超快速液相色谱-四极杆/静电场轨道阱高分辨质谱快速筛查淀粉中的224种农药残留

建立了超快速液相色谱-四极杆/静电场轨道阱高分辨质谱对淀粉中224种农药残留的快速分析方法.淀粉样品加水后经含1%冰醋酸的乙腈溶液提取,无需净化直接取提取液进行分析.以C18柱作为色谱柱分离,静电场轨道阱高分辨质谱采集数据.检测数据表明,224种农药在0.5—50μg·L-1范围内线性关系良好,线性相关系数(R2)均大于0.99.检出限(LOD,S/N≥3)达到1μg·kg-1的农药种类为208种,定量限(LOQ,S/N≥10)均小于或等于10μg·kg-1,添加回收试验的回收率范围为60%—114%.相对标准偏差范围分别为0.3%—29.4%.经实际样品验证,可满足淀粉中多种农药快速筛查和确证检测的要求.     

同位素稀释气相色谱-高分辨质谱法测定土壤和沉积物中20种多溴联苯

本文建立了土壤和沉积物中20种多溴联苯的同位素稀释气相色谱-高分辨质谱分析方法.样品经索氏提取、多层硅胶柱净化,采用气相色谱-高分辨质谱分析,各组分在10—1000 ng·m L~(-1)范围内线性良好,平均相对响应因子(RRF)的偏差在2.9%—15.1%之间.方法检出限在2.57—135 ng·kg~(-1)之间,批间偏差为1.0%—15.1%.低、中、高的3个加标水平实际样品平均回收率为64.8%±5.5%—156%±7.1%.该方法可用于土壤和沉积物中痕量多溴联苯的检测.     

自动索氏抽提-凝胶渗透色谱(GPC)-气相色谱/质谱法测定沉积物中多环芳烃和有机氯农药

采用自动索氏抽提-凝胶渗透色谱(GPC)-气相色谱/质谱技术,建立了沉积物中多环芳烃和有机氯农药的检测方法.通过对自动索氏抽提提取条件、凝胶渗透色谱净化条件进行优化.以丙酮∶正己烷(V∶V=1∶1)作为提取溶剂,提取温度160℃,用乙酸乙酯∶环己烷(V∶V=1∶1)定容至40 mL,转移上GPC.GPC在线浓缩系统真空腔真空度为180 mbar/190 mbar,以乙酸乙酯∶环己烷(V∶V=1∶1)为流动相,流速为5 mL·min-1,并采用气相色谱-质谱法定性和定量分析.在优化条件下,16种多环芳烃和19种有机氯农药在10—1000μg·L-1范围内具有良好的线性关系(R20.99),检出限(S/N=3)为0.008—0.353μg·kg-1.加标水平为10、50、100μg·kg-1时,平均加标回收率分别为77.6%—106.1%、79.9%—108.7%和80.6%—107.8%,相对标准偏差(RSDs,n=5)均小于10%.     

气相色谱/三重四极杆质谱法测定环境样品中二噁英

建立了同位素稀释-气相色谱/三重四极杆质谱法(GC-MS/MS)测定环境样品中痕量二噁英(PCDD/Fs)的分析方法.方法具有良好的灵敏度和重现性,对绝对进样量为20—200 fg的17种PCDD/Fs信噪比均大于50,色谱峰面积的相对标准偏差(RSD)小于20%(n=12).方法在较宽的浓度范围内具有良好的线性,标准曲线的相对响应因子(RRF)的RSD均小于15%.利用本方法测定了大气、土壤和污泥3种不同环境样品中二噁英的浓度,其检测结果与高分辨气相色谱/高分辨质谱法(HRGC/HRMS)结果具有良好的一致性,可以满足EPA 1613B方法的技术要求.     

叶类蔬菜有机氯农药残留测定过程中的提取和净化

用柱萃取法提取 ,气相色谱 电子捕获检测器 (GC ECD)测定蔬菜中的多种有机氯农药 .比较了不同提取溶剂对蔬菜中有机氯农药的提取效率 .就回收率而言 ,正己烷和丙酮 (V/V ,4∶1 ) >石油醚和丙酮 (V/V ,4∶1 ) >二氯甲烷和丙酮 (V/V ,4∶1 ) >纯正己烷 .用正己烷和丙酮作提取溶剂时 ,1 2种有机氯农药中有 1 0种的回收率在 80 %以上 ,变异系数在 1 %— 1 5 %之间 .不同固相萃取 (SPE)填料对有机氯农药的纯化效率为 :硅胶对目标物质的净化效率要高于硅藻土和氟罗里硅土 ,硅胶做填料时变异系数在 1 5 %以下 .因此 ,本实验认为用正己烷和丙酮 (V/V ,4∶1 )做提取剂、选择硅胶做填料能够对蔬菜中多种有机氯农药有较好的提取和净化效果 ,是一种较理想的蔬菜中有机氯农药的分析方法 .     

高效气相色谱串联四极杆质谱联用测定飞灰和鲤鱼中的二(口恶)英及筛选方法的建立

高分辨气相色谱/高分辨磁质谱(HRGC/HRMS)分析痕量二(口恶)英(PCDD/Fs,即多氯二苯并二(口恶)英和多氯二苯并呋喃)具有高灵敏度和高选择性,美国环保局(Environmental Protection Agency,EPA)1997年颁布的检测环境样品中二(口恶)英的标准方法1613规定使用HRGC/HRMS,高分辨质谱数据可面向法规是二(口恶)英分析行业法定检测方法.但HRGC/HRMS成本高,而且对仪器操作人员也提出了较高的要求.如果在HRGC/HRMS分析前,采用快速简单的筛选区分出低、高浓度检测样品,就可以有效提高HRGC/HRMS的工作效率.     

采用安捷伦5977B GC-MS测定土壤中有机氯农药含量

本文采用安捷伦7890B_5977B GC-MS测定土壤样品中的有机氯农药含量.本文中所涉及的样品前处理方法以及仪器分析方法完全参考环境标准《土壤和沉积物有机氯农药的测定气相色谱-质谱法》环境报批稿以及土壤样品前处理标准HJ783-2016规定的样品前处理要求和仪器分析条件.采用加压快速溶剂萃取的提取方法,结合弗罗里硅土净化法,对土壤样品进行提取与净化,建立了详细的前处理标准操作步骤和方法分析流程.此方法成功应用于土壤中26种有机氯农药的分析测定,样品加标回收率达到了73.0%—116.2%(标准要求40%—150%),仪器最低检出限为0.07—0.39μg·kg~(-1)(标准0.02—0.09 mg·kg~(-1)),方法检出限为0.01—0.08μg·kg~(-1)(标准0.08—0.36 mg·kg~(-1)).     

高分辨气相色谱-质谱法同时测定土壤及沉积物中二英、溴代二英、多氯联苯和多溴联苯醚

采用同位素内标稀释-高分辨气相色谱-高分辨质谱法同时测定土壤及沉积物样品中PCDD/Fs、PBDD/Fs、DL-PCBs和PBDEs 4种二英类持久性有机物的含量.利用凝胶渗透色谱、多层酸碱硅胶净化柱、活性炭分散硅胶净化柱针对不同二英类污染物的不同吸附特性,运用不同极性的溶剂淋洗,实现二英组分(PCDD/Fs、PBDD/Fs)和其他两个组分(DL-PCBs、PBDEs)的分离,排除了同系物间及其他物质的干扰.所建方法的精密度变化范围在1.4%—13.6%之间,净化内标回收率范围在61%—104%之间,PCDD/Fs和PBDD/Fs的检出限分别在0.048—0.153 pg·g-1和0.044—0.395 pg·g-1之间,DL-PCBs和PBDEs的检出限分别在0.028—0.105 pg·g-1和0.034—10.2 pg·g-1之间,目标物检测结果大部分在质控样品标准范围之内,本文所建立的方法可以用于土壤及沉积物中PCDD/Fs、PBDD/Fs、DL-PCBs和PBDEs的同时净化分离.     

典型烧结厂周边土壤多氯联苯的环境污染特征

本文以唐山某典型烧结厂为研究对象,对铁矿石烧结厂排放的烟气及周边土壤样品进行采集,应用同位素稀释高分辨气相色谱-高分辨质谱联用法(HRGC/HRMS)测定了多氯联苯(PCBs)的含量,并研究了PCBs的同类物分布特征.其中烟气样品中类二英PCBs(dl-PCBs)总浓度为1.04—1.77ng·m~(-3),毒性当量值为8.99—19.32pg·WHO-TEQ·m~(-3).烧结厂周边土壤样品中dl-PCBs的总浓度为8.81—403.59pg·g~(-1),毒性当量值为0.05—0.65pg·WHO-TEQ·g~(-1),是背景土壤样品的(0.035pg·WHO-TEQ·g~(-1))的1—19倍.可以看出,该烧结厂周边环境土壤受到了企业所排放PCBs等有毒污染物的影响.大部分土壤样品的同类物分布特征相似;CB-118对土壤dl-PCBs浓度贡献率最大,贡献率为31.74%.CB-101对土壤指示性PCBs浓度贡献率最大,贡献率为52.82%.将土壤样品和烟气样品的同类物分布进行比较发现二者略有不同.尽管都是以低氯代同类物为主,但是烟气样品中最高的同类物是TrCBs,且随着氯代数的增加,浓度呈现明显下降的趋势;而土壤样品PeCBs浓度最高,PeCBs前后都呈现逐级下降的趋势.唐山市此烧结厂周边土壤无论是TEQ值,指示性PCBs总浓度,PCBs总浓度与其它研究相比都处于较高水平.     

GC-MS测定土壤中阿特拉津、六氯苯等十种农药残留

建立了气相色谱-质谱-选择离子监测(GC-MS-SIM)同时测定土壤中10种农药(三嗪类除草剂、酰胺类除草剂和有机氯农药)的多残留分析方法.样品采用正己烷/丙酮(1:1,V/V)超声提取、氟罗里硅土柱层析净化、GC-MS-SIM测定.10种农药在0.01(0.02)-1.0(2.0)mg·l~(-1)范围内线性良好,相关系数介于0.9963-0.9998之间;在10,50和250 ng·g~(-1)添加水平下,平均回收率介于81%-117%之间,相对标准偏差均小于14.4%;方法检出限达到ppb至sub-ppb级(0.1-1.3 ng·g~(-1)).将此方法应用于辽宁省不同性质土壤中70个实际土壤样品的分析,阿特拉津、乙草胺、六氯苯、丁草胺、狄氏剂和艾氏剂有检出,该法对不同性质土壤具有广泛适用性.     

高分辨率气相色谱/高分辨率质谱同位素内标法测定烟气样品中的多氯萘

多氯萘(PCNs)同二噁英(PCDD/Fs)和类二噁英多氯联苯(PCBs)类似,在烟气中的含量处于痕量水平,一般都在pg·m-3以下,因此分析方法要求有较高的灵敏度和选择性.以国内外的研究方法和参考文献为基础,建立了同位素内标稀释高分辨气相色谱/高分辨率质谱联用对垃圾焚烧发电厂的烟气样品中的PCNs进行分析.结果表明,该方法对17种氯取代位的PCNs单体的空白干扰在N.D.—2.1 pg之间;方法检出限范围为2.8—9.1 pg·nm-3,线性范围为0.40—240 pg·μL-1;空白加标实验中目标化合物的回收率为84.62%—116.21%,提取内标回收率为40.41%—75.79%,采样内标的回收率为88.92%—89.89%.实际烟气样品测得17种PCNs的同系物浓度分布在8.79—509 pg·nm-3之间,PCN-6的含量最高,PCNs-31S含量最低,相对标准偏差在4.43%—14.44%.该分析方法具有较高的准确性和可靠性,适用于烟气样品中多氯萘物质的测定.     

Instrument tuning for trace analysis of dioxins and furans for the vg 70s/se gas chromatography/mass spectrometry system using electron impact mode

We present the salient characteristics of tuning procedures that have evolved from our 3 years of experience while producing large amounts of data of the highest quality. Our laboratory routinely analyzes 2,3,7,8‐substituted dioxins and furans at parts per quadrillion levels in 50–100 g of human serum samples using the VG 70S/SE stand‐alone gas chromatography/mass spectrometry (GC/MS) system at 10000 resolution (defined by 5% overlap) in the selected ion recording mode. Trace measurement of dioxins and furans in human biological matrices—for example, whole blood, serum, or adipose tissue‐requires reproducible instrument tuning within day as well as among days for quality results. Additionally, instument‐tuning procedures among operators must be reproducible to minimize operator bias because periodically different operators are used. Instrument tuning is highly subjective and argumentive; therefore, to minimize the ambiguity within our laboratory, we have standardized our technique to reproducibly tune the GC/MS system.     

偏远高山湖泊沉积物中持久性有机污染物的沉积记录研究

持久性有机污染物(POPs)因具有半挥发性,可随大气长距离传输迁移到偏远的高山地区,对当地生态环境造成潜在威胁,因而POPs在这些地区的归趋及行为受到广泛关注.偏远高山地区环境中的POPs主要来源于大气沉降过程,湖芯能较好地保存大气污染物的沉降信息以及年代信息,被称为"天然档案室",常被用于研究污染物的沉降历史和演变规律.本文首先介绍了几种常用于湖芯定年的放射性核素定年方法,然后综述了不同区域高山湖芯中POPs的时空变化趋势以及影响因素,最后针对偏远高山沉积物研究存在的不足对未来研究提出了几点建议.     

Determination of persistent organic pollutants by gas chromatography/laser multiphoton ionization/time-of-flight mass spectrometry

An authentic mixture of polychlorinated biphenyls was measured using a short wide-bore capillary column for the group separation of major components present in an actual sample of Kanechlor. The limits of detection were improved by ca. 2 fold in comparison with those obtained using a conventional capillary column, since the retention time was reduced and the amount of analytes introduced into the mass spectrometer per unit time could be increased. On the other hand, surface-water and sediment samples containing polycyclic aromatic hydrocarbons (PAHs) were collected from the river located in the vicinity of a waste water treatment plant. Even acenaphthylene, a minor component of the mixture could be measured for the sediment sample, and the concentrations were determined for several heavy PAHs. As demonstrated, a technique involving laser multiphoton ionization/time-of-flight mass spectrometry was useful as a sensitive and selective analytical tool for the trace analysis of persistent organic pollutants in an environmental sample.     

Pyrolysis behaviors of oil sludge based on TG/FTIR and PY-GC/MS

Pyrolysis is an alternative technology for oil sludge treatment. Thermogravimetric Analysis-Fourier Transform Infrared Spectroscopy and Pyrolysis-Gas Chromatography/Mass Spectrometry were employed to investigate the pyrolysis process and products of oil sludge. The pyrolysis process was divided into five stages: drying and gas desorption, oil volatilization, main pyrolysis, semi-coke charring, and mineral decomposition. The main reaction temperatures ranged from 497.6 K to 753.2 K. The products were mainly composed of pairs of alkane and alkene (carbon number ranges from 1 to 27). The mechanisms consisted of random chain scission followed by end chain scission at high temperatures with volatilization occurring during the whole process. This study is useful not only for the proper design of a pyrolysis system, but also for improving the utilization of liquid oil products.     

隆回县高海拔山区高效生态经济型退耕还林造林模式研究

通过对六种植物配置方式及三种开发模式的对比试验分析，试验出了一种融水土保持效益与经济效益于一体的高效生态经济型造林模式，并探讨了灰毡毛忍冬产量与海拔高度的关系．结果表明：在自然条件恶劣的小沙江高海拔山区，采用金银花(品种为灰毡毛忍冬) 三木药材或其它草本药材，运用景观生态学原理进行设计开发，可获得很好的经济效益与社会效益，并能保持山区的可持续发展．同时还试验出了主栽树种灰毡毛忍冬在海拔1000～1400m之间时经济效益最好．     

不同C/N值下亚硝酸盐氧化菌和异养菌混合体系的微生物多样性

采用PCR-RFLP技术研究了不同C/N比下亚硝酸盐氧化菌及异养菌混合体系的微牛物多样性,并探讨了微生物菌群结构与其功能(硝化件能)的关系.C/N=0时,混合体系主要由自养菌和寡营养菌(85.1%)组成,包括亚硝酸盐氧化菌(NOB)、拟杆菌门、α-变形菌纲、浮霉菌门和绿色非硫细菌中的一些菌株.C/N=0.44时,混合体系中的自养菌减少,异养菌(主要是γ-变形菌纲的成员)大量出现.C/N=8.82时,γ-变形菌纲的菌株尤其是反硝化菌Pseudomonas sp.占主导(93.8%),与此同时,随着C/N升高,该混合体系的硝化性能也由专一的亚硝酸盐氧化过程转变为同时硝化反硝化过程.微生物菌群结构的转变较好地解释了其硝化性能的改变.本研究揭示了微生物菌群结构与其功能的内在联系,同时表明PCR-RFLP技术与化学分析相结合是研究微生物菌群结构与功能的有力工具.图3表2参13     

基于液相色谱法分析水环境中大环内酯类抗生素污染的研究进展

大环内酯抗生素广泛使用,在水环境中的残留越来越引起世界关注.本文综述了国内外基于液相色谱技术分析水环境中大环内酯的方法,比较不同预处理法以及分析方法的灵敏度和检出限.固相萃取法可以同时富集和净化,消耗试剂少,方便,野外操作可行,是理想的预处理技术.液相色谱串联质谱技术选择性好、特异性高、灵敏度高,可以检测浓度低于ng.L-1的目标物,是一种可靠理想的分析方法.最后对大环内酯分析研究进行了展望.     

Effects of connectivity and spatial resolution of analyses on conservation prioritization across large extents

The outcome of analyses that prioritize locations for conservation on the basis of distributions of species, land cover, or other elements is influenced by the spatial resolution of data used in the analyses. We explored the influence of data resolution on prioritization of Finnish forests with Zonation, a software program that ranks the priority of cells in a landscape for conservation. We used data on the distribution of different forest types that were aggregated to nine different resolutions ranging from 0.1 × 0.1 km to 25.6 × 25.6 km. We analyzed data at each resolution with two variants of Zonation that had different criteria for prioritization, with and without accounting for connectivity and with and without adjustment for the effect on the analysis of edges between areas at the project boundary and adjacent areas for which data do not exist. Spatial overlap of the 10% of cells ranked most highly when data were analyzed at different resolutions varied approximately from 15% to 60% and was greatest among analyses with similar resolutions. Inclusion of connectivity or edge adjustment changed the location of areas that were prioritized for conservation. Even though different locations received high priority for conservation in analyses with and without accounting for connectivity, accounting for connectivity did not reduce the representation of different forest types. Inclusion of connectivity influenced most the outcome of fine-resolution analyses because the connectivity extents that we based on dispersal distances of typical forest species were small. When we kept the area set aside for conservation constant, representation of the forest types increased as resolution increased. We do not think it is necessary to avoid use of high-resolution data in spatial conservation prioritization. Our results show that large extent, fine-resolution analyses are computationally feasible, and we suggest they can give more flexibility to implementation of well-connected reserve networks.     

酚类化合物结构与醇/水分配系数(logK_(ow))关系研究

将不同非氢原子自身及非氢原子之间的关系参数化并构建出新的结构描述符,对部分酚类化合物分子结构进行了参数化表达。采用逐步回归(SMR)与多元线性回归(MLR)相结合的方法建立了化合物结构与醇/水分配系数(log Kow)之间的关系模型,模型的建模相关系数(r)为0.988,标准偏差(SD)为0.121;"留一法"交互检验的相关系数(Q2)为0.966,标准偏差(SDCV)为0.148。结果表明结构描述符能较好地表征化合物分子结构特征,所建模型稳定性好,预测能力强,对于酚类化合物QSPR研究具有一定的参考价值。