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环境介质中典型新型有机污染物分析技术研究进展

朱帅, 沈亚婷, 贾静, 田芹

朱帅, 沈亚婷, 贾静, 田芹. 环境介质中典型新型有机污染物分析技术研究进展[J]. 岩矿测试, 2018, 37(5): 586-606. DOI: 10.15898/j.cnki.11-2131/td.201603300054
引用本文: 朱帅, 沈亚婷, 贾静, 田芹. 环境介质中典型新型有机污染物分析技术研究进展[J]. 岩矿测试, 2018, 37(5): 586-606. DOI: 10.15898/j.cnki.11-2131/td.201603300054
Shuai ZHU, Ya-ting SHEN, Jing JIA, Qin TIAN. Review on the Analytical Methods of Typical Emerging Organic Pollutants in the Environment[J]. Rock and Mineral Analysis, 2018, 37(5): 586-606. DOI: 10.15898/j.cnki.11-2131/td.201603300054
Citation: Shuai ZHU, Ya-ting SHEN, Jing JIA, Qin TIAN. Review on the Analytical Methods of Typical Emerging Organic Pollutants in the Environment[J]. Rock and Mineral Analysis, 2018, 37(5): 586-606. DOI: 10.15898/j.cnki.11-2131/td.201603300054

环境介质中典型新型有机污染物分析技术研究进展

基金项目: 

中国地质科学院基本科研业务费项目 CSJ201603

国家自然科学基金青年基金项目 21607033

国家自然科学基金青年基金项目(21607033);中国地质科学院基本科研业务费项目(CSJ201603);中国地质调查局地质调查项目(12120113015200)

中国地质调查局地质调查项目 12120113015200

详细信息
    作者简介:

    朱帅, 硕士, 助理研究员, 主要研究方向为有机污染物检测与环境行为研究。E-mail:zhu15131215153@126.com

  • 中图分类号: O652.62;O657.71

Review on the Analytical Methods of Typical Emerging Organic Pollutants in the Environment

  • 摘要: 环境中持久性有机污染物(POPs)、药物及个人护理品(PPCPs)和消毒水副产物(DBPs)等新型有机污染物对生态环境和人体健康具有潜在威胁,研究其来源、检测方法、环境分布和迁移转化已经成为热点。新型有机污染物组成复杂,如短链氯化石蜡有7000多种同类物,采用传统分析手段无法实现分离,对这些物质的准确定性和定量面临挑战。近年来在新型有机污染物检测技术开发方面已取得较大进展:根据待测样品的性质可使用快速溶剂萃取、固相微萃取等多种提取方法,凝胶渗透色谱、多层复合层析柱和固相萃取柱是有效的净化手段,采用气相色谱-质谱或液相色谱-质谱实现了对指示性单体准确定性定量,检出限可达ng/g级。但对于环境影响较大的新型有机污染物如手性多氯联苯(PCBs),由于各手性PCBs单体之间在分离过程中发生峰共溢现象,需要应用专门的手性色谱柱进行分析,尚未建立可靠的检测方法。本文认为,一方面需要探索磁性固相基质分散萃取技术等高效的前处理技术对干扰物质进行有效分离;另一方面需要提高全二维气相/液相色谱、傅里叶变换质谱等色谱/质谱检测技术的识别性和灵敏度,开发出简便、标准化的定量方法。
    要点

    (1) 新型有机污染物在环境中会转化为更持久或有毒的化合物,由于这类污染物组成复杂,采用传统分析手段无法实现其分离,需要不断开发准确的定性和定量方法。

    (2) 阐述了环境样本中POPs、PPCPs和DBPs的分析技术和及其应用进展,总结了样品提取、分离技术和仪器分析方法。

    (3) 色谱和质谱技术的发展是推动POPs、PPCPs和DBPs等新型有机污染物研究的关键。

    HIGHLIGHTS

    (1) Emerging organic pollutants can be transformed in the environment to more persistent or toxic compounds. The composition of these pollutants is complex, thus it is difficult to separate them using traditional analytical methods. It is therefore necessary to develop accurate qualitative and quantitative methods.

    (2) Recent analytical techniques for the determination of POPs, PPCPs and DPBs in environmental and biological samples and application progress are introduced, and the extraction, separation and instrumental analytical methods are summarized.

    (3) Advances in Chromatography and Mass Spectrometry technologies are keys for promoting research on emerging organic pollutants such as POPs, PPCPs and DPBs.

  • 铜矿床的伴生元素Co、Ag、Au、Pd、Pt、Fe、Cd、Bi、In、Tl、Se、Te等都具有较高的经济价值,而目前这些伴生元素没有获得有效应用,其原因在于没有相应的研究方法对这些伴生元素进行深入研究,使其赋存特征不清楚,直接影响了原生铜矿床的评价、开采和选炼[1-6],进而影响了铜矿床的价值和开发技术路线的设定,导致资源流失较为严重。

    传统的化学分析方法[7-8]可以测定铜矿床成矿元素含量,现代大型分析仪器如X射线荧光光谱法(XRF)[9]、电感耦合等离子体质谱法(ICP-MS)[10]可以解决伴生元素的微量分析问题,但上述方法均是通过样品的碎样加工、溶解或是粉末压片分析,其结果反映的是岩石矿物的整体状况,不能反映矿物的个体信息[11]。光学显微镜鉴定虽然能提供一定粒径的矿物学相关信息,但由于一方面受到光学显微镜放大倍数的制约,另一方面受到矿物本身的限制(如矿物被氧化、蚀变、包裹等情况),矿物的光性特征会随之发生一定的变化。铜矿床中的伴生矿物往往颗粒细小,从微米级到纳米级,元素或以类质同象[12]形式存在于其他矿石矿物中,以往由于技术条件的限制而难以被发现和利用。就铜矿床中常见的金矿物而言,自然金是原生金矿石最主要的金矿物,在扫描电镜(SEM)出现以前,只有粒径大于200μm的金矿物才能被光学显微镜发现,而现在的电子探针、扫描电子显微镜[13]已能观察、测定纳米级的矿物[14]。Wang等[15]利用透射电子显微镜(TEM)和扫描俄歇显微镜(SAM)分析观察到20~100nm的金颗粒。但是,由于种种原因,漏测、错定的现象常有发生,一是受仪器分辨率所限,例如探测极限很高的同步辐射X射线荧光光谱仪[16]、扫描质子探针[17]等也无法获得微细矿物的形貌特征;二是即使有足够的分辨率,在常规分析条件下也难以发现和鉴别这些微细矿物。到目前为止,中国还没有相关的一套标准方法可以借鉴。因此,鉴定这类较复杂的矿物时,特别是研究矿床中具有较高经济价值的Au、Ag、Co、Se、W、Ge、Cd等伴生元素时[18-21],由于其所含元素的成分未知、赋存状态及含量特征各异,其微区分析方法有别于矿床中常见主成矿元素的分析方法。

    本文以“里伍式”铜矿床中的矿石矿物为研究对象,通过低倍的背散射图像捕获了矿物的异常灰度,找到其赋存的空间,结合高倍背散射图像完成赋存状态、矿物间相关关系等物相特征的观察;利用二次电子像获取矿物的晶体形态等形貌特征;利用能量色散X射线荧光光谱仪的点、线、面分析方法,获得铜矿床伴生元素矿物定性/定量及分布规律等信息,解决了铜矿床伴生矿物微细不易辨识、容易遗漏和错定的难题,形成了一套有关铜矿床伴生元素的能谱-扫描电镜(EDX-SEM)[22-24]微区分析方法,为矿产资源的综合利用提供重要支持。

    铜矿床的种类繁多,矿物成分和微区形貌特征变化多样。本次方法研究选取“里伍式”铜矿床的矿石矿物[25]:黄铜矿、辉铜矿、孔雀石等为研究对象。样品选自四川九龙县里伍铜矿床,不同的编号代表不同的采样地点,相关信息见表 1

    表  1  矿石样品采集信息及化学分析结果
    Table  1.  Collection information and chemical analysis results of ore samples
    样品编号 矿石性状或岩性 采样地点 Cu含量(×10-2) Au含量(×10-6) Ag含量(×10-6)
    KKLWB2-1 块状矿石 里伍本部B2矿体 12.92 0.30 < 10.0
    KKLWB2-2 块状矿石 里伍本部B2矿体 21.70 0.31 < 10.0
    KKLWB2-5 块状矿石 里伍本部B2矿体 3.70 < 0.10 16.8
    KKLWB2-6 块状矿石 里伍本部B2矿体 1.56 < 0.10 < 10.0
    JKLWB2-7 浸染状矿石 里伍本部B2矿体 4.15 0.17 16.8
    WYLWB2-16 浸染状矿石 里伍本部B2矿体 - 0.15 < 10.0
    WYLWB2-17 浸染状矿石 里伍本部B2矿体 - 0.15 < 10.0
    KKLW-3 块状矿石 里伍本部 3.04 < 0.10 < 10.0
    KKLWB1-1-1 块状矿石 里伍本部B1矿体 16.55 < 0.10 17.9
    KKLWA2-3 块状矿石 里伍本部A2矿体 10.06 0.72 59.0
    KKLWA2-8 块状矿石 里伍本部A2矿体 7.37 0.55 64.9
    GKLWE1-8 网脉状-块状矿石 里伍本部E1矿体 5.45 0.14 123.0
    GKLWA2-10 网脉状-块状矿石 里伍本部A2矿体 3.93 0.16 36.3
    GKLWA2-11 网脉状-块状矿石 里伍本部A2矿体 10.98 2.38 16.5
    KKHN-1 块状矿石 黑牛洞 19.99 0.11 < 10.0
    KKHN-2 块状矿石 黑牛洞 14.74 0.18 < 10.0
    KKHN-3 块状矿石 黑牛洞 15.61 < 0.10 < 10.0
    KKHN-4 块状矿石 黑牛洞 15.88 0.15 < 10.0
    KKHN-7 块状矿石 黑牛洞 15.35 0.87 51.1
    KKHN-13 块状矿石 黑牛洞 19.10 0.12 -
    HWJG-6 块状矿石 挖金沟 10.77 0.13 34.4
    WJG-7 块状矿石 挖金沟 1.58 0.23 11.6
    JK207H141/6 浸染状矿石 黑牛洞 - 0.20 < 10.0
    TK207H154/5 条带状矿石 黑牛洞 - 0.16 14.2
    KK207H16-1 块状矿石 黑牛洞 - 0.11 < 10.0
    KK207H222/6 块状矿石 黑牛洞 - 0.13 33.0
    KK207H234/6 块状矿石 黑牛洞 - 0.20 20.5
    TKZK20841H18 条带状矿石 黑牛洞 - 0.12 -
    KKZZ-5 块状矿石 中咀 4.37 < 0.10 29.0
    KKZZ-6 块状矿石 中咀 4.97 < 0.10 29.6
    KKZZ-7 块状矿石 中咀 17.72 < 0.10 15.4
    WY1P-7 二云母石英片岩 中咀 - 0.10 10.8
    下载: 导出CSV 
    | 显示表格

    样品制备:观察野外采回的岩石标本,选取有代表性的区域进行切取(光片),然后粗磨、细磨、抛光制样,使其样品表面达到最佳光洁度。将制好的岩石光片放入干燥器内干燥一周左右,以确保在切割、抛光样品时,样品内的微孔、缝隙中吸附的水分被充分干燥。干燥好的光片在高真空镀膜仪中蒸镀碳导电膜,厚度控制在25nm左右。本次实验采集的矿石样品化学分析结果见表 1

    实验采用显微镜和能谱-扫描电镜(EDX-SEM)从不同尺度观察和分析样品的形貌和性状。样品测试分析前采用Hitachi HUS-5GB真空镀膜仪在样品表面镀碳。

    能谱-扫描电镜(EDX-SEM)为牛津能谱仪IE250X-Max50与日本日立Hitachi S-4800型场发射扫描电镜,扫描电镜二次电子分辨率可达到1nm,放大倍数为20~8×105。该仪器具体的工作条件列于表 2

    表  2  能谱-扫描电镜工作条件
    Table  2.  Working conditions of EDX-SEM instrument
    实验内容 加速电压(kV) 发射电流(μA) 工作距离(mm) 处理时间(s) 活时间(s) 死时间
    扫描电镜的背散射电子(BSE)观察 20 10 15 - - -
    二次电子(SE)影像观察 20 10 15 - - -
    EDX定性分析 20 10 - 6 100 20%~40%
    EDX定量分析 20 10 - 6 100 20%~40%
    EDX线分析 20 10 - 2 依据线扫描的长短和元素含量高低而定 20%~40%
    EDX面分析 20 10 - 2 依据面分析区域大小和元素含量高低而定 20%~40%
    下载: 导出CSV 
    | 显示表格

    运用日立S-4800型扫描电子显微镜,在加速电压20kV、发射电流10μA、工作距离15mm的条件下,根据铜矿矿物与载体矿物及基岩不同的灰度识别矿物,捕获不同粒径或同一粒径矿物的形态特征及其与金属矿物、脉石矿物间的包裹关系、穿插关系,以及在岩石中的分布规律等矿物学特征。在完成矿物的相关关系观察之后,采集二次电子,再利用二次电子图像,获得铜矿床伴生矿物的晶体形态、表面光洁度等形貌特征。

    在完成上述矿物学特征观察的同时,运用X射线光谱仪可快速、准确地对含量达千分之一的元素进行定性/定量分析,同时可清晰地呈现分析视域中组成元素的相关关系及分布规律等信息。首先利用点分析方法,对粒径较大的矿物,在同一矿物或同一灰度的矿物测几个点位,根据重现性给出正确的分析结果。对粒径较小的矿物,或存在环带等特殊结构的矿物进行线扫描分析,排除载体矿物组成元素的干扰,重构矿物组成元素的谱图,再利用面扫描分析可获得矿物间的穿插、包裹关系及元素在整个视域的分布规律,同时可防止矿物遗漏。面扫描分析也可以与线扫描分析同时进行,开展综合分析。

    铜矿床样品伴生元素赋存状态研究实验的具体流程如图 1所示。

    图  1  铜矿床伴生元素赋存状态研究方法流程
    Figure  1.  Flow chart of method for occurrence study of associated elements in copper deposit

    本方法研究的元素中涵盖了从元素周期表第二周期到第六周期的元素,还有原子序数较高的元素Au,兼顾定量分析所需加速电压应为分析特征X射线激发电压的2~3倍的原则,在同一发射电流、对比度、亮度及放大倍数的条件下,分别用10kV、15kV、20kV、25kV的加速电压轰击样品。加速电压在10kV、15kV时,电子束无法激发出较高能量元素的特征X射线(如Fe、Ni元素的特征X射线未激发出),无法准确对矿物进行定性/定量分析;在20kV的加速电压下空间分辨率适中,激发出的背散射电子、特征X射线等电子信号强烈,背散射电子图像的灰度略低,对于原子序数较高的矿物会遗失部分矿物的细节特征,电子束能够激发Au元素等重元素的特征X射线,确保元素特征X射线信息的全面采集;25kV的加速电压较高,空间分辨率降低,激发的电子信号太强烈,得到的背散射电子图像灰度低,整个背散射电子图像呈亮色调,原子序数接近的矿物间不存在色差,无法观察到重原子组成矿物的细节特征。因此,考虑到整个方法的适用性及分析效率,本方法首选20kV作为加速电压的分析条件。

    发射电流的大小与岩石中元素的含量相关。为确保铜矿床伴生元素在较低含量的情况下能检出元素的含量,尽可能地准确获取矿物中类质同象元素的相关信息,本实验选择束电流10μA为电流的分析条件。

    能谱处理处理时间长, 可以获得较好的谱图分辨率,避免重叠峰,获得准确的分析结果,但采集速率较低,耗时长。条件实验中分别为处理时间为6(档)和5(档)的条件下,对同一银金矿颗粒进行研究。结果表明处理时间为6(档)时,银金矿的元素含量为:Cu 0.81%,Fe 1.57%,Au 82.63%,Ag 14.99%;处理时间为5(档)时,得到的谱图中出现了元素U的干扰谱线(图 2),删除干扰谱线后银金矿中元素含量为:Cu 1.40%,Fe 0.80%,Au 79.38%,Ag 18.42%。从成分结果可以看出,主元素Au含量(Au 82.63%)高于处理时间为5(档)的条件下Au含量(Au 79.38%),可以理解为处理时间长,搜集到的主要元素的信号越多。考虑到结果精准性,基本上选择的处理时间都为最长时间6(档)。因此,选定活时间为100s,处理时间为6(档),对应的最佳死时间参数在20%~40%范围内。

    图  2  铀元素的干扰谱线
    Figure  2.  Interference spectrum of uranium element

    矿物的背散射电子(BSE)的产率主要受元素的原子序数决定,矿物的组分及含量不同,所产生的背散射信号量也不同,因此成像区域中选择适中的灰度、形成色阶清晰的图像,是研究矿物赋存状态等物相特征的首要前提。在观察过程中,应遵循低倍下寻找矿物、高倍下观察矿物的原则,同时结合铜矿床伴生矿物的粒径特征,选择合适的观察倍数,获得适宜的观察视域,确保观察的系统性与全面性。其次是BSE观察到疑似目标矿物时,需经二次电子影像(SE)确认是否为光片内的自身矿物,而非污染物,同时应根据矿物的特征,选择有效放大倍率对代表性的区域进行观察,采用过高的放大倍数会减少矿物的形貌信息、降低观察效率。此外,还应规避二次电子边缘效应及调节适宜的对比度与亮度,使图像灰度适中,矿物细节清晰。

    本次利用场发射扫描电镜观察, 发现铜矿床中伴生元素的存在形式为:①金元素[26-28]。主要以独立金矿物(图 3a)——银金矿形式(图 3中的bc))分布在黄铜矿、磁黄铁矿的裂隙中,其次少量以类质同象(图 3d)形式分布在铋矿物和银矿物中。②银元素[29]。主要以独立银矿物单质银、块硫铋铅银矿、碲银矿(图 3e)、块辉铋铅银矿、硫铋银矿(图 3f)、硫铋金银矿、碲铋银矿、碲银矿的形式存在,这些银矿物主要以包裹体形式包裹在黄铜矿、闪锌矿、磁黄铁矿中,另外也有少量的Ag元素以类质同象形式分布在铋矿物(如单质铋、自然铋、叶碲铋矿)中,或以类质同象形式分布在方铅矿中。③钴元素[30-32]。主要以独立钴矿物硫锑钴矿形式存在,硫锑钴矿与磁黄铁矿共生,另外少量的钴元素以类质同象形式分布在独居石中。④铋元素。独立矿物有铋华、叶碲铋矿、赫碲铋矿、铋碲矿,这些铋矿物往往与碲矿物(如碲银矿)紧密共生(图 3gkj),且往往呈包裹体形式主要分布在矿石矿物方铅矿(图 3i)、闪锌矿、黄铜矿、磁黄铁矿(图 3h)、铈独居石(图 3l)中。⑤硒元素[33]。主要以类质同象形式分布在方铅矿中。

    图  3  铜矿床中伴生元素的赋存状态图
    Figure  3.  Occurrence state images of associated elements in copper deposit

    应用能谱进行铜矿床伴生元素成分点分析时,关键是要确认低含量的元素是否真实存在,这关系到检测极限的问题。在EDX定量分析的软件中,设有测试结果对应的标准偏差值,以3倍标准偏差值作为判定元素是否存在的依据。只需依据“质量百分含量>3δ或<3δ”进行取舍。如在测试银金矿的元素Fe、Cu、Ag、Au时,各元素的标准偏差分别为Fe 0.15,Cu 0.22,Ag 0.44,Au 0.49,以3倍标准偏差值作为判定元素是否存在依据,这些元素的质量百分含量分别为Fe 0.80%,Cu 1.40%,Ag 18.42%,Au 79.38%,符合要求。

    开展线分析时,通常选择矿物背散射电子像明暗分布变化(即矿物成分变化)较明显的部位进行线定位,且铜矿床伴生矿物与载体矿物间的物相分界线应在分析视域的中心部位,以确保图像质量。本次实验在观察含Au矿物中Au元素的分布情况时,由于Au的含量较其他元素低,在图 4中的ab(蓝色线为金的含量分布曲线)很难看出Au的含量情况及其与其他元素的相关关系,因此采取峰值曲线累加的办法,将Au元素在该直线上的含量分布情况放大累加显示出来(图 4c)。从图中可以看出,Au的含量在该直线较背景值含量高,并重复出现4个波峰峰值,由此说明,Au元素在该直线上的分布有变化,分别以类质同象形式分布在含铋的单矿物和含银的单矿物中,该载金矿物又嵌布于磁黄铁矿中,从而推断该单质铋是由辉铋矿或铋的硫化物氧化而来,Au、Ag元素可能为成矿后期在低温条件下随迁移富集并不均匀地分布在单质铋中。

    图  4  含金矿物的线扫描图
    Figure  4.  Line scan images of gold-bearing minerals

    本次利用能量色散X射线荧光光谱仪,测试条件设置为采集速率1.3kcps、采集时间100s、脉冲处理时间100μs,可准确地分析铜矿床伴生元素的组成及含量,结果列于表 3。从表中数据可以看出,铜矿床中的伴生元素Au、Ag、Co、Bi、Te、W等的含量被准确测出,并根据元素在矿物中含量,确定元素赋存状态。如:Au元素含量为98.74%,忽略背景值Fe 1.24%的含量,确定Au以自然金的形式存在。Au元素含量为86.23%,Ag含量为2.83%,忽略10.64%的背景值影响,确定Au以银金矿的形式存在。Co元素含量为24.23%,Sb含量为57.56%, S含量为15.59%,忽略Fe和Te分别为0.83%和1.89%的含量,确定Co元素赋存在硫锑钴矿中。用同样的方法,确定Bi以单质铋、赫碲铋矿、硫铋银矿、碲铋矿等形式存在;Te以碲铋矿、赫碲铋矿形式存在;W以白钨矿形式存在。

    表  3  矿物能谱分析结果
    Table  3.  Energy spectrum analysis results of the minerals
    矿物名称 化学式 元素含量(%)
    S Fe Co Sb Te Zn Te Bi Au Ag W Ca O
    硫锑钴矿 CoSbS 15.59 0.83 24.13 57.56 1.89- - - - - - - - -
    赫碲铋矿 Bi7Te3 - 0.73 - - - 3.12 24.70 71.45 - - - - -
    赫碲铋矿 Bi7Te3 - 1.04 - - - 2.26 25.19 71.50 - - - - -
    自然金 Au - 1.26 - - - - - - 98.74 - - - -
    银金矿 AgAu - 1.06 - - - - - - 76.51 22.43 - - -
    类质同象金 Au 3.15 4.11 - - 34.93 - - - 5.60 52.22 - - -
    银金矿 AgAu - 10.64 - - - - - - 86.53 2.83 - - -
    碲银矿 Ag2Te 1.61 3.42 - - - 37.38 - 57.59 - - -
    硫铋银矿 AgBiS2 17.31 1.54 - - - - 0.98 65.53 - 14.65 - - -
    单质铋 Bi - 3.73 - - - - 96.27 - - - - -
    单质铋 Bi - - - - - - 100 - - - - -
    碲铋矿 Bi2Te3 - - - - - - 36.62 63.38 - - - - -
    碲铋矿 Bi2Te3 - - - - - - 46.75 53.25 - - - - -
    白钨矿 CaWO4 - - - - - - - - - - 63.14 13.97 22.89
    白钨矿 CaWO4 - 0.98 - - - - - - - - 60.55 13.59 24.88
    注:“-”表示未能检出该元素。
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    在对粒径较小的矿物进行定量分析时,由于电子束呈水滴状扩散,载体矿物的组成元素同时会被激发,导致定量分析结果存在较大的不准确性。为了对定量分析结果进行修正,需结合元素的线、面分布图像排除载体矿物组成元素的干扰,重构待测矿物组成元素的谱图,以修订定量分析结果,进而获得元素在整个视域的分布规律、矿物间的穿插、包裹关系及分布规律等矿物学信息。

    综上所述,为了准确获得铜矿床伴生元素定性/定量及分布规律等信息,避免出现矿物的漏定和错定,本研究的重点在于如何确定含研究元素的独立矿物,而此时的矿物是光学显微镜及其他方法不能确定的,特点一定是粒径很小。因此,在研究前首先要判断元素可能以何种矿物形式存在(不常见的矿物需查阅矿物手册)[34],并且要根据可能的矿物计算其矿物平均原子序数,再根据平均原子序数估计BSE像的灰度范围,然后以合适的放大倍数观察样品,匹配适中的亮度、对比度,使得图像灰度适中、层次清晰,从而捕获所需矿物信息。

    本次所研究的铜矿床伴生元素其原子序数均较高,因此,在低倍下观察时,将目标确定在矿物的背散射像较亮的矿物,然后放大观察,通过能谱点、线、面分析,排除基体干扰,确定其所含元素,进而得知特定元素在该矿物中的含量,从而了解该伴生元素的赋存特征。其次,制样过程中一定要保证分析面抛光,彻底清除表面污染物,样品至少保证在24h以上充分干燥,镀膜时考虑样品的特性确保所镀碳膜的厚度,粘接样品时一定要保证粘稳。

    本文建立了铜矿床伴生元素的赋存状态特征的EDX-SEM分析方法,该方法解决了铜矿床伴生矿物微细不易辨识、容易遗漏和错定的难题,通过低、高倍的背散射图像、二次电子像以及能谱色散X射线荧光光谱仪点、线、面分析等技术手段的相互结合,消除基体干扰,确保了测试数据的准确性。优化选取扫描电镜的加速电压20kV、发射电流10μA、能谱脉冲处理活时间100s,准确获得矿物定性/定量及分布规律等信息。通过该方法,查明了里伍铜矿床矿石中金、银、钴、铋、硒等伴生元素的赋存状态,这些元素以独立矿物存在或类质同象的形式分布在黄铜矿、闪锌矿、磁黄铁、铈独居石等其他矿物中。

    本研究结果为矿床的成因研究、资源评价、勘查手段以及矿山的开采、选矿以及冶炼工艺过程的制定等地质工作提供了充分的微观依据。

  • 图  1   一些国家2007—2013年氯化石蜡产量[56]

    Figure  1.   Production summary of chlorinated paraffin in some countries in 2007—2013[56]

    图  2   氯含量51.5%的SCCPs与氯含量52%的MCCPs混合物在GC×GC-ECNI-HRTOF-MS上的总离子流图[31]

    Figure  2.   GC×GC-ECNI-HRTOF-MS TIC chromatograms and GC×GC elution pattern for a mixture of a technical 51.5%-Cl SCCPs mixture and a technical 52%-Cl MCCPs mixture

    图  3   抗生素在环境中迁移转化途径[70]

    Figure  3.   Anticipated environmental pathways for antibiotics used in humans and livestock animals[70]

    图  4   阿昔洛韦在氧化过程中的相对毒性和转化[77-78]

    Figure  4.   Relative toxicity and transformation of acyclovir during ozonation[77-78]

    表  1   环境介质中新型POPs分析技术与方法

    Table  1   Analytical methods for the determination of POPs in environmental samples

    下载: 导出CSV

    表  2   环境介质中PPCPs分析技术与方法

    Table  2   Analytical methods for the determination of PPCPs in environmental samples

    下载: 导出CSV

    表  3   水样中DBPs分析技术与方法

    Table  3   Analytical methods for the determination of DBPs in water samples

    下载: 导出CSV
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