2014年APEC期间北京市PM10和PM2.5氧化性损伤能力研究

为评估APEC会议期间联防联控措施对北京市大气可吸入颗粒物毒性的影响,采集2014年APEC会议前后3个月北京市大气PM₁₀和PM_2.5样品,应用质粒DNA损伤评价法来研究其氧化性损伤能力. 结果表明,APEC会议期间PM₁₀对DNA的损伤率高于PM_2.5,颗粒物对 DNA损伤率随剂量的增加而增加. 本研究用TD30值来指示颗粒物氧化性损伤能力,TD30为引起30%的DNA损伤率所需要的颗粒物剂量（单位为 μg·mL^-1）,TD30值越低,颗粒物氧化性损伤能力越强,APEC会议前后样品的TD30值表现为 APEC期间（11月）>APEC前（10月）>APEC后（12月）,说明氧化能力APEC后 >APEC前 >APEC期间. 用PM₁₀质量浓度乘上其在250 μg·mL^-1 剂量下的DNA损伤率得到颗粒物暴露毒性指数TI（toxic index）,与往年具有代表性月份样品的数据对比,TI大小顺序为2004年 >2014年 >2008年,说明大气中颗粒物暴露毒性随着政策控制力度的加大而降低.     

乌鲁木齐大气PM2.5对质粒DNA的损伤研究

2012年1月~2012年12月采集乌鲁木齐大气PM2.5样品,使用质粒DNA评价法研究了不同季节PM2.5的氧化能力,并进行氧化性毒性与相应气象因素和质量浓度之间的相关性研究.结果表明,乌鲁木齐大气PM2.5的质量浓度具有冬季最高,春季和秋季次之,夏季最低的季节性变化特征;PM2.5全样和水溶部分氧化能力的季节差异较大,对质粒DNA的氧化性损伤具有冬季最大,春季和夏季之次,秋季最低.冬、春、夏、秋季大气PM2.5全样的TD30(PM2.5对质粒DNA造成破坏达到30%所需要的颗粒物的剂量)平均值分别为440,491,503,515μg/mL,水溶部分分别为474,721,666,600μg/mL.绝大部分PM2.5样品全样的TD30值均小于水溶部分样,表明全样的毒性大于相应的水溶部分样.全样TD30值与平均温度显著(P<0.05)正相关,表明寒冷的天气/季节可能造成PM2.5的高毒性.水溶样TD30值与风速显著(P<0.01)正相关,与相对湿度显著负相关.这表明,高的风速和低的相对湿度可能跟较低和较高的PM2.5的毒性有关.PM2.5氧化性损伤能力的大小与其质量浓度之间的相关性不明显,表明仅以颗粒物的质量浓度来评价大气颗粒物氧化性损伤能力大小的方法并不能真实地反映其对人体健康的危害程度,起决定作用的还是颗粒物的化学组成及其表面吸附的有害成分.     

3种氯酚对噬热四膜虫的毒性效应

以原生动物噬热四膜虫作为受试生物,研究了3种氯酚的急性毒性和遗传毒性及环境因子对污染物的生物效应,探讨了水体硬度对3种氯酚生物毒性的影响.结果表明,3种氯酚毒性大小依次为五氯酚(PCP)>2,4,6-三氯酚(2,4,6-TCP)>2,4-二氯酚(2,4-DCP),表明随着氯原子数目的增加,生物毒性增强.硬度实验结果显示随水体硬度升高,3种氯酚对四膜虫的急性毒性先降低后增加,但不同的水体硬度下2,4-DCP对四膜虫的24、48、72和96 h EC50值分别为3.69、3.54、3.02和2.34 mg·L-1;2,4,6-TCP分别为3.23、2.83、2.56和1.97 mg·L-1;PCP分别为0.63、0.45、0.34和0.28 mg·L-1,3种氯酚的EC50值分别在同一数量级上,表明对四膜虫的毒性影响不大.采用单细胞凝胶电泳技术(SCEG)研究了3种氯酚对四膜虫核DNA的损伤作用,结果显示氯酚类化合物具有细胞毒性,彗星实验可以较好地指示氯酚类化合物的遗传毒性.     

化学消毒的中和剂对水中内毒素活性检测的影响

本研究选取化学消毒的常用6种中和剂组氨酸、甘氨酸、抗坏血酸、吐温80、亚硫酸钠和硫代硫酸钠,采用动态浊度鲎试验定量检测样品中内毒素活性,研究中和剂在不同浓度范围内单独使用对内毒素活性检测的影响,旨在优选出适于鲎法检测细菌内毒素的中和剂种类,确定合适的浓度范围.结果表明在0~1.0%浓度范围内,除了甘氨酸和硫代硫酸钠之外,组氨酸、抗坏血酸、吐温80、亚硫酸钠(碱性和中性)均对鲎试验结果有不同程度的干扰,都不能在鲎试验之前作为化学消毒的中和剂.虽然0~1.0%浓度的甘氨酸对鲎试验结果基本无明显影响,但是甘氨酸和戊二醛的中和产物显黄色,所以不适于在光度法鲎试验中用作戊二醛的中和剂.0~1.0%浓度的硫代硫酸钠对鲎试验结果基本无明显干扰,但是当浓度升高至1.0%~5.0%时会对鲎试验结果有一定的抑制作用.与组氨酸、甘氨酸、抗坏血酸、吐温80和亚硫酸钠相比,硫代硫酸钠更适于在内毒素活性检测之前用作消毒剂的中和剂,但是浓度应控制在0.5%范围以内.     

Micronucleus frequency in sheep lymphocytes after in vitro exposure to fungicide tolylfluanid

The fungicide tolylfluanid (N - dichlorofluoromethylthio-N′, N - dimethyl - N - p - tolylsulfamide), was investigated by cytokinesis-block micronucleus assay. Tolylfluanid at the lowest concentration (1 × 10^{? 6}mol L^{? 1})did not influence significantly the frequency of micronuclei in sheep lymphocyte cultures in comparison with control (32.33 ± 3.51/1000 binucleated cells versus 30.33 ± 2.82/1000 binucleated cells in dimethylsulfoxide (DMSO) control, P = 0.44). Higher tolylfluanid concentrations (1 × 10^{? 4} and, 1 × 10^{? 5} mol L^{? 1}) resulted in a significant dose-dependent increase in the number of micronuclei in comparison with control (74.00 ± 13.00/1000 binucleated cells and 52.67 ± 10.12/1000 binucleated cells versus 30.33 ± 2. 82/1000 binucleated cells in DMSO control, P = 0.005 and 0.02, respectively, ANOVA followed by Tukey test P < 0.05). Many of the treated cells also possessed multiple micronuclei. Tolylfluanid did not affect the nuclear division index at all treatment concentrations. Our in vitro results thus demonstrate that tolylfluanid had a significant genotoxic effect at only the highest concentration tested.     

Estrogen receptor mediated activity in bankside groundwater, with flood suspended particulate matter and floodplain soil - an approach combining tracer substance, bioassay and target analysis

Bankside groundwater is widely used as drinking water resource and, therefore, contamination has to be avoided. In the European Union groundwater protection is explicit subject to Water Framework Directive. While groundwater pollution may originate from different sources, this study investigated on impacts via flood events.Groundwater was sampled with increasing distance to the river Rhine near Karlsruhe, Germany. Samples were HPLC-MS-MS analyzed for the river contaminant carbamazepine to indicate river water infiltration, giving permanent presence in 250 m distance to the river (14-47 μg L⁻¹). Following a flood event, concentrations of about 16-20 μg L⁻¹ could also be detected in a distance of 750 m to the river. Furthermore, estrogenic activity as determined with the Yeast Estrogen Screen assay was determined to increase up to a 17β-ethinylestradiol equivalent concentration (E-EQ) = 2.9 ng L⁻¹ near the river, while activity was initially measured following the flood with up to E-EQ = 2.6 ng L⁻¹ in 750 m distance. Detections were delayed with increasing distance to the river indicating river water expansion into the aquifer.Flood suspended matter and floodplain soil were fractionated and analyzed for estrogenic activity in parallel giving up to 1.4 ng g⁻¹ and up to 0.7 ng g⁻¹, respectively. Target analysis focusing on known estrogenic active substances only explained <1% of measured activities.Nevertheless, river water infiltration was shown deep into bankside groundwater, thus, impacting groundwater quality. Therefore, flood events have to be in the focus when aiming for groundwater and drinking water protection as well as for implementation of Water Framework Directive.     

Development of IC-ELISA for detection of organophosphorus pesticides in water

Diethyl (carboxymethyl) phosphonate (DECP) was used as the hapten to develop an indirect competitive enzyme-linked immunosorbent assay (IC-ELISA) for detecting organophosphorus pesticides (OPs). Conjugator of DECP with bovin serum albumin (BSA) was used as the immunogen for producing the polyclonal antibodies (PcAbs). Three antisera were obtained after the immune procedure. Characterization studies of the PcAbs indicated that the titer of antiserum-1 was highest in 3 antisera, and antiserum-1 had high affinity and specificity to the parathion, dichlorvos and pirimiphos. The IC-ELISA showed an IC₅₀ of 0.428 μ g/mL with a detection limit of 0.0125 μ g/mL to parathion. The assay also indicated that the IC₅₀ values of pirimiphos and dichlorvos were 0.331 μ g/mL and 1.25 μ g/mL respectively, and the detection limits of pirimiphos and dichlorvos were 0.0116 μ g/mL and 0.048 μ g/mL respectively. Recoveries of parathion, pirimiphos and dichlorvos spiked into water samples ranged from 90% to 160%. The results indicated that the ELISA could be a convenient and supplemental analytical tool for monitoring OPs residues in environmental water samples.     

Effect of tracer dyes on initial deposits and persistence of bacillus thuringiensis subsp. kurstaki toxin after application of two commercial formulations onto spruce trees

Abstract

The effect of two tracer dyes [Erio Acid Red (EAR) and Acid Black 48 (AB‐48)] on initial deposits and persistence of Bacillus thuringiensis subsp. kurstaki (Btk) toxin (delta‐endotoxin) was studied after spraying two commercial formulations, Foray® 48B and Foray® 76B, over potted white spruce [Picea glauca (Moench) Voss] seedlings, at a dosage rate of 30 billion international units (BIU) per ha. Spray was applied using a spinning disc atomizer calibrated to deliver droplet sizes similar to those utilized in ultra‐low‐volume (ULV) treatments in operational insect control programs. The sprayed seedlings were left outdoors at the Sault Ste. Marie laboratory for 18 days under natural conditions of sunlight, wind and rainfall. Initial deposits and persistence of delta‐endotoxin protein in spruce foliage were determined by immunoassay [enzyme linked immunosorbent assay (ELISA)] quantification of the delta‐endotoxin. The total protein (inactive plus active) and delta‐endotoxin (active protein) concentrations in the two formulations were determined by a gravimetric procedure and by ELISA respectively.

The initial deposit levels of the toxin on foliage were not markedly affected by the addition of either of the two tracer dyes, and showed only a narrow range of 1521 to 1625 ng/g foliage (fresh weight) for Foray 48B, and 1789 to 2056 ng/g for Foray 76B. However, the persistence of the toxin was significantly influenced by the presence of the dyes. The toxin persisted in foliage only for 7 d post‐spray When the EAR dye was added to Foray 48B, compared to 10 d when no dye was added. The average half‐life (DT₅₀) of disappearance was 17.4 h for Foray 48B with EAR, and 20.9 h when no dye was present. In contrast, the situation was reversed in Foray 76B, since the duration of persistence was 10 d when EAR was added to Foray 76B, compared to 7 d when no dye was added. The average DT₅₀ was 27.9 h for Foray 76B with EAR, and 22.2 h without the dye. Persistence was the longest (14 d) when the AB‐48 dye was added to Foray 76B, and the DT₅₀ was 44.9 h.     

Ecotoxicity and biodegradability of antielectrostatic dicephalic cationic surfactants

Four series of dicephalic cationic surfactants, considered as new antielectrostatic agents have been investigated in order to establish their toxicity and biodegradability. Among them N,N-bis[3,3′-(dimethylamine)propyl]alkylamides, N,N-bis[3,3′-(dimethylamine)propyl]alkylamide dihydrochlorides, N,N-bis[3,3′-(trimethylammonio)propyl]alkylamide dibromides and N,N-bis[3,3′-(trimethylammonio)propyl]alkylamide dimethylsulphates with different hydrophobic chain length (n-C₉H₁₉ to n-C₁₅H₃₁) and type of counterion (chloride, bromide and methylsulfate) have been studied. The inhibitory effect against microorganisms has been examined using model gram-positive and gram-negative bacteria, and yeasts. None of the tested surfactants have shown antimicrobial activity against gram-negative bacteria (Escherichia coli, Pseudomonas putida) and yeasts (Saccharomyces cerevisiae, Rhodotorula glutinis) at a concentration below 1000 μg mL⁻¹, however some of them were moderately active against gram-positive bacteria (Staphylococcus aureus, Bacillus subtilis). The Microtox® test was successfully applied to measure EC₅₀ values of the studied dicephalic cationic surfactants. Their toxicity to Vibrio fischeri depended upon the alkanoyl chain length with the EC₅₀ values in a range of 2.6-980 mg L⁻¹. N,N-bis[3,3′-(dimethylamine)propyl]alkylamide dihydrochlorides 2a-b and N,N-bis[3,3′-(trimethylammonio)propyl]alkylamide dibromides 3a-b comprising n-decanoyl and n-dodecanoyl hydrophobic tails appeared to be the least toxic. Furthermore, the biodegradability under aerobic conditions of 2a-b, 3a-b was evaluated using OECD Method 301F. According to the obtained results 2a, 3a-3b can be considered as almost readily biodegradable and they are not expected to be persistent in the environment. Additionally, partial biodegradation was observed for 2b, indicating its possible biodegradation in wastewater treatment systems.     

Bioanalytical and instrumental analysis of thyroid hormone disrupting compounds in water sources along the Yangtze River

Thyroid hormone (TH) agonist and antagonist activities of water sources along the Yangtze River in China were surveyed by a green monkey kidney fibroblast (CV-1) cell-based TH reporter gene assay. Instrumental analysis was conducted to identify the responsible thyroid-active compounds. Instrumentally derived l-3,5,3′-triiodothyronine (T₃) equivalents (T₃-EQs) and thyroid receptor (TR) antagonist activity equivalents referring to dibutyl phthalate (DBP-EQs) were calculated from the concentrations of individual congeners. The reporter gene assay demonstrated that three out of eleven water sources contained TR agonist activity equivalents (TR-EQs), ranging from 286 to 293 ng T₃/L. Anti-thyroid hormone activities were found in all water sources with the TR antagonist activity equivalents referring to DBP (Ant-TR-EQs), ranging from 51.5 to 555.3 μg/L. Comparisons of the equivalents from instrumental and biological assays suggested that high concentrations of DBP and di-2-ethylhexyl phthalate (DEHP) were responsible for the observed TR antagonist activities at some locations along the Yangtze River.