Fractionation of plutonium in environmental and bio-shielding concrete samples using dynamic sequential extraction

Fractionation of plutonium isotopes (²³⁸Pu, ^239,240Pu) in environmental samples (i.e. soil and sediment) and bio-shielding concrete from decommissioning of nuclear reactor were carried out by dynamic sequential extraction using an on-line sequential injection (SI) system combined with a specially designed extraction column. Plutonium in the fractions from the sequential extraction was separated by ion exchange chromatography and measured using alpha spectrometry. The analytical results show a higher mobility of plutonium in bio-shielding concrete, which means attention should be paid to the treatment and disposal of nuclear waste from decommissioning.     

Analysis of trace dicyandiamide in stream water using solid phase extraction and liquid chromatography UV spectrometry

An improved method for trace level quantification of dicyandiamide in stream water has been developed. This method includes sample pretreatment using solid phase extraction. The extraction procedure (including loading, washing, and eluting) used a flow rate of 1.0 mL/min, and dicyandiamide was eluted with 20 mL of a methanol/acetonitrile mixture (V/V = 2:3), followed by pre-concentration using nitrogen evaporation and analysis with high performance liquid chromatography–ultraviolet spectroscopy (HPLC–UV). Sample extraction was carried out using a Waters Sep-Pak AC-2 Cartridge (with activated carbon). Separation was achieved on a ZIC^®-Hydrophilic Interaction Liquid Chromatography (ZIC-HILIC) (50 mm × 2.1 mm, 3.5 μm) chromatography column and quantification was accomplished based on UV absorbance. A reliable linear relationship was obtained for the calibration curve using standard solutions (R² > 0.999). Recoveries for dicyandiamide ranged from 84.6% to 96.8%, and the relative standard deviations (RSDs, n = 3) were below 6.1% with a detection limit of 5.0 ng/mL for stream water samples.     

高效液相色谱-电感耦合等离子体质谱联用测定生物样品中的有机汞

建立了酸提取-高效液相色谱-电感耦合等离子体质谱联用技术(HPLC-ICP-MS)测定生物样品中甲基汞、乙基汞、苯基汞等3种有机汞的分析方法。鱼肉和贝类样品经盐酸消解,苯萃取,硫代硫酸钠溶液反萃取后,采用醋酸铵/L-半胱氨酸缓冲盐及甲醇体系组成的流动相按一定比例进行梯度洗脱,经前处理的生物样品在液相色谱中经C18柱分离后,进入电感耦合等离子体质谱检测其甲基汞、乙基汞和苯基汞的浓度。3种有机汞化合物均在0.50~50.0μg/L范围内呈现良好的线性关系,线性相关系数(r)均大于0.9998。方法检出限为0.010~0.038mg/kg;3种有机汞样品加标的RSD均小于12.2%;两个水平的加标回收率在50.8~129%。     

微波萃取技术在分析土壤中有机污染物的应用

介绍了微波萃取技术及其使用的试剂、设备和条件，对微波萃取在分析土壤中有机污染物的应用予以综述，阐述了微波萃取技术是分析土壤中有机污染物的好方法。     

微波-亚临界水萃取底泥中两种多氯联苯的研究

微波亚临界水萃取模拟土样中的2,3-二氯联苯和3,3′-二氯联苯,用气相色谱进行分析。与亚临界水萃取方法相比,该法缩短了萃取时间,分析物的萃取回收率有所提高。对微波亚临界水的萃取条件进行优化,确定了最佳萃取条件为时间20min、温度区段为210℃～225℃。方法对长江镇江段内江的底泥中的多氯联苯进行分析,测定结果与索氏提取-GC分析结果吻合,且不受底泥中腐殖质等有机物影响。     

Electrochemical study of the fungicide acibenzolar-s-methyl and its voltammetric determination in environmental samples

The electrochemical behavior of new generation fungicide acibenzolar-s-methyl (S-methyl 1,2,3-benzothiadiazole-7-carbothioate, ASM) on the hanging mercury drop electrode (HMDE) was investigated using square wave adsorptive stripping voltammetry. This method of determination is based on the irreversible reduction of ASM at the HMDE. The well-defined ASM peak was observed at ?0.4 V (vs. Ag/AgCl) in BR buffer at pH 2.2. The reduction peak current was proportional to concentration of ASM from 1.0 × 10^?8 to 6.0 × 10^?8 mol L^?1 with detection and quantification limit 3.0 × 10^?9 and 1.0 × 10^?8 mol L^?1, respectively. The applicability of the developed method for analysis of spiked samples of tap water, river water, and soil is illustrated. The effect of adsorption on the mercury electrode was studied in detail using the AC impedance method. Possible interferences with other common pesticides and heavy metal ions were examined. Clarification of the electrode mechanism was made using cyclic voltammetry (CV) technique.     

Modulation of steroidogenesis by coastal waters and sewage effluents of Hong Kong, China, using the H295R assay

BACKGROUND, AIM, AND SCOPE: The presence of a variety of pollutants in the aquatic environment that can potentially interfere with the production of sex steroid hormones in wildlife and humans has been of increasing concern. The aim of the present study was to investigate the effects of extracts from Hong Kong marine waters, and influents and effluents from wastewater treatment plants on steroidogenesis using the H295R cell bioassay. After exposing H295R cells to extracts of water, the expression of four steroidogenic genes and the production of three steroid hormones were measured. MATERIALS AND METHODS: Water samples were collected during the summer of 2005 from 24 coastal marine areas and from the influents and effluents of two major waste water treatment plants (WWTPs) in Hong Kong, China. Samples were extracted by solid phase extraction (SPE). H295R cells were exposed for 48 h to dilutions of these extracts. Modulations of the expression of the steroidogenic genes CYP19, CYP17, 3betaHSD2, and CYP11beta2 were determined by measuring mRNA concentrations by real-time polymerase chain reaction (Q-RT-PCR). Production of the hormones progesterone (P), estradiol (E2), and testosterone (T) was quantified using enzyme linked immunosorbent assays (ELISA). RESULTS: Extracts from samples collected in two fish culture areas inhibited growth and proliferation of H295R cells at concentrations greater or equal to 10(5) L equivalents. The cells were exposed to the equivalent concentration of active substances in 10,000 L of water. Thus, to observe the same level of effect as observed in vitro on aquatic organisms would require a bioaccumulation factor of this same magnitude. None of the other 22 marine samples affected growth of the cells at any dilution tested. Twelve of the marine water samples completely inhibited the expression of CYP19 without affecting E2 production; inhibition of CYP17 expression was observed only in one of the samples while expression of CYP11beta2 was induced as much as five- and ninefold after exposure of cells to extracts from two locations. The expression of the progesterone gene 3betaHSD2 was not affected by any of the samples; only one sample induced approximately fourfold the production of E2. Although more than twofold inductions were observed for P and T production, none of these values were statistically significant to conclude effects on the production of these two hormones. While influents from WWTPs did not affect gene expression, an approximately 30% inhibition in the production of E2 and a 40% increase in P occurred for the exposure with influents from the Sha Tin and Stonecutters WWTPs, respectively. Effluents from WWTPs did not affect the production of any of the studied hormones, but a decrement in the expression of the aldosterone gene CYP11beta2 was observed for the Sha Tin WWTP exposure. No direct correlation could be established between gene expression and hormone production. DISCUSSION: Observed cytotoxicity in the two samples from fish culture areas suggest the presence of toxic compounds; chemical analysis is required for their full identification. Although effluents from WWTPs did not affect hormone production, other types of endocrine activity such as receptor-mediated effects cannot be ruled out. Interactions due to the complexity of the samples and alternative steroidogenic pathways might explain the lack of correlation between gene expression and hormone production results. CONCLUSIONS: Changes observed in gene expression and hormone production suggest the presence in Hong Kong coastal waters of pollutants with endocrine disruption potential and others of significant toxic effects. The aromatase and aldosterone genes seem to be the most affected by the exposures, while E2 and P are the hormones with more significant changes observed. Results also suggest effectiveness in the removing of compounds with endocrine activity by the WWTPs studied, as effluent samples did not significantly affect hormone production. The H295R cell showed to be a valuable toll in the battery required for the analysis of endocrine disrupting activities of complex environmental samples. RECOMMENDATIONS AND PERSPECTIVES: Due to the intrinsic complexity of environmental samples, a combination of analytical tools is required to realistically assess environmental conditions, especially in aquatic systems. In the evaluation of endocrine disrupting activities, the H295R cell bioassay should be used in combination with other genomic, biological, chemical, and hydrological tests to establish viable modes for endocrine disruption and identify compounds responsible for the observed effects.     

中美淡水生物区系中汞物种敏感度分布比较

通过收集无机汞对中国与美国淡水水生生物的毒性数据,构建了脊椎动物(包括鱼类)、无脊椎动物(包括节肢动物和非节肢无脊椎动物)及所有物种对汞的物种敏感度分布(SSD:species sensitivity distributions)曲线,并在此基础上对中国和美国不同类别生物对汞的敏感性分布进行了分析.结果表明:中国与美国各类生物及所有物种对汞的SSD敏感性分布曲线没有显著差异.然而,中国淡水水生物种对汞短期暴露的HC5(hazardous concentration for 5% of the species)较美国淡水物种的阈值小,尤其是非节肢无脊椎动物,汞对美国非节肢动物的HC5值是我国对应物种的7.4倍.在保护95%的物种水平下,中国不同类别试验生物对汞的敏感性排序为无脊椎动物>脊椎动物,其中节肢动物>非节肢无脊椎动物>鱼类;而对应的美国生物对汞的敏感性排序无脊椎动物>脊椎动物,其中节肢动物>鱼类>非节肢无脊椎动物.另外,中美所有节肢动物对汞的敏感性要强于所有鱼类和所有非节肢无脊椎动物.所以在使用所有物种推导水质基准时应考虑其中各类别物种敏感度分布的影响,且需要注意采用美国淡水水生物种推导的水质基准可能会对我国淡水水生物种造成"保护不足".     

厦门杏林湾水系表层沉积物中PAHs分析与风险评估

利用ASE-GC-MS(加速溶剂萃取与气相色谱质谱仪联用)方法分析了USEPA(美国环保署)16种优控PAHs在厦门城郊杏林湾水系的19个表层沉积物样点中的含量,并对其组成、来源和风险进行了探讨.结果表明,杏林湾水系表层沉积物中PAHs含量介于413.00~2 748.81 ng·g-1,均值为949.56 ng·g-1;在检测出的13种PAHs中,强致癌性的Bk F和Bghi P检出率高达73.68%,均值分别为69.15 ng·g-1和49.86 ng·g-1;PAHs以2~4环为主,其中2+3环比例均值为61.03%,4环比例均值为23.53%;5和6环均值为15.82%.在所采集的沉积物样品中,中度污染占调查样品数的68.42%,高度污染的占31.58%.利用Ant/(Ant+Phe)和Fla/(Fla+Pyr)比值法和主成分分析方法对杏林湾流域中PAHs其来源进行分析,以及平均沉积物质量基准商(m SQG-Q)法进行生态风险评估,结果表明其PAHs的主要来源为石油源以及石油燃烧源;SQG-Q小于0.50;综合含量、组成特征以及沉积物质量基准商等评价表明,研究区域内靠近杏林工业区一侧的2、3、5和9号采样区以及13号港头采样区表层沉积物中PAHs具有较高的生态安全风险;值得进一步关注.     

Prenatal diagnosis of congenital cytomegalovirus infection in 189 pregnancies with known outcome

An Erratum has been published for this article in Prenatal Diagnosis 21(7) 2001, 605. Prenatal diagnosis (PD) of fetal cytomegalovirus (CMV) infection was performed in 242 pregnancies, with known outcome in 189 cases. In 141/189 pregnancies, PD was carried out on account of suspicious maternal CMV serology up to gestational week (WG) 23, and in 48 cases on account of abnormal ultrasonic findings detected between WG 18 and 39. Chorionic villus samples (n=6), amniotic fluid (AF, n=176) and/or fetal blood specimens (n=80) were investigated for detection of virus by cell culture, shell vial assay, PCR and/or CMV-specific IgM antibodies. Of 189 fetuses correctly evaluated by CMV detection either in fetal tissue following therapeutic abortion/stillbirth (n=24) or in urine of neonates within the first 2 weeks of life (n=33), 57 were congenitally infected. In women with proven or suspected primary infection, the intrauterine transmission rates were 20.6% (7/34) and 24.4% (10/41), respectively. Of the congenitally infected live-born infants, 57.6% (19/33) had symptoms of varying degree. The overall sensitivity of PD in the serologic and ultrasound risk groups was 89.5% (51/57). A sensitivity of 100% was achieved by combining detection of CMV-DNA and CMV-specific IgM in fetal blood or by combined testing of AF and fetal blood for CMV-DNA or IgM antibodies. There was no instance of intrauterine death following the invasive procedure. The predictive value of PD for fetal infection was 95.7% (132/138) for negative results and 100% (51/51) for positive results. Correct results for congenital CMV infection by testing AF samples can be expected with samples obtained after WG 21 and after a time interval of at least 6 weeks between first diagnosis of maternal infection and PD. In case of negative findings in AF or fetal blood and the absence of ultrasound abnormalities at WG 22–23, fetal infection and neonatal disease could be excluded with high confidence. Positive findings for CMV infection in AF and/or fetal blood in combination with CMV suspicious ultrasound abnormalities predicted a high risk of cytomegalic inclusion disease (CID). Furthermore, detection of specific IgM antibodies in fetal blood was significantly correlated with severe outcome for the fetus or the newborn (p=0.0224). However, normal ultrasound of infected fetuses at WG 22–23 can neither completely exclude an abnormal ultrasound at a later WG and the birth of a severely damaged child nor the birth of neonates which are afflicted by single manifestations at birth or later and of the kind which are not detectable by currently available ultrasonographic techniques. Copyright © 2001 John Wiley & Sons, Ltd.