Anaerobic microbial degradation of the herbicide propanil

The fate of propanil (3,4-dichloropropionanilide) in an anaerobic soil environment was studied. Two mineral salts media, one amended with 0.05% yeast extract and 0.05% tryptone, and both with 33 μg propanil ml^?1, were inoculated with 10% (v/v) soil to establish enrichment cultures. Cultures were incubated at 30°C under an atmosphere of 95% N₂ and 5% CO₂. There was a complete loss of propanil in 15 days in soil enrichment cultures. One degradation product was detected and identified by HPLC and TLC co-chromatography as 3,4-dichloroaniline. Propanil was also degraded in a soil-free medium containing 0.05% yeast extract and 0.05% tryptone and inoculated with supernatant from a soil enrichment culture. After 100 days, propanil concentration decreased by 81%; 3,4-dichloroaniline and meta-chloroaniline were produced. No decrease in propanil concentration was detected in soil-free cultures without yeast extract and tryptone. No labeled CO₂ or volatile products were detected after 80 days in soil-free enrichment cultures containing ¹⁴C-ring-labeled propanil.     

Equilibrium and spectroscopic studies of lead retention in smectite

Abstract

Heavy metal pollution of soils and water is a serious environmental problem. Sorption onto solid surfaces from aqueous solutions is an important process influencing transport and accumulation of heavy metals in the environment. Lead (Pb) sorption in smectite SWy‐2 was investigated by equilibrium sorption studies, coupled with spectroscopic methods. The isotherm and pH‐edge of lead sorption in the smectite were measured in batch experiments. The sorption isotherms under uncontrolled pH were best‐fitted with the Langmuir equation, while those with a fixed pH 5.5 were best‐fitted with the Freundlich equation. The pH‐edge of lead sorption shifted to a higher pH as the Pb concentration increased. The ionic strength only affected Pb sorption in the low pH range. The effects of associated nitrate and perchlorate anions were significant only for the Pb sorption at high Pb concentration (>2 mM). FTIR and XRD spectroscopies were performed with oriented clay samples. In the infrared spectra, apeak with a maximum near 1398 cm^‐1 and a shoulder centered near 1470 cm^‐1 was significant for the samples treated with >1 mM Pb at pH >5.6. This peak may be composed of several IR bands, including an OH bending band from Pb hydroxides and CO₃ ^2‐ stretching bands from Pb carbonates. The basal spacing of Pb‐treated smectites increased with increasing Pb content in the clay and correlated well with the intensity of OH bending band (around 1621 cm^‐1) of adsorbed water. The increase of basal spacing at low pH (pH <3.3) was poorly correlated with the intensity of water OH bending band. The comprehensive studies provided many evidences for revealing the structure of various lead complexes on clay surfaces.     

Antioxidation mechanism studies of caffeic acid: identification of antioxidation products of methyl caffeate from lipid oxidation

As a part of a research project on the elucidation of the chain-breaking antioxidation mechanism of natural phenols in food components, caffeic acid, a polyphenolic acid widely distributed in edible plants, was investigated. The identification and time course analysis of the antioxidation reaction products from methyl caffeate were carried out in the ethyl linoleate oxidation system. The antioxidation reaction produced a quinone derivative of methyl caffeate as an antioxidation product during the initial stage, which was identified by (13)C NMR. The quinone, however, was not the final product, and a further reaction occurred to produce several new peroxides. The isolation and structure determination of the peroxides revealed that they had tricyclic structures, which consisted of ethyl linoleate, methyl caffeate, and molecular oxygen. On the basis of the formation pathway of these products, an antioxidation reaction mechanism of methyl caffeate, including the redox reaction of the caffeate and Diels-Alder reaction of the produced peroxides, was proposed.     

Molecular spectroscopic studies of farrerol interaction with calf thymus DNA

The interaction between farrerol and calf thymus DNA in a pH 7.4 Tris-HCl buffer was investigated with the use of neutral red (NR) dye as a spectral probe by UV-vis absorption, fluorescence, and circular dichroism (CD) spectroscopy, as well as viscosity measurements and DNA melting techniques. It was found that farrerol molecules could intercalate into the base pairs of DNA as evidenced by decreases in iodide quenching effect and single-stranded DNA (ssDNA) quenching effect, induced CD spectral changes, and significant increases in relative viscosity and denaturation temperature of DNA. Furthermore, the spectral data matrix of the competitive reaction between farrerol and NR with DNA was resolved with an alternative least-squares (ALS) algorithm, and the concentration profiles in the reaction and the corresponding pure spectra for three species (farrerol, NR, and DNA-NR complex) were obtained. This ALS analysis demonstrated the intercalation of farrerol to the DNA by substituting for NR in the DNA-NR complex. Moreover, the thermodynamic parameters enthalpy change (ΔH°) and entropy change (ΔS°) were calculated to be -16.49 ± 0.51 kJ mol(-1) and 32.47 ± 1.02 J mol(-1) K(-1) via the van't Hoff equation, which suggested that the binding of farrerol to DNA was driven mainly by hydrophobic interactions and hydrogen bonds.     

Phenoxy herbicide degradation in soils: Quantitative studies of 2,4-D- and MCPA-degrading microbial populations

Microbial populations able to degrade 2,4-D (2,4-dichlorophenoxyacetate) and MCPA (4-chloro-2-methylphenoxyacetate) were enumerated by means of a most probable number (MPN) procedure in eight Natal soils not previously treated with these herbicides. Estimated 2,4-D-degrading populations ranged from 1.26 to 245.2 and MCPA-degrading populations from 0.34 to 1377 g^?1 dry soil; in seven of the soils the populations of these organisms were less than 40 and 30 g^?1, respectively. Such counts indicate that for the successful isolation of 2,4-D- or MCPA-degrading microorganisms from soil, at least 1 g dry weight of soil should be used for enrichment cultures. The 2,4-D-degrading organisms occurred among the aerobic soil bacteria detectable by plate count, at frequencies of only 1 in 30 × 10³ to 1 in 36 × 10⁶ and the MCPA-degrading organisms at frequencies of 1 in 5 × 10³ to 1 in 133 × 10⁶; the ease with which the herbicide-degrading organisms can be isolated from enriched soil cultures treated with 2,4-D or MCPA is evidence of their massive preferential proliferation in response to the herbicides.Log 2,4-D- and MCPA-degrading populations did not differ significantly in four soil samples, but in the others either the 2,4-D- or the MCPA-degrading population was dominant. The longer persistence of MCPA compared with that of 2,4-D could therefore not be ascribed to quantitative differences in the populations of MCPA- and 2,4-D-degrading soil microorganisms.No relationship was evident between the soil populations of 2,4-D- or MCPA-degrading microorganisms and aerobic soil bacteria, and variations of the three populations among the soil samples were not associated in any obvious way with the soil physical and chemical characteristics, except perhaps an association of the highest counts of herbicide-degrading organisms with a sugar cane soil of sandy texture and high C: N ratio.     

Nuclear magnetic resonance spectroscopic based studies of the metabolism of black tea polyphenols in humans

Epidemiological studies indicate that a high intake of flavonoids is associated with an improved health status. Tea is one of the most abundant sources of flavonoids in the human diet. The bioavailability and biotransformation of tea flavonoids are, however, not clearly understood. The aim of the present study was to investigate the metabolism of black tea via a nonspecific screening method. (1)H nuclear magnetic resonance (NMR) spectroscopy was used to obtain nonselective profiles of urine samples collected from three human volunteers before and after a single dose of black tea. The complex spectroscopic profiles were interpreted with the use of pattern recognition techniques. Hippuric acid was confirmed as the major urinary black tea metabolite. One previously unknown metabolite was detected and identified as 1,3-dihydroxyphenyl-2-O-sulfate (sulfate conjugate of pyrogallol) using HPLC directly coupled to mass spectrometry and (1)H NMR spectroscopy. This study shows that NMR-pattern recognition studies can be used for the discovery of unknown flavonoid metabolites in humans.     

植物耐旱机制研究进展

干旱环境下植物通过不同耐旱途径抵御干旱胁迫。简介了植物耐旱机制中的渗透调节、质膜保护和抗氧化防御系统,水孔蛋白及其在水分平衡和抗脱水中的作用,胚胎发育晚期丰富表达蛋白(Lea蛋白)等研究进展。     

Gamma-ray spectroscopic determination of iodine-131 and cesium-137 in foods: two collaborative studies

The AOAC method for iodine-131, cesium-137, and barium-140 in milk by gamma-ray spectroscopy (48.025-48.029) was extended to include other foods for the radionuclides iodine-131 and cesium-137. Two collaborative studies were performed to validate this extension. In the first study, a food sample containing 119 pCi 131I/kg and 53 pCi 137Cs/kg was sent to each of 45 laboratories for triplicate analyses. For 25 responses, the mean of the reported values was 123.8 pCi/kg for iodine-131, and for 27 responses, the mean was 53.4 pCi/kg for cesium-137. Repeatability (within-laboratory) standard deviations (Sr) for iodine-131 and cesium-137 were 4.6 and 3.7 pCi/kg, respectively. Reproducibility (among-laboratories) standard deviations (SR) for iodine-131 and cesium-137 were 12.1 and 6.0 pCi/kg, respectively. In the second study, a food sample containing 25 pCi 131I/kg and 27 pCi 137Cs/kg was sent to each of 54 laboratories for triplicate analyses. For 21 responses, the mean of the reported values was 25.0 pCi/kg for iodine-131, and for 19 responses, the mean was 28.9 pCi/kg for cesium-137. Sr Values were 4.0 and 1.6 pCi/kg for iodine-131 and cesium-137, respectively, and SR values were 5.0 and 2.8 pCi/kg, respectively. The method extension was adopted official first action.     

Photostabilization of the herbicide norflurazon by using organoclays

Photostable formulations of the herbicide norflurazon [4-chloro-5-(methylamino)-2-(alpha,alpha, alpha-trifluoro-m-tolyl)pyridazin-3-(2H)-one] were achieved by adsorbing it on pillared clay or on montmorillonite preadsorbed with the organic cation thioflavin T (TFT). Diffuse reflectance Fourier transform infrared spectra showed the existence of strong interactions between the aromatic moieties of preadsorbed TFT and the herbicide, particularly after irradiation. The photostabilization of norflurazon obtained with TFT-clay was mainly due to energy transfer from the herbicide to the organic cation via pi-pi interactions. An additional mechanism is the lower production of radicals from the clay when the clay mineral surface is covered with the organic cation. These radicals are responsible for the enhanced photodegradation observed when norflurazon was irradiated in the presence of untreated montmorillonite.     

Growth and development of Cirsium arvense in relation to herbicide dose,timing of herbicide application and crop presence

The aim of this study is to assess control effects of 2-methyl-4-chlorophenoxyacetic acid (MCPA) dosage, application timing and crop presence on the weed Cirsium arvense. Swedish farmers are recommended to control C. arvense chemically when most shoots are 10-20 cm tall, and mechanically at the compensation point (CP). Recent studies have shown that the CP occurs before shoots reach the three-leaf stage. We hypothesised that (i) herbicide application near the three-leaf stage gives the strongest control, (ii) crop presence increases herbicide effects, and (iii) a 50% herbicide dose gives the same effect as 100%. Treatments of the pot experiment consisted of MCPA 750; 0%, 50% and 100% of the recommended dose applied at leaf stages 3-8, with and without barley. The strongest control was obtained at four leaves and a maximum shoot height of 13 cm, using the recommended dose and with spring barley. In a field population, a maximum shoot height of 13 cm corresponded to a medium height of 6 cm. The 50% dose gave poorer control. Spraying with the recommended dose at the four-leaf stage reduced the development of C. arvense most effectively. Based on this, we recommend that herbicide spraying should be performed at earlier leaf stages/median heights than previously recommended.     

Isolation and characterization of microorganisms capable of hydrolysing the herbicide mefenacet

Three strains—Nocardioides sp. MFC-A, Rhodococcus rhodochrous MFC-B, and Stenotrophomonas sp. MFC-C—were newly isolated from rice soil or bark compost as microorganisms capable of cometabolically degrading mefenacet (2-benzothiazol-2-yloxy-N-methyl-acetanilide). Several other species belonging to the genera Nocardioides, Rhodococcus, and Stenotrophomonas were also capable of degrading mefenacet, suggesting that the ability is not specific to these isolates, but common at least in these genera. N-methylaniline and 2-benzothiazoloxy acetic acid were identified as the metabolites by liquid chromatography-mass spectrometry. Besides mefenacet, the isolates could degrade one or more other amide pesticides, such as flutolanil, mepronil, metolachlor, and pretilachlor. These results indicate that the strains Nocardioides sp. MFC-A, Rhodococcus rhodochrous MFC-B, and Stenotrophomonas sp. MFC-C degrade mefenacet via hydrolysis of the amide bond, but their substrate specificities differ.     

Kinetic studies of cholesterol oxidation as inhibited by stearylamine during heating

The formation of cholesterol oxidation products (COPs) during heating in the presence of stearylamine at 140 degrees C was analyzed by high-performance liquid chromatography (HPLC) and kinetically studied by use of nonlinear regression models. Results indicated that the COPs concentration increased with increasing heating time, and stearylamine was shown to reduce both oxidation and degradation rates of cholesterol. Without stearylamine, the highest rate constant (per hour) was observed for epoxidation (545.4), followed by free radical chain reaction (251.0), reduction (147.3), dehydration (95.8), triol dehydrogenation (4.7), degradation (0.34), triol formation (0.31), and dehydrogenation (0.13). With stearylamine, the epoxidation and free radical chain reaction rates could be reduced by about 800- and 3.4-fold, respectively, and triol formation during oxidation could be completely inhibited. In addition, the reactions for reduction, dehydration, degradation, and dehydrogenation could proceed slower in the presence of stearylamine. The kinetic model developed in this study can be used to predict the inhibition of COPs formation by stearylamine during heating of cholesterol.     

Microbial populations hydrolyzing propanil and accumulation of 3,4-dichloroaniline and 3,3',4,4'-tetrachloroazobenzene in soils

The rate of propanil decomposition and amounts of 3,4-dichloroaniline and 3,3',4,4'-tetrachloroazobenzene formed in five soils were unrelated to soil texture or organic matter content. The TCAB that accumulated in the soils after decomposition of propanil was still present after 280 days of incubation. As determined by the most-probable-number method, propanil-hydrolyzing Arthrobacter and Nocardia spp. were present in the soils in large numbers. When finely divided propanil was applied to moist soils, a portion was rapidly hydrolysed, by an acylamidase directly extractable from the soils by aid of sonification.     

Model studies on the degradation of phenylalanine initiated by lipid hydroperoxides and their secondary and tertiary oxidation products

The reaction of methyl 13-hydroperoxyoctadeca-9,11-dienoate (MeLOOH), methyl 13-hydroperoxyoctadeca-9,11,15-trienoate (MeLnOOH), methyl 13-hydroxyoctadeca-9,11-dienoate (MeLOH), methyl 13-oxooctadeca-9,11-dienoate (MeLCO), methyl 9,10-epoxy-13-hydroxy-11-octadecenoate (MeLEPOH), and methyl 9,10-epoxy-13-oxo-11-octadecenoate (MeLEPCO) with phenylalanine was studied to determine the comparative reactivity of primary, secondary, and tertiary lipid oxidation products in the Strecker degradation of amino acids. All assayed lipids were able to degrade the amino acid to a high extent, although the lipid reactivity decreased slightly in the following order: MeLEPCO > or = MeLCO > MeLEPOH > or = MeLOH > MeLOOH approximately = MeLnOOH. These data confirmed the ability of many lipid oxidation products to degrade amino acids by a Strecker-type mechanism and suggested that, once the lipid oxidation is produced, a significant Strecker degradation of surrounding amino acids should be expected. The contribution of different competitive mechanisms to this degradation is proposed, among which the conversion of the different lipid oxidation products assayed into the most reactive MeLEPCO and the fractionation of long-chain primary and secondary lipid oxidation products into short-chain aldehydes are likely to play a major role.