Copper and zinc speciation in the solution of a soil-sludge mixture

Only a small fraction of the transition metals content in sludge-amended soils is soluble, and yet this fraction is a major contributor to the mobility and bioavailability of the metals. The chemical species of zinc (Zn) and copper (Cu) in the soluble fractions of soil-sludge mixtures were characterized with respect to their charge, molecular weight, and stoichiometry using ion exchange resin and gel chromatography procedures. The change in the metals' species with time after sludge application was followed for 100 d. Copper in the water extracts of the sludge-sand mixtures was found almost exclusively in low molecular weight (below 1000 Da) complexes. Higher molecular weight (around 2500 Da) dissolved organic carbon (DOC) was present in the extracts as well, but this DOC fraction exhibited little complexation. Copper was present in the extracts mainly as negatively charged species throughout the incubation period, and zinc tended to form zwitter ions. As incubation progressed, the relative content of positively charged Zn in solution increased. Complexation capacity of DOC in sludge water extract, extrapolated to infinite dilution, was 8.75 mM Ca g(-1) DOC. When the complexation capacity of the extract is near saturation, a mean Cu-DOC complex can be defined. It consists of 1.9 Cu atoms attached to DOC species containing 5.6 C atoms. Thus, the organic Cu complexes consist primarily of about two Cu ions attached to DOC species containing only five or six C atoms. Amino acids and small peptides or polycarboxylic acids, such as citric acid, thus may be important complexing agents of the metal.     

Genotoxicity is unrelated to total concentration of priority carcinogenic polycyclic aromatic hydrocarbons in soils undergoing biological treatment

A solid-phase microbiological assay was used to determine the changes in genotoxicity associated with sequestration or biodegradation of carcinogenic compounds in contaminated soils. The concentration of six carcinogenic polycyclic aromatic hydrocarbons (PAHs) did not change in 59 d in sterile soil, but the genotoxicity declined markedly. In a soil undergoing bioremediation in the field for 147 d or biodegradation in the laboratory for 180 d, the concentrations either changed little or declined at different rates, but the genotoxicity increased followed by a decline. The genotoxicity of a second soil declined as a result of biological treatment. The data show that genotoxicity of contaminated soils may be unrelated to the concentration of carcinogenic PAHs because of aging or new mutagens formed during biological treatment.     

Vegetation stress detection through chlorophyll a + b estimation and fluorescence effects on hyperspectral imagery

Physical principles applied to remote sensing data are key to successfully quantifying vegetation physiological condition from the study of the light interaction with the canopy under observation. We used the fluorescence-reflectance-transmittance (FRT) and PROSPECT leaf models to simulate reflectance as a function of leaf biochemical and fluorescence variables. A series of laboratory measurements of spectral reflectance at leaf and canopy levels and a modeling study were conducted, demonstrating that effects of chlorophyll fluorescence (CF) can be detected by remote sensing. The coupled FRT and PROSPECT model enabled CF and chlorophyll a + b (Ca + b) content to be estimated by inversion. Laboratory measurements of leaf reflectance (r) and transmittance (t) from leaves with constant Ca + b allowed the study of CF effects on specific fluorescence-sensitive indices calculated in the Photosystem I (PS-I) and Photosystem II (PS-II) optical region, such as the curvature index [CUR; (R675.R690)/R2(683)]. Dark-adapted and steady-state fluorescence measurements, such as the ratio of variable to maximal fluorescence (Fv/Fm), steady state maximal fluorescence (F'm), steady state fluorescence (Ft), and the effective quantum yield (delta F/F'm) are accurately estimated by inverting the FRT-PROSPECT model. A double peak in the derivative reflectance (DR) was related to increased CF and Ca + b concentration. These results were consistent with imagery collected with a compact airborne spectrographic imager (CASI) sensor from sites of sugar maple (Acer saccharum Marshall) of high and low stress conditions, showing a double peak on canopy derivative reflectance in the red-edge spectral region. We developed a derivative chlorophyll index (DCI; calculated as D705/D722), a function of the combined effects of CF and Ca + b content, and used it to detect vegetation stress.     

Modeling the fate of benzo[a]pyrene in the wastewater-irrigated areas of Tianjin with a fugacity model

A Level III fugacity model was applied to characterize the transfer processes and environmental fate of benzo[a]pyrene in wastewater-irrigated areas of Tianjin, China. The physical-chemical properties and transfer parameters of benzo[a]pyrene were used in the model and the concentration distribution of benzo[a]pyrene in sediment, soil, water, air, fish, and crop compartments, as well as transfer fluxes across the compartments, were then derived under steady-state assumptions. The calculated results were compared with monitoring data for air, soil, water, and sediment collected from the literature. The results indicate that there was generally good agreement and the differences were within an order of magnitude for air, soil, and sediment. The concentration of benzo[a]pyrene in the ambient air in the area was very low with a majority present sorbed to aerosol. In the water compartment, approximately 70% of benzo[a]pyrene dissolved in water phase. Relatively high concentrations of the compound were found in the soil and sediment, with the soil serving as the dominant sink in the area. Benzo[a]pyrene, with a slow metabolic rate, was found to accumulate in fish in the area.     

Changes in soil quality and below-ground carbon storage with conversion of traditional agricultural crop lands to bioenergy crop production

Berm-isolated (0.5 ha) plots have been used since 1995 to quantify changes in soil and water quality with conversion from agricultural to bioenergy crops. Soil quality improvements, including increases in soil carbon storage, have occurred on sites planted to woody or herbaceous species, and no-till corn compared with tilled corn or cotton. Initial increases in soil carbon occurred within the upper 10 cm of the soil profile. Soil carbon on plantings of switchgrass, no-till corn, and sweetgum with a cover crop between the rows increased over the first 3 years. Soil carbon decreased by 6% on the sweetgum plantings without a cover crop and remained lower through the fifth growing season. Overall, the greatest increases in below ground carbon storage have occurred primarily within the upper 40 cm. Former land use, growth characteristics, management practices, and soil characteristics appear to be the primary factors determining the timing, depth. and extent of changes in soil carbon storage for bioenergy and no-till crops.     

Use of pyrolysis molecular beam mass spectrometry (py-MBMS) to characterize forest soil carbon: method and preliminary results

The components of soil organic matter (SOM) and their degradation dynamics in forest soils are difficult to study and thus poorly understood, due to time-consuming sample collection, preparation, and difficulty of analyzing and identifying major components. As a result, changes in soil organic matter chemical composition as a function of age, forest type, or disturbance have not been examined. We applied pyrolysis molecular beam mass spectrometry (py-MBMS), which provides rapid characterization of SOM of whole soil samples. to the Tionesta soil samples described by Hoover, C.M., Magrini, K.A., Evans, R.J., 2002. Soil carbon content and character in an old growth forest in northwestern Pennsylvania: a case study introducing molecular beam mass spectrometry (PY-MBMS). Environmental Pollution 116 (Supp. 1), S269-S278. Our goals in this work were to: (1) develop and demonstrate an advanced, rapid analytical method for characterizing SOM components in whole soils, and (2) provide data-based models to predict soil carbon content and residence time from py-MBMS analysis. Using py-MBMS and pattern recognition techniques we were able to statistically distinguish among four Tionesta sites and show an increase in pyrolysis products of more highly decomposed plant materials at increasing sample depth. For example, all four sites showed increasing amounts of older carbon (phenolic and aromatic species) at deeper depths and higher amounts of more recent carbon (carbohydrates and lignin products) at shallower depths. These results indicate that this type of analysis could be used to rapidly characterize SOM for the purpose of developing a model, which could be used in monitoring the effect of forest management practices on carbon uptake and storage.     

The influence of nitrogen deposition,competition and desiccation on growth and regeneration of Racomitrium lanuginosum (Hedw.) brid

Racomitrium lanuginosum shoot growth was studied under the combined effects of N deposition (0, 20, 40 and 60 kg N ha(-1) year(-1)). competition with Festuca ovina, and a drought pre-treatment. Moss regeneration from shoot fragments was also investigated. Growth was initially stimulated at the 60 kg N level. However, after 6 months, growth was lower in all N treatments than in the 0 kg N control. Reductions in shoot growth first became apparent in the pre-desiccated moss, while moss shoots grew longer when surrounded by a F. ovina canopy. Optimum regeneration occurred at 20-40 kg N on bare soil, and at 0-20 kg N under a F. ovina canopy. These results suggest that current N deposition in upland Wales is already detrimental to growth of this species, and to regeneration under certain conditions. This species may be affected under predicted climatic scenarios of increased summer drought in Britain.     

Radioactive contamination in the Arctic--sources, dose assessment and potential risks

Arctic residents, whose diets comprise a large proportion of traditional terrestrial and freshwater foodstuffs, have received the highest radiation exposures to artificial radionuclides in the Arctic. Doses to members of both the average population and selected indigenous population groups in the Arctic depend on the rates of consumption of locally-derived terrestrial and freshwater foodstuffs, including reindeer/caribou meat, freshwater fish, goat cheese, berries, mushrooms and lamb. The vulnerability of arctic populations, especially indigenous peoples, to radiocaesium deposition is much greater than for temperate populations due to the importance of terrestrial, semi-natural exposure pathways where there is high radiocaesium transfer and a long ecological half-life for this radionuclide. In contrast, arctic residents with diets largely comprising marine foodstuffs have received comparatively low radiation exposures because of the lower levels of contamination of marine organisms. Using arctic-specific information, the predicted collective dose is five times higher than that estimated by UNSCEAR for temperate areas. The greatest threats to human health and the environment posed by human and industrial activities in the Arctic are associated with the potential for accidents in the civilian and military nuclear sectors. Of most concern are the consequences of potential accidents in nuclear power plant reactors, during the handling and storage of nuclear weapons, in the decommissioning of nuclear submarines and in the disposal of spent nuclear fuel from vessels. It is important to foster a close association between risk assessment and practical programmes for the purposes of improving monitoring, formulating response strategies and implementing action plans.     

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.     

An analysis of the environmental mobility of radiostrontium from weapons testing and Chernobyl in Finnish river catchments

The mobility of radiostrontium within the Arctic environment and surrounding area has been studied by analysing the mobility of 90Sr in river catchments that are within Finland. The environmental mobility of 90Sr deposited by both nuclear weapons testing and the Chernobyl accident has been investigated in five Finnish river catchments. Different models assessing the time-dependent mobility of 90Sr have been evaluated. No significant differences were found between the mobility of 90Sr from nuclear weapons tests and from the Chernobyl accident. Model parameters obtained by fitting to the measurements of the deposition and runoff rates of the nuclear weapons test fallout gave predictions which were consistent with the mid- and long-term contamination by the Chernobyl fallout. A comparison of 90Sr with 137Cs showed that they had similar mobility on deposition but, as time passed, the relative mobility of 90Sr increased with respect to 137Cs over a period of 5-8 years. Once the relative migration of 90Sr with respect to 137Cs reached equilibrium, its runoff rate was, on average, approximately an order of magnitude greater than 137Cs.