective of this work was to adapt the biobed to Italian operating conditions, for example, to identify organic materials as effective as those in the original Swedish composition. The capacity of urban and garden composts alone or mixed with citrus peel or straw to degrade chlorpyrifos and its metabolite TCP was compared to the typical Swedish biomix consisting of straw, peat, and soil. A tendency for higher 14C-chlorpyrifos mineralization and lower TCP levels was observed in the biomixes with garden compost alone or amended with straw. In a second trial, a high correlation of lower TCP with increasing levels of straw in typical Swedish biomixes was observed. Straw stimulates production of lignin-degrading enzymes such as manganese peroxidase (MnP), and further trials with pure MnP showed that this enzyme degrades TCP. Materials with an active lignin-degrading microflora are a prerequisite for effective dissipation of chlorpyrifos and non-accumulation of TCP. Thus, lignocellulosic materials as straw and garden composts should be present in biomixes to be used under Italian conditions.

Chlorpyrifos↗
PubMed2005

Adsorption of organic matter at mineral/water interfaces. IV. Adsorption of humic substances at boehmite/water interfaces and impact on boehmite dissolution.

The adsorption of Suwannee River fulvic acid (SRFA) and Pahokee peat humic acid (PPHA) at the boehmite (gamma-AlOOH)/water interface and the impact of SRFA on boehmite dissolution have been examined over a wide range of solution pH conditions (pH 2-12), SRFA surface coverages (Gamma(SRFA), total SRFA binding site concentration normalized by the boehmite surface area) of 0.0-5.33 micromol m(-2), and PPHA surface coverages (Gamma(PPHA), PPHA binding site concentration normalized by boehmite surface area) of 0.0-4.0 micromol m(-2), using macroscopic adsorption and in situ attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy. At relatively high SRFA surface coverages (Gamma(SRFA) = 5.33 micromol m(-2)), in situ ATR-FTIR spectral features of adsorbed SRFA are very similar to those measured for SRFA in solution at approximately 1-3 pH units higher. At sub-monolayer surface coverages (Gamma(SRFA) = 1.20 and 2.20 micromol m(-2)), several new peaks and enhancements of the intensities of a number of existing peaks are observed. The latter spectral changes arise from several nonorganic extrinsic species (i.e., adsorbed carbonate and water, for alkaline solution conditions), partially protonated SRFA carboxyl functional groups (near-neutral pH conditions), and small quantities of inner-spherically adsorbed SRFA carboxyl groups and/or Al(III)-SRFA complexes (for acidic conditions). The spectra of PPHA adsorbed at boehmite/water interfaces also showed changes generally consistent with our observations for SRFA sorbed on boehmite. These observations confirm that SRFA and PPHA are predominantly adsorbed at the boehmite/water interface in an outer-sphere fashion, with minor inner-sphere adsorption complexes being formed only under quite acidic conditions. They also suggest that the positively charged boehmite/water interface stabilizes SRFA and PPHA carboxyl functional groups against protonation at lower pH. Measurements of the concentration of dissolved Al(III) ions in the absence and presence of SRFA showed that the boehmite dissolution process is clearly inhibited by the adsorption of SRFA, which is consistent with previous observations that outer-spherically adsorbed organic anions inhibit Al-(oxyhydr)oxide dissolution.

Journal Article↗
PubMed2000

Bioremediation of oil polluted aquatic systems and soils with novel preparation 'Rhoder'.

This paper summarises the experience accumulated during the field application of biopreparation 'Rhoder' (solely or in a combination with preliminary mechanical collection of free oil) for remediation of oil polluted aquatic systems and soils in the Moscow region and Western Siberia during 1994-1999. It was demonstrated that 'Rhoder' had a very high efficiency (>99%) for bioremediation of the open aquatic surfaces (100 m2 bay of the River Chernaya, two 5,000 m2 lakes in Vyngayakha) at initial level of oil pollution of 0.4-19.1 g/l. During remediation of the wetland (2,000 m2) in Urai (initial level of oil pollution of 10.5 g/l), a preliminary mechanical collection of oil was applied (75% removal) followed by a triple treatment with 'Rhoder'. It resulted in an overall treatment efficiency of 94%. Relatively inferior results of bioremediation of the 10,000 m2 wetland in Vyngayakha (65% removal) and the 1,000 m2 marshy peat soil in Nizhnevartovsk (19% removal) can be attributed to the very high initial level of oil pollution (24.3 g/l and >750 g/g dry matter, respectively) aggravated by the fact that it was impossible to apply a preliminary mechanical collection of oil on these sites. A possible strategy for remediation of such heavily polluted sites is discussed.

Biodegradation, Environmental↗
PubMedDate not supplied

Anatomical, cellular and molecular analysis of 8,000-yr-old human brain tissue from the Windover archaeological site.

Recovery and analysis of ancient tissue and bone of human origin has long been extensively investigated. Only recently, however, has it been technically possible to recover genetic material from ancient human and animal samples. As both previous studies involved dried tissue, it is important to determine whether other conditions may also preserve ancient tissue and genetic material. We describe here an analysis of preserved human bone and soft matter discovered in 1984-85 buried in a small swampy pond in central Florida. The recovered skeletal material represented a minimum of 40 individuals of both sexes and various ages. Corrected radiocarbon dates directly from bone and from peat matrix gave consistent ages in the range of 7,790 to 8,290 yr before present (BP). Nine individuals with intracranial soft matter were recovered and, in five of these, material recognizable as preserved or replaced brain tissue was present. Further analysis demonstrated gross anatomical features, remnant cellular structure and human DNA. As this find appears to be the oldest-known example of preserved human cell structure and DNA, it represents a significant resource for both anthropological and genetic studies.

Adult↗
PubMed2004

Millennial and orbital variations of El Niño/Southern Oscillation and high-latitude climate in the last glacial period.

The El Niño/Southern Oscillation (ENSO) phenomenon is believed to have operated continuously over the last glacial-interglacial cycle. ENSO variability has been suggested to be linked to millennial-scale oscillations in North Atlantic climate during that time, but the proposals disagree on whether increased frequency of El Niño events, the warm phase of ENSO, was linked to North Atlantic warm or cold periods. Here we present a high-resolution record of surface moisture, based on the degree of peat humification and the ratio of sedges to grass, from northern Queensland, Australia, covering the past 45,000 yr. We observe millennial-scale dry periods, indicating periods of frequent El Niño events (summer precipitation declines in El Niño years in northeastern Australia). We find that these dry periods are correlated to the Dansgaard-Oeschger events--millennial-scale warm events in the North Atlantic climate record--although no direct atmospheric connection from the North Atlantic to our site can be invoked. Additionally, we find climatic cycles at a semiprecessional timescale (approximately 11,900 yr). We suggest that climate variations in the tropical Pacific Ocean on millennial as well as orbital timescales, which determined precipitation in northeastern Australia, also exerted an influence on North Atlantic climate through atmospheric and oceanic teleconnections.

Asia↗
PubMed2005

Regional insolation forcing of late Quaternary climate change in the Southern Hemisphere.

In agreement with the Milankovitch orbital forcing hypothesis it is often assumed that glacial-interglacial climate transitions occurred synchronously in the Northern and Southern hemispheres of the Earth. It is difficult to test this assumption, because of the paucity of long, continuous climate records from the Southern Hemisphere that have not been dated by tuning them to the presumed Northern Hemisphere signals. Here we present an independently dated terrestrial pollen record from a peat bog on South Island, New Zealand, to investigate global and local factors in Southern Hemisphere climate changes during the last two glacial-interglacial cycles. Our record largely corroborates the Milankovitch model of orbital forcing but also exhibits some differences: in particular, an earlier onset and longer duration of the Last Glacial Maximum. Our results suggest that Southern Hemisphere insolation may have been responsible for these differences in timing. Our findings question the validity of applying orbital tuning to Southern Hemisphere records and suggest an alternative mechanism to the bipolar seesaw for generating interhemispheric asynchrony in climate change.

Greenhouse Effect↗
PubMed2002

Gamma spectrometry of 234Th (238U) in environmental samples.

Environmental samples from a wide-range of aquatic and soil deposits, mainly of Scandinavian origin, were analysed for 234Th (238U) using low-level gamma-spectrometry. The diversity of the samples, in terms of composition and ages, allowed a detailed evaluation of the analytical problems associated with gamma-ray spectrometry with focus on the reliability of the 234Th peaks for absolute determination of the 234Th activities. The X-ray contributions in the 93 keV peak were compared with the corresponding self-absorption corrected activities of the 63 keV peak. These X-ray contributions were, also, correlated with the 238U, 232Th, 235U, 40K and 137Cs activities of the samples. Despite the difficulties imposed by the self-absorption corrections, the 63 keV peak is still the best option. Large variability in the 93 keV peak interferences, due to X-rays from Th, exists in sediment and soil samples. Only in the case of young ombrotrophic peat samples was it possible to conclude that the 93 keV peak is free from X-ray contributions and can be as good as the 63 keV Monte-Carlo self-absorption corrected peak. X-ray contributions in the samples correlated with the 238U and 232Th activities, only, in closed environmental systems where a secular equilibrium with the daughters of the U/Th series can occur.

Radioisotopes↗
PubMed2003

Depth profiling of Pu, 241Am and 137Cs in soils from southern Belarus measured by ICP-MS and alpha and gamma spectrometry.

The depth distribution of plutonium, americium, and 137Cs originating from the 1986 accident at the Chernobyl Nuclear Power Plant (NPP) was investigated in several soil profiles in the vicinity from Belarus. The vertical migration of transuranic elements in soils typical of the 30 km relocation area around Chernobyl NPP was studied using inductively coupled plasma mass spectrometry (ICP-MS), alpha spectrometry, and gamma spectrometry. Transuranic concentrations in upper soil layers ranged from 6 x 10(-12) g g(-1) to 6 x 10(-10) g g(-1) for plutonium and from 1.8 x 10(-13) g g(-1) to 1.6 x 10(-11) g g(-1) for americium. These concentrations correspond to specific activities of (239+240)Pu of 24-2400 Bq kg(-1) and specific activity of 241Am of 23-2000 Bq kg(-1), respectively. Transuranics in turf-podzol soil migrate slowly to the deeper soil layers, thus, 80-95%, of radionuclide inventories were present in the 0-3 cm intervals of turf-podzol soils collected in 1994. In peat-marsh soil migration processes occur more rapidly than in turf-podzol and the maximum concentrations are found beneath the soil surface (down to 3-6 cm). The depth distributions of Pu and Am are essentially identical for a given soil profile. (239+240)Pu/137Cs and 241Am/137Cs activity ratios vary by up to a factor of 5 at some sites while smaller variations in these ratios were observed at a site close to Chernobyl, suggesting that 137Cs is dominantly particle associated close to Chernobyl but volatile species of 137Cs are of relatively greater importance at the distant sites.

Americium↗
PubMed2004

Characterisation of "bog butter" using a combination of molecular and isotopic techniques.

The chemical analyses of "bog butters" recovered from peat bogs of Scotland were performed with the aim of determining their origins. Detailed compositional information was obtained from "bog butter" lipids using high temperature gas chromatography (HTGC) and GC-mass spectrometry (GC-MS). The results indicate the degree to which "bog butters" have undergone diagenetic alterations during burial to form an adipocere like substance, consisting predominantly of hexadecanoic (palmitic) and octadecanoic (stearic) acids. GC-combustion-isotope ratio MS (GC-C-IRMS) was used to determine delta13C values for the dominant fatty acids present, revealing for the first time that "bog butters" were derived from both ruminant dairy fats and adipose fats. The results are compared and contrasted with modern reference fats and adipoceres produced in vitro.

Journal Article↗
PubMed2005

Uranium speciation in moorland river water samples: a comparison of experimental results and computer model predictions.

An on-line method has been developed for separating inorganic and organic bound uranium species present in river water samples. The method utilised a small chelating resin (Hyphan) column incorporated into the sample introduction manifold of an ICP-MS instrument. The method was evaluated for samples from rivers on Dartmoor (Devon, UK), an area of granite overlain with peat bogs. The results indicate that organic-uranium species form a major proportion (80%) of the total dissolved uranium present. Further work with synthetic water samples indicated that the level of dissolved organic carbon played a greater role in determining the level of organic-uranium species than did sample pH. Computer models for the water samples were constructed using the WHAM program (incorporating uranium data from the Nuclear Energy Agency Thermochemical Database project) in order to predict the levels of organic-uranium species that would form. By varying the proportion of humic and fulvic acids used in the humic component, predictions within 10% of the experimental results were obtained. The program did exhibit a low bias at higher pH values (7.5) and low organic carbon concentrations (0.5 microg ml(-1)), but under the natural conditions prevalent in the Dartmoor water samples, the model predictions were successful.

Benzopyrans↗
PubMed2000

Genetic structure of Proclossiana eunomia populations at the regional scale (Lepidoptera, nymphalidae).

Populations of Proclossiana eunomia (Lepidoptera, Nymphalidae) occur in middle Europe in patchy habitats of hay meadows along valleys or peat bogs. Samples of P. eunomia populations from the Ardennes region (northern France and southern Belgium) were analysed by allozyme electrophoresis. Patches isolated by more than 2 km of mature forests proved genetically distinct from their neighbouring populations. Mantel tests and regression analysis showed that the degree of genetic differentiation between the 26 studied populations is related to the geographical distances between them. Autocorrelation analysis (Moran's I ) showed that allele frequencies are positively correlated for populations up to 13 km apart and that the genetic neighbourhood of individuals is in the range of 0.9 km, which is in accordance with movement studies in this species conducted in the same area. Analysis using Wright's F-statistics revealed that the highest differentiation occurs between populations of the same subregion, whereas the whole Ardennes region is not genetically partitioned into subregions. This is probably because the connectivity of the network of suitable habitats has significantly weakened only since the 1950s, and thus subregional differentiation has not yet occurred.

Animals↗
PubMed2000

Physiology and taxonomy of thiobacillus strain TJ330, which oxidizes carbon disulphide (CS2).

A bacterium (strain TJ330) capable of using carbon disulphide (CS2) as its sole energy source in an acidic environment was isolated from a peat biofilter used in experiments to remove CS2 and hydrogen sulphide (H2S) from air. Its physiology and taxonomy are described here. The strain oxidized CS2, H2S and elemental sulphur to sulphate chemolithotrophically. The rate of sulphate production was highest at pH 2. The maximum growth rate constant (micromax) using CS2 as a substrate was 3.9 x 10(-2) h(-1) (generation time 18 h) and the Monod constant (Ks) was 0.97-2.6 micromol l(-1) CS2 (74-198 microg l(-1)), corresponding to an equilibrium with 15-40 ppm CS2 in the headspace. The optimum growth temperature using elemental sulphur as a substrate was 28 degrees C. The strain bears morphological and physiological similarities to Thiobacillus thiooxidans, but the latter is incapable of oxidizing CS2. The strain TJ330 (DSM 8985) showed only 44.2 + 11.8% DNA homology with the type strain T. thiooxidans ATCC 19377, while its homology with T. ferrooxidans ATCC 23270 was 17.1 + 3.4%. The strain TJ 330 represents a high-affinity bacterium which can effectively remove low CS2 concentrations in an acid environment. These properties can be utilized in biotechnological purification applications.

Carbon Disulfide↗