同位素稀释高分辨气相色谱-高分辨质谱法测定氯化石蜡工业品中二噁英

氯化石蜡（CPs）作为一种用途广泛、产量大的有机氯化学工业品,具有组成多样、基质复杂等特点,对其中产生的二噁英（PCDD/Fs）检测是当前工作面临的难题。建立了同位素稀释高分辨气相色谱-高分辨质谱法检测CPs工业品中PCDD/Fs的分析方法。对样品净化过程进行了优化,通过提取溶剂筛选,去除固体CPs中部分基质,建立的双活性炭柱法可高效去除CPs基质。方法采用¹³ C₁₂标记的PCDD/Fs内标物进行定性和定量分析。17种PCDD/Fs同系物的检出限为0.1～3 pg/g,回收率为31.7%～100%。该方法可对高纯度工业品中痕量持久性有机污染物进行高效的定性和定量分析,能够满足国家标准方法对PCDD/Fs检测的要求。     

深圳市大气中PCDD/Fs污染水平初步研究

目的:了解深圳市大气中二噁(PCDD/Fs)的污染水平和分布特征。方法:利用大流量空气采样器分别采集6个采样点的空气样品,每个采样点采集两个平行样品。参照美国环保总局(US EPA Method TO-9A)二噁的检测方法,通过高分辨气相色谱-高分辨双聚焦磁式质谱仪(HRGC/HRMS)对大气样品中17种具有毒性当量因子(TEF)的单体进行了定性和定量分析。结果:∑PCDD/Fs的浓度范围为0.23～11.88pg/m3(平均值为3.84 pg/m3)。毒性当量浓度范围为0.014～0.29 pg I-TEQ/m3(平均值为0.135 pg I-TEQ/m3)。OCDD、HpCDD、HpCDF、OCDF、HxCDF是丰度较大的单体,分别占总浓度的48.21%、15.85%、11.37%、7.40%、6.59%。PCDDs和PCDFs单体浓度(除OCDF之外)均随氯原子取代个数的增加而增大。2,3,4,7,8-PeCDF对总的毒性当量贡献最大,占总毒性当量浓度的38.87%。六个采样点中有三个地点二噁同系物分布显示了"源"的特征,而另外三个地点则显示了"汇"的特征。成人的PCDD/Fs暴露量为0.0023～0.047 pg I-TEQ/kg.day;儿童PCDD/Fs暴露量为0.0052～0.11 pg I-TEQ/kg.day。结论:深圳市大气样品中二噁浓度低于国内一些城市研究水平,而高于日本、欧美国家的研究水平。     

废线路板粉末中二噁英含量的测定

采用加速溶剂萃取-柱层析-高分辨质谱法检测废线路板粉末样品中17种2,3,7,8-PCDD/Fs的含量。采用TRDIOXIN-5MS毛细管色谱柱(60 m×0.25 mm×0.25μm)进行分离和多离子检测(MID)模式进行检测,以保留时间和同位素特征离子丰度比进行定性,用13C标记同位素稀释内标法进行定量。结果表明,17种2,3,7,8-PCDD/Fs化合物的标准曲线的线性相关性良好,线性相关系数均大于0.999 9,该方法分析的提取内标的平均回收率范围为37.25%~82.75%,RSD8%,样品中各异构体的加标回收率为112.66%~124.26%,RSD7%。应用该方法检测废线路板粉末样品,回收率在58.67%~123.00%范围内,1,2,3,4,6,7,8-Hp CDF、1,2,3,4,6,7,8-Hp CDD、OCDF、OCDD的质量比分别为2.74、2.50、5.57、16.37 pg/g,TEQ分别为0.027 4、0.025 0、0.005 6、0.016 4 ng/kg。     

M12半自动净化法与手工净化法应用于飞灰中二噁英类检测比较

研究比较了M12半自动净化法与手工净化法应用于二噁英检测的效果。结果显示,采用高分辨气相色谱-高分辨质谱法(HRGC-HRMS)检测飞灰样品中的二噁英,手工净化法的回收率要优于M12半自动净化法的回收率,但M12半自动净化法除2种单体外,其余单体回收率均满足对二噁英的分析要求,且2种净化方法所得二噁英的总毒性当量结果相近,证明手工净化法与HRGC-HRMS联用检测飞灰中二噁英的效果较好,但M12半自动净化法也能够满足HRGC-HRMS检测二噁英的净化要求。应用酶联免疫法检测飞灰样品中二噁英的总毒性量,当样品中二噁英浓度较高时,M12半自动净化法和手工净化法净化测得结果与基准值一致性较好;当样品中二噁英浓度较低时,手工净化法检测结果与基准值差别较大,表明酶联免疫法更适合用M12半自动净化法进行净化。     

上海市崇明岛农业土壤中二噁英的现状研究及来源分析

为了解上海市崇明岛农用土壤中二噁英类化合物(PCDD/Fs)现状水平及其来源,于2021年6-7月采集上海市崇明岛31个农业土壤样品,采用同位素稀释法测定样品中17种2,3,7,8-PCDD/Fs的含量,并且对其现状水平、异构体特征以及来源进行初步分析。结果表明,31个土壤样品中均检出PCDD/Fs,质量分数为88.14~356.55 pg/g,对应毒性当量为0.64~2.20 pg I-TEQ/g,统计频率分析发现呈右侧拖尾的偏态分布,中位数为1.05 pg I-TEQ/g。经过比较,崇明岛农用土壤属于典型的背景土壤,土壤中二噁英类物质的污染属于较低水平。利用主成分分析(PCA)和正定矩阵因子分解法(PMF)对可能的来源进行分析,结果显示上海市崇明岛农业土壤中PCDD/Fs的主要来源为五氯酚(PCP)、水稻秸秆烟(RSS)和交通源(TS),占比分别为61.6%,23.2%和15.2%。结合采样地理位置推断,上海市崇明岛农业土壤中PCDD/Fs可能受到来自崇明岛自身农耕以及交通等因素的影响。     

杭州市环境空气中二噁英类物质检测与分析

为了解二噁英类物质(PCDD/Fs)在环境空气中污染现状及不同季节不同时段浓度、组成和存在形式等的变化情况,于夏、冬两季对杭州西湖区空气中PCDD/Fs进行了采样分析。结果表明,空气中PCDD/Fs毒性当量浓度与国内其他城市(北京、上海、广州)相近,夏、冬两季空气中PCDD/Fs质量浓度和毒性当量浓度分别为4.92 pg/m3、0.34 I-TEQ pg/m3和4.51 pg/m3、0.40 I-TEQ pg/m3,夏季PCDD/Fs毒性当量浓度略低于冬季;在分时段采样检测结果中,晚间空气中PCDD/Fs质量浓度和毒性当量浓度均高于白天空气中的PCDD/Fs浓度;夏季样品中TCDD/Fs、PeCDD/Fs主要以气相的形式存在,HpCDD/Fs、OCDD/F主要以颗粒相的形式存在,冬季样品中PCDD/Fs主要以颗粒相形式存在。     

珠三角地区造纸行业排水中二 NFDA1 英(PCDD/Fs)特征分析

研究采用¹³C同位素内标稀释定量法,高分辨气相色谱质谱法(HRGC-HRMS)对珠三角地区造纸行业排水中PCDD/Fs特征进行了分析。结果表明,该地区造纸行业PCDD/Fs含量为:4.75~80.05 pg/L,且以OCDD占主导地位;同时该类行业PCDD/Fs的TEQ为:0.21~2.02 pg TEQ/L。最后通过对该类行业排水中PCDD/Fs的TEQ年排放量进行讨论,其结果为0.30~12.97 mg TEQ,且年平均排放量(4.42 mgTEQ)只占我国造纸行业TEQ总排放量的很小一部分。     

交通限行对大气颗粒物及PM_(2.5)中二■英的影响

为了研究北京大气颗粒物和二■英(PCDD/Fs)的污染状况以及评估交通限行对大气颗粒物和PCDD/Fs的影响。利用同位素稀释高分辨率气相色谱/高分辨率质谱(HRGC/HRMS)联用法和USEPA 1613B标准方法,以中国地质大学(北京)东门为采样点,采集大气PM_(2.5)、PM_(10)、TSP样品,对北京市交通限行期间以及交通限行前后等不同交通状况下颗粒物浓度及大气PM_(2.5)中17种2,3,7,8-PCDD/Fs污染特征进行了监测。结果表明,PM_(2.5)、PM_(10)、TSP的日均质量浓度在交通限行前分别为126、202、304μg/m~3,限行期间分别为39、78、93μg/m~3,限行结束后分别为79、126μg/m~3。PM_(2.5)中17种PCDD/Fs的质量浓度(毒性浓度) 3个时段分别为1 804 fg/m~3(70 fg I-TEQ/m~3)、252 fg/m~3(9 fg I-TEQ/m~3)和1 196 fg/m~3(48 fg I-TEQ/m~3)。北京市交通限行期间颗粒物浓度和二■英浓度显著低于交通限行前后,交通源减排措施的实施是大气颗粒物和二■英污染水平降低的主要原因,从减排效果看,交通源减排措施对大气细颗粒物(PM_(2.5))的控制效果明显好于大气粗颗粒物。     

广州某观测点春季大气样品中二NFDA1英日均浓度变化分析

在广州某商住区楼顶开展为期1个月的大气样品连续采样,利用高分辨气相色谱-高分辨质谱仪测定了样品中17种毒性二 NFDA1 英(PCDD/Fs)的含量。结果表明,该采样点位样品二 NFDA1 英I-TEQ浓度范围为0.094~1.34 pg I-TEQ/m³,样品日平均浓度相对偏差范围为3.2%~118.8%,6日平均浓度相对偏差范围为1.2%~60.1%,6日平均值更能较好地反映样品长期平均浓度。气象变化对样品中二 NFDA1 英I-TEQ浓度有明显影响,降雨后样品中的二 NFDA1 英I-TEQ浓度明显低于降雨前,降雨前或降雨中样品的二 NFDA1 英I-TEQ浓度与降雨后样品比值最高达到9.0,样品二 NFDA1 英I-TEQ浓度与PM_2.5的线性相关性高于其与TSP、温度相关性,上述三者的r值和P值分别为0.637、-0.296、0.271和0.611、0.326、0.329。     

高分辨电感耦合等离子体质谱法测定地下水中稀土元素

采用高分辨电感耦合等离子体质谱法测定地下水中14种稀土元素,并选择Rh作内标,可消除测定中的质谱干扰和非质谱干扰,使方法在0μg/L~100μg/L范围内线性良好。方法检出限为0.002μg/L~0.005μg/L,实际水样的加标回收率为80.0%~117%,RSD为2.1%~3.8%。     

Development of a new automated clean-up system for the simultaneous analysis of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and 'dioxin-like' polychlorinated biphenyls (dl-PCB) in flue gas emissions by GPC-SPE

A comprehensive clean-up method for quantitative analysis of polychlorinated biphenyls (PCBs) and polychlorinated dibenzo-p-dioxins and dibenzo-furans (PCDD/Fs) in one single extract of environmental samples was developed. Since the chemical nature and toxicity of planar PCBs are similar to those of PCDD/Fs, dioxin-like PCBs and PCDD/Fs are often surveyed together in their exposure assessments. The development of a method for the simultaneous analysis of PCBs and PCDD/Fs in environmental samples is invaluable. The automated clean-up system evaluated in this work consists of three additional steps after traditional extraction: the chromatography on gel permeation (GPC), the concentration of the solvent through the use of an in-line evaporation module and the further purification and separation of PCDDs/Fs and dl-PCBs on an alumina cartridge in the 'SPE module'. In this work, three fly ash samples from an interlaboratory study with different PCDD/F and PCB levels were Soxhlet-extracted and then cleaned up using an automated system. PCDD/Fs and PCBs were determined using isotope dilution and high resolution gas chromatography/high resolution mass spectrometry. The determined values of 17 PCDD/Fs were consistent with the certified values and the relative standard deviations (RSDs) of the determined values were less than 20%. The recoveries of (13)C labeled PCDD/Fs and planar PCBs, and their RSDs were within the ranges specified in EPA1613 and 1668a methods, respectively. An accurate and reliable method was successfully developed and can be used in the simultaneous analysis of PCDD/Fs and planar PCBs in environmental samples.     

气相色谱-质谱法测定废酸油渣中的16种多环芳烃

建立了废酸油渣中16种多环芳烃超声萃取、Florisil萃取柱净化、气相色谱-质谱测定的方法。笔者对提取方式、提取剂类型和体积、提取时间和次数、净化方式等进行研究,采用无水硫酸钠分散,二氯甲烷作为提取剂超声40 min,提取液经纯水清洗、离心后取适量有机相经过3 g Florisil萃取柱净化,采用气相色谱-质谱选择离子模式(SIM),加入内标进行定量分析。结果表明:二氯甲烷提取效率比正己烷好,丙酮可能引起酸性样品中多环芳烃的降解,丙酮超声萃取时加入无水硫酸钠能在一定程度上防止目标物降解,但萃取效率不可控制,宜采用二氯甲烷作为萃取剂。分散提取能有效减少提取时间,超声清洗仪超声40 min提取效率为86.2%～104%。3g Florisil萃取柱净化比1 g Florisil萃取柱净化和GPC净化效果略好。方法检出限为0.4～1.3 mg/kg,6次空白加标的相对标准偏差为2.3%～15.3%,6个实际样品测定结果的相对标准偏差为1.2%～27.3%,基体加标回收率为51.3%～126%,连续校准稳定。该方法适用于废酸油渣样品中16种多环芳烃的检测,比直接溶解有效,比加速溶剂萃取、索氏提取、微波萃取和超声探头萃取简单、快捷,能有效减少设备污染和腐蚀,净化方法有效,测定结果准确可靠,是实现大批量样品检测的可行方法。     

Dioxins and polychlorinated biphenyls (PCDD/Fs and PCBs) in food from farms close to foot and mouth disease animal pyres

To control the outbreak of foot and mouth disease, which occurred in the UK in early 2001, a large number of farm animals were slaughtered. Where it was not possible to render or landfill the carcasses, they were destroyed by burning on open pyres, with wood, coal and other materials. Uncontrolled combustion such as this is known to produce small quantities of dioxins and an investigation was made into whether, as a result of the burning, there was an elevation in the concentrations of these compounds in food produced in the areas close to the pyres. With few exceptions, concentrations of PCDD/Fs and PCBs were within the expected ranges as predicted by reference data. No accumulation over time was evident from a repeat milk sampling exercise. Where elevated concentrations of PCDD/Fs and PCBs were found in chickens and eggs, they were in samples not destined for the food chain. Elevated levels in some samples of milk from Dumfries and Galloway were not found in earlier or later samples and may have been found as a result of a temporary feeding regime. Elevated concentrations in lamb from Carmarthenshire were from very young animals which would not have entered the food chain. There was no evidence of any significant increase in dietary exposure to PCDD/Fs and PCBs as a result of the FMD pyres.     

Distribution patterns of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans in sediments of the Xiangjiang River, China

We investigated the occurrence and distribution patterns of 2,3,7,8-substituted polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in six sediment samples from the Xiangjiang River, Hunan Province, People’s Republic of China. Total concentrations of PCDD/Fs ranged from 876 to 497,759 (mean 160,766) ng/kg dw, the highest of which exceeded that have ever been reported for sediment samples. World Health Organization total toxicity equivalent (WHO-TEQ) concentrations in three out of six samples were significantly higher than the guidance level (21.5?ng WHO-TEQ/kg dw) suggested by Canadian Sediment Quality Guideline. A predominance of octachlorodibenzo-p-dioxin (OCDD) was observed with an average contribution of 90.8% to the total PCDD/F concentrations, while 1,2,3,4,6,7,8-heptachlorodibenzo-p-dioxin (HpCDD) was the major contributor to the PCDD/F WHO-TEQ concentrations in most of the sites. Such high levels of OCDD and HpCDD may be attributed to the presence of PCP/PCP-Na pollution, although MB-WW, agricultural straw open burning, and boilers–hazardous wastes were also the potential sources of PCDD/Fs. This is the first report for the concentrations and congener profiles of PCDD/Fs in sediment samples from the Xiangtan, Zhuzhou, and Changsha sections of the Xiangjiang River, providing scientific evidence for establishing priorities to reduce ecological risks posed by PCDD/Fs in the rapidly developing areas of Hunan Province and elsewhere.     

Chlorinated and brominated dibenzo-p-dioxins and dibenzofurans in surface sediment from Taihu Lake, China

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs) in surface sediment samples from Taihu Lake--an important water supply of the Yangtze River Delta, China--were investigated in the present study. Concentrations of PCDD/Fs ranged from 0.91 to 4.8 pg TEQ g(-1) dw (mean: 2.9 pg TEQ g(-1) dw, TEQ: Toxic Equivalent), which were all higher than the threshold effect level established by interim sediment quality guidelines in Canada (0.85 pg TEQ g(-1) dw). The levels of PBDD/Fs ranged from 0.16 to 1.6 pg TEQ g(-1) dw (mean: 0.52 pg TEQ g(-1) dw) and accounted for 5-33% (mean: 14%) of the total PCDD/Fs and PBDD/Fs TEQ. Comparatively, the abundance of sedimentary PCDD/Fs in the three regions (Meiliang Bay, Gonghu Bay, and Xukou Bay) showed a decreasing trend from the inflow region to the outflow region, while no significant difference was observed among their 2,3,7,8-PBDD/Fs levels, which suggested that the sources of PCDD/Fs and PBDD/Fs differed in this area. Principal component analysis suggested that the historical production/usage of pentachlorophenol and sodium pentachlorophenate was the dominant source of PCDD/Fs in the sediment of these regions. Although the specific sources of PBDD/Fs in the sediment of Taihu Lake were unclear, it was suspected to be due to atmospheric deposition; however, an additional study is needed to confirm this.     

Temporal variation of PCDD/PCDF levels in environmental samples collected near an old municipal waste incinerator

In 1996 and 1997, the levels of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) were determined in soil and herbage samples taken from 24 sites in the vicinity of an old municipal solid waste incinerator (Montcada, Barcelona, Spain). To determine the temporal variation in the concentrations of PCDD/Fs, recently 24 soiland 24 herbage samples were again collected at the same sampling points and analyzed for PCDD/F levels. In the currentsurvey, PCDD/F concentrations in soils ranged between 0.06 and127 ng I-TEQ kg^-1 (dry matter), with median and mean values of 4.80 and 9.95 ng I-TEQ kg^-1 (dry matter), respectively. In turn, the levels of PCDD/Fs in herbage samples ranged from 0.40 to 1.94 ng I-TEQ kg^-1 (dry matter), with median and mean values of 0.86 and 0.95 ng I-TEQ kg^-1 (dry matter), respectively. The comparison with the data obtained in 1996 and 1997 show that while PCDD/F concentrations in herbage samples decreased substantially during the last two years, no significant differences in the levels of PCDD/Fs in soils were noted. On the other hand, the potential intake of polluted soils from the vicinity of the plant would not imply any significant health risk for the general population living in the area under influence of the facility.     

广州大气颗粒物中二噁含量的初步研究

2004年夏季在广州四个不同区域采集大气颗粒物样品,参照美国环保局(US EPA)标准方法测定其中二噁的含量,采用热分解光学分析法测定元素碳和有机碳的含量。结果表明,花都、荔湾、天河、黄埔大气颗粒物中二噁浓度(毒性当量)平均值分别为3815fg/m3(104.6fg I-TEQ/m3)、12777fg/m3(430.5fg I-TEQ/m3)、6963fg/m3(163.7fg I-TEQ/m3)、10953fg/m3(769.3fg I-TEQ/m3)。简单地分析了广州大气颗粒物中二噁的含量特征,以及与元素碳、有机碳之间的相关性。     

Occurrence of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in Lake Maggiore (Italy and Switzerland)

Samples of air (gas and particulate phases), bulk deposition, aquatic settling material and sediments were collected in Lake Maggiore (LM) in order to determine their content of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs). Air (gas and particulate phases) concentrations were 0.5 pg m(-3), 80 pg m(-3), 13 pg m(-3) and 106 pg m(-3) for SigmaPCDD/Fs, SigmaPCBs, Sigma dioxin-like PCBs (DL-PCBs) and SigmaPBDEs, respectively. Deposition fluxes ranged from 0.7 ng m(-2) d(-1) for SigmaPCDD/Fs to 32 ng m(-2) d(-1) for SigmaPCBs. Aquatic settling material presented concentrations of 0.4 ng g(-1) dry weight (dw) for SigmaPCDD/Fs, 13 ng g(-1) dw for SigmaPCB, 3.4 ng g(-1) dw for SigmaDL-PCBs and 5.7 ng g(-1) dw for SigmaPBDEs. Mean sediment concentrations were 0.4 ng g(-1) dw for SigmaPCDD/Fs, 11 ng g(-1) dw for SigmaPCB, 3 ng g(-1) dw for SigmaDL-PCBs and 5.1 ng g(-1) dw for SigmaPBDEs. Similar PCDD/F and DL-PCB congener patterns in all the environmental compartments of LM point to an important, if not dominant, contribution of atmospheric deposition as source of these pollutants into LM. In contrast, PBDE congener distribution was not similar in the different environmental compartments. BDE 47 dominated air and settling material, while BDE 209 was the predominant congener in the bulk atmospheric deposition. Moreover, sediments showed two distinct PBDE congener profiles. Lower PBDE concentrated sediments were dominated by congeners 47 and 99, while BDE 209 dominated in higher PBDE concentrated samples. This suggests the influence of local sources as well as atmospheric input of PBDEs into LM.