Improvements in the two-dimensional nuclear magnetic resonance spectroscopy of humic substances

Understanding pollutant sorption, bioremediation of these pollutants, and their interactions with humic substances requires knowledge of molecular-level processes. New developments with nuclear magnetic resonance (NMR) experiments and labeled compounds have improved the overall understanding of these mechanisms. The advancements made with two-dimensional NMR show great promise, as structural information and hydrogen-carbon bond connectivity can be discerned. This communication presents the application of improved two-dimensional NMR methods, the double quantum filtered (DQF) correlation spectroscopy (COSY) and echo/anti-echo heteronuclear single quantum coherence (HSQC) experiments, for use in structural studies of humic substances. Both experiments were found to produce significant improvements over the conventional COSY and heteronuclear multiple quantum coherence (HMQC) experiments that have been previously employed in similar studies. The more sensitive echo/anti-echo HSQC experiment produced more cross-peaks with higher resolution when compared with the HMQC spectra. The DQF-COSY significantly suppressed the diagonal signals and allowed numerous signals previously hidden in the standard COSY experiment to be observed. These improvements will aid current characterization strategies of humic substances from soils, sediments, and water and their subsequent reactions with pollutants and microorganisms.     

Influence of manure application on surface energy and snow cover: model development and sensitivities

Winter landspreading is an important part of manure management in the U.S. Upper Midwest. Although the practice is thought to lead to excessive P runoff losses, surprisingly little has been learned from field experiments or current water quality models. We captured knowledge gained from winter manure landspreading experiments by modifying a mechanistic snow ablation model to include manure. The physically based, modified model simulated the observed delay in snow cover disappearance and surface energy balance changes caused by application of the manure. Additional model simulations of surface energy balance estimates of radiation and turbulent fluxes showed that during intense melting events the manure on top of snow significantly reduced the energy available for melt of the snow underneath, slowing melt. The effect was most pronounced when snowmelt was driven by both relatively high solar radiation and turbulent heat fluxes. High absorbed shortwave radiation caused significant warming of the manure, which led to substantial losses in turbulent fluxes and longwave radiation. Simulations of snowmelt also showed that manure applications between 45 and 100 Mg ha(-1) significantly reduced peak snowmelt rates, in proportion to the manure applied. Lower snowmelt rates beneath manure may allow more infiltration of meltwater compared with bare snow. This infiltration and attenuated snowmelt runoff may partially mitigate the enhanced likelihood of P runoff from unincorporated winter-spread manure.     

Natural uranium and thorium distributions in podzolized soils and native blueberry

Plant uptake of radionuclides is one of many vectors for introduction of contaminants into the human food chain. Thus, it is critical to understand soil-plant relationships that control nuclide bioavailability. Our objectives in this study were to (i) determine the extent of U and Th uptake and cycling by blueberry (Vaccinium pallidum Aiton) in native habitat and (ii) identify the soil properties and processes that contribute most to U and Th bioavailability in this system. We collected composite samples of plant leaves and stems, and samples from surface (AE) horizons and from the upper part of the Bs horizon at two sites. Concentration ratios (CRs) for U and Th were calculated for all plant tissues, using both the AE and Bs horizons as the base. Soil concentrations of U ranged from 16 to 25 microg g(-1), with a mean of 21.1 microg g(-1). Soil concentrations of Th ranged from 14 to 97 microg g(-1), with a mean of 41.8 microg g(-1). Mean U concentrations were 8.65 x 10(-3) microg g(-1) in leaf tissue, and 7.95 x 10(-3) microg g(-1) in stem tissue. Mean Th concentrations were 1.59 x 10(-1) microg g(-1) in leaf tissue, and 9.10 x 10(-2) microg g(-1) in stem tissue. Blueberry plants are cycling both U and Th in this system, with Th cycling occurring to a greater extent than U. In addition, Th was translocated preferentially to plant leaves while U concentrations showed little preferential translocation. Uranium uptake, however, seemed more sensitive than Th uptake to soil properties.     

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.     

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.     

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.     

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.     

Temporal trends for 99Tc in Norwegian coastal environments and spatial distribution in the Barents Sea

The objective of this study was to reassess 99Tc transit times and transfer factors, from Sellafield to northern Norway, and to determine the extent of 99Tc migration to the Barents Sea. Filtered seawater samples were collected on a monthly basis from Hilles?y, northern Norway, and in February 1999 from the Barents Sea. Results showed an increase in levels of 99Tc at Hilles?y where activity concentrations have increased from a baseline of 0.2-0.4Bq m(-3) to a maximum of 1.6 Bq m(-3). A transit time of 42 months and a transfer factor of 6Bq m(-3) per PBq a(-1) have been derived, using cross-correlation analysis. The current study predicts that future levels are unlikely to increase dramatically over the levels observed in 1998. Levels of 99Tc in the Barents Sea ranged from 0.2 Bq m(-3) to 1.1 Bq m(-3) showing the influence of new 99Tc inputs by early 1999.     

Transfer of 137Cs and 60Co from irrigation water to a soil-tomato plant system

An experiment has been performed at the nuclear power plant of Garigliano (Caserta, Italy), aiming at the measurement of transfer factors of 137Cs and 60Co radionuclides from the irrigation water to a soil-plant system, with particular attention to the influence on such transfers of the irrigation technique (ground or aerial). Tomato plants were irrigated weekly with water contaminated with 137Cs and 60Co (about 375 Bq/m2 week), using both irrigation techniques. After 13 weeks, fruits, leaves, stems, roots and soil were sampled, and radionuclide concentrations were measured by high-resolution gamma spectroscopy. It was found that the activity allocated to the plant organs is significantly dependent upon the irrigation technique, amounting to 2.1% and 1.6% of the activity given in the cultivation for aerial treatment and 0.4% and 0.3% for the ground treatment, for 137Cs and 60Co respectively. The activity absorbed by plants is allocated mainly in leaves (> 55%), while less then 10% is stored in the fruits, for both irrigation techniques. Transfer factors (soil-plant and irrigation water-plant) of tomato plants and of weeds have been determined for 137Cs and 60Co, as well as for natural 40K in the soil.