Simultaneous determination of eight metabolites of organophosphate and pyrethroid pesticides in urine

A simultaneous method for quantifying eight metabolites of organophosphate pesticides and pyrethroid pesticides in urine samples has been established. The analytes were extracted using liquid–liquid extraction coupled with WCX solid phase extraction (SPE) cartridges. Eight metabolites were chemically derivatized before analysis using gas chromatography–tandem mass spectrometry (GC–MS–MS). The separation was performed on a HP-5MS capillary column (30 m × 0.25 mm × 0.25 µm) with temperature programming. The detection was performed under electro-spray ionization (ESI) in multiple reaction monitoring (MRM) mode. An internal standard method was used. The extraction solvent, types of SPE cartridges and eluents were optimized by comparing the sample recoveries under different conditions. The results showed that the calibration curves of the five organophosphorus pesticides metabolites were linear in the range of 0.2–200 μg/L (r² ≥ 0.992) and that of the three pyrethroid pesticides metabolites were linear in the range of 0.025–250 μg/L (r² ≥ 0.991). The limits of detection (LODs, S/N ≥ 3) and the limits of quantification (LOQs, S/N ≥ 10) of the eight metabolites were 0.008–0.833 μg/L and 0.25–2.5 μg/L, respectively. The recoveries of the eight metabolites ranged from 54.08% to 82.49%. This efficient, stable, and cost-effective method is adequate to handle the large number of samples required for surveying the exposure level of organophosphorus and pyrethroid pesticides in the general population.     

瓯江河口潮汐特征变化及其原因分析

利用瓯江河口沿程4个长期潮位站的监测数据,结合潮流数学模型,计算分析1960~2014年各站年均高、低潮位,年均涨落潮历时特征值,得出瓯江河口近54 a来潮汐特征变化过程,分析相关影响因素,探讨河口潮汐特征变化原因。结果表明:瓯江河口下游的龙湾站多年来潮汐特征尚无明显趋势性变化;河口中上游的温州、梅岙和花岩头站趋势性变化明显且变化规律基本一致,整体表现为高潮位上升、低潮位下降、潮差增大,涨潮历时延长、落潮历时缩短的特征,时空格局上,上游站位潮汐特征变幅大于下游站位,低潮位变幅大于高潮位变幅。原因分析表明,流域来水对河口潮汐特征的影响不明显;堤线调整和围垦工程等人类活动主要引起工程局部河段潮位变化;河口高强度的采砂活动应是温州、梅岙、花岩头站潮汐特征变化的主因。瓯江河口不同河段因受径流、潮流、人类活动等因素的影响程度不同,其潮位特征沿程的变化特点也不同,需要在河口工程设计、防洪减灾与河口治理等方面予以关注。     

Using sequential extraction techniques to assess the partitioning of plutonium and neptunium-237 from multiple sources in sediments from the Ob River (Siberia)

Sequential extraction techniques have been developed to assess partitioning of anthropogenic radionuclides (²⁴⁰Pu, ²³⁹Pu, and ²³⁷Np), originating from a variety of sources, as identified by using bulk sediment isotopic composition. Sediments were leached sequentially with a series of six chemical treatments designed to approximate different environmental processes that may occur or to selectively extract trace metals contained in different solid phases of the sediments (i.e., exchangeable, reducible, carbonate, organic, acid leachable, and refractory). Results indicate the majority of Pu and Np is similarly distributed within many of the extracted fractions, with the largest percentage (66–97%) of both elements being observed in sediments treated with buffered citrate dithionite (CDB), which targets easily reduced constituents such as Mn and Fe hydrous oxides. While these results do indicate an association of Pu and Np with redox sensitive elements, the environmental implications are unclear given that the CDB treatment is more extreme than naturally occurring conditions. Minor amounts of Np partition differently from Pu in sediments. The NH₄-acetate treatment, which is designed to liberate trace metals that are loosely adsorbed onto the surfaces of sedimentary materials such as hydrated iron oxides and humic substances, or present at exchangeable sites in clay minerals, mobilized ∼12% of the total Np while Pu levels were below detection. The H₂O₂ treatment, which is designed to liberate trace metals bound to organic matter, mobilized ∼8 and ∼1% of Np and Pu, respectively. These results indicate that a minor portion of the total Np may be affected by environmental conditions that have little or no effect on Pu. Between 7 and 24% of the Pu was observed in treatments designed to liberate Pu and Np that are tightly bound to lithogenic phases or refractory silicates. The ²⁴⁰Pu/²³⁹Pu observed in accessible and refractory fractions ranged between 0.11 and 0.18. With the exception of one sample, the ²⁴⁰Pu/²³⁹Pu isotope ratios measured in the refractory fractions are essentially identical having a mean ratio value of 0.123 ± 0.001 (1σ). The ²⁴⁰Pu/²³⁹Pu ratios provide isotopic evidence that suggests a portion of non-fallout contamination has a refractory nature. The presence of similarly low ²⁴⁰Pu/²³⁹Pu ratios in refractory fractions of sediments from the Ob and Irtysh Rivers suggests the existence of a source of refractory Pu which is consistent with refractory “hot particles” derived from surface tests at the Semipalitinsk test site.     

乌江中上游水库-河流体系夏秋季N、Si分布特征

测定了乌江中上游的洪家渡至乌江渡水库段水体中总氮、氨氮和溶解态硅等营养物质含量,并现场测定水深、温度、溶解氧和叶绿素浓度等理化参数。研究结果表明：在夏秋水库分层现象不断减弱期间,氮、硅的空间分布受水库生物地球化学作用差异的影响,在空间上具有明显不同的分布特征。流域内地表水总氮含量变化不大,水库内垂直分布也较均一;7至9月份河流和水库表层水体总氮含量平均值呈下降趋势,分别为347、317和 3.00 mg/L。7、8月份水库表层水溶解态硅含量明显低于上下游水体,说明水库生物吸收作用强而导致水库滞留溶解态硅;在垂直剖面上,0～30 m 水体溶解态硅含量随水深增加而增加,30～60 m 溶解态硅含量变化不大,这反映了水库上层水体生物对硅的吸收,和下层水体溶解态硅的吸收和释放平衡。     

中温焙烧/钠化氧化法回收电镀污泥中的铬

采用中温焙烧/钠化氧化法从电镀污泥中回收铬.结果表明,影响铬浸出率的最主要因素为焙烧温度.电镀污泥与碳酸钠质量比、焙烧时间、水浸时间对铬浸出率的影响较接近,在水浸水固比为10.0 ; 1.0(质量比)、室温、焙烧温度为650℃、焙烧时间为2.0h、电镀污泥与碳酸钠质量比为1:1、水浸时间为60 min的最佳浸出条件下,铬浸出率为99.3%;去除氢氧化铝、氢氧化锌的最佳反应温度和pH分别为90～95℃和7.5;去除硫酸钠晶体的最佳pH为4.0,在最佳试验条件下,铬回收率为90.57%.     

咪唑类[PF6]^-型离子液体萃取胺类化合物

以眯唑类[PF6]^-型离子液体1-丁基-3-甲基咪唑六氟磷酸盐（[Bmim][PF6]）、1-己基-3-甲基咪唑六氟磷酸盐（[Hmim][PF6]）和1-辛基-3-甲基咪唑六氟磷酸盐（[Omim][PF6]）对苯胺、对氯苯胺等7种胺类化合物的萃取,考察了溶液初始浓度、相比、盐类、pH及离子液体眯唑基团上取代烷基对萃取平衡的影响,并研究了萃取过程的热效应。实验结果表明：溶液初始浓度对分配系数影响较小;相比10：1是离子液体对胺类化合物的溶解饱和临界点,当相比大于10：1时,分配系数降低;NaCl、K2SO4可以增大萃取分配系数,ZnSO4对分配系数几乎没有影响;pH增加,分配系数增大;离子液体对不同取代基的胺类萃取能力有较大的差异,咪唑基团上取代烷基的长度对不同胺类物质的分配系数影响较显著;萃取过程属于焓增大的吸热过程。     

Assessment of heavy metal pollutants accumulation in the Tisza river sediments

In this study we have worked on the evaluation of heavy metal contamination in the sediments taken from the Tisza River and its tributaries, and thereby used the sequential extraction method, geochemical normalization, the calculation of the enrichment factor (EF), and the methods of statistical analysis. The chemical fractionation of Ni, Cu, Zn, Cr, Pb, Fe, and Mn, carried out by using the modified Tessier method, points to different substrates and binding mechanisms of Cu, Zn and Pb in sediments of the tributaries and sediments of the Tisza River. The similarities in the distributions of Fe and Ni in all types of sediments are the result of geochemical similarity as well as of the fact that natural sources mainly affect the concentration levels of these elements. The calculated enrichment factors (EF, measured metal vs. background concentrations) indicated that metal contamination (Cu, Pb, Zn and Cr) was recorded in the sediments of the Tisza River, while no indications of pollution were detected in the tributaries of the Tisza River and the surrounding pools. The maximum values of the EF were close to 6 for Cu and Pb (moderately severe enrichment) and close to 4.5 for Zn (indicating moderate enrichment). It can be said that the Tisza River is slightly to moderately severely polluted with Cu, Zn, and Pb, and minorly polluted with Cr. It is concluded that sediments of the Tisza serve as a repository for heavy metal accumulation from adjacent urban and industrial areas.     

Copper and zinc bioavailabilities to ryegrass (Lolium perenne L.) and subterranean clover (Trifolium subterraneum L.) grown in biosolid treated Chilean soils

The purpose of this study was assessing Cu and Zn availabilities in soils amended with a biosolid through the determination of their sequentially extracted chemical forms and their relationship with the contents of these metals in ryegrass (Lolium perenne L.) and subterranean clover (Trifolium subterraneum L.) plant tissues cultivated in a greenhouse using four soils classified as Aquic Xerochrepts and Ultic Haploxeralfs representatives of potential areas for biosolids application in the central zone of Chile. The soils were treated with sewage sludge at a rate of 0 and 30 Mg ha⁻¹. The greenhouse experiment was carried out through a completely randomized block design in a 2 × 4 (biosolid rate × soil) arrangement, considering three repetitions per treatment. The soils used in the greenhouse experiment before and after cultivation, were sequentially extracted with specific reagents and conditions in order to obtain the following fractions: exchangeable, sodium acetate-soluble, soluble in moderately reducing condition, K₄P₂O₇-soluble, soluble in reducing condition, and soluble in strongly acid and oxidizing condition. It was established that Cu and Zn were predominantly found in soils in less available forms, associated to organic matter, oxides and clay minerals. Zinc concentration in ryegrass plants was higher than that found in subterranean clover plants in biosolid-amended soils. Zinc contents in ryegrass shoot and root correlated with the exchangeable, bound-to-carbonate, and bound-to-FeOx metal forms in control soil. Copper and Zn bioavailabilities were estimated through satisfactorily fitted multiple linear regression models, with determination coefficients from 0.77 to 0.99, which showed a positive contribution of the labile metal forms in soils, especially in relation to Zn in both plant species.     

二元有机酸的络合萃取研究

研究了磷酸三丁酯（ＴＢＰ）和甲基异丁基酮（ＭＩＢＫ）对乙二酸,丙二酸,丁二酸和己二酸等二元有机酸的萃取及其影响因素。结果表明,萃取反应为中性络合萃取机理,有机相中生成１：２的萃合物;空腔效应,偶极作用和氢键等是影响萃取性能的主要因素;稀释剂,无机盐,温度及二元有机酸结构等对萃取性能都有重要影响。     

水中痕量多环芳烃(PAHs)类环境污染物检测方法的研究

对水中多环芳烃（ＰＡＨｓ）检测方法进行了系统研究,采用固相萃取技术进行样品前处理,以取代传统的液液萃取,并建立了优化的ＰＡＨｓ液相色谱分析条件,可以适用于美国ＥＰＡ优先监控的水中１６种ＰＡＨｓ的同时分析