The influence of organic acids in relation to acid deposition in controlling the acidity of soil and stream waters on a seasonal basis

Much uncertainty still exists regarding the relative importance of organic acids in relation to acid deposition in controlling the acidity of soil and surface waters. This paper contributes to this debate by presenting analysis of seasonal variations in atmospheric deposition, soil solution and stream water chemistry for two UK headwater catchments with contrasting soils. Acid neutralising capacity (ANC), dissolved organic carbon (DOC) concentrations and the Na:Cl ratio of soil and stream waters displayed strong seasonal patterns with little seasonal variation observed in soil water pH. These patterns, plus the strong relationships between ANC, Cl and DOC, suggest that cation exchange and seasonal changes in the production of DOC and seasalt deposition are driving a shift in the proportion of acidity attributable to strong acid anions, from atmospheric deposition, during winter to predominantly organic acids in summer.

Identifying management zones in agricultural fields using spatially constrained classification of soil and ancillary data

Site-specific management requires accurate knowledge of the spatial variation in a range of soil properties within fields. This involves considerable sampling effort, which is costly. Ancillary data, such as crop yield, elevation and apparent electrical conductivity (ECa) of the soil, can provide insight into the spatial variation of some soil properties. A multivariate classification with spatial constraint imposed by the variogram was used to classify data from two arable crop fields. The yield data comprised 5 years of crop yield, and the ancillary data 3 years of yield data, elevation and ECa. Information on soil chemical and physical properties was provided by intensive surveys of the soil. Multivariate variograms computed from these data were used to constrain sites spatially within classes to increase their contiguity. The constrained classifications resulted in coherent classes, and those based on the ancillary data were similar to those from the soil properties. The ancillary data seemed to identify areas in the field where the soil is reasonably homogeneous. The results of targeted sampling showed that these classes could be used as a basis for management and to guide future sampling of the soil.

Evaluation of ozone and water vapor fields from the ECMWF reanalysis ERA-40 during 1991-1999 in comparison with UARS satellite and MOZAIC aircraft observations

[ 1] The European Centre for Medium-Range Weather Forecasts (ECMWF) 40-year Reanalysis (ERA-40) ozone and water vapor reanalysis fields during the 1990s have been compared with independent satellite data from the Halogen Occultation Experiment (HALOE) and Microwave Limb Sounder (MLS) instruments on board the Upper Atmosphere Research Satellite (UARS). In addition, ERA-40 has been compared with aircraft data from the Measurements of Ozone and Water Vapour by Airbus In-Service Aircraft (MOZAIC) program. Overall, in comparison with the values derived from the independent observations, the upper stratosphere in ERA-40 has about 5 - 10% more ozone and 15 - 20% less water vapor. This dry bias in the reanalysis appears to be global and extends into the middle stratosphere down to 40 hPa. Most of the discrepancies and seasonal variations between ERA-40 and the independent observations occur within the upper troposphere over the tropics and the lower stratosphere over the high latitudes. ERA-40 reproduces a weaker Antarctic ozone hole, and of less vertical extent, than the independent observations; values in the ozone maximum in the tropical stratosphere are lower for the reanalysis. ERA-40 mixing ratios of water vapor are considerably larger than those for MOZAIC, typically by 20% in the tropical upper troposphere, and they may exceed 60% in the lower stratosphere over high latitudes. The results imply that the Brewer-Dobson circulation in the ECMWF reanalysis system is too fast, as is also evidenced by deficiencies in the way ERA-40 reproduces the water vapor "tape recorder'' signal in the tropical stratosphere. Finally, the paper examines the biases and their temporal variation during the 1990s in the way ERA-40 compares to the independent observations. We also discuss how the evaluation results depend on the instrument used, as well as on the version of the data.

Oxidation of biogenic and water-soluble compounds in aqueous and organic aerosol droplets by ozone: a kinetic and product analysis approach using laser Raman tweezers

The results of an experimental study into the oxidative degradation of proxies for atmospheric aerosol are presented. We demonstrate that the laser Raman tweezers method can be used successfully to obtain uptake coeffcients for gaseous oxidants on individual aqueous and organic droplets, whilst the size and composition of the droplets is simultaneously followed. A laser tweezers system was used to trap individual droplets containing an unsaturated organic compound in either an aqueous or organic ( alkane) solvent. The droplet was exposed to gas- phase ozone and the reaction kinetics and products followed using Raman spectroscopy. The reactions of three different organic compounds with ozone were studied: fumarate anions, benzoate anions and alpha pinene. The fumarate and benzoate anions in aqueous solution were used to represent components of humic- like substances, HULIS; a alpha- pinene in an alkane solvent was studied as a proxy for biogenic aerosol. The kinetic analysis shows that for these systems the diffusive transport and mass accommodation of ozone is relatively fast, and that liquid- phase di. ffusion and reaction are the rate determining steps. Uptake coe. ffcients, g, were found to be ( 1.1 +/- 0.7) x 10(-5), ( 1.5 +/- 0.7) x 10 (-5) and ( 3.0 - 7.5) x 10 (-3) for the reactions of ozone with the fumarate, benzoate and a- pinene containing droplets, respectively. Liquid- phase bimolecular rate coe. cients for reactions of dissolved ozone molecules with fumarate, benzoate and a- pinene were also obtained: k(fumarate) = ( 2.7 +/- 2) x 10 (5), k(benzoate) = ( 3.5 +/- 3) x 10 (5) and k(alpha-pinene) = ( 1-3) x 10(7) dm(3) mol (-1) s (- 1). The droplet size was found to remain stable over the course of the oxidation process for the HULIS- proxies and for the oxidation of a- pinene in pentadecane. The study of the alpha- pinene/ ozone system is the first using organic seed particles to show that the hygroscopicity of the particle does not increase dramatically over the course of the oxidation. No products were detected by Raman spectroscopy for the reaction of benzoate ions with ozone. One product peak, consistent with aqueous carbonate anions, was observed when following the oxidation of fumarate ions by ozone. Product peaks observed in the reaction of ozone with alpha- pinene suggest the formation of new species containing carbonyl groups.

Contributions of matric and osmotic potentials to the unfrozen water content of frozen soils

Recent reports show that biogeochemical processes continue when the soil is frozen, but are limited by water availability. However, there is little knowledge about the interactive effects of soil and environmental variables on amounts of unfrozen water in frozen soils. The aims of this study were to determine the contributions of matric and osmotic potentials to the unfrozen water content of frozen soil. We determined the effects of matric and osmotic potential on unfrozen water contents of frozen mineral soil fractions (ranging from coarse sand to fine silt) at -7 degrees C, and estimated the contributions of these potentials to liquid water contents in samples from organic surface layers of boreal soils frozen at -4 degrees C. In the mineral soil fractions the unfrozen water contents appeared to be governed solely by the osmotic potential, but in the humus layers of the sampled boreal soils both the osmotic and matric potentials control unfrozen water content, with osmotic potential contributing 20 to 69% of the total water potential. We also determined pore size equivalents, where unfrozen water resides at -4 degrees C, and found a strong correlation between these equivalents and microbial CO2 production. The larger the pores in which the unfrozen water is found the larger the microbial activity that can be sustained. The osmotic potential may therefore be a key determinant of unfrozen water and carbon dynamics in frozen soil. (C) 2008 Elsevier B.V. All rights reserved.

Estimating the spatial scale of herbicide and soil interactions by nested sampling, hierarchical analysis of variance and residual maximum likelihood

An unbalanced nested sampling design was used to investigate the spatial scale of soil and herbicide interactions at the field scale. A hierarchical analysis of variance based on residual maximum likelihood (REML) was used to analyse the data and provide a first estimate of the variogram. Soil samples were taken at 108 locations at a range of separating distances in a 9 ha field to explore small and medium scale spatial variation. Soil organic matter content, pH, particle size distribution, microbial biomass and the degradation and sorption of the herbicide, isoproturon, were determined for each soil sample. A large proportion of the spatial variation in isoproturon degradation and sorption occurred at sampling intervals less than 60 m, however, the sampling design did not resolve the variation present at scales greater than this. A sampling interval of 20-25 m should ensure that the main spatial structures are identified for isoproturon degradation rate and sorption without too great a loss of information in this field.

A geostatistical analysis of soil, vegetation, and image data characterizing land surface variation

The elucidation of spatial variation in the landscape can indicate potential wildlife habitats or breeding sites for vectors, such as ticks or mosquitoes, which cause a range of diseases. Information from remotely sensed data could aid the delineation of vegetation distribution on the ground in areas where local knowledge is limited. The data from digital images are often difficult to interpret because of pixel-to-pixel variation, that is, noise, and complex variation at more than one spatial scale. Landsat Thematic Mapper Plus (ETM+) and Satellite Pour l'Observation de La Terre (SPOT) image data were analyzed for an area close to Douna in Mali, West Africa. The variograms of the normalized difference vegetation index (NDVI) from both types of image data were nested. The parameters of the nested variogram function from the Landsat ETM+ data were used to design the sampling for a ground survey of soil and vegetation data. Variograms of the soil and vegetation data showed that their variation was anisotropic and their scales of variation were similar to those of NDVI from the SPOT data. The short- and long-range components of variation in the SPOT data were filtered out separately by factorial kriging. The map of the short-range component appears to represent the patterns of vegetation and associated shallow slopes and drainage channels of the tiger bush system. The map of the long-range component also appeared to relate to broader patterns in the tiger bush and to gentle undulations in the topography. The results suggest that the types of image data analyzed in this study could be used to identify areas with more moisture in semiarid regions that could support wildlife and also be potential vector breeding sites.

Environmental and human health impacts of growing genetically modified herbicide-tolerant sugar beet: a life-cycle assessment

There is ongoing debate concerning the possible environmental and human health impacts of growing genetically modified (GM) crops. Here, we report the results of a life-cycle assessment (LCA) comparing the environmental and human health impacts of conventional sugar beet growing regimes in the UK and Germany with those that might be expected if GM herbicide-tolerant (to glyphosate) sugar beet is commercialized. The results presented for a number of environmental and human health impact categories suggest that growing the GM herbicide-tolerant crop would be less harmful to the environment and human health than growing the conventional crop, largely due to lower emissions from herbicide manufacture, transport and field operations. Emissions contributing to negative environmental impacts, such as global warming, ozone depletion, ecotoxicity of water and acidification and nutrification of soil and water, were much lower for the herbicide-tolerant crop than for the conventional crop. Emissions contributing to summer smog, toxic particulate matter and carcinogenicity, which have negative human health impacts, were also substantially lower for the herbicide-tolerant crop. The environmental and human health impacts of growing GM crops need to be assessed on a case-by-case basis using a holistic approach. LCA is a valuable technique for helping to undertake such assessments.

An application of life-cycle assessment for environmental planning and management: the potential environmental and human health impacts of growing genetically-modified herbicide-tolerant sugar beet

Life-Cycle Assessment (LCA) was used to assess the potential environmental and human health impacts of growing genetically-modified (GM), herbicide-tolerant sugar beet in the UK and Germany compared with conventional sugar beet varieties. The GM variety results in lower potential environmental impacts on global warming, airborne nutrification, ecotoxicity (of soil and water) and watercourse enrichment, and lower potential human health impacts in terms of production of toxic particulates, summer smog, carcinogens and ozone depletion. Although the overall contribution of GM sugar beet to reducing harmful emissions to the environment would be relatively small, the potential for GM crops to reduce pollution from agriculture, including diffuse water pollution, is highlighted.

Development of the Surface Urban Energy and Water balance Scheme (SUEWS) for cold climate cities

The Surface Urban Energy and Water Balance Scheme (SUEWS) is developed to include snow. The processes addressed include accumulation of snow on the different urban surface types: snow albedo and density aging, snow melting and re-freezing of meltwater. Individual model parameters are assessed and independently evaluated using long-term observations in the two cold climate cities of Helsinki and Montreal. Eddy covariance sensible and latent heat fluxes and snow depth observations are available for two sites in Montreal and one in Helsinki. Surface runoff from two catchments (24 and 45 ha) in Helsinki and snow properties (albedo and density) from two sites in Montreal are also analysed. As multiple observation sites with different land-cover characteristics are available in both cities, model development is conducted independent of evaluation. The developed model simulates snowmelt related runoff well (within 19% and 3% for the two catchments in Helsinki when there is snow on the ground), with the springtime peak estimated correctly. However, the observed runoff peaks tend to be smoother than the simulated ones, likely due to the water holding capacity of the catchments and the missing time lag between the catchment and the observation point in the model. For all three sites the model simulates the timing of the snow accumulation and melt events well, but underestimates the total snow depth by 18–20% in Helsinki and 29–33% in Montreal. The model is able to reproduce the diurnal pattern of net radiation and turbulent fluxes of sensible and latent heat during cold snow, melting snow and snow-free periods. The largest model uncertainties are related to the timing of the melting period and the parameterization of the snowmelt. The results show that the enhanced model can simulate correctly the exchange of energy and water in cold climate cities at sites with varying surface cover.

GISQ, a multifunctional indicator of soil quality

We present here an indicator of soil quality that evaluates soil ecosystem services through a set of 5 subindicators, and further combines them into a single general Indicator of Soil Quality (GISQ). We used information derived from 54 properties commonly used to describe the multifaceted aspects of soil quality. The design and calculation of the indicators were based on sequences of multivariate analyses. Subindicators evaluated the physical quality, chemical fertility, organic matter stocks, aggregation and morphology of the upper 5 cm of soil and the biodiversity of soil macrofauna. A GISQ combined the different subindicators providing a global assessment of soil quality. Research was conducted in two hillside regions of Colombia and Nicaragua, with similar types of land use and socio-economic context. However, soil and climatic conditions differed significantly. In Nicaragua, soil quality was assessed at 61 points regularly distributed 200 m apart on a regular grid across the landscape. In Colombia, 8 plots representing different types of land use were arbitrarily chosen in the landscape and intensively sampled. Indicators that were designed in the Nicaragua site were further applied to the Colombian site to test for their applicability. In Nicaragua, coffee plantations, fallows, pastures and forest had the highest values of GISQ (1.00; 0.80; 0.78 and 0.77, respectively) while maize crops and eroded soils (0.19 and 0.10) had the lowest values. Examination of subindicator values allowed the separate evaluation of different aspects of soil quality: subindicators of organic matter, aggregation and morphology and biodiversity of macrofauna had the maximum values in coffee plantations (0.89; 0.72 and 0.56, respectively on average) while eroded soils had the lowest values for these indicators (0.10; 0.31 and 0.33, respectively). Indicator formulae derived from information gained at the Nicaraguan sites were not applicable to the Colombian situation and site-specific constants were calculated. This indicator allows the evaluation of soil quality and facilitates the identification of problem areas through the individual values of each subindicator. It allows monitoring of change through time and can guide the implementation of soil restoration technologies. Although GISQ formulae computed on a set of data were only valid at a regional scale, the methodology used to create these indices can be applied everywhere.

Determination of the total antioxidant activity of fruits and vegetables by a liposome assay

The effects of mixtures of antioxidants on the oxidation of phospholipids have been investigated in large unilamellar liposomes following initiation by 2,2'-azobis(2-aminopropane) dihydrochloride. The lag phase increased linearly with antioxidant concentration. The lag phases of mixtures containing alpha-tocopherol with ascorbic acid showed synergy between the antioxidants, but mixtures of beta-carotene with cc-tocopherol or ascorbic acid were not synergistic. The liposome system was used to investigate the total antioxidant activity of lipid- and water-soluble extracts from 16 samples of fruits, vegetables, and related food products. The water-soluble extracts caused greater increases in lag phase than the lipid-soluble extracts. The lag phase of liposomes containing the water-soluble extracts from fruits and vegetables increased linearly with the total phenolic concentration, with the continental salad extract having the longest lag phase. The lipid-soluble extract from apples caused the largest increase in lag phase of the lipid-soluble extracts. The lag phases of the lipid-soluble and water-soluble extracts of all fruits and vegetables studied were additive, but no synergy was detected. The lag phase of the liposomes containing both the water-soluble and lipid-soluble extracts varied from 611.5 min for the continental salad extracts to 47.5 min for the cauliflower extracts.

Water reuse for irrigated agriculture in Jordan: challenges of soil sustainability and the role of management strategies

Reclaimed water provides an important contribution to the water balance in water-scarce Jordan, but the quality of this water presents both benefits and challenges. Careful management of reclaimed water is required to maximize the nutrient benefits while minimizing the salinity risks. This work uses a multi-disciplinary research approach to show that soil response to irrigation with reclaimed water is a function of the management strategies adopted on the farm by the water user. The adoption of management methods to maintain soil productivity can be seen to be a result of farmers’ awareness to potentially plant-toxic ions in the irrigation water (70% of Jordan Valley farmers identified salinization as a hazard from irrigation with reclaimed water). However, the work also suggests that farmers’ management capacity is affected by the institutional management of water. About a third (35%) of farmers in the Jordan Valley claimed that their ability to manage salinization was limited by water shortages. Organizational interviews revealed that institutional awareness of soil management challenges was quite high (34% of interviewees described salinization as a risk from water reuse), but strategies to address this challenge at the institutional level require greater development.

The determination of total nitrogen and total phosphorus concentrations in freshwaters from land use, stock headage and population data: testing of a model for use in conservation and water quality management

1. Nutrient concentrations (particularly N and P) determine the extent to which water bodies are or may become eutrophic. Direct determination of nutrient content on a wide scale is labour intensive but the main sources of N and P are well known. This paper describes and tests an export coefficient model for prediction of total N and total P from: (i) land use, stock headage and human population; (ii) the export rates of N and P from these sources; and (iii) the river discharge. Such a model might be used to forecast the effects of changes in land use in the future and to hindcast past water quality to establish comparative or baseline states for the monitoring of change. 2. The model has been calibrated against observed data for 1988 and validated against sets of observed data for a sequence of earlier years in ten British catchments varying from uplands through rolling, fertile lowlands to the flat topography of East Anglia. 3. The model predicted total N and total P concentrations with high precision (95% of the variance in observed data explained). It has been used in two forms: the first on a specific catchment basis; the second for a larger natural region which contains the catchment with the assumption that all catchments within that region will be similar. Both models gave similar results with little loss of precision in the latter case. This implies that it will be possible to describe the overall pattern of nutrient export in the UK with only a fraction of the effort needed to carry out the calculations for each individual water body. 4. Comparison between land use, stock headage, population numbers and nutrient export for the ten catchments in the pre-war year of 1931, and for 1970 and 1988 show that there has been a substantial loss of rough grazing to fertilized temporary and permanent grasslands, an increase in the hectarage devoted to arable, consistent increases in the stocking of cattle and sheep and a marked movement of humans to these rural catchments. 5. All of these trends have increased the flows of nutrients with more than a doubling of both total N and total P loads during the period. On average in these rural catchments, stock wastes have been the greatest contributors to both N and P exports, with cultivation the next most important source of N and people of P. Ratios of N to P were high in 1931 and remain little changed so that, in these catchments, phosphorus continues to be the nutrient most likely to control algal crops in standing waters supplied by the rivers studied.