Multinuclear magnetic resonance analysis of two humic acid fractions from lowland rice soils

To determine the effects of intensive cropping of tropical lowland rice (Oryza sativa L.) and the associated long-term soil submergence on chemical properties of soil organic matter, we used solid-state 13C and 15N and solution 31P nuclear magnetic resonance (NMR) spectroscopy to analyze the labile mobile humic acid (MHA) and the more recalcitrant calcium humate (CaHA) fractions extracted from a series of soils supporting several long-term field experiments in the Philippines. The soils varied mainly in degree of submergence and cropping intensity, ranging from a rainfed rice field without soil submergence to irrigated double- and triple-cropped fields in which soil remains submerged almost all year long. As reported previously, all analyses associated increasing intensity of rice cropping with larger proportions of less humified material in the MHA and CaHA, such as diester phosphorus (P), amide nitrogen (N), and phenolic carbon (C). We established significant correlations between proportions of various spectral areas as well as between some spectral areas and other humic acid (HA) properties such as visible light absorption and free radical concentration (positive indices of humification) and hydrogen (H) concentration (negative index of humification). For example, spectral proportions of heterocyclic N were positively, and proportions of amide N and phenolic C negatively, correlated with visible light absorption and free radical concentration, and each of these spectral proportions had an opposite sign when correlated with H concentration. The correlations of N-alkyl C proportions were the strongest with these properties and with other functional group proportions.     

Coupled abiotic-biotic mineralization of 2,4,6-trinitrotoluene (TNT)

Munitions wastes such as TNT are widespread contaminants in soils and ground waters. We investigated a coupled abiotic-biotic treatment scheme for remediation of aqueous solutions of TNT. Mineralization of aqueous TNT (0.22 mM) was initially optimized with minimum reactant use (Fe3+ and H2O2) in light-assisted and dark, modified Fenton reactions at acidic and neutral pH. Complete TNT degradation occurred under all reaction conditions within 24 h. Using the optimum reactant concentrations, coupled abiotic-biotic reactions showed an increase in TNT mineralization, from 47 to 80%, after biomass addition to the acidic, dark Fenton-like reaction. Comparable increases of TNT mineralization were observed under neutral pH with similar reaction conditions. In light-assisted Fenton-like reactions at neutral pH, no increase in cumulative TNT mineralization (66%) was seen in coupled abiotic-biotic reactions. Abiotic photo-Fenton-like reactions alone, at acidic pH, produced complete TNT mineralization and required no biotic assistance. While light-enhanced Fenton reactions alone can provide high levels of TNT mineralization, the dark abiotic-biotic reaction scheme has perhaps a wider use due to a similar extent of TNT mineralization in the absence of light, leading to possible applications in soil slurry and in situ processes in the subsurface.     

Landscape metrics and estuarine sediment contamination in the mid-Atlantic and southern New England regions

In a previously published study, quantitative relationships were developed between landscape metrics and sediment contamination for 25 small estuarine systems within Chesapeake Bay. These analyses have been extended to include 75 small estuarine systems across the mid-Atlantic and southern New England regions of the USA. Because of the different characteristics and dynamics of the estuaries across these regions, adjustment for differing hydrology, sediment characteristics, and sediment origins were included in the analysis. Multiple linear regression with stepwise selection was used to develop statistical models for sediment metals, organics, and total polycyclic aromatic hydrocarbons (PAHs). The landscape metrics important for explaining the variation in sediment metals levels (R2 = 0.72) were the percent area of nonforested wetlands (negative contribution), percent area of urban land, and point source effluent volume and metals input (positive contributions). The metrics important for sediment organics levels (R2 = 0.5) and total PAHs (R2 = 0.46) were percent area of urban land (positive contribution) and percent area of nonforested wetlands (negative contribution). These models included silt-clay content (metals) or total organic C (organics, total PAHs) of sediments and grouping by estuarine hydrology, suggesting the importance of sediment characteristics and hydrology in mitigating the influence of the landscape metrics on sediment contamination levels. The overall results from this study are indicative of how statistical models can be developed relating landscape metrics to estuarine sediment contamination for distributions of land cover and point source discharges.     

Modelling the long-term dynamics of radiocaesium in closed lakes

During the years after the Chernobyl accident the radioceasium activity concentration in most contaminated aquatic ecosystems decreased markedly. Lakes with no permanent inflows and outflows (closed lakes), however, still present a radioecological problem which is expected to continue for some time. In this paper, a mechanistic model for the long-term prediction of radiocaesium behaviour in closed lakes is developed. The model of Prokhorov (Radiokhimiya (Radiochemistry) 11 (1969) 317) was modified to describe the effects of bottom sediment bioturbation, surface runoff from the catchment and suspended solids formation and sedimentation. The model input parameters are the effective diffusion coefficient in bottom sediments, depth of the completely mixed layer, the distribution coefficient in the sediment-water system, the runoff coefficient, sedimentation rate, and deposition density. Values of all these parameters can be independently estimated or measured in a short-term experiment. Given negligible runoff and sedimentation, the dynamics of radiocaesium in lake water is described by a simple equation with only one unknown parameter. This allows us to make long-term predictions on the basis of a series of measurements carried out during the relatively short period. The model was tested against 137Cs activity concentrations measured between 1993 and 1999 in Svyatoe lake in the Bryansk region of Russia. Calculated and measured activity concentrations are in good agreement.     

Thermal neutron fluence from ultra low-level gamma-ray spectrometry of spoons activated during the JCO criticality accident at Tokai-mura in 1999

During the JCO-accident in Tokai-mura in 1999, the surrounding village was irradiated by an uncontrolled neutron flux. At some locations in that village, the thermal neutron flux was determined retrospectively by measurement of the very low activity of 51Cr and 60Co in stainless-steel spoons using gamma-ray spectrometry in underground laboratories. Activities determined in the HADES underground facility are presented here, together with calibrations performed using a well-defined thermal neutron flux to directly estimate the fluence of thermal neutrons independent of most assumptions. The results show measurable 51Cr in three samples and 60Co in four samples taken from locations at distances of up to 430m from the accident location despite the elapse of 4 half-lives of 51Cr before measurement. Effects of air transport of the samples were considered and shown to be negligible.     

Intercomparison of INAA and ICP-MS results for thorium determination in Pakistani diet

A pilot study on ingestion and organ content of trace elements of importance in radiological protection was to be carried out in Pakistan. Baseline analytical data on daily dietary intake of thorium was to be measured using Instrumental Neutron Activation Analysis (INAA) technique. To determine the accuracy and reliability of our technique, some samples were measured in Pakistan using INAA and in Japan using Inductively Coupled Plasma-Mass Spectrometry. For intercomparison of results overall mean Z-scores were calculated. The results showed validity of our technique. Mean value of 232Th concentration in Pakistani diet samples using INAA technique is 0.0062 +/- 0.0028 microg/g and with ICP-MS technique is 0.0069 +/- 0.0032 microg/g.     

Effect of water extract of the bark of Buchanania lanzan linn. on behaviour and chromatophores of a fresh water fish,Labeo rohita

Fish exposed to 150 ppm and 250 ppm doses saparately, showed eratic swimming with hyper-excitability, spiralling, convulsion and mortality. However at 350 ppm dose fish became lethargic and steady at the bottom of aquarium. This behaviour appears to be due to sedative effects of fish implicating the phychoactive nature of the plant B. Ianzan. At 150 ppm to 350 ppm doses, fish scale changed from reticulate to punctate chromatophores; and treated fish when transferred to fresh water, were slowly regained to normal behaviour after 96 h exposure. Hence doses regaining from 150 ppm to 350 ppm is considered to be psychoative in nature. In higher doses 450 ppm and 550 ppm fish could survive only 76 h and 4.30 h respectively and then died indicating toxicity of plant for the said doses. It is found that scale present on its body is most suitable test system for the study of psychoactivity and toxicity of plant extracts on fish, Labeo rohita.     

Ni and Cu migration and accumulation in forest ecosystems on the Kola Peninsula

Biogeochemical cycles of Ni and Cu in pine forests on the northern tree line (Kola peninsula) in the background and industry-disturbed areas have been investigated. Total, bio-available and exchangeable concentrations of Ni and Cu in the soil, atmospheric Ni and Cu fluxes and soil water migration, and metal uptake by plants are considered. In the polluted area, forest ecosystems are seen as biogeochemical barriers which may attenuate intensity of Ni and Cu migration down the soil profile. A quantitative assessment is given of the role of dominating forest plants and soil horizons as barriers to heavy metal fluxes.     

Concentration changes for 5 PCDD/F congeners after administration in beef cattle

Ten cattle were treated with daily doses of five PCDD/F congeners, over a 4 week period. Four control animals were not treated. They were subsequently slaughtered as three groups, at 5, 18 and 31 weeks after the first dose. All congeners showed an increase in concentration within animal tissues when sampled at 5 weeks post-dosing. Concentrations had reduced after 18 weeks and there was a further small reduction after 31 weeks. Halflives for each congener were calculated at 13-21 weeks (93-148 days). Concentrations of congeners were different in the various tissues analysed. At 5 weeks after dosing commenced, concentrations in sub-cutaneous fat and in perirenal fat were close to 40 ng/kg (a predicted level based on 50% absorption of the dosed compounds). Concentrations on a fat basis in muscle tissue and liver were, however, about 5 and 10 times higher, respectively. The concentrations found in muscle tissue and liver samples taken at 18 and 31 weeks were approximately twice that found in fat deposits, thus the differences were still apparent, but at a reduced level. It is possible that the distribution phase was incomplete and that PCDD/Fs remained predominantly in association with circulating blood lipids rather than in equilibrium with depot fat. It follows that if livestock were recently exposed to PCDD/Fs (for example, through the consumption of contaminated feed), the analysis of depot fats would not necessarily provide a reliable indicator of the concentrations of PCDD/Fs in edible tissues.     

Immunotoxicity risks associated with land-treatment of petrochemical wastes revealed using an in situ rodent model

Land-treatment of petrochemical wastes is a widely used method to dispose of hazardous and non-hazardous waste by biodegradation. However, no comprehensive assessment of the impact of such disposal techniques on terrestrial ecosystems has been conducted. Despite the presence of suspected immunotoxicants in the soil, wild rodents frequently reside on these waste sites after closure or abandonment. We explored the seasonal sensitivity of the immune system of the hispid cotton rat (Sigmodon hispidus) to in situ exposures on sites land-treated with petrochemical wastes. Animals were monitored on five contaminated land-treatment sites and five ecologically matched-reference sites in Oklahoma, USA, over two seasons (summer and winter). Most hematological parameters were not adversely affected by land-treatment; however, platelet counts were 26% greater in cotton rats from land-treatment sites compared to reference sites in winter. Significant treatment-related differences were observed in total serum protein concentrations, organ mass and organ cellularity, but these differences were not consistent across the five land-treatment units. Lymphoproliferative responses of cotton rat splenocytes stimulated in vitro were elevated for a T-cell mitogen and depressed for a B-cell mitogen in animals from land-treatment compared to reference sites. The ability of splenocytes to proliferate in response to interleukin-2 receptor-binding was not influenced by treatment. Total yields of peritoneal cells, yield of peritoneal macrophages, and yield of peritoneal lymphocytes were influenced to varying degrees by land-treatment. Functionally, in vitro metabolic activity of peritoneal macrophages was 114% greater in cotton rats from land-treatment sites compared to reference sites during summer. These results indicate that petrochemical wastes applied to soils on these five land-treatment sites had variable immunomodulatory effects in resident cotton rats. Immune alterations for some assays were indicative of enhancement on some land-treatment sites while suppressive on other land-treatment sites, which could have been a function of type and concentration of immunotoxicants present on each site and highlights the uniqueness of each land-treatment site.