邻苯二甲酸酯类化合物土壤吸附系数的测定及相关性研究

研究测定了邻苯二甲酸二甲酯（ＤＭＰ）、二乙酯（ＤＥＰ）、二丙酯（ＤＰＰ）、二丁酯（ＤＢＰ）、丁基苄基酯（ＢＢＰ）和二异辛酯（ＤＥＨＰ）等６种化合物土壤吸附系数Ｋｏｃ，并研究了Ｋｏｃ与正辛醇一水分配系数Ｋｏｗ、水溶解度Ｓ之间的相关性，建立了相关方程式。     

DHDPS的细胞表达、提纯和结晶

ＤＨＤＰＳ是赖氢酸合成通路中第一步的合成酶。将中国春小麦的ＤＨＤＰＳ基因质粒移植入ＲＤＡ８中，得到ＲＤＡ８／ｐＤＢ２６菌株，本研究通过细胞培养、层析提纯和结晶条件的探索，给出了一个较好的技术路线，并为开展义衍射分析蛋白结构创造了条件，通过该研究，对中国春小麦ＤＨＤＰＳ和野种大肠杆菌的ＤＨＤＰＳ差异有了一定的了解，并且对细胞培养的ＭＭ介质处理，ＤＥＡＥ－Ｓｅｐｈａｒｏｓｅ，Ｐｈｅｎｙｌ－Ｓｅｐｈａｒｏｓｅ和ＭｏｎｏＱ层析的方法给出具体实验条仲。酶活的检测和蛋白浓度测定都是采取高灵敏度的方法。结晶的ＳＣｒｅｅｎｉｎｇ条件对于二种ＤＨＤＰＳ有很大的差异。对野种大肠杆茵的ＤＨＤＰＳ，需要表面活性剂Ｎ－ｏｃｔｙｌ－Ｄ－ｇｌｕｃｏｐｙｒａｎｏｓｉｄｅ，ｐＨ１０．０～１０．５，对于中国春小麦一ＤＨＤＰＳ则未找到较好的表面活性剂，ｐＨ６．８～７．６。中国春小麦一ＤＨＤＰＳ晶体培养条件在以往文献中未见报导。     

利用高效脱色降解菌和活性污泥接种处理印染废水的比较研究

本文研究了用染料高色降解菌和活性污泥在厌氧酸化一好氧生物氧化和生物活性炭池三级串联系统中接种处理印染废水的效果。结果表明，在厌氧池中用高效菌接种比用活性污泥接种对ＣＯＤｃｒ、ＰＶＡ的色度的去除率分别提高５．３％，１２．７％和９．９７％。经过好氧池处理后，用聚乙烯醇（ＰＶＡ）降解菌混合液接种比用活性污泥接种对ＣＯＤｃｒ、ＢＯＤ５、ＰＶＡ、色度的法除分别提高１０．８８％， １２．９％，２０％和１２％。     

利福平废水的絮凝和生化处理研究

种福平生产的废水ＣＯＤ高达６万,用ＰＦＳ、Ｃ－ＰＡＭ脱稳,密集网捕式絮凝处理后,ＣＯＤ去除率达２７％,ＢＯＤ５／ＣＯＤｃｒ从０．１９上升到０．３２,絮凝前后水质和色谱分析表明,絮凝后５种有机物去除效率均在２２％以上,使生化处理成为可能,进生化池废水经稀释后,用活性污泥法处理９天后,ＣＯＤ从１．５万降至ＣＯＤ〈３００ｍｇ／Ｌ,达到治理要求。     

生物膜反应器连续处理餐饮废水

用生物膜反应器连续处理餐水能有效降低废水中的ＢＯＤ及ＣＯＤ浓度。研究了水力停留时间对有机物去除率的影响,结果表明当水力停留时间大于７．８ｈ时,废水的ＣＯＤ,ＢＯＤ及ＴＳＳ的去除率均高于９０％。实验操作时,水力停留时间应略大于５．７ｈ。     

白洋淀几种不同食性鱼类对六六六、DDT的富集

对白洋淀几种不同食性鱼体内六六六和ＤＤＴ残留量分析表明，草食性鱼体内农药残留量最少，六六六含量为５９．３μｇ／ｋｇ，ＤＤＴ含量为２９．６μｇ／ｋｇ；其次是杂食性鱼类，六六六含量为９０．４μｇ／ｋｇ，ＤＤＴ含量为１０８．５μｇ／ｋｇ；肉食性鱼体内农药残留量最高，六六六含量为１１０．７μｇ／ｋｇ，ＤＤＴ含量为１２４．４μｇ／ｋｇ。鱼体对ＤＤＴ的浓缩因子为３１１～１２４４，明显高于六六六的１７７～３６８。鱼体内ＢＨＣ４种异构体的残留顺序为δ＞α＞γ＞β，与其在水体中的比例α＞γ＞δ＞β略有不同。鱼体内ＤＤＴ主要以代谢物ｐ，ｐ＇－ＤＤＥ的形式存在，但个别样品中少量的ｐ，ｐ＇－ＤＤＤ及ｏ，ｐ＇－ＤＤＴ的检出，表明白洋淀水生生态系统最近受到ＤＤＴ的轻度污染。本项研果与１９７５～１９７７年检测结果进行比较；白洋淀鱼体内六六六残留量显著下降，下降率为１５．８％～７９．２％；ＤＤＴ残留量却明显增加（草食性鱼类除外），增加率约为４７．８％～９７．８％。     

销毁含多氯联苯废弃物焚烧炉的二噁、类二噁和多氯联苯排放

我国正在研制专用于销毁高浓度多氯联苯（ＰＣＢｓ）的焚烧炉,主要处理废旧的含（ＰＣＢｓ）的电力电容器和变压器,应用可靠准确的监测方法测定了试验性焚烧炉渣、烟灰排气和废水中的二口恶口英（ｄｉｏｘｉｎｓ）,类二口恶口英多氯联苯（ｄｉｏｘｉｎｌｉｋｅＰＣＢｓ）和ＰＣＢｓ含量,结果表明该炉试烧高浓度ＰＣＢｓ时,焚毁率可以达到９９．９９９９％,炉渣中的２,３,７,８ＴＣＤＤ毒性当量为８７．８６ｐｇＴＥＱ／ｇ,烟灰中残留二口恶口英和类二口恶口英的总２,３,７,８ＴＣＤＤ毒性当量为４７．２３ｎｇＴＥＱ／ｇ．     

母乳与牛乳中微量元素的比较

用ＩＣＰ－ＡＥＳ法对母乳和牛乳中Ｋ、Ｎａ、Ｃａ、Ｍｇ、Ｐ、Ｆｅ、Ａｌ、Ｚｎ、Ｓｒ、、Ｐｂ、Ｍｎ、Ｂａ和Ｃｕ等１３种元素含量进行了测定。结果发现母乳与牛乳的营养成分差异较大。研究了深入探讨微量元素在人体内重要的生理功能提供了有用的参考数据。     

Fe^2＋—H2O2氧化法处理氨基J酸工业废水的研究

用Ｆｅ＾２＋－Ｈ２Ｏ２氧化法处理氨基Ｊ酸工业废水。结果表明,当溶液ｐＨ＝１－３,Ｈ２Ｏ２和Ｆｅ＾２＋用量分别为Ｈ２Ｏ２：Ｆｅ＾２＋１０：１,Ｈ２Ｏ２：ＣＯＤＣｒ＝２ｇ：ｇ时,Ｊ酸废水的ＣＯＤＣｒ去除率达６６．７％,氨基去除率达６８．４％。处理后的废水ＢＯＤ５／ＣＯＤＣｒ＝０．５,已达到生化处理的要求。该法可作为氨基Ｊ酸废水的预处理方法。     

锐颈特与马拉硫磷交替使用对麦穗鱼脑乙酰胆碱酯酶活性恢复的 …

研究了５％锐颈特县浮剂与９５％马拉硫磷文替使用对麦穗鱼（Ｐｓｅｕｄｏｒａｓｂｏｒａ ｐａｒｏａ）乙酰胆碱酯酶（ＡＣｈＥ,ＥＣ３．１．１．７）活性的影响。结果表明,０．２ｍｇ／Ｌ,锐颈物与２ｍｇ／Ｌ马拉硫磷交替使用均影响被抑制的ＡＣｈＥ活性恢复。文中还探讨了研究农药影响对于合理评价农药环境毒性的意义。     

Effect of DBP/DEHP in vegetable planted soil on the quality of capsicum fruit

Field experiment was conducted to investigate the di-n-butyl phthalate (DBP) and di-2-ethylhexyl phthalate (DEHP) contamination in Capsicum annum fruit grown in DBP and DEHP contaminated soil, and to evaluate the effect of DBP and DEHP on the quality of capsicum fruit. The top layer soil (0-10 cm) of plots was treated with a mixture of DBP and DEHP (1:1 w/w) and capsicum seedlings were transplanted. After 90 days, capsicum fruit, shoot and root samples were collected. DBP and DEHP concentration in various parts of the samples were determined by gas chromatography. Vitamin C and capsaicin contents in fruit were determined using 2,4-dinitrophenylhydrazine colorimetric analysis and sodium nitrite-sodium molybdate colorimetric analysis, respectively. The results showed that DBP concentration in fruit, shoot and root increased with the increase of soil-applied DBP/DEHP concentration, but DEHP was not detected in all samples. When the soil-applied DBP/DEHP concentration was 5, 10, 20, 40, 80 and 160 mg kg(-1) soil, compared with control, vitamin C and capsaicin content in capsicum fruit decreased by 1.6%, 5.9%, 10.6%/o, 18.2%, 19.2%, 22.6% and 1.6%, 2.5%, 12.9%, 20.1%, 22.2%, respectively. Pearson correlation analysis demonstrated that the decrease of vitamin C and capsaicin content was negatively correlated to the increase of DBP concentration in capsicum fruit, which suggested that DBP uptake by the plant might be mainly responsible for quality degradation of capsicum fruit.     

组合工艺去除垃圾渗滤液中的DBP和DEHP

探讨了采用实验室规模的生物处理组合工艺(上流式厌氧污泥床+曝气生物滤池+缺氧反应器+膜生物反应器,UASB+BAF+ANO+MBR)处理垃圾渗滤液过程中,邻苯二甲酸二丁酯(DBP)和邻苯二甲酸二(2-乙基己基)酯(DE-HP)两种内分泌干扰物在各工艺段的去除效率和机理。测定结果表明,对于DBP和DEHP浓度分别为164.4μg/L和215.0μg/L的原水,总出水浓度分别降至11.8μg/L和10.4μg/L,去除率分别达到92.9%和95.2%,处理效果良好。其中DBP在处理工艺中逐级降解,主要是微生物的降解作用。MBR是DEHP的主要去除工艺段,去除比例达到56.6%,膜截留效果明显。采用生物处理组合工艺可实现对垃圾渗滤液中DBP和DEHP的同时高效去除。     

Occurrence and microbial degradation of phthalate esters in Taiwan river sediments

Concentrations and microbial degradation rates were measured for eight phthalate esters (PAEs) found in 14 surface water and six sediment samples taken from rivers in Taiwan. The tested PAEs were diethyl phthalate (DEP), dipropyl phthalate (DPP), di-n-butyl phthalate (DBP), diphenyl phthalate (DPhP), benzylbutyl phthalate (BBP), dihexyl phthalate (DHP), dicyclohexyl phthalate (DCP), and di-(2-ethylhexyl) phthalate (DEHP). In all samples, concentrations of DEHP and DBP were found to be higher than the other six PAEs. DEHP concentrations in the water and sediment samples ranged from ND to 18.5 μg/l and 0.5 to 23.9 μg/g, respectively; for DBP the concentration ranges were 1.0–13.5 μg/l and 0.3–30.3 μg/g, respectively. Concentrations of DHP, BBP, DCP and DPhP were below detection limits. Under aerobic conditions, average degradation half-lives for DEP, DPP, DBP, DPhP, BBP, DHP, DCP and DEHP were measured as 2.5, 2.8, 2.9, 2.6, 3.1, 9.7, 11.1 and 14.8 days, respectively; under anaerobic conditions, respective average half-lives were measured as 33.6, 25.7, 14.4, 14.6, 19.3, 24.1, 26.4 and 34.7 days. In other words, under aerobic conditions we found that DEP, DPP, DBP, DPhP and BBP were easily degraded, but DEHP was difficult to degrade; under anaerobic conditions, DBP, DPhP and BBP were easily degraded, but DEP and DEHP were difficult to degrade. Aerobic degradation rates were up to 10 times faster than anaerobic degradation rates.     

固相萃取—气相色谱—质谱测定再生水中邻苯二甲酸酯类物质

探讨了一种再生水中邻苯二甲酸酯类物质的测定方法——固相萃取—气相色谱—质谱,检测了相关再生水标准中涉及的邻苯二甲酸二丁酯(DBP)和邻苯二甲酸二(2-乙基己基)酯(DEHP)两类物质。在质量浓度为20～1 000μg/L时,两类物质的回归方程的相关系数均大于0.999,检出限分别是0.060、0.002μg/L,DBP、DEHP的相对标准偏差分别为4.1%～7.4%、5.1%～6.1%。利用固相萃取技术进行预处理,平均加标回收率为96.6%、89.6%。检测了北京市4座再生水厂出水中DBP和DEHP含量,其中,DBP在1.74～5.59μg/L,低于《城市污水再生利用景观环境用水水质》(GB/T 18921—2002)规定的限值(不超过0.1mg/L),但高于《城市污水再生利用地下水回灌水质》(GB/T 19772—2005)规定的限值(不超过3μg/L);DEHP在0.42～4.93μg/L,满足GB/T 19772—2005要求(不超过8μg/L)。     

Biodegradation of phthalate esters during the mesophilic anaerobic digestion of sludge

Phthalic acid esters (PAE) are commonly found in the sludge generated in the wastewater treatment plants. Anaerobic digestion followed by land application is a common treatment and disposal practice of sludge. To date, many studies exist on the anaerobic biodegradation rates of PAE, especially of the easily biodegradable ones, whereas the higher molecular weight PAE have reported to be non-biodegradable under methanogenic conditions. Furthermore, there is no information on the effect of the PAE on the performance of the anaerobic digesters treating sludge. In this study, the anaerobic biodegradation of di-n-butyl phthalate (DBP), di-ethyl phthalate (DEP) and di-ethylhexyl phthalate (DEHP) was investigated and their relative rates of anaerobic degradation were calculated. Also, the biological removal of PAE during the anaerobic digestion of sludge in bench-scale digesters was investigated using DBP and DEHP as model compounds of one biodegradable and one recalcitrant PAE respectively. The degradation of all the PAE tested in this study (DEP, DBP and DEHP) is adequately described by first-order kinetics. Batch and continuous experiments showed that DEP and DBP present in sludge are rapidly degraded under mesophilic anaerobic conditions (a first-order kinetic constant of 8.04 x 10(-2) and 13.69 x 10(-2)-4.35 day(-1) respectively) while DEHP is degraded at a rate between one to two orders of magnitude lower (0.35 x 10(-2)-3.59 x 10(-2) day(-1)). It is of high significance that experiments with anaerobic sludge of different origin (US and Europe) showed that degradation of DEHP occurs under methanogenic conditions. Accumulation of high levels of DEHP (more than 60 mg/l) in the anaerobic digester has a negative effect on DBP and DEHP removal rates as well as on the biogas production.     

厌氧降解两种苯二甲酸酯的试验研究

以邻苯二甲酸二[2-乙基己]酯(DEHP)和邻苯二甲酸二丁酯(DBP)为研究对象,以废水污泥和填埋场沥出液为接种物,在严格厌氧环境下,进行了苯二甲酸酯生物降解的研究试验。结果表明,DBP有较好的可降解性,去除率大于95％;而DEHP在填埋场沥出液培养样中去除率小于30％;但当接种物为消化污泥时,DEHP的去除率为89．7％。产甲烷的微生物群在邻苯二甲酸二酯的降解过程中起着非常重要的作用。     

UV/TiO2薄膜体系光降解酞酸酯研究

采用自制玻璃负载TiO2薄膜,研究了UV-V is/TiO2以及UV/TiO2/H2O2体系对2种酞酸酯DBP和DEHP的光催化降解情况。研究结果表明,TiO2在暗处对酞酸酯没有降解作用;UV/TiO2体系能有效光降解DBP和DEHP,TiO2具有明显的光催化作用,增强因子分别为fDBP=2.06,fDEHP=1.53;在一定浓度范围内DBP在UV/TiO2体系中的降解速率与其初始浓度成负一级动力学关系;UV/TiO2/H2O2体系对DBP的光降解能力远大于UV/TiO2和UV/H2O2体系,H2O2能显著提高TiO2的光催化活性。     

Effect of introduced phthalate-degrading bacteria on the diversity of indigenous bacterial communities during di-(2-ethylhexyl) phthalate (DEHP) degradation in a soil microcosm

Four previously isolated di-butyl-phthalate (DBP) degraders were tested for their abilities to degrade di-(2-ethylhexyl) phthalate (DEHP). In aqueous medium supplemented with 100mg/l of DEHP, both isolate G1 and Rhodococcus rhodochrous G2 showed excellent degradative activity; in three days they were able to degrade more than 97% of the added DEHP. Rhodococcus rhodochrous G7 degraded 32.5% of the added DEHP and Corynebacterium nitrilophilus G11 showed the least amount of DEHP degradation. The addition of surfactant Brij 30 at 0.1x critical micelle concentration (2mg/l) significantly improved DEHP degradation by Rhodococcus rhodochrous G2 (more than 90% of the added DEHP was degraded within 24 hours), but slightly inhibited the degradation of DEHP by the isolate G1 and Rhodococcus rhodochrous G7. Based on the 16S rDNA sequence data, isolate G1 was identified as Gordonia polyisoprenivorans. Soil inhibited DEHP degradation by G. polyisoprenivorans G1; fourteen days after a second addition of DEHP, 11.5% of the total added DEHP (i.e., 243.4 microg/g soil) remained detectable. Changes in the bacterial community were monitored using denaturing gradient gel electrophoresis (DGGE) and respective dendrogram analysis. It is clear that DEHP and DEHP plus G. polyisoprenivorans G1 substantially affected the bacterial community structure in the soils. However, as the population of indigenous DEHP degraders increased in the DEPH-treated soil, its bacterial communities resembled those in the DEHP plus G. polyisoprenivorans G1-inoculated soil by Day 17.     

Diminution of migration of phthalic acid esters in tequila beverage by the year of production

Abstract

The presence of diethyl-phthalate (DEP), dibutyl-phthalate (DBP), butylbenzyl-phthalate (BBP), diethylhexyl-phthalate (DEHP) and diisononyl-phthalate (DINP) was determined in 295 tequila samples. They were grouped by age of maturation (white, aged, extra aged or ultra aged) and year of production (between 2013 and 2018). Gas Chromatography coupled with Mass Spectrometry was used for identification and quantification. The results showed that 65 samples (22% of the total) were phthalate free. DEP (0.13-0.27?mg/kg), BBP (0.05–2.91?mg/kg) and DINP (1.64–3.43?mg/kg) were detected in 11 (3.73%), 37 (12.54%) and 5 (1.69%) samples, respectively. But, these concentrations did not exceed the maximum permitted limits (MPL) of phthalates for alcoholic beverages. DBP (0.01–2.20?mg/kg) and DEHP (0.03–4.64?mg/kg) were detected in 96 (32.54%) and 224 (75.93%) samples, from them only 10 (3.39%) and 15 (5.08%) samples, respectively, exceeded the MPL for alcoholic beverages and they were few tequilas produced in the year 2014 or before. DEHP was the most frequent phthalate found in tequila and observed DEHP concentrations were 2-times higher in ultra aged tequilas compared to those in white tequilas. We concluded that all tequilas produced in 2015 and after, satisfied the international standards for these compounds.     

Anaerobic degradation of diethyl phthalate, di-n-butyl phthalate, and di-(2-ethylhexyl) phthalate from river sediment in Taiwan

We investigated anaerobic degradation rates for three phthalate esters (PAEs), diethyl phthalate (DEP), di-n-butyl phthalate (DBP), and di-(2-ethylhexyl) phthalate (DEHP), from river sediment in Taiwan. The respective anaerobic degradation rate constants for DEP, DBP, and DEHP were observed as 0.045, 0.074, and 0.027 1/day, with respective half-lives of 15.4, 9.4, and 25.7 days under optimal conditions of 30 °C and pH 7.0. Anaerobic degradation rates were enhanced by the addition of the surfactants brij 35 and triton N101 at a concentration of 1 critical micelle concentration (CMC), and by the addition of yeast extract. Degradation rates were inhibited by the addition of acetate, pyruvate, lactate, FeCl₃, MnO₂, NaCl, heavy metals, and nonylphenol. Our results indicate that methanogen, sulfate-reducing bacteria, and eubacteria are involved in the degradation of PAEs.