Microbial perchlorate reduction: A precise laboratory determination of the chlorine isotope fractionation and its possible biochemical basis

Perchlorate-reducing bacteria fractionate chlorine stable isotopes giving a powerful approach to monitor the extent of microbial consumption of perchlorate in contaminated sites undergoing remediation or natural perchlorate containing sites. This study reports the full experimental data and methodology used to re-evaluate the chlorine isotope fractionation of perchlorate reduction in duplicate culture experiments of Azospira suillum strain PS at 37 degrees C (Delta Cl-37(Cr)--ClO4-) previously reported, without a supporting data set by Coleman et al. [Coleman, M.L., Ader, M., Chaudhuri, S., Coates,J.D., 2003. Microbial Isotopic Fractionation of Perchlorate Chlorine. Appl. Environ. Microbiol. 69, 4997-5000] in a reconnaissance study, with the goal of increasing the accuracy and precision of the isotopic fractionation determination. The method fully described here for the first time, allows the determination of a higher precision Delta Cl-37(Cl)--ClO4- value, either from accumulated chloride content and isotopic composition or from the residual perchlorate content and isotopic composition. The result sets agree perfectly, within error, giving average Delta Cl-37(Cl)--ClO4- = -14.94 +/- 0.15%omicron. Complementary use of chloride and perchlorate data allowed the identification and rejection of poor quality data by applying mass and isotopic balance checks. This precise Delta Cl-37(Cl)--ClO4-, value can serve as a reference point for comparison with future in situ or microcosm studies but we also note its similarity to the theoretical equilibrium isotopic fractionation between a hypothetical chlorine species of redox state +6 and perchlorate at 37 degrees C and suggest that the first electron transfer during perchlorate reduction may occur at isotopic equilibrium between art enzyme-bound chlorine and perchlorate. (C) 2008 Elsevier B.V. All rights reserved.

Exploring the enzymatic landscape: distribution and kinetics of hydrolytic enzymes in soil particle-size fractions

The location of extracellular enzymes within the soil architecture and their association with the various soil components affects their catalytic potential. A soil fractionation study was carried out to investigate: (a) the distribution of a range of hydrolytic enzymes involved in C, N and P transformations, (b) the effect of the location on their respective kinetics, (c) the effect of long-term N fertilizer management on enzyme distribution and kinetic parameters. Soil (silty clay loam) from grassland which had received 0 or 200 kg N ha(-1) yr(-1) was fractionated, and four particle-size fractions (> 200, 200-63, 63-2 and 0. 1-2 mum) were obtained by a combination of wet-sieving and centrifugation, after low-energy ultrasonication. All fractions were assayed for four carbohydrases (beta-cellobiohydrolase, N-acetyl-beta-glucosammidase, beta-glucosidase and beta-xylosidase), acid phosphatase and leucine-aminopeptidase using a microplate fluorimetric assay based on MUB-substrates. Enzyme kinetics (V-max and K-m) were estimated in three particle-size fractions and the unfractionated soil. The results showed that not all particle-size fractions were equally enzymatically active and that the distribution of enzymes between fractions depended on the enzyme. Carbohydrases predominated in the coarser fractions while phosphatase and leucine-aminopeptidase were predominant in the clay-size fraction. The Michaelis constant (K.) varied among fractions, indicating that the association of the same enzyme with different particle-size fractions affected its substrate affinity. The same values of Km were found in the same fractions from the soil under two contrasting fertilizer management regimes, indicating that the Michaelis constant was unaffected by soil changes caused by N fertilizer management. (C) 2004 Elsevier Ltd. All rights reserved.

Uptake kinetics of metals by the earthworm Eisenia fetida exposed to field-contaminated soils

It is well known that earthworms can accumulate metals. However, most accumulation studies focus on Cd-, Cu-, Pb- or Zn-amended soils, additionally few studies consider accumulation kinetics. Here we model the accumulation kinetics of 18 elements by Eisenia fetida, exposed to 8 metal-contaminated and 2 uncontaminated soils. Tissue metal concentration was determined after 3, 7,14, 21, 28 and 42 days. Metal elimination rate was important in determining time to reach steady-state tissue metal concentration. Uptake flux to elimination rate ratios showed less variation and lower values for essential than for non-essential metals. In theory kinetic rate constants are dependent only on species and metal. Therefore it should be possible to predict steady-state tissue metal concentrations on the basis of very few measurements using the rate constants. However, our experiments show that it is difficult to extrapolate the accumulation kinetic constants derived using one soil to another. (C) 2009 Elsevier Ltd. All rights reserved.

Reduction of arsenic uptake by lettuce with ferrous sulfate applied to contaminated soil

Soil contamination by arsenic (As) presents a hazard in many countries and there is a need for techniques to minimize As uptake by plants. A proposed in situ remediation method was tested by growing lettuce (Lactuca sativa L. cv. Kermit) in a greenhouse pot experiment on soil that contained 577 mg As kg(-1), taken from a former As smelter site. All combinations of iron (Fe) oxides, at concentrations of 0.00, 0.22, 0.54, and 1.09% (w/w), and lime, at concentrations of 0.00, 0.27, 0.68, and 1.36% (w/w), were tested in a factorial design. To create the treatments, field-moist soil, commercial-grade FeSO4, and ground agricultural lime were mixed and stored for one week, allowing Fe oxides to precipitate. Iron oxides gave highly significant (P < 0.001) reductions in lettuce As concentrations, down to 11% of the lettuce As concentration for untreated soil. For the Fe oxides and lime treatment combinations where soil pH was maintained nearly constant, the lettuce As concentration declined in an exponential relationship with increasing FeSO4 application rate and lettuce yield was almost unchanged. Iron oxides applied at a concentration of 1.09% did not give significantly lower lettuce As concentrations than the 0.54% treatment. Simultaneous addition of lime with FeSO4 was essential. Ferrous sulfate with insufficient lime lowered soil pH and caused mobilization of Al, Ba, Co, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, Pb, Sr, and Zn. At the highest Fe oxide to lime ratios, Mn toxicity caused severe yield loss.

Carbon dioxide induced stomatal closure increases radiative forcing of climate via a rapid reduction in low cloud

We performed an ensemble of twelve five-year experiments using a coupled climate-carbon-cycle model with scenarios of prescribed atmospheric carbon dioxide concentration; CO2 was instantaneously doubled or quadrupled at the start of the experiments. Within these five years, climate feedback is not significantly influenced by the effects of climate change on the carbon system. However, rapid changes take place, within much less than a year, due to the physiological effect of CO2 on plant stomatal conductance, leading to adjustment in the shortwave cloud radiative effect over land, due to a reduction in low cloud cover. This causes a 10% enhancement to the radiative forcing due to CO2, which leads to an increase in the equilibrium warming of 0.4 and 0.7 K for doubling and quadrupling. The implications for calibration of energy-balance models are discussed.

The synthesis of chiral N-heterocyclic carbene–borane and –diorganoborane complexes and their use in the asymmetric reduction of ketones

Chiral N-heterocyclic carbene–borane complexes have been synthesised, and have been shown to reduce ketones with Lewis acid promotion. Chiral N-heterocyclic carbene–borane and –diorganoborane complexes can reduce ketones with enantioselectivities up to 75% and 85% ee, respectively.

Atmospheric chemistry of C4F9OC2H5 (HFE-7200), C4F9OCH3 (HFE-7100), C3F7OCH3 (HFE-7000) and C3F7CH2OH: temperature dependence of the kinetics of their reactions with OH radicals, atmospheric lifetimes and global warming potentials

The atmospheric chemistry of several gases used in industrial applications, C4F9OC2H5 (HFE-7200), C4F9OCH3 (HFE-7100), C3F7OCH3 (HFE-7000) and C3F7CH2OH, has been studied. The discharge flow technique coupled with mass-spectrometric detection has been used to study the kinetics of their reactions with OH radicals as a function of temperature. The infrared spectra of the compounds have also been measured. The following Arrhenius expressions for the reactions were determined (in units of cm3 molecule-1 s-1): k(OH + HFE-7200) = (6.9+2.3-1.7) × 10-11 exp(-(2030 ± 190)/T); k(OH + HFE-7100) = (2.8+3.2-1.5) × 10-11 exp(-(2200 ± 490)/T); k(OH + HFE-7000) = (2.0+1.2-0.7) × 10-11 exp(-(2130 ± 290)/T); and k(OH + C3F7CH2OH) = (1.4+0.3-0.2) × 10-11 exp(-(1460 ± 120)/T). From the infrared spectra, radiative forcing efficiencies were determined and compared with earlier estimates in the literature. These were combined with the kinetic data to estimate 100-year time horizon global warming potentials relative to CO2 of 69, 337, 499 and 36 for HFE-7200, HFE-7100, HFE-7000 and CF3CF2CF2CH2OH, respectively.

Public values for badgers, bovine TB reduction and management strategies

This paper applies an attribute-based stated choice experiment approach to estimate the value that society places on changes to the size of the badger population in England and Wales. The study was undertaken in the context of a rising incidence of bovine tuberculosis (bTB) in cattle and the government's review of current bTB control policy. This review includes consideration of culling badgers to reduce bTB in cattle, since badgers are thought to be an important wildlife reservoir for the disease. The design of the CE involved four attributes (size of badger population, cattle slaughtered due to bTB, badger management strategy and household tax) at four levels with eight choice sets of two alternatives presented to respondents. Telephone interviews were undertaken with over 400 respondents, which elicited their attitudes and preferences concerning badgers, bTB in cattle and badger management strategies. The study estimated a willingness to pay of 0.10 pound per household per year per 100,000 badgers and 1.52 pound per household per year per 10,000 cattle slaughtered due to bTB which aggregated to 22 per badger and 3298 pound per bTB slaughtered animal for all households in England and Wales. Management strategy toward badgers had a very high valuation, highlighting the emotive issue of badger culling for respondents and the importance of government policy towards badgers.

The private sector, poverty reduction and international development

The private sector, after shifting fortunes in development theory and practice over the years, is now widely recognised as the key to economic growth, which itself is indispensable for poverty reduction. The Development Studies Association (DSA) Annual Conference in 2006 brought together academics, private sector actors, NGOs and policy makers to share insights and experiences on how this vital contribution to growth, development and poverty reduction can be realised. This paper summarises the main themes and discussions of the conference and introduces the papers selected for inclusion in this conference issue.

Effects of volatile fatty acid supply on their absorption and on water kinetics in the rumen of sheep sustained by intragastric infusions

Three sheep fitted with a ruminal cannula and an abomasal catheter were used to study water kinetics and absorption of VFA infused continuously into the rumen. The effects of changing VFA concentrations in the rumen by shifting VFA infusion rates were investigated in an experiment with a 3 x 3 Latin square design. On experimental days, the animals received the basal infusion rate of VFA (271 mmol/h) during the first 2 h. Each animal then received VFA at a different rate (135, 394, or 511 mmol/h) for the next 7.5 h. Using soluble markers (polyethylene glycol and Cr-EDTA), ruminal volume, liquid outflow, apparent water absorption, and VFA absorption rates were estimated. There were no significant effects of VFA infusion rate on ruminal volume and water kinetics. As the VFA infusion rate was increased, VFA concentration and osmolality in the rumen were increased and pH was decreased. There was a biphasic response of liquid outflow to changes in the total VFA concentration in the rumen, as both variables increased together up to a total VFA concentration of 80.1 mM, whereas, beyond that concentration, liquid outflow remained stable at an average rate of 407 mL/h. There were significant linear (P = 0.003) and quadratic (P = 0.001) effects of VFA infusion rate on the VFA absorption rate, confirming that VFA absorption in the rumen is mainly a concentration-dependent process. The proportion of total VFA supplied that was absorbed in the rumen was 0.845 (0.822, 0.877, and 0.910 for acetate, propionate, and butyrate, respectively). The molar proportions of acetate, propionate, and butyrate absorbed were affected by the level of VFA infusion in the rumen, indicating that this level affected to a different extent the absorption of the different acids.