Determination of 15 phthalate esters in air by gas-phase and particle-phase simultaneous sampling

Based on previous research, the sampling and analysis methods for phthalate esters (PAEs) were improved by increasing the sampling flow of indoor air from 1 to 4 L/min, shortening the sampling duration from 8 to 2 hr. Meanwhile, through the optimization of chromatographic conditions, the concentrations of 9 additional PAE pollutants in indoor air were measured. The optimized chromatographic conditions required a similar amount of time for analysis as before, but gave high responsivity, the capability of simultaneously distinguishing 15 kinds of PAEs, and a high level of discrimination between individual sample peaks, as well as stable peak generation. The recovery rate of all gas-phase and particle-phase samples of the 15 kinds of PAEs ranged from 91.26% to 109.42%, meeting the quantitative analysis requirements for indoor and outdoor air sampling and analysis. For the first time, investigation of the concentration levels as well as characteristics of 15 kinds of PAEs in the indoor air from four different traffic micro-environments (private vehicles, busses, taxis and subways) was carried out, along with validation of the optimized sampling and analytical method. The results show that all the 9 additional PAEs could be detected at relatively high pollution levels in the indoor air from the four traffic micro-environments. As none of the pollution levels of the 15 kinds of PAEs in the indoor air from the 4 traffic micro-environments should be neglected, it is of great significance to increase the types of PAEs able to be detected in indoor air.     

“引江济太”过程中塑化剂类污染物的输入特征和环境健康风险评价

为了解"引江济太"过程中塑化剂类污染物对贡湖的输入特征,于2013年8月对14个采样点的7种邻苯二甲酸酯类化合物(PAEs)的浓度进行采样分析,并通过美国环保署(USEPA)推荐的方法,对其环境风险进行评价.结果表明:各采样点邻苯二甲酸二丁酯(DBP)和邻苯二甲酸二环己酯(DCHP)均有检出,除采样点10、11和12外,邻苯二甲酸二乙酯(DEP)也有检出,其余4种均未检出,长江引水经望虞河进入贡湖后,DEP、DBP和DCHP浓度均有不同程度的降低,且其最高浓度均出现在望虞河长江引水处(采样点1),说明在引水过程中长江水对望虞河有明显的PAEs输入,而贡湖锡东水厂DEP浓度高于贡湖其他采样点,南泉水厂DBP和DCHP浓度高于贡湖其他采样点,金墅湾水厂PAEs浓度总体处于较低水平.环境健康风险评价结果显示:DEP的最大非致癌风险值为3.91×10-8a~(-1),未超过国际组织规定范围,而DBP的最大非致癌风险值为1.17×10-5a~(-1),超过英国皇家协会RS规定的1×10-6a~(-1),但均对人体无明显非致癌危害.     

Pollution levels and characteristics of phthalate esters in indoor air of offices

The pollution status and characteristics of PAEs (phthalate esters) were investigated in indoor air of offices, and PAEs of both gas-phase and particulate-phase were detected in all the samples. The concentration (sum of the gas phase and the particulate phase) was 4748.24 ng/m³, ranging between 3070.09 and 6700.14 ng/m³. Diethyl phthalate, dibutyl phthalate, and di(2-ethylhexyl) phthalate were the most abundant compounds, together accounting for 70% of the Σ6PAEs. Dividing the particulate-phase PAEs into four size ranges (<2.5, 2.5-5, 5-10, >10 μm), the result indicated that PAEs in PM_2.5 were the most abundant, with the proportion of 72.64%. In addition, the PAE concentration in PM_2.5 correlated significantly with the total particulate-phase PAEs (R² = 0.85). Thus, the amount of PAEs in PM_2.5 can be estimated from the total amount of particulate-phase PAEs using this proportion. In a comparison between the offices and a newly decorated study room, it was found that pollution characteristics were similar between these two places. Thus, it is implied that the PAE concentration decreased by 50% 2 yr after decorating.     

Pollution levels and characteristics of phthalate esters in indoor air of offices

The pollution status and characteristics of PAEs(phthalate esters) were investigated in indoor air of offices, and PAEs of both gas-phase and particulate-phase were detected in all the samples. The concentration(sum of the gas phase and the particulate phase) was4748.24 ng/m3, ranging between 3070.09 and 6700.14 ng/m3. Diethyl phthalate, dibutyl phthalate, and di(2-ethylhexyl) phthalate were the most abundant compounds, together accounting for 70% of the ∑ 6PAEs. Dividing the particulate-phase PAEs into four size ranges( 2.5, 2.5–5, 5–10, 10 μm), the result indicated that PAEs in PM2.5were the most abundant,with the proportion of 72.64%. In addition, the PAE concentration in PM2.5correlated significantly with the total particulate-phase PAEs(R2= 0.85). Thus, the amount of PAEs in PM2.5can be estimated from the total amount of particulate-phase PAEs using this proportion. In a comparison between the offices and a newly decorated study room, it was found that pollution characteristics were similar between these two places. Thus, it is implied that the PAE concentration decreased by 50% 2 yr after decorating.     

Pollution levels and characteristics of phthalate esters in indoor air in hospitals

The concentrations of phthalate esters(PAEs) in Chinese hospitals were investigated by simultaneously determining concentrations of gas- and particle-phase PAEs. PAEs were detected in two third-class first-grade hospitals, two second-class first-grade hospitals, and a community health service center. Hospital drugstores had the highest concentration(24.19 μg/m3), which was 1.54 times that of newly decorated houses. The second highest concentration was found in the transfusion rooms, averaging 21.89 μg/m3; this was followed by the concentrations of PAEs in the nurse's workstations, the wards, and the doctor's offices, with mean concentrations of 20.66, 20.0, and 16.92 μg/m3, respectively. The lowest concentrations were found in the hallways(16.30 μg/m3). Of the six different kinds of PAEs found, major pollutants included diethyl phthalates, dibutyl phthalates, butylbenzyl phthalates and di(2-ethylhexyl) phthalates, comprising more than 80% of all PAEs present.Meanwhile, a comparison between different wards showed that PAE concentrations in the maternity wards were 1.63 times higher than in the main wards. Based on known health hazards, our results suggest that the PAEs seriously influence the health of the pregnant women and babies; therefore, it is of great importance to take the phthalate concentrations in hospitals into consideration. In addition, hospital indoor air was more seriously contaminated than the air of newly decorated houses.     

珠江三角洲蔬菜基地蔬菜中邻苯二甲酸酯的含量特征

邻苯二甲酸酯是一类重要的环境激素类污染物。本文以气相色谱/质谱(GC/MS)联用检测技术,对珠江三角洲地区典型蔬菜生产基地蔬菜中6种邻苯二甲酸酯化合物进行测试分析。结果发现:(1)珠江三角洲地区典型蔬菜生产基地的蔬菜样品中,多数样品检测出6种邻苯二甲酸酯,总含量为0.46～12.02mg/kg。(2)基地蔬菜中单个邻苯二甲酸酯化合物的种类和含量因蔬菜种类、品种、部位和生长环境等因素而异。(3)同种类蔬菜在不同基地或同一基地不同种类蔬菜中邻苯二甲酸酯的含量分布不同。(4)大部分蔬菜中以邻苯二甲酸正二丁酯(DnBP)和邻苯二甲酸双(2-乙基己基)酯(DEHP)为主。     

土壤中酞酸酯类化合物监测方法的质量控制研究

从监测结果控制的角度对近10年的土壤中PAEs监测方法进行了探讨,重点比较了索氏萃取柱净化GC/MS、微波萃取柱净化GC、加速溶剂萃取柱净化GC/MS和加速溶剂萃取GPCGC/MS方法的检出限、精密度和准确度。旨在为中国土壤监测方法的建立提供基础支撑,为开展质量控制工作提供评价依据。     

阳离子表面活性剂十六烷基三甲基溴化铵对酞酸酯类化合物增溶性研究

用阳离子表面活性剂十六烷基三甲基溴化铵对六种酞酸酯类化合物(五种脂肪链酞酸酯和一种苯基酞酸酯)进行了增溶性实验．结果表明,在表观浓度(Ｃｓ)小于临界胶速浓度(ＣＭＣ)时,十六烷基三甲基溴化铵对四种酞酸酯(ＤＭＰ和ＤＰｈＰ除外)有一定程度的增溶作用;当Ｃｓ大于ＣＭＣ时,对六种化合物的增溶性显著增强．其增溶性(Ｓｔ/Ｓｗ)随Ｃｓ增大而线性递增:当Ｃｓ＜ＣＭＣ时,Ｓｔ/Ｓｗ＝ａ＋Ｋｍｎ·Ｃｓ,ｒ＞０．９０,ｎ＝５;当Ｃｓ＞ＣＭＣ时,Ｓｔ/Ｓｗ＝ａ＋Ｋｍｃ·Ｃｓ,ｒ＞０．９９,ｎ＝５． 各化合物增溶系数随各自固有水溶性(Ｓｗ)减小而增大(苯基酞酸酯有所反常),ｌｇＫｍｎ和ｌｇＫｍｃ与各自ｌｇｌ/Ｓｗ具有良好的线性正相关性．本文进一步对增溶机理进行了分析解释．     

利用餐饮业废油脂制造生物柴油

世界的石油产量将会逐渐减少，石化柴油燃烧后所排放的废气是造成的城市空气污染的主要原因，生物柴油是石化柴油很好的替代能源，文章介绍了国外废油脂处理利用和甸餐饮业废油脂的概况，提出了利用餐饮业废油脂制造生物柴油的方法和工艺流程，并讨论了利用餐饮业废油脂制造生物柴油的几个问题。     

Larval chemical defence and evolution of host shifts in Chrysomela leaf beetles

Summary. Larvae of Chrysomela leaf beetles release for defence volatile compounds belonging to various chemical families. This study focuses on the defensive strategy based on the esterification of isobutyric acid and 2-methylbutyric acid with a wide variety of alcohols taken up from the host plant. To date, only two species are known to produce these repellents C. interrupta, which is associated with Betulaceae and C. lapponica which occurs either on Betulaceae or Salicaceae.? In order to know if other species have developed this chemical defence and how the food plant influences the secretion of these toxins, we targeted by mass spectrometry the presence of iso- and 2-methylbutyric acids and esters of them in the defensive secretions of Chrysomela larvae exclusively associated with Betulaceae or Salicaceae. ?Screening analyses reveal that the synthesis of these compounds is a common character restricted to all the members belonging to the C. interrupta group sensu Brown (1956) regardless of the host-plant family. These results suggest that the biochemical mechanism leading to the synthesis of these compounds could be considered as a synapomorphy meaning that the group is probably monophyletic. ?Defensive secretions of the members of the interrupta group are quantitatively assayed for iso- and 2-methylbutyric acids and their (Z)-3-hexenyl esters. Results reveal a chemical plasticity developed by Chrysomela species associated with Salicaceae. The amounts of iso- and 2-methylbutyric acids derivatives and of salicylaldehyde in their larval secretions depend on the food plant and on its content in phenolglucosides. Received 5 October 1998; accepted 25 November 1998.