Changes of main secondary metabolites in leaves of Ginkgo biloba in response to ozone fumigation

To investigate the effect of elevated O3 on the accumulation of main secondary metabolites in leaves of Ginkgo biloba L., four-year-old trees were exposed in open-top chambers with ambient air and the air with twice ambient O3 concentration in Shenyang in 2006.Elevated O3 increased the concentrations of terpenes, but decreased the concentrations of phenolics in G.biloba leaves.The results showed that secondary compounds from G.biloba leaves responded to the elevated O3 exposure in a different way when compared to previous studies which showed elevated O3 increased the concentrations of phenolics but had no effect on the terpenes in leaves of other deciduous trees.Furthermore, reduced synthesis of phenolics may decrease the resistance of G.biloba to O3 and other environmental factors.On the other hand, the induced synthesis of terpenes may enhance the antioxidant abilities in G.biloba leaves at the end of O3 fumigation.     

多溴二苯醚毒理学研究进展及展望(Research Progress and Future Perspectives in Toxicology Study on Polybrominated Diphenyl Ethers)

多溴二苯醚(PBDEs)虽然已在一些国家禁止生产和使用,商品五溴和八溴二苯醚也在2009年被列入《关于持久性有机污染物(POPs)的斯德哥尔摩公约》受控范围内,但目前学术界对PBDEs的毒理学效应及其机制尤其是环境剂量效应的认识并不十分清楚. 论文从甲状腺干扰、神经毒性、生殖内分泌干扰3个方面介绍了近年来PBDEs毒理学研究的进展,分析了该领域研究中存在的几个问题,提出今后应大力开展环境相关剂量下PBDEs及代谢物的毒性研究,以推进对实际环境中PBDEs真实毒性的认识;同时探索能够反映PBDEs毒性的非创性生物标记物,为开展PBDEs人体健康影响的流行病学调查提供线索.     

不同官能团微塑料对斑马鱼胚胎菌群和代谢功能的胁迫效应

为探究官能团修饰对微塑料生物效应的影响规律和机制,分析了3种聚苯乙烯微塑料（PS、PS—NH₂和PS—COOH）在斑马鱼（Danio rerio）胚胎内的累积特征,并利用微生物组学和代谢组学相结合的分析技术,解析了斑马鱼幼鱼体内代谢功能及微生物群落的响应规律.结果显示,3种微塑料都可以在斑马鱼体内产生累积,其含量范围为143~175 μg·g^-1,且不存在明显差异性.斑马鱼胚胎绒毛膜是微塑料早期暴露的主要累积场所,但不能有效阻止小粒径微塑料的穿透.未修饰的PS明显影响了斑马鱼幼鱼体内氨基糖苷类的代谢能力,PS—NH₂主要对氨基酸的代谢过程产生了影响,而PS—COOH则主要作用于三羧酸循环、氨基酸及糖酵解等代谢通路.3种微塑料均导致了斑马鱼幼鱼体内代谢功能的变化,从而对斑马鱼产生了毒性效应,而微塑料的官能团修饰则加强了这一影响程度.与对照组相比,PS—NH₂明显降低了斑马鱼幼鱼体内的微生物群落的多样性,显著增加了变形菌门（Proteobacteria）的占比,导致斑马鱼幼鱼体内的菌群失衡,从而引起鱼体代谢功能的紊乱.微塑料的官能团修饰可能会明显改变其对生物体的胁迫效应,导致难以预测的生态风险.     

Isolation and identification of 3-bromocarbazole-degrading bacteria

In this study, a bacterial strain, CH-1, capable of degrading 3-bromocarbazole (3-BCZ) was isolated from a polluted soil. Based on its physio-biochemical characteristics and 16S rRNA genes, strain CH-1 was identified as a Stenotrophomonas sp. Strain CH-1 was able to degrade 70% of 50 mg/L 3-BCZ within 8 d at pH 7.0 and 30°C in mineral salt medium (MSM). During the process, the main intermediate metabolite was identified as (2E, 4Z)-6-(2-amino-5-bromophenyl)-2-hydroxy-6-oxhexa-2, 4-dienoic by gas (2E, 4Z)-6-(2-amino-5-bromophenyl)-2-hydroxy-6-oxhexa-2,4-dienoic via gas chromatograph-mass spectrometry (GC-MS) analysis. The metabolite disappeared after 14 d, suggesting that the metabolite can also be degraded by strain CH-1. 3-BCZ is a new persistent organic pollutant. This is the first report of the biodegradation of 3-BCZ. The results indicated that strain CH-1 may be a promising bacterial candidate for the bioremediation of environments polluted with polyhalogenated carbazoles (PHCs).     

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.     

苯并［a］芘对黑鲷肝脏GST活性的影响及其与肝脏代谢酶和胆汁代谢产物之间的变化关系

为探讨苯并[a]芘(B[a]P)暴露对鱼类的影响并筛选特异、敏感的生物标志物,研究了B[a]P对黑鲷(Sparus macrocephalus)肝脏谷胱甘肽-S-转移酶(GST)活性的影响,并分析了肝脏7-乙氧基异吩唑酮-脱乙基酶(EROD)、GST活性与胆汁中B[a]P典型代谢产物3-羟基-苯并[a]芘(3-OHB[a]P)3者之间及与B[a]P之间的剂量、时间-效应关系.结果显示:在B[a]P(0.5、1.0、2.0和5.0μg·L-1)暴露期间,肝脏GST活性随暴露时间总体呈"钟"形的变化趋势,在第2d时达到峰值;在第12h、1d和2d时,GST活性与B[a]P暴露浓度呈显著正相关(R12h=0.966(p<0.05)、R1d=0.953(p<0.05)、R2d=0.824(p<0.05)).与前期研究结果对比分析发现,B[a]P(0.5、1.0、2.0和5.0μg·L-1)暴露7d时,胆汁中3-OHB[a]P浓度与B[a]P暴露浓度呈显著的剂量-效应关系(R=0.943,p<0.05);黑鲷肝脏GST、EROD活性与3-OHB[a]P的对数浓度均呈显著正相关(RGST=0.740(p<0.05)、REROD=0.839(p<0.05));2.0μg·L-1B[a]P暴露后,黑鲷肝脏EROD、GST活性与3-OHB[a]P随暴露时间的变化趋势基本相同,但并不完全一致.鱼类肝脏EROD、GST与胆汁中B[a]P代谢产物3者之间的变化关系较为复杂,暴露浓度和时间是影响其变化的重要因素,肝脏GST和EROD活性比胆汁中代谢产物更易受其影响,在B[a]P的环境监测中代谢产物可能是一种更为可行的生物标志物.     

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.     

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.     

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.     

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.