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请教测铬不用内标是否可以

ICP-MS

  • 做样品固体粉末,微波消化,微波赶酸后,定量,再分别使用Rh、Sc为内标(非在线而是单独配制)或不用内标,进行添加0.5、1、1.5 ppm,于0.5ppm及1.5ppm添加量时,回收率偏高,如下,请教问题出在那里
    我应该以不使用内标的检测值为依据,还是要如何决择? 谢谢!
    添加0.5ppm 500ppb
    AnalyteMass#1#2#3#4#5平均值SDrsd
    Cr50541.456551.265586.945553.046584.61563.5 20.9 3.70%
    Cr52540.136557.958606.738564.482592.188572.3 26.8 4.69%
    Cr53554.493561.792610.139567.176592.489577.2 23.3 4.04%
    Rh103
    Cr-150515.482522.928554.886521.568550.306533.0 18.1 3.40%
    Cr-152514.782529.669574.007532.681557.839541.8 23.7 4.38%
    Cr-153528.288533.073577.058534.969557.831546.2 20.7 3.78%
    Sc45
    Cr-250462.525477.821477.214484.475493.575479.1 11.4 2.38%
    Cr-252462.275484.366494.295495.14500.8487.4 15.2 3.12%
    Cr-253473.891487.122496.256496.984500.421490.9 10.7 2.18%
    填加量ppb517.5907515.519504.2498495.3418501.8025
    Cr50104.6%106.9%116.4%111.6%116.5%
    Cr52104.4%108.2%120.3%114.0%118.0%
    Cr53107.1%109.0%121.0%114.5%118.1%
    Rh1030.0%0.0%0.0%0.0%0.0%
    Cr-15099.6%101.4%110.0%105.3%109.7%
    Cr-15299.5%102.7%113.8%107.5%111.2%
    Cr-153102.1%103.4%114.4%108.0%111.2%
    Sc450.0%0.0%0.0%0.0%0.0%
    Cr-25089.4%92.7%94.6%97.8%98.4%
    Cr-25289.3%94.0%98.0%100.0%99.8%
    Cr-25391.6%94.5%98.4%100.3%99.7%
    添加1.0ppm 1000ppb
    AnalyteMass#1#2#3#4#5#6#7平均值SDrsd
    Cr501047.4871074.8771065.7111053.2641064.651096.891062.651066.50416.069021.51%
    Cr521092.121096.891103.3661094.8551098.0581111.0561091.0461098.1996.9885110.64%
    Cr531101.4111104.9781114.2481103.7621107.5221115.2951096.6571106.2686.7162190.61%
    Rh103
    Cr-150997.0011018.223995.721001.9671000.6151006.015995.981002.2177.974580.80%
    Cr-1521039.8061039.4811031.3071042.0581032.6181019.5551023.0481032.5538.6775380.84%
    Cr-1531048.3991046.921041.1741050.2551041.2041023.11028.0041039.86510.454741.01%
    Sc45
    Cr-250883.428947.359914.414888.233906.968975.474913.97918.549432.647623.55%
    Cr-252921.895967.41947.282924.172936.248988.634939.009946.378624.076872.54%
    Cr-253929.081974.038956.046931.021943.686991.938943.255952.723623.109952.43%
    填加量ppb995.2721011.7611005.8011013.5481009.5751006.9931015.138
    Cr50104.24%105.25%104.96%102.93%104.46%107.93%103.70%
    Cr52108.73%107.43%108.71%107.04%107.77%109.34%106.49%
    Cr53109.66%108.23%109.79%107.91%108.71%109.76%107.05%
    Cr-15099.17%99.65%98.00%97.87%98.12%98.91%97.13%
    Cr-152103.47%101.75%101.54%101.83%101.29%100.25%99.79%
    Cr-153104.33%102.49%102.52%102.63%102.14%100.61%100.28%
    Cr-25087.76%92.65%89.92%86.65%88.85%95.88%89.05%
    Cr-25291.62%94.63%93.19%90.20%91.75%97.18%91.52%
    Cr-25392.34%95.28%94.06%90.87%92.48%97.51%91.93%
    添加1.5ppm 1500ppb
    AnalyteMass#1#2#3#4#5平均值SDrsd
    Cr501739.2891718.6591603.7731611.8351681.6981671.1 61.4 3.67%
    Cr521729.581766.9221666.0611662.5871759.5011716.9 50.0 2.91%
    Cr531729.361764.3471658.4481663.2381757.0191714.5 50.7 2.96%
    Rh103
    Cr-15015541629.7081508.2321509.5121581.8921556.7 51.4 3.30%
    Cr-1521546.1621675.8551567.1921557.8511655.8471600.6 60.5 3.78%
    Cr-1531545.4631673.1041559.6431558.1991653.0521597.9 60.2 3.77%
    Sc45
    Cr-2501545.1341459.4461420.1471422.0361393.9991448.2 59.0 4.08%
    Cr-2521537.1631501.2371475.9041467.4291459.1521488.2 31.6 2.12%
    Cr-2531536.5231498.4481468.7161467.5141456.471485.5 32.5 2.19%
    填加量1504.1331517.141513.3011503.8521525.613
    Cr50115.6%113.3%106.0%107.2%110.2%
    Cr52115.0%116.5%110.1%110.6%115.3%
    Cr53115.0%116.3%109.6%110.6%115.2%
    Rh1030.0%0.0%0.0%0.0%0.0%
    Cr-150103.3%107.4%99.7%100.4%103.7%
    Cr-152102.8%110.5%103.6%103.6%108.5%
    Cr-153102.7%110.3%103.1%103.6%108.4%
    Sc450.0%0.0%0.0%0.0%0.0%
    Cr-250102.7%96.2%93.8%94.6%91.4%
    Cr-252102.2%99.0%97.5%97.6%95.6%
    Cr-253102.2%98.8%97.1%97.6%95.5%
  • 该帖子已被版主-阶前尘加3积分,加2经验;加分理由:发帖奖励
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  • tuxlin

    第1楼2018/05/27

    应助达人

    如果样品量比较少、基体简单,不加内标当然也是可以的。如测淡水样品,一般都是不加内标的。如果是基体比较复杂的样品,最好还是加内标。
    从你们的结果来看,加了内标的数据还是明显要好于未加内标的数据,Rh内标的结果要好于Sc内标的结果。

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  • yangsm

    第2楼2018/05/27

    抱歉,单位为ug/Kg,补充
    因为定量是以50毫升抛弃式消化瓶定量,故样品包含检量线皆以重量/重量为单位,
    不知您为何认为以Rh为内标的数据较好?
    因为有消化及赶酸前处理,回收率皆大于100%好像不太可能(空白值大约为20ppb以下)(我是空白基质称重0.45g后,分别加入标准品99.3285mg / Kg 0.25mL,0.5mL,0.75mL,以天平计算重量差换算加入量,消化赶酸後以抛弃式消化瓶定量至50毫升,再计算定量后净重,故样品及检量线皆以ppb即ug/Kg为单位)(添加1000ppb的样品在检测一星期前消化并定量完成)
    检量线标准品浓度为2000、1500、1000、500、200、100、0 ppb
    上机前,取标准品(样品亦同)10mL,加入Sc,Rh内标混合液200ppb 1mL,以VORTEX批次混合10秒,上机检测。

    tuxlin(tuxlin) 发表:如果样品量比较少、基体简单,不加内标当然也是可以的。如测淡水样品,一般都是不加内标的。如果是基体比较复杂的样品,最好还是加内标。
    从你们的结果来看,加了内标的数据还是明显要好于未加内标的数据,Rh内标的结果要好于Sc内标的结果。

0
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  • 玉米馒头

    第3楼2018/05/28

    应助达人

    因为有赶酸操作,那样品中残留有机物的增敏效应应该也可以消除。
    但加标量相比待测样品中Cr的含量应该是偏高了,试试标准品稀释后再加标看看。
    最后,表格中三组数据到底是1组Rh内标,2组Sc内标,3组无内标;还是1组无内标,2组Rh内标,3组Sc内标?从问题描述来看貌似是第一种情况。

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  • yangsm

    第4楼2018/05/29

    是1组Rh内标,2组Sc内标,3组无内标

    我是使用PE DRC II,反应气体为NH3,
    52Cr,53Cr反应气体流量开0.3;50Cr,铑,SC为标准模式。
    推想好像是
    1. 52Cr,53Cr反应气体流量开太大(52-17 = 38Ar,52-17 = 39K),
    2.赶酸不完全(赶完酸后,消化瓶大约余2mL液体,定量至50mL,则定量后酸浓度大约是4%,理想是定量50mL赶酸后剩余体积约为0.5mL)
    3.流洗时间1min好像不是很够(?),目标物浓度偏高,样品酸度大于标准液酸度,造成记忆效应之目标物流洗出来。
    4.赶完酸后需静置,让氮化合物逸散?(50-14 = 36 Ar,Cl,S)
    功率= 1350W,torch温度在点火后40分钟的变动会趋于稳定(30分至1小时不变),interface及cooling温度会基本不变。
    我的经验告诉我酸度高,铑的感度会下降(好像是比重高,气动式进样量降低的缘故)
    现在正逐步检讨中,希望先进能多指点一二。

    玉米馒头(alhoon) 发表:因为有赶酸操作,那样品中残留有机物的增敏效应应该也可以消除。
    但加标量相比待测样品中Cr的含量应该是偏高了,试试标准品稀释后再加标看看。
    最后,表格中三组数据到底是1组Rh内标,2组Sc内标,3组无内标;还是1组无内标,2组Rh内标,3组Sc内标?从问题描述来看貌似是第一种情况。

0
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  • 阶前尘

    第5楼2018/05/31

    应助达人

    我觉得做得挺好的啊,你加标量和样品实际含量不知道相当不,如果加标量差距超过一个数量级,回收率偏高是很正常的,另外Sc这个内标一般波动较大,不知道是否有记忆效应,这是我日常检测中发现的问题

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