Hollow-fiber liquid-phase microextraction based on carrier-mediated transport for determination of urinary methyl hippuric acids

Hollow-fiber liquid-phase microextraction based on carrier-mediated transport for analysis of methyl hippuric acids in aqueous samples is described. Under optimized conditions, relative recoveries of 83%–98% and limits of detection of 2–3 µg L^?1 were obtained, with linear calibration curves for the three isomers in the range of 10–50,000 µg L^?1. The method was applied for the determination of urine samples of volunteers at various working environments.     

Metabolism of benzo[a]pyrene in peroxynitrite/Fe(Ⅲ) porphyrin system

The peroxynitrite/porphyrin biomimetic system was established to investigate the effects of peroxynitrite on benzo[a]pyrene (B[a]P) metabolism. Through the comparison of three model systems consisting of different iron porphyrins, we found that the peroxynitrite/T(p-Cl)PPFeCl system showed the highest catalytic efficiency in the metabolism of B[a]P. We analyzed the B[a]P metabolites produced from this system by RP-HPLC method and firstly identified the formation of nitrobenzo[a]pyrenes which are the special metabolites of B[a]P induced by peroxynitrite.     

Relation of hepatic EROD activity and CYP1A level in Sebastiscus marmoratus exposed to benzo[a]pyrene

This study was designed to investigate the in vivo effects of benzo[a]pyrene (BaP) on hepatic ethoxyresorufin-O-deethylase (EROD) activity and its correlation with cytochrome P450 1A (CYP1A) protein levels in Sebastiscus marmoratus, which were exposed through a water column to BaP (10, 100, 1000 ng/L, respectively) or were treated with intraperitoneal injections of BaP (0.5, 1, 5, 10 mg/kg, respectively) every 7 d. The results showed that after 25 d of waterborne exposure to 1000 ng/L BaP, fish hepatic CYP1A levels and EROD activity were significantly induced. In contrast, EROD activity was not altered 7 d after second ip injections, whereas, CYP1A protein levels were increased. Dose-dependent increase of biliary BaP metabolites demonstrated that the catalytic activity of CYP1A was induced by treatment with BaP. The lowest observable effect concentration with regard to biliary BaP metabolites (100 ng/L) was much lower than that with reference to EROD activity (1000 ng/L). The results suggest that biliary polycyclic aromatic hydrocarbon (PAH) metabolites were shown to better reflect the contamination gradients of PAHs than EROD activity. It appeared to be necessary to measure CYP1A protein levels to complement the EROD activity in relevant toxicological assessments.     

Matrix effects in analysis of dialkyl phosphate metabolites of organophosphate pesticides in urine by gas chromatography/tandem mass spectrometer

Urinary dialkyl phosphate metabolites (DAPs) are used as biomarkers to evaluate human exposure to organophosphate pesticides. The objective was to evaluate potential artifacts in urinary DAPs analysis during sample preparation and method calibration. Diluted urine pools were commonly used to prepare calibration standards to minimize the effects due to the complexity of urine matrix. Matrix effects on measurements of DAPs were evaluated by spiking known amount of standards into distilled water, synthetic urine and diluted urine pool. Different matrices resulted in similar concentrations detected for all target compounds, except dimethylphosphate (DMP) with the deviation of measurement as large as eight times the spiked amount. In this study, we also found that urinary particles, which usually appeared after thawing frozen human urine samples, could affect the measurements of DAPs, especially DMP and diethylthiophosphate (DETP). Results of DAPs measurements in three types of sample matrices, i.e. urine without particles, urine with particles and particles only were compared. DETP could be subject to large error during this preparation step. The use of deuterated and ¹³C₁₂-labeled DAPs as internal standards is also evaluated. Overall, these issues can cause misidentification and inaccuracies, which may significantly affect the data quality.     

Identification and comprehensive evaluation of a novel biocontrol agent Bacillus atrophaeus JZB120050

Abstract

Bacillus spp. have long been used as biocontrol agents because of their efficient broad-spectrum antimicrobial activity. We identified a novel strain of Bacillus atrophaeus, named JZB120050, from soil. B. atrophaeus JZB120050 had a strong inhibitory effect against Botrytis cinerea and many other phytopathogens. Gas chromatography-mass spectrometry showed that B. atrophaeus JZB120050 produced many secondary metabolites, such as alkanes, alkenes and acids; some of which were related to pathogen inhibition. Enzyme activity analysis showed that B. atrophaeus JZB120050 secreted cell-wall-degrading enzymes, including chitinase, glucanase and protease, which degraded fungal cell walls. Both the novel glucanase gene bglu and chitinase gene chit1 were cloned and heterologously expressed in Escherichia coli and the products showed strong enzyme activity. In addition, B. atrophaeus JZB120050 secreted siderophores and formed a significant biofilm. Future studies should focus on these antimicrobial factors to facilitate widespread application in the field of agricultural biocontrol.     

Metabolism of 14C‐carbaryl and 14C‐1‐naphthol in moist and flooded soils

Abstract

The metabolism of ¹⁴C‐carbaryl and ¹⁴C‐1‐naphthol in moist and flooded soils was studied in a continuous flow‐through system over a period of 28 days permitting ¹⁴C‐mass balance. The percent distribution of radiocarbon in organic volatiles, carbon dioxide, extractable and non‐extractable (bound) fractions of soils were determined. Organic volatiles could not be detected in both carbaryl and 1‐naphthol treated soils. More of ¹⁴CO₂ (25.6%) was evolved from moist than flooded soil (15.1%) treated with carbaryl. However, the mineralization of ¹⁴C‐1‐naphthol was negligible. The extractable radiocarbon was more in flooded soil (28.9%) than moist soil (5.5%) from carbaryl treatment. Less than one percent was present as parent compound, whereas carbaryl was mainly metabolized to 5‐hydroxy carbaryl in moist soil and to 4‐ and 5‐hydroxy carbaryl in flooded soil. The extractable radiocarbon amounted to 18.2 and 24.3% in moist and flooded soils respectively and the parent compound was less than one percent with 1‐naphthol treatment. Most of the radiocarbon was found as soil bound residues; the formation being more with 1‐naphthol than carbaryl. Humin fraction of the soil organic matter contributed most to soil bound residues of both carbaryl and 1‐naphthol.     

Degradation of disulfoton,oxydemeton‐methyl,methamidophos and demeton in asparagus plant

Abstract

Disulfoton and methamidophos (both at 1.12 kg a.i./ha), oxydemeton‐methyl and demeton, (both at 0.56 kg a.i./ha) were applied as post‐harvest foliar sprays to control the European asparagus aphid, Brachycolus asparagi. Oxidation of disulfoton, oxydemeton‐methyl and demeton to their corresponding sulfoxides and sulfones occurred in asparagus foliage 2 to 5 days after application. The total residues of these three compounds, including their toxic oxidative metabolites declined to less than 0.5 ppm about 47 days after the spray application whereas methamidophos persisted longer; 0.84 ppm of its residue was found even after 85 days. No residue was found above the limit of detection of 0.002 ppm in any asparagus spears which were produced in the following spring; the four compounds were sprayed on the asparagus plants during the previous season at realistic rates for aphid control.     

耐盐类固醇激素降解菌交替赤杆菌MH-B5的降解特性、降解途径及其固定化

从咸水湖中分离得到1株具有类固醇激素降解能力的耐盐菌株,利用16S rRNA基因序列同源性分析确定菌株MH-B5属于交替赤杆菌属(Altererythrobacter),其可生长p H范围为5.5~9.0,可耐受盐度生长范围为0~7%,单碳降解实验表明该菌可以利用雌酮、雌二醇、雌三醇和睾酮.应用超高压液相色谱串联四级杆飞行时间质谱分析得出菌株降解睾酮的过程中主要中间代谢产物为4-雄烯二酮、宝丹酮和雄二烯二酮.应用单一载体和复合载体两种方法分别制备的菌株MH-B5固定化颗粒均可降解雌二醇,批次降解实验表明菌株MH-B5固定化颗粒可有效降解2 mg·L~(-1)雌二醇及其初级代谢产物雌酮.上述研究结果表明菌株MH-B5可在海水中生长良好,其能降解典型雌激素及雄激素睾酮,且经过微生物固定化过程后依然具有类固醇激素的降解特性,因此对类固醇激素污染的咸水环境修复,具有潜在应用前景.     

6-2氟调醇在活性污泥中的降解

为了解6-2氟调醇(6-2 FTOH)在城市污水处理厂活性污泥中的好氧降解规律,利用室内模拟实验装置,研究了6-2FTOH在未经稀释驯化的活性污泥中的降解动力学及降解产物分布.结果表明,6-2 FTOH能被活性污泥快速吸附并发生降解,降解反应符合一级动力学,半衰期为0.9d.降解产物包括6-2氟调酸(6-2 FTCA)、6-2不饱和氟调酸(6-2 FTUCA)、5-3氟调酸(5-3 FTCA)、5-2s氟调醇(5-2s FTOH)和全氟己酸(PFHxA).第28 d实验结束时,6-2 FTOH残留率为5.5％,6-2 FTCA和6-2 FTUCA的最终产率分别为0和1.2％.5-3FTCA、5-2s FTOH、PFHxA最终产率分别为23.4％、17.6％和1.3％.     

ZnO-NPs对好氧反硝化细菌Zobellella sp. B307的致毒机制

本文以一株筛自胶州湾沉积物中的好氧反硝化细菌Zobellella sp.B307为研究对象，在短期暴露条件下，通过细菌的生长、脱氮能力，相关酶活以及代谢途径等指标的变化，研究纳米氧化锌（ZnO-NPs）对该菌株的毒性效应；结合锌离子溶出试验、CAT和ROS等氧化应激水平测定，探讨ZnO-NPs对该菌株的致毒机制.结果表明，200mg/L的ZnO-NPs会使菌株硝酸盐氮去除率降至57.53%，LDH升高至对照组的378%，ROS水平高达对照组的5.34倍，SOD活性比对照组升高了60.32%，NIR活性仅为对照组的14.46%；ZnO-NPs主要通过诱导菌株活性氧的生成使其膜通透性改变、相关酶活性下降，并使相关蛋白质、氨基酸的合成及基因表达等代谢通路受到影响，进而抑制该菌株的反硝化能力；游离锌离子的产生可能不是ZnO-NPs对菌株的主要致毒途径.