协同试验报告

附件1协同实验报告1、合作实验室合作实验室共8家，名单汇总于表1。表1合作实验室序号实验室名称1北京市茶叶质量监督检验站2北京市食品质量监督检验二站3成都海关技术中心4四川省食品检验研究院5四川省轻工业研究设计院有限公司6成都市产品质量监督检验研究院7雅安市质量检验检测院8中国测试技术研究院生物研究所2、原始数据2.1示差检测器示差数据汇总于表2。2.2蒸发光散射检测器蒸发光散射数据汇总于表3。2.3回收率回收率数据汇总于表4。注：表2、表3中实验室代码与表1中实验室序号不对应。3、均匀性检验采用F检验法（单因素方差分析）进行均匀性检验。证明用于方法研究的A、B、C、D各批次样品采用示差法、蒸发光散射法检测，均匀性良好。样品均匀性检验最小取样量均为2g。表2示差法原始数据质控E1=19.64%测量次数实验室1实验室2实验室3实验室4样品编号质控E1样品编号质控E1样品编号质控E1样品编号质控E1A-18B-7C-17A-23B-19C-29AB-6C-13ABC119.55713.5875.04219.10319.66313.6755.81918.96718.89112.7244.84818.81619.03213.1994.95019.283219.65713.6625.11219.25219.91913.5965.59719.12618.60612.5195.04218.97118.90912.9065.11519.141319.80213.5694.908/19.58813.6955.743/18.54113.0284.973/19.04713.0304.902/419.64513.7194.989/19.58013.6965.815/18.81212.6494.820/18.89412.9894.853/519.50913.7045.081/19.51813.5685.814/18.66612.4635.047/19.60713.0465.014/619.48513.6085.096/19.52213.5235.860/18.56312.9455.020/18.95313.0625.019/测量次数实验室5实验室6实验室7实验室8样品编号质控E1样品编号质控E1样品编号质控E1样品编号质控E1A-8B-29C-21ABCA-9B-16C-24A-29B-28C-12119.01612.7654.86319.51018.77512.6484.98218.73519.45213.6365.87819.73122.80414.6606.35919.289219.10012.9154.94019.47018.97913.0515.04618.86219.60413.6615.71119.63722.97014.2616.18019.905319.33012.8744.824/18.67512.6905.365/19.68613.5975.660/24.34014.1926.026/418.91012.8794.855/17.95212.6715.162/19.51413.6185.825/22.73514.2496.101/518.93512.9264.846/18.70212.5255.048/19.49613.5475.838/23.86114.4756.222/619.14212.8524.928/18.76512.8904.990/19.68713.5945.805/23.17914.4236.307/表3蒸发光散射法原始数据质控E2=2.34%实验室1实验室2实验室3实验室4样品编号质控E2样品编号质控E2样品编号质控E2样品编号质控E2B-11C-28D-29B-22C-30D-1B-30C-20D-28BCD113.9345.2292.2542.27614.6915.2292.2542.27613.8855.0562.1692.12612.8475.1982.2202.573213.8745.1482.2652.24814.4975.1412.2482.22913.2635.0222.2412.11512.7715.1892.2462.348313.9375.1622.270/14.7315.1722.246/13.3784.8862.120/13.2604.9052.189/413.6875.2802.242/14.3345.2532.277/13.7634.9452.086/12.8075.1862.262/513.8115.2742.236/13.9775.2832.240/12.9774.9112.223/13.1205.0792.236/613.9515.2832.247/14.1095.2382.256/13.4084.9452.237/12.9045.0882.256/实验室5实验室6实验室7实验室8样品编号质控E2样品编号质控E2样品编号质控E2样品编号质控E2B-27C-6D-4BCDB-15C-24D-9B-20C-8D-25113.4664.9592.2592.26213.3504.9352.1492.37315.1565.7982.3322.33014.6484.2112.0202.520213.2794.9562.0462.33213.3665.3122.1762.45914.9295.6872.3072.34114.1034.0741.9622.553312.9104.9132.129/13.0605.2912.171/15.2145.5582.345/14.3364.4932.027/413.4934.6652.047/13.2564.9612.132/15.0725.7292.353/13.9994.6572.137/512.9854.7182.216/13.0025.0222.024/14.9215.8052.320/13.8654.4232.102/613.9975.0552.063/13.0674.9262.070/15.1305.7022.356/14.0514.4382.008/表4回收率原始数据实验室代码示差蒸发光散射加标量(g/100g)加标量(g/100g)5102021020平均值

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（%）199.730.41100.180.2399.711.09104.331.49101.320.3099.921.70298.230.9199.760.2099.600.82102.370.79103.330.74102.341.49399.570.31096.070.59196.930.96196.981.52102.601.25101.900.882496.462.9493.074.0495.860.85112.052.03102.401.79101.042.74595.450.1897.010.9297.370.66102.311.7999.751.09100.580.366100.123.4996.972.5097.431.5699.323.16102.721.5197.141.06799.321.4397.681.1397.670.8099.031.6497.201.1797.520.92893.781.9794.772.5494.430.29101.652.6993.991.8393.660.57对应样品C样B样A样D样B样A样注：回收率不在95%~105%，表示测量有明显系统偏差，因此：1、实验室4，去除示差10g/100g(回收率93.07%)，和蒸发2g/100g（回收率112.05%）的测量数据，即示差B，蒸发D；2、实验室8，去除回收率低于95%的测量数据，即只留蒸发D。表5组内标准差、组间标准差、方法重复性与再现性示差检测器A样（均值19.1875）B样（均值13.2019）C样（均值5.5964）正态峰度拒绝偏度拒绝组内标准差组间标准差rR组内标准差组间标准差rR组内标准差组间标准差rR0.13760.40970.3891.2230.13020.45600.3690.4740.08820.38910.2501.129相对量2.03%6.37%相对量2.79%10.17%相对量4.46%20.18%蒸发光散射检测器B样（均值13.7516）C样（均值5.1689）D样（均值2.1872）正态峰度拒绝正态组内标准差组间标准差rR组内标准差组间标准差rR组内标准差组间标准差rR0.25370.74260.7182.2210.11140.26800.3150.8210.05520.09720.1560.316相对量5.22%16.15%相对量6.10%15.89%相对量7.14%14.46%4稳定性检验本批样品在协同实验前与结束后，由牵头实验室分别进行了测量。采用t检验法验证样品稳定。5方法重复性和复现性5.1统计步骤数据汇总后，按如下步骤进行核查分析：（1）核查原始数据是否有粗大误差；（2）回收率界于95%~105%的数据用于统计分析；（2）正态分布检验；（3）组内离群值检验；（4）组间离群值检验；（5）等精度检验；（6）计算组内标准偏差sr；计算组间标准偏差sl；（8）计算方法重复性r；（9）计算方法再现性R；5.2统计分析方法5.2.1正态分布检验SPSS软件中的峰度偏度法进行正态分布检验。5.2.2离群值检验格拉布斯（Grubbs）法进行离群值检验。5.2.3等精度检验科克伦（Cochran）法进行等精度检验，统计处理后，计算得到的组内标准差、组间标准差、方法重复性与再现性数据列于表5。6、讨论对于示差检测器，从表５观察到再现性与含量呈一定的线性关系、采用最小二乘法线拟合后，图形及拟合公式如下：含量（g/100g）r（％）R（％）19.18752.036.3713.20192.7910.175.59644.4620.18对于蒸发光散射检测器，采用表5数据拟合重复性、再现性与含量的关系，线性相关系数（R2）均达不到0.95，可假设无线性关系，也即测量方法的精密度不依赖于样品中蔗糖含量水平。含量（g/100g）r（％）R（％）13.75165.2216.155.16896.1015.892.18727.1414.46结合表5中数据和样本量，对方法重复性与再现性可采用