Determination of 27 pharmaceuticals and personal care products (PPCPs) in water: The benefit of isotope dilution

• Isotope dilution method was developed for the determination of 27 PPCPs in water. • The established method was successfully applied to different types of water samples. • The correction effect of corresponding 27 ILSs over 70 d was investigated. • Benefit of isotopic dilution method was illustrated for three examples. Pharmaceuticals and personal care products (PPCPs) are a unique group of emerging and non-persistent contaminants. In this study, 27 PPCPs in various water samples were extracted by solid phase extraction (SPE), and determined by isotope dilution method using liquid chromatography coupled to tandem triple quadruple mass spectrometer (LC-MS/MS). A total of 27 isotopically labeled standards (ILSs) were applied to correct the concentration of PPCPs in spiked ultrapure water, drinking water, river, effluent and influent sewage. The corrected recoveries were 73%–122% with the relative standard deviation (RSD)<16%, except for acetaminophen. The matrix effect for all kinds of water samples was<22% and the method quantitation limits (MQLs) were 0.45–8.6 ng/L. The developed method was successfully applied on environmental water samples. The SPE extracts of spiked ultrapure water, drinking water, river and wastewater effluent were stored for 70 days, and the ILSs-corrected recoveries of 27 PPCPs were obtained to evaluate the correction ability of ILSs in the presence of variety interferences. The recoveries of 27 PPCPs over 70 days were within the scope of 72%–140% with the recovery variation<37% in all cases. The isotope dilution method seems to be of benefit when the extract has to be stored for long time before the instrument analysis.     

基于ZIF-L的微固相萃取技术测定地表水中痕量典型多环芳烃

制备类沸石咪唑酯骨架ZIF-L材料,将其用作微固相萃取吸附剂,处理水中萘、苊、苊烯、芴、菲、蒽、荧蒽、芘等8种痕量典型多环芳烃,再用HPLC测定。试验表明,ZIF-L对上述多环芳烃的萃取效率明显高于商品化萃取材料C 18和多壁碳纳米管。方法在0.100μg/L^200μg/L范围内线性良好,方法检出限为0.02μg/L^0.03μg/L,标准溶液5次测定结果的RSD为4.7%~9.5%,实际水样加标回收率为84.5%~115%。将该方法用于北太湖5个点位水样的测定,测定值为未检出~3.40μg/L。     

Variability of pesticide residues in cauliflower units collected from a field trial and market places in Greece

To estimate the variability of pesticide residue levels present in cauliflower units, a total of 142 samples were collected from a field trial of a cooperative farmer, and 120 samples were collected from different market places in Thessaloniki, Greece. The collected samples were extracted using the quick, easy, cheap, effective, rugged, and safe (QuEChERS) extraction technique, and the residues were determined by liquid chromatography–tandem mass spectrometry. The developed method was validated by evaluating the accuracy, precision, linearity, limit of detection (LOD), and limit of quantification (LOQ). The average recoveries for all the analytes, derived from the data of control samples fortified at 0.01, 0.05, 0.1, and 0.2 mg/kg, ranged from 74 to 110% with a relative standard deviation of ≤8%. The correlation coefficient (R²) was ≥0.997 for all the analytes using matrix-matched calibration standards. The LOD values ranged from 0.001 to 0.003 mg/kg, and the LOQ was determined at 0.01 mg/kg for all the sought analytes. The matrix effect was found to be at a considerable level, especially for cypermethrin and deltamethrin, amounting to +90% and +145%, respectively. For the field samples, the unit-to-unit variability factors (VFs) calculated for cypermethrin and deltamethrin were 2.38 and 2.32, respectively, while the average VF for the market basket samples was 5.11. In the market basket samples, residues of cypermethrin, deltamethrin, chlorpyrifos, and indoxacarb were found at levels ≥LOQ and their respective VFs were 7.12, 5.67, 5.28, and 2.40.     

黑水河下游鱼类资源现状及其保护措施

为了解白鹤滩蓄水运行前黑水河下游鱼类资源的现状、受到的主要威胁及其保护措施,于2014年1~12月在黑水河下游干支流江段采用电捕法进行了渔获物调查。结果显示:12个月共调查发现鱼类28种,隶属于3目8科23属,其中喜流水生境、产粘沉性卵、以着生藻类或/和底栖动物为食物的鱼类种类较多;调查区域鱼类个体规格普遍较小,其中齐口裂腹鱼Schizothorax prenanti、短体副鳅Paracobitis potanini、红尾副鳅Paracobitis varigatus、短须裂腹鱼Schizothorax wangchiachii、前鳍高原鳅Triplophysa anterodorsalis、中华纹胸鮡Glyptothorax sinense和凹尾拟鲿Pseudobagrus emarginatus为调查区域的主要经济鱼类;上半年和下半年的渔获物结构在统计学上差异显著(R=0.81,p=0.1%0.05),鱼类在金沙江干流和黑水河下游之间的相互迁徙比较明显;CPUE呈现先波动下降然后逐月上升的趋势,其中10月份的CPUE最低;丰度生物量比较曲线显示2014年各月的渔获物结构均处于严重干扰状态。黑水河下游河道采砂以及过度捕捞是白鹤滩蓄水前影响黑水河下游鱼类资源的主要因素,建议通过控制采砂的江段、采砂的时间以及全面禁捕保护该区域的鱼类资源。     

不同市场结构组合下稀土最优开采路径研究

本文从价格视角将我国稀土市场结构的变化历程划分为不同阶段,分别从理论和现实视角上探讨了在国际、国内都是完全竞争市场,国际市场垄断、国内市场完全竞争,国际市场完全竞争、国内市场垄断,国际、国内都是垄断市场条件下稀土最优开采路径及最优耗竭时间,并通过设定参数判断其相对大小关系。发现在一定的假设条件下,开采前期当国内和国际市场都是完全竞争时,稀土最优开采量是最大的;当国内和国际市场都是垄断时,稀土最优开采量是最小的;其他两种市场情况下稀土最优开采量居于中间,当国际市场是稀土的主要消费地时,国际竞争-国内垄断市场情况下稀土最优开采量大于国际垄断-国内竞争市场情况下稀土最优开采量,反之,国际垄断-国内竞争市场情况下稀土最优开采量大于国际竞争-国内垄断市场情况下稀土最优开采量。     

茶叶蛋白的研究现状分析及发展对策研究

茶叶中含有15%—30%的蛋白质,对生物体具有多种重要功能,但其中绝大多数是非水溶性蛋白质,难以直接被人体吸收。目前对茶叶蛋白的研究主要集中在提取工艺上,研究表明用复合法提取的效果最好。为了更好地利用茶叶资源,可通过对非水溶性蛋白改性(溶解性、吸水性、吸油性、乳化性、胶凝性等)来提高人体对茶叶蛋白的利用率,发挥茶叶蛋白的生物功能。     

Accumulation of heavy metals from contaminated soil to plants and evaluation of soil remediation by vermiculite

We evaluated the distribution of 15 metal ions, namely Al, Cd, Cu, Cr, Fe, La, Mn, Ni, Pb, Sc, Ti, V, Y, Zn and Zr, in the soil of a contaminated site in Piedmont (Italy). This area was found to be heavily contaminated with Cu, Cr and Ni. The availability of these metal ions was studied using Tessier’s sequential extraction procedure: the fraction of mobile species, which potentially is the most harmful for the environment, was much higher than that normally present in unpolluted soils. This soil was hence used to evaluate the effectiveness of treatment with vermiculite to reduce the availability of the pollutants to two plants, Lactuca sativa and Spinacia oleracea, by pot experiments. The results indicated that the addition of vermiculite significantly reduces the uptake of metal pollutants by plants, confirming the possibility of using this clay in amendment treatments of metal-contaminated soils. The effect of plant growth on metal fractionation in soils was investigated. Finally, the sum of the metal percentages extracted into the first two fractions of Tessier’s protocol was found to be suitable in predicting the phytoavailability of most of the pollutants present in the investigated soil.     

一种简便高效的土壤石油烃提取方法的建立

通过开展单因子实验与正交实验,考察不同参数下超声萃取法对土壤中总石油烃(TPH)的提取效率,并对比了超声萃取法、超声-索氏萃取法及传统索氏萃取法对不同原油污染土壤的提取效果。结果表明:超声萃取法的最优工作参数为20 m L二氯甲烷,超声10 min,4000 r/min离心10 min,萃取4次。3种提取方法中,超声萃取法对石油烃平均回收率最高,为100.95%,而传统的索氏萃取法最低,仅为94.54%。可见,超声萃取法操作简单,效率高,可广泛用于土壤中总石油烃含量的提取测定。     

电晕放电辐射信号的特征提取和模式识别方法研究

目的研究电晕放电辐射信号的特征提取和模式识别方法。方法在分析信号特征提取方法的基础上,对实测的电晕放电辐射信号特征提取,利用概率神经网络开展电晕放电辐射信号目标识别,检验特征提取的有效性。结果以奇异值作为输入特征量的PNN在整体上效果更优,稳定性好,对两类不同放电辐射信号的正确识别率均可达到80%以上,并且当输入特征量个数达到10个时,对实测样本的正确识别率均达到了最高值。电晕放电的正确识别率为96.7%,火花放电的正确识别率为93.3%。结论该方法能基本满足实际放电信号的识别应用。     

沉积物中雌激素及壬基酚、辛基酚、双酚A的测定

近些年来雌激素及烷基酚类化合物由于其对水生生物的内分泌干扰作用越来越受到广泛关注.沉积物作为环境中有机污染物的重要储存库,研究目标物在其中的浓度分布对于探明此类物质在环境中的迁移转化具有重要意义.但沉积物中基质组成复杂而雌激素又痕量存在,这增加了前处理的难度.本研究从雌激素及烷基酚类化合物的理化性质入手,采用碱液提取、液液萃取和LC-MS/MS分析测定沉积物样品中的雌激素及壬基酚、辛基酚、双酚A.结果表明,经过优化的方法对7种目标物的回收率介于61.9%～93.7%之间.该方法能有效去除沉积物中那些不溶于强碱和既溶于酸又溶于碱的有机污染物,同时操作简单、成本低,但回收率高、检出限低,可广泛适用于河流沉积物样品及土壤样品的前处理.