Partitioning of penoxsulam, a new sulfonamide herbicide

Penoxsulam (trade name Granite) is a new acetolactate synthase (ALS) inhibitor herbicide for postemergence control of annual grasses, sedges, and broadleaf weeds in rice culture. This study was done to understand the equilibrium phase partitioning of penoxsulam to soil and air under conditions simulating California rice field conditions. Partitioning of penoxsulam was determined between soil and water (Kd) by the batch equilibrium method and between air and water (K(H)) by the gas-purge method. In four representative soils from the Sacramento Valley, the Kd values ranged from 0.14 to 5.05 and displayed a modest increase with soil pH. In soil amended with manure compost, soil sorption increased 4-fold with increasing soil organic matter content, but was still low with a Kd of 0.4 in samples with high organic carbon contents of 15%. Penoxsulam was confirmed to be extremely nonvolatile and did not partition into air at any measurable rate at 20 or 40 degrees C. K(H) (pH 7) was estimated at 4.6 x 10(-15) Pa x L x mol(-1) on the basis of available water solubility and vapor pressure data. The results imply that soil and air partitioning of penoxsulam do not significantly affect its potential for degradation or offsite movement in water.     

The Potted-Plant Microcosm Substantially Reduces Indoor Air VOC Pollution: I. Office Field-Study

Volatile organic compounds (VOCs) are major contaminants of indoor air, with concentrations often several times higher than outdoors. They are recognized as causative agents of “building-related illness” or “sick-building syndrome”. Our previous laboratory test-chamber studies have shown that the potted-plant/root-zone microorganism microcosm can eliminate high concentrations of air-borne VOCs within 24 hours, once the removal response has been induced by an initial dose. However, the effectiveness of the potted-plant microcosm in ‘real-world’ indoor spaces has never previously been tested experimentally. This paper reports the results of a field-study on the effects of potted-plant presence on total VOC (TVOC) levels, measured in 60 offices (12 per treatment), over two 5–9 week periods, using three planting regimes, with two ‘international indoor-plant’ species. Fourteen VOCs were identified in the office air. When TVOC loads in reference offices rose above 100 ppb, large reductions, of from 50 to 75% (to <100 ppb), were found in planted offices, under all planting regimes The results indicate that air-borne TVOC levels above a threshold of about 100 ppb stimulate the graded induction of an efficient metabolic VOC-removal mechanism in the microcosm. Follow-up laboratory dose-response experiments, reported in the following paper, confirm the graded induction response, over a wide range of VOC concentrations. The findings together demonstrate that potted-plants can provide an efficient, self-regulating, low-cost, sustainable, bioremediation system for indoor air pollution, which can effectively complement engineering measures to reduce indoor air pollution, and hence improve human wellbeing and productivity.     

Characterization of anthocyanins and proanthocyanidins in some cultivars of Ribes, Aronia, and Sambucus and their antioxidant capacity

Anthocyanins and proanthocyanidins were characterized by HPLC-ESI-MS/MS coupled with a diode array and/or fluorescent detector in seven cultivars of Ribes nigrum (black currant) and Ribes rubrum (red currant, Red Lake), six cultivars of Ribes grossularia (gooseberries), Aronia melanocarpa(chokeberry), and Sambucus nigra (elderberry). Thirty-one different anthocyanins were detected in these berries, but not every anthocyanin was observed in each berry. A number of minor anthocyanins were identified from these berries for the first time. The concentrations of individual anthocyanins in all of the berries were quantified using relevant anthocyanidin 3-glucoside standards. Among the berries studied in this paper and in berries in general, chokeberry has the highest total anthocyanin concentrations [1480 mg/100 g of fresh weight (FW)], whereas the lowest total anthocyanin concentration in the berries studied was found in the gooseberry cv. Careless, which contained only 0.07 mg/100 g of FW. Two cultivars of gooseberries (Marigold and Leveller) did not contain any anthocyanins. Total proanthocyanidin concentrations in the berries studied ranged from 23 to 664 mg/100 g of FW in elderberry and chokeberry, respectively. Procyanidin or prodelphinidin polymers were the predominant components (>65% w/w) in most of the berries. The lipophilic and hydrophilic antioxidant capacities were measured by the oxygen radical absorbance capacity (ORAC(FL)) procedure. The total antioxidant capacity varied from 21 micromol of TE/g of FW in Careless gooseberry to 161 micromol of TE/g of FW in chokeberry. Total phenolics in the berries in general paralleled hydrophilic antioxidant capacity.     

N-(1-deoxy-D-fructos-1-yl) fumonisin B(1), the initial reaction product of fumonisin B(1) and D-glucose

Incubation of fumonisin B(1) and D-glucose in aqueous solutions resulted in the formation of N-(1-deoxy-D-fructos-1-yl) fumonisin B(1) in addition to the previously reported N-(carboxymethyl) fumonisin B(1). N-(1-Deoxy-D-fructos-1-yl) fumonisin B(1) is the first stable product formed after the Amadori rearrangement of the Schiff base formed by the reaction of the primary amine of fumonisin B(1) and the aldehyde group of D-glucose. N-(1-Deoxy-D-fructos-1-yl) fumonisin B(1) was synthesized by reacting fumonisin B(1) with an excess of D-glucose in methanol and heating for 6 h at 64 degrees C. It was purified using C(18) and strong cation exchange solid-phase extraction cartridges and characterized by nuclear magnetic resonance and liquid chromatography-mass spectrometry. Subsequently, N,N-dimethylformamide was found to be a better reaction solvent, requiring reaction for only 2-3 h at 64 degrees C and eliminating the formation of methyl esters. Alkaline hydrolysis of N-(1-deoxy-D-fructos-1-yl) fumonisin B(1) gave a mixture of hydrolyzed fumonisin B(1) and hydrolyzed N-(carboxymethyl) fumonisin B(1).     

Metabolic profiling: a new tool in the study of wood formation

In the realm of plant genomics, metabolic profiling has become a valuable tool with which to assess the effect of genetic and/or environmental factors on plant development. This paper reports the first application of metabolic profiling on differentiating xylem tissue of loblolly pine. A protocol is presented for the analysis of loblolly pine xylem tissue. The effects of sample preparation, extraction, and derivatization on the corresponding metabolite profiles and yields have been investigated and are reported. Gas chromatography-mass spectroscopy has been used to quantify >60 polar and lipophilic metabolites from wood-forming tissue. It was possible to assign chemical structures to approximately half of these compounds. Comparison of six loblolly pine genotypes, three high cellulose (50-52%) and three medium (45-48%) cellulose, showed distinct metabolic profiles. Principal component analysis enabled the assignment of metabolic phenotypes using these large data sets. Metabolic phenotype clustering occurred in which the three high-cellulose genotypes were segregated from the medium-cellulose genotypes. These results demonstrate the use of metabolic profiling for the study of wood-forming tissue and as a tool in functional genomics.     

FUM13 encodes a short chain dehydrogenase/reductase required for C-3 carbonyl reduction during fumonisin biosynthesis in Gibberella moniliformis

Fumonisins are polyketide-derived mycotoxins produced by the filamentous fungus Gibberella moniliformis (anamorph Fusarium verticillioides). Wild-type strains of the fungus produce predominantly four B-series fumonisins, designated FB(1), FB(2), FB(3), and FB(4). Recently, a cluster of 15 putative fumonisin biosynthetic genes (FUM) was described in G. moniliformis. We have now conducted a functional analysis of FUM13, a gene in the cluster that is predicted by amino acid sequence similarity to encode a short chain dehydrogenase/reductase (SDR). Mass spectrometric analysis of metabolites from FUM13 deletion mutants revealed that they produce approximately 10% of wild-type levels of B-series fumonisins as well as two previously uncharacterized compounds. NMR analysis revealed that the new compounds are similar in structure to FB(3) and FB(4) but that they have a carbonyl function rather than a hydroxyl function at carbon atom 3 (C-3). These results indicate that the FUM13 protein catalyzes the reduction of the C-3 carbonyl to a hydroxyl group and are the first biochemical evidence directly linking a FUM gene to a specific reaction during fumonisin biosynthesis. The production of low levels of FB(1), FB(2), FB(3), and FB(4), which have a C-3 hydroxyl, by the FUM13 mutants suggests that G. moniliformis has an additional C-3 carbonyl reductase activity but that this enzyme functions less efficiently than the FUM13 protein.     

Soil Factors Affecting Heavy Metal Solubility in Some New Zealand Soils

Heavy metal contamination of soils is usually quantified and guidelines set solely on the basis of total heavy metal content. However, it is recognised that water soluble heavy metal concentrations may provide a better indication of the potential risk that heavy metals may pose to the soil environment. The aim of this study was to use a semi-empirical model based on the competitive adsorption of metal and H⁺ ions [dependent on solution pH, total metal content, total carbon content and soil oxide content] to predict water soluble Cu, Cr, Cd, Pb, Ni and Zn concentrations in a range of field contaminated soils. The results of multiple linear regressions showed that basic soil properties could predict 85, 72, 66, 78, 50 and 75% of the variation in soluble Ni, Cu, Cr, Pb, Cd and Zn concentrations respectively. Water soluble metal concentrations were best predicted using empirical linear regressions which included total metal content, while the importance of other soil properties such as soil pH, total carbon and oxalate extractable Fe and Al oxides varied between metals. The models have the potential to provide valuable information on metal availability in contaminated soils and offer an indication of the potential risk a metal may pose to a given soil environment, along with providing a basis for developing soil quality guidelines for the prevention, investigation and clean-up of soil metal contamination.     

Degradation and binding of atrazine in surface and subsurface soils

Understanding the dissipation rates of chemicals in unsaturated and saturated zones of subsurface soils will help determine if reductions of concentrations to acceptable levels will occur. Chemical properties and microbial biomass and activity were determined for the surface (0-15 cm), lower root (50-105 cm), and vadose (175-220 cm) zones in a Huntington silty clay loam (Fluventic Hapludoll) collected from an agricultural field near Piketon, OH. The rates of sorption, mineralization, and transformation (formation of bound residues and metabolites) of atrazine were determined. Microbial activity was estimated from the mineralization of (14)C-benzoate. We observed decreased levels of nutrients (total organic carbon, N, and P) and microbial biomass with depth, while activity as measured with benzoate metabolism was higher in the vadose zone than in either the surface or the root zones. Sorption coefficients (K(f)) declined from 8.17 in the surface to 3.31 in the vadose zone. Sorption was positively correlated with organic C content. Rates of atrazine mineralization and bound residues formation were, respectively, 12-2.3-fold lower in the vadose than in the surface soil. Estimated half-lives of atrazine ranged from 77 to 101 days in the surface soil, but increased to over 900 days in the subsurface soils. The decreased dissipation of atrazine with increasing depth in the profile is the result of decreased microbial activity toward atrazine, measured either as total biomass or as populations of atrazine-degrading microorganisms. The combination of reduced dissipation and low sorption indicates that there is potential for atrazine movement in the subsurface soils.     

Application of low‐phosphorus‐containing legume residues reduces extractable phosphorus in a tropical Ultisol

Application of legume green manure (GM) is suggested to be effective in increasing the availability of native soil phosphorus (P) and the dissolution and utilization of phosphate rock (PR)‐P by food crops. Experiments were conducted to study the dynamics of extractable P (P extracted by Bray‐1‐extracting solution) of an Ultisol amended with or without GM residues of contrasting P concentrations in the absence of growing plants. In two separate experiments, GM residues of Aschynomene afraspera (a flood‐tolerant legume) and of Crotalaria micans (upland) with varying P concentrations were added to an acidic soil amended with PR‐P or triple superphosphate (TSP) in plastic bottles. Soil moisture was brought to field capacity of the soil in the upland experiment and saturated with distilled water in the lowland setup. This was done to simulate aerobic upland and anaerobic lowland soil conditions in the relevant plastic bottles. Only P concentration of the residues added varied, while lignin and C : N ratios were similar. A temperature of 25°C was maintained throughout the experiment. Changes in soil extractable Bray‐1‐P were measured at the end of the incubation period (60 or 80 d). In the aerobic soils, extractable P in the combined PR+GM or TSP+GM treatments was significantly lower than in the PR‐ or TSP‐ treated soils. The amendment with GM residues alone significantly increased Bray‐1‐P over the unamended control in the case of the inorganic P‐fertilized GM residues. The trend in extractable P was similar in the soils incubated under anaerobic conditions. However, in the case of PR, concentrations of P extracted by Bray‐1 solution did not significantly change in the presence or absence of GM. The results suggest that the incorporation of GM residues with low P concentration does not lead to a net P release in upland or lowland soils. These results have implications for nutrient cycling in farming systems in W Africa as most of the soils are poor and very low in available P.     

Whither or wither microbicides?

After disappointing results from all efficacy trials conducted to date, the field of microbicides research now faces substantial challenges. Poor coordination among interested parties and the choice of nonvalidated scientific targets for phase III studies have hampered progress and created mistrust about the use of microbicides as a method to prevent HIV-1 sexual transmission. Although new promising strategies are available, there will need to be serious reappraisals of how decisions are made to advance the next generations of candidates into clinical trials, and the use of appropriate animal models in this process will be critical.