Near- and mid-infrared diffuse reflectance spectroscopy for measuring soil metal content

Rapid and nondestructive methods such as diffuse reflectance infrared spectroscopy provide potentially useful alternatives to time-consuming chemical methods of soil metal analysis. To assess the utility of near-infrared reflectance spectroscopy (NIRS) and diffuse mid-infrared reflectance spectroscopy (DRIFTS) for soil metal determination, 70 soil samples from the metal mining region of Tarnowskie Gory (Upper Silesia, Poland) were analyzed by both chemical and spectroscopic methods. Soils represented a wide range of pH (4.0-8.0), total carbon (5.1-73.2 g kg(-1)), and textural classes (from sand to silty clay loam). Soils had various contents of metals (14-4500 mg kg(-1) for Zn, 18-6530 mg kg(-1) for Pb, and 0.17-34 mg kg(-1) for Cd), ranging from natural background levels to high contents indicative of industrial contamination in the region. Soil samples were scanned at the wavelengths from 400 to 2498 nm (near-infrared region) and from 2500 to 25000 nm (mid-infrared region). Calibrations were developed using the one-out validation procedure under partial least squares (PLS) regression. Mid-infrared spectroscopy markedly outperformed NIRS. Iron, Cd, Cu, Ni, and Zn were successfully predicted using DRIFTS. The coefficients of determination (R(2)) between actual and predicted contents were 0.97, 0.94, 0.80, 0.99, and 0.96 for those metals, respectively. Only Pb content was predicted poorly. Calibrations using NIRS were less accurate. Root mean squared deviation (RMSD) values were from 1.27 (Pb) to 3.3 (Ni) times higher for NIRS than for DRIFTS. Results indicate that DRIFTS may be useful for accurate predictions of metals if samples originate from one region.     

Wasting women: The environmental justice of including women in municipal waste management

This paper explores the opportunities for and the benefits of considering gender in municipal waste management (MWM) policy. Two case studies in Ireland and the UK are presented. These show that the structural mechanisms for achieving a more consistent and coherent approach to ensuring that MWM policy is sensitive to gender differences and inequalities are still weak. They also show that political structures and champions for gender equality and equal opportunities make a difference to the way in which women are involved and considered in MWM policy making. The research is set within the broader context of environmental justice which, to date, has been more concerned with race, ethnicity and wealth inequalities than with gender inequalities.     

Influence of ash on the fiber composition of dried dairy manures

The objective of this work was to examine the role of ash in the compositional analysis of dried dairy manures. Ninety-nine dairy manures obtained from Connecticut, Maryland, New York, Pennsylvania and Virginia were dried at 60 degrees C, and ground to 20 mesh. Samples were analyzed for neutral and acid detergent fiber, acid detergent lignin, total carbon, total nitrogen, and ash. In addition, cellulose and hemicellulose were computed by difference. Results indicated that high ash contents (8-52% of dry matter) can dramatically and unpredictably alter various measures of fiber composition and are a significant source of error in the determination of manure composition and how it relates to mineralization or other compositional influenced factors. Also, while the ash content of the dried intact manure can easily be determined, it is difficult to estimate the ash contribution to the individual fiber determinations, especially if sequential assays are performed.     

Addressing analytical uncertainties in the determination of trichloroacetic acid in soil

Soil is an important compartment in the environmental cycling of trichloroacetic acid (TCA), but soil TCA concentration is a methodologically defined quantity; analytical methods either quantify TCA in an aqueous extract of the soil, or thermally decarboxylate TCA to chloroform in the whole soil sample. The former may underestimate the total soil TCA, whereas the latter may overestimate TCA if other soil components (e.g. humic material) liberate chloroform under the decarboxylation conditions. The aim of this work was to show that extraction and decarboxylation methods yield different TCA concentrations because the decarboxylation method can also determine "bound" TCA. Experiments with commercial humic acid solutions showed there was no additional chloroform formation under decarboxylation conditions, and that all TCA in a TCA-humic acid mixture could be quantitatively determined (108 +/- 13%). Anion exchange resin was used as a provider of solid-phase TCA binding; only 5 +/- 1% of a TCA solution mixed with the resin was present in the aqueous extract subsequently separated from the resin, yet the decarboxylation method yielded mass balance (123 +/- 22%) with TCA remaining in the resin. In aqueous extraction of a range of soil samples (with or without added TCA spike), the decarboxylation method was able to satisfactorily account for TCA in the extractant + residue post-extraction, compared with whole-soil TCA (+ spike) pre-extraction: e.g. mass balances for unspiked soil from Sikta spruce and larch forest were 99 +/- 8% and 93 +/- 6%, respectively, and for TCA-spiked forest and agricultural soils were 114 +/- 13% and 102 +/- 2%. In each case recovery of TCA in the extractant was substantially less than 100%(<20% for unspiked soils, <55% for spiked soils). Extraction efficiencies were generally lower in more organic soils. The results suggest that analytical methods which utilise aqueous extraction may underestimate whole-soil TCA concentrations. Application of both methodologies together may enhance insight into TCA behaviour in soil.     

An Assessment of Changes in Kunzea ericoides var. microflora and Other Hydrothermal Vegetation at the Wairakei–Tauhara Geothermal Field, New Zealand

Hydrothermal ecosystems are of high conservation and scientific value, but they are sensitive to external perturbations that result from development. This study examines the composition of vegetation at four plots at the Wairakei-Tauhara geothermal field, New Zealand, using the Scott height-frequency method, ground temperatures at 0.1- and 1-m depth, soil pH, and photographic surveys. It highlights the response of plant communities, in particular that of Kunzea ericoides var. microflora, in terms of composition, structure, and biomass index values, measures changes in ground temperature, as well as provides baseline data against which to compare future changes. It was found that optimal growing conditions for K. ericoides var. microflora are at temperatures above background conditions with a slightly acidic pH. Plots with cooler, less acidic conditions support more diverse plant communities, which also promote the establishment of invasive species. This suggests that the largest threats to thermotolerant vegetation in New Zealand, including K. ericoides var. microflora, are further decreases in ground temperature because the establishment of invasive species may result in thermolerant vegetation being out-competed in hydrothermal ecosystems. Recognising and understanding the ecological diversity and dynamics of hydrothermal ecosystems, as well as acknowledging the competing interests between development and conservation, is key to the management and protection of these areas.     

Alkyl nitrate photochemistry during the tropospheric organic chemistry experiment

Alkyl nitrates (C₁–C₅) were measured at two sites (near urban and rural) in southeast England during the Tropospheric Organic Chemistry Experiment (TORCH). Methyl nitrate was the dominant species during both campaigns accounting for on average about one third of the total measured alkyl nitrates. High mixing ratios (>50 pptv) and variability of methyl nitrate were observed at the near urban site (TORCH1) that were not seen at the rural site (TORCH2) and which could not be explained by local photochemical production or direct emissions. The diurnal variation of methyl nitrate during TORCH1 showed a morning maximum that would be consistent with nighttime chemistry followed by transport to the surface by boundary layer dynamics. Similarly, elevated morning mixing ratios were also observed during TORCH2 although the magnitudes were much smaller. As a result, methyl nitrate could represent a tracer for nighttime chemistry seen at the ground the following day. At both campaigns, the dominant source of short chain alkyl nitrates and carbonyl precursor radicals (≤C₄) were from decomposition of larger compounds. The magnitude of the source increased with decreasing carbon number consistent with increasing total precursor abundance. Non-photochemical emissions of acetaldehyde and acetone could not be accounted for by automobile exhaust emissions alone and indicated that other direct sources are likely important in this environment.     

An improved dual channel PERCA instrument for atmospheric measurements of peroxy radicals

This paper describes a new dual-channel PEroxy RadiCal Amplification (PERCA) instrument, which has been designed to improve the time resolution and signal to noise and to reduce the interference caused by variations in ambient ozone concentrations. The instrument was run at the Weybourne Atmospheric Observatory (WAO), North Norfolk, during WAOWEX (Weybourne Atmospheric Observatory Winter Experiment) in January/February 2002 and INSPECTRO (Influence of clouds on the spectral actinic flux in the lower troposphere) in September 2002. The performance of the instrument is assessed and compared to that of a single channel instrument. In particular, it is shown how the precision is greatly improved in fluctuating background ozone conditions. In addition the improved time response of the instrument allows changes in peroxy radical concentrations to be related to rapid changes in nitric oxide concentrations and the ozone photolysis frequency, j(O(1)D).     

Spatial predictions of phylogenetic diversity in conservation decision making

Considering genetic relatedness among species has long been argued as an important step toward measuring biological diversity more accurately, rather than relying solely on species richness. Some researchers have correlated measures of phylogenetic diversity and species richness across a series of sites and suggest that values of phylogenetic diversity do not differ enough from those of species richness to justify their inclusion in conservation planning. We compared predictions of species richness and 10 measures of phylogenetic diversity by creating distribution models for 168 individual species of a species-rich plant family, the Cape Proteaceae. When we used average amounts of land set aside for conservation to compare areas selected on the basis of species richness with areas selected on the basis of phylogenetic diversity, correlations between species richness and different measures of phylogenetic diversity varied considerably. Correlations between species richness and measures that were based on the length of phylogenetic tree branches and tree shape were weaker than those that were based on tree shape alone. Elevation explained up to 31% of the segregation of species rich versus phylogenetically rich areas. Given these results, the increased availability of molecular data, and the known ecological effect of phylogenetically rich communities, consideration of phylogenetic diversity in conservation decision making may be feasible and informative.     

Modeling radium and radon transport through soil and vegetation

A one-dimensional flow and transport model was developed to describe the movement of two fluid phases, gas and water, within a porous medium and the transport of 226Ra and 222Rn within and between these two phases. Included in this model is the vegetative uptake of water and aqueous 226Ra and 222Rn that can be extracted from the soil via the transpiration stream. The mathematical model is formulated through a set of phase balance equations and a set of species balance equations. Mass exchange, sink terms and the dependence of physical properties upon phase composition couple the two sets of equations. Numerical solution of each set, with iteration between the sets, is carried out leading to a set-iterative compositional model. The Petrov-Galerkin finite element approach is used to allow for upstream weighting if required for a given simulation. Mass lumping improves solution convergence and stability behavior. The resulting numerical model was applied to four problems and was found to produce accurate, mass conservative solutions when compared to published experimental and numerical results and theoretical column experiments. Preliminary results suggest that the model can be used as an investigative tool to determine the feasibility of phytoremediating radium and radon-contaminated soil.