In situ Self-transforming Membrane as Solid Phase Microextraction Coating Extraction of PAHs in Environmental Water Samples
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摘要: 多环芳烃(PAHs)是一类具有致癌作用且难以降解的持久性有机污染物,广泛存在于环境中。环境中痕量PAHs的直接分析往往因检测手段的检出限达不到要求而存在困难,需要结合分离富集手段。常规的样品前处理技术如索氏提取、液液萃取等存在耗时长、使用大量有机溶剂等问题。因此为了提高效率、避免对自然环境的二次污染,有必要开发一种简便、环境友好的新型样品前处理技术。固相微萃取(SPME)是一种集采样、富集、进样于一体的无溶剂前处理技术,与气相色谱-质谱(GC-MS)等技术联用可实现复杂基质中痕量有机物的快速富集和检测。目前SPME技术的研究热点主要集中在改善涂层的萃取性能以及提高其机械强度方面。本文采用铁丝(IW)作为载体,同时又提供了铁离子来源,以原位自转化的方式在具有良好机械稳定性的铁丝上生长出一层多孔结构的金属有机骨架化合物多孔膜[MIL-53(Fe)];将其作为固相微萃取涂层[IW@MIL-53(Fe)],以7种难挥发的稠环PAHs作为目标分析物,以浸入式模式进行萃取,并结合GC-MS作为检测手段验证其萃取性能。结果表明:新涂层的萃取性能是商用100μm PDMS涂层的1~2倍,且涂层可稳定使用120次以上。该方法的检出限为0.03~2.25ng/L,线性范围为250~10000ng/L,相关系数为0.9903~0.9991。将建立的方法应用于自然水体中PAHs的检测,加标回收率为80.1%~108.5%。本研究不仅为高性能SPME涂层简单、快速制备提供了新思路,而且所建立的方法有望应用于水体中痕量有机污染物的准确和高灵敏检测。
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关键词:
- 固相微萃取涂层 /
- MIL-53(Fe)膜 /
- 气相色谱-质谱法 /
- 多环芳烃 /
- 原位自转化
要点(1) 金属基质原位自转化技术制备固相微萃取涂层(MOFs)。
(2) MOFs材料作为固相微萃取涂层材料有效萃取多种多环芳烃。
(3) 固相微萃取技术与GC-MS联用实现自然水体中多环芳烃的高效检测。
HIGHLIGHTS(1) Preparation of solid phase microextraction coating by in situ self-transformation of the metal matrix.
(2) MOFs material as solid phase microextraction coating for effective extraction of PAHs.
(3) High efficient detection of PAHs in natural water by solid phase microextraction coupled with GC-MS.
Abstract:BACKGROUNDPolycyclic aromatic hydrocarbons (PAHs) are one of the persistent organic pollutants which are carcinogenic and difficult to degrade, and are widespread in the environment. The direct analysis of trace PAHs in the environment is often difficult because of the low sensitivity of the detection methods. It is necessary to combine separation and enrichment methods. Conventional sample pretreatment techniques, such as Soxhlet extraction and liquid-liquid extraction, are time-consuming and use a large number of organic solvents.OBJECTIVESTo develop a new, simple, and environmentally-friendly method for sample pretreatment.METHODSSolid phase microextraction (SPME) is a solvent-free pretreatment technology which integrates sampling, enrichment and injection. Combined with gas chromatography-mass spectrometry (GC-MS), it can produce the rapid enrichment and detection of trace organic compounds in a complex matrix. At present, the research focus of improving SPME technology is to improve the mechanical strength and extraction performance of the coating. Using iron wire (IW) as the carrier, which also provided the iron ion source, a porous MOFs film[MIL-53(Fe)] was grown on iron wire with good mechanical stability by in-situ self-transformation. It was used as the solid phase microextraction coating[IW@MIL-53(Fe)]. Seven kinds of non-volatile condensed ring PAHs were used as the target analyte, and immersion extraction mode combined with GC-MS as detection means were used to verify its extraction performance.RESULTSResults showed that the extraction performance of the new coating was 1-2 times higher than that of the commercial 100μm PDMS coating, and the coating can be used stably for more than 120 times. The detection limits of the methods were 0.03-2.25ng/L, the linear ranges were 250-10000ng/L, and the correlation coefficients were in the range of 0.9903-0.9991. The coating was applied successfully to the detection of PAHs in natural water, where the recoveries were from 80.1% to 108.5%.CONCLUSIONSThis study not only provides an idea for the simple and rapid preparation of high-efficiency SPME coatings, but also has great potential to be applied to determinate trace volatile organic pollutants in water with high accurateness and efficiency. -
中国是稀土资源大国,占世界稀土矿产资源的80%,稀土元素对岩石形成过程、元素的迁移等研究都有一定的作用,提供了有价值的信息[1-3]。由于稀土元素的化学性质极其相似,因此采用传统化学法分析时需要冗长的分离富集过程[4],且只能测定稀土总量,而不能测定特定元素的含量[5]。样品中的稀土元素含量超过0.1%,对于这种通常概念上的微量元素,其实已转变为常量组分,大多采用电感耦合等离子体发射光谱法(ICP-OES)[6]测定,相对于应用X射线荧光光谱法(XRF)的前处理程序比较繁琐且试剂用量大。
XRF法具有制样方法简单、分析速度快、重现性好等特点[7],熔融制样法能消除粒度效应,降低元素间的基体效应影响,使复杂的试样也能完全熔融[8],适合于多种固体样品中主量、次量多元素的同时测定。目前XRF法分析稀土矿石类样品,主要的应用有:混合稀土氧化物中稀土分量的测定[9-11];采用同步辐射XRF法测定稀土元素的最低浓度[12];利用粉末压片法制备样品,通过无标定量分析软件添加与待测组分相似样品来建立标签,从而实现稀土矿物中五氧化二磷的准确测定[13];以及在其他地质矿化类样品中测定主次量元素开展了大量的研究[5, 14-17]。但应用于测定稀土矿石、矿化样品中的主、次量元素的相关报道较少。对于稀土样品的分析,存在现有的稀土国家标准物质少、稀土元素含量较低、重稀土元素谱线重叠严重等问题,从而导致了应用XRF分析稀土矿石类样品中的主量元素和稀土元素仍存在一定的困难。
鉴于此,本文通过现有的国家稀土标准样品和高纯稀土氧化物混合均匀制得的人工标准样品绘制工作曲线,扩大了自然界丰度较大的稀土元素镧、铈、钇的线性范围,应用熔融制样-波长色散XRF法测定样品,采用理论α系数的校准方法对主量元素进行校正的同时加入稀土元素的校正系数,其余元素用经验系数法来校正元素间的基体效应,对有谱线重叠的元素进行重叠干扰校正。通过对未知样品的检测和对标准样品的反测检验方法的可行性,证明了建立的测定方法可满足稀土矿化类样品分析的可靠性,可为地质评估提供满意的数据要求。
1. 实验部分
1.1 仪器和测量条件
Axios型X射线荧光光谱仪(荷兰帕纳科公司)。主要测量参数:X光管最大电压60 kV,最大电流125 mA,满功率4.0 kW,真空光路,视野光栏直径为32 mm,试样盒面罩直径32 mm。各待测元素的谱线选择和测量条件见表 1。
表 1 仪器分析条件Table 1. Working conditions of the elements by XRF元素及谱线 分晶体 准直器
(μm)探测器 电压
(kV)电流
(mA)2θ(°) PHD范围 峰值 背景1 背景2 Si Kα PE 002 550 FL 32 100 109.14 -2.3160 1.7938 26~76 K Kα LiF 200 150 FL 32 100 136.73 -1.1730 2.2190 26~74 Ti Kα LiF 200 150 FL 40 90 86.215 -0.6320 0.8640 26~75 Mn Kα LiF 200 150 DUP 55 66 62.998 -0.7190 0.7868 13~72 Na Kα PX1 550 FL 32 100 27.895 -1.8910 2.1214 22~82 Mg Kα PX1 550 FL 32 100 23.077 -1.8760 2.1788 20~78 Al Kα PE 002 550 FL 32 100 144.98 2.9372 -1.2490 21~76 P Kα Ge 111 550 FL 32 100 141.02 -1.3960 2.8040 23~78 S Kα Ge 111 550 FL 32 100 110.74 -1.5160 1.4708 16~74 Ca Kα LiF 200 150 FL 32 100 113.16 -0.8730 1.6258 28~70 Fe Kα LiF 200 150 DUP 55 66 57.530 -0.7130 0.8854 16~69 Cr Kα LiF 200 150 DUP 55 66 69.365 -0.6450 0.7386 12~73 Ni Kα LiF 200 150 DUP 55 66 48.658 -0.5890 0.8294 18~70 Y Kα LiF 200 150 SC 55 66 23.767 0.7668 -0.7400 23~78 Rb Kα LiF 200 150 SC 55 66 26.581 0.7720 -0.5110 22~78 Sr Kα LiF 200 150 SC 55 66 25.121 -0.5610 0.7542 22~78 Zr Kα LiF 200 150 SC 55 66 22.470 -0.7750 0.8758 24~78 Nb Kα LiF 200 150 SC 55 66 21.372 -0.5870 0.4690 24~78 Cu Kα LiF 200 150 DUP 55 66 45.010 -0.6960 0.9256 20~69 Zn Kα LiF 200 150 SC 55 66 41.796 -0.7050 0.6534 15~78 Ba Kα LiF 200 150 FL 40 90 87.204 0.6376 - 33~71 Rh Kαc LiF 200 150 SC 55 66 18.447 - - 26~78 V Kα LiF 200 150 DUP 40 90 76.929 -0.6230 - 15~74 Br Kα LiF 200 150 SC 55 66 29.940 -0.6830 0.9706 20~78 La Lα LiF 200 150 FL 40 90 82.938 -0.9010 24~78 Ce Lα LiF 200 150 DUP 40 90 79.047 -0.8740 - 26~78 Pr Lα LiF 200 150 DUP 55 66 75.379 -0.8580 - 15~74 Nd Lα LiF 200 150 DUP 55 66 72.141 -0.9860 - 13~74 Sm Lα LiF 200 150 DUP 55 66 66.237 0.9598 - 15~73 Tb Lα LiF 200 150 DUP 55 66 58.800 0.3626 - 15~72 Dy Lα LiF 200 150 DUP 55 66 56.600 -0.8020 - 15~71 Ho Lα LiF 200 150 DUP 55 66 54.575 -0.6550 - 16~71 Er Lα LiF 200 150 DUP 55 66 52.605 0.7728 - 17~71 Yb Lα LiF 200 150 DUP 55 66 49.038 0.8474 - 18~70 Lu Lα LiF 200 150 DUP 55 66 47.417 -0.4030 - 19~70 Ta Lα LiF 200 150 DUP 55 66 44.403 0.9066 - 20~69 Eu Lα LiF 200 150 DUP 55 66 63.591 0.4858 - 15~73 Gd Lα LiF 200 150 DUP 55 66 61.115 -0.8880 - 15~72 注: FL为流气式正比计数器, SC为闪烁计数器。DUP为流气式正比计数器和封闭式正比计数器串联使用,以提高探测效率。PHD为脉冲高度分析器。 Front-1型电热式熔样机(国家地质实验测试中心研制)。
铂金坩埚(95%铂+5%金)。石英表面皿:直径20 cm。
1.2 主要试剂
偏硼酸锂+四硼酸锂混合熔剂[8](质量比22:12,购自张家港火炬仪器厂):将混合溶剂置于大表面皿中,于马弗炉中650℃灼烧2 h,待冷却转入试剂瓶,置于干燥器中保存备。
碘化锂[18](脱模剂):优级纯,浓度为40 g/L。配制方法:称取40.0 g碘化锂溶于100 mL棕色试剂瓶中,待用。
硝酸铵(氧化剂):分析纯。
氧化镧、氧化钇、氧化铈:均为分析纯, 纯度99.99%。
1.3 样片制备
样品及熔剂的称量:精确称取灼烧后的混合溶剂5.8500±0.0002 g于30 mL瓷坩埚中,精确称取0.6500±0.0002 g样品置于瓷坩埚中[16],用玻璃棒充分搅匀(样品的要求:样品的粒径需小于200目,分取样品于纸质样品袋置于烘箱中,在105℃温度下烘样2 h。于干燥器内保存[16])。
熔样机条件设定:熔样温度1150℃,预熔2 min,上举1.5 min,摆平0.5 min,往复4次,熔样时间约为10 min;先粗略称取0.100 g硝酸铵[8]试剂平铺于铂金坩埚中,将称量好的试剂及样品倒入铂金坩埚中,滴两滴碘化锂溶液[18],当熔样机温度到达1150℃后,用坩埚钳将装有试样的铂金坩埚放入熔样机,启动熔样机开始熔样。待熔样机提示熔样完成后,将铂金坩埚取出,此时样品为玻璃熔融状态。观察试样底部是否有气泡,如有气泡可手动将气泡摇出[16],将铂金坩埚置于水平冷却台待样品底部与铂金坩埚分离后吹风冷却约3 min, 此时在玻璃样片上贴上标签,倒出样片置于干燥器中保存, 待测。
制备样片时,将稀土矿石标准物质(GBW07187、GBW07158、GBW07159、GBW07160、GBW07161)和人工配制标准样品(HC-XT-1~HC-XT-8)分别制备两套重复样片,一套用于建立标准曲线,另一套用作样品测量,检测方法的可行性。GBW07188、HC-XT-8分别重复制备10个,用于精密度的分析。岩石国家一级标准物质(GBW07122、GBW07123、GBW07124、GBW07125、GBW07104~GBW07106),碳酸盐岩石标准物质(GBW07127~GBW07136)和超基性岩石样品(DZΣ1、DZΣ2)各制备一个用于建立标准曲线。
1.4 样品配制及制备标准曲线的范围
在自然界中,镧、铈、钇的丰度较大,日常样品检测中这三个元素矿化的样品最为常见,因此本文重点通过人工标准物质来解决镧、铈、钇高含量样品的定量问题。在不同的稀土矿石国家标准物质(GBW07187、GBW07188、GBW07158、GBW07159、GBW07160、GBW07161)中加入不等量高纯的稀土氧化物(La2O3、CeO2、Y2O3)扩大稀土的含量范围,既使各人工标准基体存在差异,镧、铈、钇含量又有一定梯度。制备人工标准样片时,各高纯稀土氧化物成分的质量和各标准物质称样量见表 2所示。
表 2 人工标准样品的配制Table 2. Preparation of artificial standard samples人工标准样品编号 La2O3加入量
(g)CeO2加入量
(g)Y2O3加入量
(g)国家标准物质编号 标准物质称样量
(g)HC-XT-1 0.0400 0.0500 - GBW07159 0.5600 HC-XT-2 0.0300 0.0400 - GBW07160 0.5800 HC-XT-3 0.0200 0.0300 - GBW07187 0.6000 HC-XT-4 0.0100 0.0200 - GBW07158 0.6200 HC-XT-5 - 0.0100 - GBW07188 0.6400 HC-XT-6 - - - GBW07187 0.3250 HC-XT-7 - - 0.0200 GBW07188 0.3250 HC-XT-8 0.0050 0.0050 - GBW07161 0.6300 GBW07188 0.6400 为满足不同类型稀土样品的测试要求,又要满足日常普通硅酸盐、碳酸盐样品的测试要求,本实验采用稀土矿石标准物质(GBW07187、GBW07188、GBW07158、GBW07159、GBW07160、GBW07161),岩石国家一级标准物质(GBW07122、GBW07123、GBW07124、GBW07125、GBW07104~GBW07106),碳酸盐岩石标准物质(GBW07127~GBW07136),DZΣ1、DZΣ2和人工配制标准样品(HC-XT-1~HC-XT-8)共33个样片作为标准样品制备标准曲线。
各元素工作曲线范围列于表 3。
表 3 各元素工作曲线浓度范围Table 3. Working range of elements concentration主量元素 含量范围(%) 稀土元素 含量范围(μg/g) SiO2 0.3~74.55 Pr6O11 5.43~890 Al2O3 0.1~19.04 Sm2O3 13.53~2000 TFe2O3 0.07~3.49 Eu2O3 0.31~75 FeO 0.007~0.49 Gd2O3 27.91~2500 TiO2 0.003~0.537 Tb4O7 5.15~550 CaO 0.0224~55.49 Dy2O3 26.04~3700 Na2O 0.014~0.66 Tm2O3 2.29~310 MnO 0.004~0.1 Yb2O3 13.45~2100 P2O5 0.0022~0.124 La2O3* 0.002~6.16 MgO 0.066~20.15 CeO2* 0.0022~7.69 K2O 0.01~5.52 Y2O3* 0.017~3.2 Nd2O3* 0.0024~0.4 Lu2O3 1.91~300 Ho2O3 5.44~640 Er2O3 15.26~2000 Σ RExOy* 0.085~13.92 注:标记“*”的元素含量单位为%。 2. 结果与讨论
2.1 基体效应及谱线重叠干扰的校正
对主量元素采用消去烧失量的理论α系数法, 其余元素用经验系数法来校正元素间的基体效应,其中NiO、Rb2O、SrO、Y2O3、ZrO2、Nb2O5、Sm2O3、CeO2、Tb4O7、Ho2O3、Er2O3、Lu2O3采用Rh Kα线康普顿散射强度作内标校正基体效应[19]。采用帕纳科公司SuperQ3.0软件所用的综合数学校正公式(1),通过回归,同时求出校准曲线的基体校正系数和谱线重叠干扰校正系数。
$ \begin{align} &{{C}_{\text{i}}}=\text{ }{{D}_{\text{i}}}-\sum {{L}_{\text{im}}}{{Z}_{\text{m}}}+{{E}_{\text{i}}}{{R}_{\text{i}}}(1+\sum\limits_{j\ne 1}^{N}{{{\alpha }_{\text{ij}}}\cdot {{Z}_{\text{j}}}+} \\ &\ \ \ \ \ \sum\limits_{j=1}^{N}{\frac{{{\beta }_{\text{ij}}}}{1+{{\delta }_{\text{ij}}}\cdot {{C}_{\text{j}}}}\cdot {{Z}_{\text{j}}}+\sum\limits_{j=1}^{N}{\sum\limits_{k=1}^{N}{{{\gamma }_{\text{ij}}}\cdot {{Z}_{\text{j}}}\cdot {{Z}_{\text{k}}}}})} \\ \end{align} $
式中:Ci为校准样品中分析元素i的含量(在未知样品分析中,Ci为基体校正后分析元素i的含量;Di为分析元素i的校准曲线的截距;Lim为干扰元素m对分析元素i的谱线重叠干扰校正系数;Zm为干扰元素m的含量或计数率;Ei为分析元素i校准曲线的斜率;Ri为分析元素i的计数率(或与内标线的强度比值);Zj、Zk为共存元素的含量;Cj为共存元素j的含量;N为共存元素的数目;α、β、δ、γ为校正基体效应的因子。
根据快速扫描的结果,对有谱线重叠干扰的元素进行谱线重叠干扰校正,表 4列出了各稀土元素所校正的元素。
表 4 稀土元素的重叠谱线和影响元素Table 4. Overlapping spectral lines and influencing elements of rare earth elements待测元素 重叠谱线 校正基体元素 Y Rb Kβ1 Al,Si,Ba,Sr,Ni,Cr,Fe,Ca La Cs Lβ1 Si,Fe,Nd Nd Ce Lβ1 La,Sm,Al Ce Ba Lβ2 - Sm Ce Lβ2 - Tb Sm Lβ1 La,Ce Ho Gd Lβ1 Er,Yb Er Tb Lβ1,Co Kα La,Ce,Fe Yb Ni Kα Y Lu Dy Lβ2,Ni Kβ1 La Pr La Lβ1 La,Ce Eu - La,Ce Gd Ce Lγ1 La,Nd,Dy P Y Lβ1 - 2.2 方法检出限
按照检出限的公式计算出各元素的检出限:
$ \text{LOD}=\frac{3\sqrt{2}}{m}\sqrt{\frac{{{I}_{\text{b}}}}{t}} $
式中:m为计数率;Ib为背景计数率;t为峰值及背景的测量时间。
采用较低的标准物质重复测定12次计算的检出限结果见表 5。因本方法考虑测定的是稀土矿化类样品中的主量元素,而稀土元素检出限均在60 μg/g以下,因此对于高含量稀土元素能够满足定量分析要求。
表 5 分析元素的检出限Table 5. Detection limits of elements元素 方法检出限
(μg/g)Na2O 56.44 MgO 44.34 Al2O3 15.82 SiO2 96.03 P2O5 18.59 K2O 25.36 CaO 30.37 TiO2 20.04 MnO 8.32 Fe2O3 6.69 Y2O3 4.52 La2O3 42.6 Nd2O3 52.85 Sm2O3 42.74 CeO2 38.11 Tb4O7 44.83 Dy2O3 39.23 Ho2O3 8.86 Er2O3 27.19 Yb2O3 30.10 Lu2O3 13.41 Pr6O11 58.19 Eu2O3 6.14 Gd2O3 29.25 2.3 方法精密度和准确度
按照所建立的方法对国家标准物质GBW07188和人工标准样品HC-XT-8分别重复制作13个样片,以表 1所选测量条件测定,计算的相对标准偏差(RSD)和相对误差等测量结果列于表 6,其中绝大多数主量元素的RSD均小于1.5%,稀土元素的RSD在7%以下,个别含量较低元素的精密度较差,例如HC-XT-8号样品的CaO标准值为0.026%,测定平均值为0.021%,RSD为16.3%。而对于其他高含量CaO样品能够实现准确定量,例如GBW07188的CaO标准值为0.29,测定平均值同样为0.29,RSD为1.4%。对于Tb4O7、Lu2O3、Pr6O11等存在相同情况。表 6中的低含量结果仅作为参考数据,在此不作讨论。
表 6 方法准确度和精密度Table 6. Accuracy and precision tests of the method元素 GBW07188 HC-XT-8 测定平均值
(%)标准值
(%)相对误差
(%)RSD
(%)测定平均值
(%)标准值
(%)相对误差
(%)RSD
(%)Na2O 0.62 0.66 5.30 2.35 0.121 0.156 3.54 5.45 MgO 0.13 0.11 11.82 4.07 0.074 0.076 25.0 4.37 Al2O3 13.8 14.26 2.52 0.27 14.51 14.47 2.14 0.213 SiO2 66.8 66.9 0.01 0.19 73.5 73.4 0.15 0.17 K2O 5.56 5.52 1.09 0.32 4.861 4.9 0.86 0.27 CaO 0.29 0.29 0.69 1.40 0.021 0.026 2.80 16.3 TiO2 0.18 0.17 4.12 1.09 0.034 0.022 3.59 7.07 MnO 0.05 0.052 7.69 1.40 0.017 0.017 7.84 2.89 Fe2O3 2.28 2.24 2.05 0.30 1.13 1.13 1.90 0.14 Y2O3 2.14 2.16 0.93 0.71 0.054 0.056 1.78 0.98 La2O3 0.21 0.23 7.83 1.64 0.768 0.771 8.85 0.49 Nd2O3 0.41 0.4 2.50 0.88 0.003 0.003 5.57 69.5 Sm2O3* 2006 2000 0.05 2.92 30 15.5 3.40 34.7 CeO2 0.0619 0.053 26.42 5.39 0.728 0.771 2.26 2.30 Tb4O7* 652 550 16.55 6.94 7.93 8.07 24.17 46.2 Dy2O3* 3645 3700 2.38 0.69 未检出 55.4 6.64 - Ho2O3* 655 640 5.16 2.05 10.8 11.8 7.30 26.9 Er2O3* 1989 2000 1.95 1.94 25.45 35.8 13.71 38.8 Lu2O3* 306 300 5.60 4.13 2.57 5.4 1.02 48.1 Pr6O11* 863 890 8.58 5.40 99.5 6.2 18.49 55.2 Yb2O3* 2063 2100 2.72 0.79 13.55 36 8.95 33.0 Gd2O3* 2536 2500 0.80 1.16 111.9 31.9 7.47 13.4 加和 99.8 - - 0.12 99.6 - - 0.14 注:标记“*”的元素含量单位为μg/g。 2.4 全分析加和结果
以本文所建立的方法测量6个国家一级稀土标准物质、8个人工标准样品及8个未知的稀土样品,分析结果列于表 7,样品中主量元素、稀土元素和烧失量的加和结果均在99.41%~100.63%之间,所建分析方法能够满足全分析加和的要求,符合DZ/T0130—2006《地质矿产实验室测试质量管理规范》规定的一级标准。
表 7 全分析加和结果Table 7. Analytical results of sam additivity标准物质和样品编号 烧失量 主量元素和稀土元素测定值(%) 加和
(%)GBW07187 5.42 94.51 99.93 GBW07188 5.53 94.36 99.89 GBW07158 6.73 93.00 99.73 GBW07159 3.70 96.39 100.09 GBW07160 3.77 96.08 99.85 GBW07161 6.80 92.61 99.41 HC-XT-1 3.19 96.58 99.77 HC-XT-2 3.36 96.18 99.55 HC-XT-3 5.00 94.90 99.90 HC-XT-4 6.42 93.21 99.63 HC-XT-5 5.35 94.52 99.87 HC-XT-6 5.43 94.70 100.13 HC-XT-7 6.59 93.00 99.59 HC-XT-8 3.64 95.93 99.57 GX-TC-F2 7.48 93.15 100.63 GX-TC-F4 5.38 94.76 100.14 GX-DB-F1 5.85 94.27 100.12 GX-DB-F2 6.02 94.59 100.61 GX-DB-F3 3.55 96.55 100.10 GX-DB-F4 3.57 96.29 99.86 GX-DB-F5 3.65 96.53 100.18 XF-WX-F3 7.13 93.28 100.41 3. 结论
通过配制人工标准样品,解决了现有国家标准物质不能满足稀土矿样品等复杂类型样品中主量元素和稀土元素的定量问题。通过加入高纯氧化镧、氧化铈和氧化钇与碳酸盐标准样品混合,配制人工标准样品扩大了La、Ce和Y的定量范围。对稀土标准物质、人工标准样品和未知稀土样品进行反测,测定结果未采用归一化处理,元素的精密度和全分析加和结果都比较理想。本方法有效地扩大了XRF方法的适用范围。
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表 1 IW@MIL-53(Fe)涂层SPME-GC-MS分析7种PAHs的分析性能
Table 1 Analysis performance of 7 kinds of PAHs by IW@MIL-53(Fe) coating with SPME-GC-MS
分析物 线性范围(ng/L) R2 LOD (ng/L, S/N=3) LOQ (ng/L, S/N=10) RSD(%) 涂层内(n=5) 涂层间(n=3) BaA 250~10000 0.9991 0.03 0.10 3.1 6.7 CHR 250~10000 0.9922 0.13 0.43 6.2 3.0 BbF 250~10000 0.9922 0.11 0.37 8.9 5.7 BKF 250~10000 0.9903 0.26 0.87 5.2 5.5 BaP 250~10000 0.9933 0.36 1.20 7.7 6.0 IPY 250~10000 0.9962 1.50 5.00 10.4 9.5 BPE 250~10000 0.9982 2.25 7.50 10.4 2.5 表 2 实际水样中PAHs分析结果
Table 2 Analytical results of PAHs in actual water samples
分析物 东湖水样 长江水样 浓度(ng/L) 加标浓度(ng/L) RSD (%, n=3) 回收率(%) 浓度(ng/L) 加标浓度(ng/L) RSD (%, n=3) 回收率(%) BaA ND 500 11.6 89.3 ND 500 3.5 80.1 CHR ND 500 8.0 102.3 ND 500 7.0 92.5 BbF ND 500 8.8 96.5 ND 500 10.6 84.6 BKF ND 500 5.5 91.1 ND 500 6.4 89.5 BaP ND 500 11.1 90.6 ND 500 9.6 83.0 IPY ND 500 8.6 91.8 ND 500 5.1 108.5 BPE ND 500 4.9 99.7 ND 500 14.4 91.8 注:ND表示未检出。 -
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