HJ834-2017-土壤-半挥发性有机物的测定方法验证报告

土壤半挥发性有机物的测定气相色谱-质谱法HJ834-2017方法验证报告1、目的本方法验证主要依据HJ168-2010环境监测分析方法标准制修订技术导则编制的要求，从设备、环境条件、人员能力、标准物质及试剂，以及检出限、精密度和准确度（参照HJ168-2010），以验证实验室能力满足HJ834-2017的要求。2、方法简介2.1适用范围本方法适用于土壤中31种半挥发性有机物的测定。2.2方法原理样品中半挥发性有机物采用适合的萃取方法（索氏提取、加压流体萃取等）提取，根据样品基体干扰情况选择合适的净化方法（凝胶渗透色谱或柱净化）对提取液净化、浓缩、定容，经气相色谱分离、质谱检测。根据保留时间、碎片离子质荷比及其丰度定性，内标法定量。2.3仪器条件（实际验证条件）2.3.1加压流体萃取条件：加热温度：100℃；预加热平衡时间：5min；静态萃取时间：5min；氮气吹扫时间：1min；静态萃取次数：2次。其余参数参照仪器使用说明书进行设定。2.3.2气相色谱条件：进样口温度：280℃；载气：氦气；不分流进样；柱流量（恒流模式）：1.0ml/min；升温程序：40℃（3.0min）→15℃/min→300℃（7.0min）。2.3.3质谱条件：扫描方式：全扫描；扫描范围：45～350amu；离子化能量：70eV；电子倍增器电压：0.96kv；接口温度：280℃；其余参数参照仪器使用说明书进行设定。2.4样品2.4.1样品采集与保存土壤样品按照HJ/T166的相关要求采集和保存，样品应于洁净的具塞磨口棕色玻璃瓶中保存。运输过程中应密封、避光、4℃以下冷藏。运至实验室后，若不能及时分析，应于4℃以下冷藏、避光、密封保存，保存时间不超过10天。本次用于方法验证采集的样品编号为：ZZM90892001。2.4.2样品含水率的测定土壤样品干物质含量测定按照HJ613执行，本次验证的样品干物质含量为88.6%，详见《土壤干重分析原始记录表》。2.5分析步骤2.5.1校准曲线取6个2ml进样瓶，用微量注射器分别量取适量的半挥发性有机物标准中间液、替代物中间液和内标中间液，用二氯甲烷溶剂配制成6个浓度点的标准系列。半挥发有机物和替代物的质量浓度均分别为1.0μg/ml、2.0μg/ml、5.0μg/ml、8.0μg/ml、10.0μg/ml、20.0μg/ml，内标质量浓度均为2.0μg/ml。详见《有机检验记录表》，按照仪器条件（2.3），从低浓度到高浓度依次测定。2.5.2样品准备称取20g（精确到0.01g）的新鲜样品，加入一定量的硅藻土混匀、脱水并研磨成细小颗粒，充分拌匀直到散粒状，全部转移至提取容器中待用。2.5.3提取按照加压流体萃取的条件（2.3.1）进行提取。2.5.4浓缩旋转蒸发仪加热温度设置在40℃，将提取液浓缩至约2ml，停止浓缩。用一次性滴管将浓缩液转移至具刻度浓缩器皿，并用少量二氯甲烷-丙酮混合溶剂将旋转蒸发瓶底部冲洗2次，合并全部的浓缩液，再用氮吹浓缩至约1ml，待净化。2.5.5净化和定容必要时，采用硅酸镁或硅胶层析柱净化。净化后的试液再次按照旋转蒸发浓缩（6.3.3）的步骤进行浓缩、加入适量内标中间液（内标液浓度为10μg/ml），并定容至1.0ml，混匀后转移至2ml样品瓶中，待测。2.6结果计算样品中目标物的含量按以下公式进行计算：3、仪器设备验证情况标准要求实验室配备气相色谱/质谱仪：具电子轰击（EI）电离源。安捷伦8890-5977B气质联用仪，EI源色谱柱：石英毛细管柱，长30m，内径0.25mm，膜厚0.25m，固定相为5%-苯基-甲基聚硅氧烷，或其他等效的毛细管色谱柱。HP-5MS毛细柱提取装置：索氏提取或加压流体萃取仪等性能相当的设备。呼客HPSE-06加压流体萃取仪浓缩装置：旋转蒸发仪、氮吹仪或其他同等性能的设备。旋转蒸发仪、氮吹仪固相萃取装置。固相萃取装置。实验室配备的仪器和设备满足标准要求，主要设备的验收详见《新项目申请仪器设备验收表》。4、环境条件验证情况环境条件符合控制要求，详见《环境监控记录表》，仪器房内设有温度湿度计及记录表，分析测试人员每日对温度湿度进行监控，监控范围为温度：15-35℃，湿度：20%-80%。5、人员能力验证情况该项目目前配备3名专业技术人员，通过培训考核并持证上岗，见表1。表1参加验证人员情况登记表姓名所学专业从事分析工作年限职称XXXXXXX5助理工程师XXXXXXXXXXXX84工程师同等能力助理工程师考核记录详见人员培训档案及《质量考核结果评价表》6、标准物质及试剂验证情况标准要求实验室配备丙酮（C3H6O)：农残级。丙酮（C3H6O)：农残级。二氯甲烷（CH2Cl2)：农残级。二氯甲烷（CH2Cl2)：农残级。乙酸乙酯（C4H8O2)：农残级。乙酸乙酯（C4H8O2)：农残级。环己烷（C6H12)：农残级。环己烷（C6H12)：农残级。半挥发性有机物标准贮备液：ρ=1000mg/L～5000mg/L，市售有证标准溶液。半挥发性有机物标准贮备液：ρ=1000mg/L，有证标准物质。内标贮备液：ρ=5000mg/L1,4-二氯苯-d4、萘-d8、苊-d10、菲-d10、䓛-d12和苝-d12，市售有证标准溶液。亦可选用其他性质相近的半挥发性有机物做内标。6种内标混标:4000mg/L，有证标准物质。（1,4-二氯苯-d4、萘-d8、苊-d10、菲-d10、䓛-d12和苝-d12）替代物贮备液：ρ=1000mg/L～4000mg/L。苯酚-d6、2-氟苯酚、2,4,6-三溴苯酚、硝基苯-d5、2-氟联苯、4’4-三联苯-d14等市售有证标准溶液。6种替代物混标，ρ=4000mg/L，有证标准物质。（苯酚-d6、2-氟苯酚、2,4,6-三溴苯酚、硝基苯-d5、2-氟联苯、4’4-三联苯-d14）十氟三苯基膦（DFTPP）：ρ=50mg/L，市售标准溶液。其他浓度用二氯甲烷（4.2）稀释成50mg/L并混匀。十氟三苯基膦，ρ=2500mg/L。实验室配备的标准物质及试剂满足标准要求，详见标准物质证书复印件。7、检出限、精密度和准确度（参照HJ168-2010）检出限、精密度和准确度实验原始测试数据详见附表《检出限、精密度、准确度原始数据汇总表》。7.1检出限称取编号为ZZM90892001的样品7份，每份样品量为20g（精确到0.01g），再分别加入混合目标物标准使用液、替代物使用液，使目标物浓度均为5.0µg/mL，替代物浓度为2.0µg/mL，按照样品分析的全部步骤（2.5），加入内标使其浓度为2ug/mL后，上机测试，进行7次平行测定。计算7次平行测定的标准偏差，按以下公式（1）计算方法检出限。QUOTE式中：MDL—方法检出限；n—样品的平行测定次数；t—自由度为n-1，置信度为99%时的t分布（单侧）；S—n次平行测定的标准偏差。其中，当自由度为n-1，置信度为99%时的t值可参考表2表2t表值平行测定次数（n）自由度（n-1）763.143872.998982.8961092.82111102.76416152.60221202.528MDL值计算出来后，需判断其合理性：对于针对多组分的分析方法，一般要求至少有50%的被分析物样品浓度在3~5倍计算出的方法检出限的范围内，同时，至少90%的被分析物样品浓度在1~10倍计算出的方法检出限的范围内，其余不多于10%的被分析物样品浓度不应超过20倍计算出的方法检出限。若满足上述条件，说明用于测定MDL的初次样品浓度比较合适。对于初次加标样品测定平均值与MDL比值不在3~5之间的化合物，要增加或减少浓度，重新进行平行分析，直至比值在3~5之间。选择比值在3~5之间的MDL作为该化合物的MDL。本次方法验证检出限详见附表1。7.2测定下限以4倍检出限作为测定下限，本次方法验证测定下限详见附表1。7.3精密度分别对实际土壤样品（样品编号为ZZM90892001）加标的方式开展精密度测定，加标浓度分别为低、中、高三个不同浓度系列（见表3）。加标样品按照样品分析的全部步骤，进行6次平行测定。计算不同浓度样品的平均值、标准偏差、相对标准偏差等各项参数。表3不同浓度土壤样中浓度值单位：mg/kg浓度水平样品编号SVOC浓度水平低浓度/（mg/kg）ZZM90892001(J7-J13)-0.25ppm0.25中浓度/（mg/kg）ZZM90892001(J1-J7)-0.50ppm0.5高浓度/（mg/kg）ZZM90892001(J1-J7)-1.0ppm1.0对某一水平浓度的样品在实验室内进行6次平行测定，实验室内相对标准偏差按如下公式（2）、（3）、（4）进行计算：（2）（3）（4）式中：xk—实验室内对某一浓度水平样品进行的第k次测试结果；xi—实验室对某一浓度水平样品测试的平均值；Si—实验室对某一浓度水平样品测试的标准偏差；RSDi—实验室对某一浓度水平样品测试的相对标准偏差。本次方法验证精密度详见附表2。7.4准确度7.4.1实际样品加标测试对样品编号为ZZM90892001的实际样品加标，分别进行6次平行测定。实际样品加标后目标物浓度值见表4。分别计算样品的加标回收率，加标回收率按如下公式（5）进行计算表4实际样品加标浓度值单位：mg/kg浓度水平样品编号SVOC浓度水平低浓度/（mg/kg）ZZM90892001(J7-J13)-0.25ppm0.25中浓度/（mg/kg）ZZM90892001(J1-J7)-0.50ppm0.5高浓度/（mg/kg）ZZM90892001(J1-J7)-1.0ppm1.0（5）本次方法验证准确度详见附表3。7.5实际样品测试对样品编号为ZZM90892001的实际样品测试，结果见表5。表5实际样品测试结果ZZM90892001ZZM90892001PZZM90892001J1-0.50ppmZZM90892001J1-1.0ppm方法检出限单位苯酚NDND0.3890.9470.1mg/kg苯胺NDND0.3490.8190.1mg/kg2-氯酚NDND0.3740.9200.06mg/kg2-甲酚NDND0.4020.9530.1mg/kg4-甲酚NDND0.4030.9410.1mg/kg硝基苯NDND0.3690.8900.09mg/kg2-硝基苯酚NDND0.3940.9740.2mg/kg2,4-二甲酚NDND0.4290.9560.09mg/kg萘NDND0.3700.8460.09mg/kg2-甲基萘NDND0.3820.8660.08mg/kg2,4,6-三氯酚NDND0.3570.9070.1mg/kg2,4,5-三氯酚NDND0.3810.9040.1mg/kg2-硝基苯胺NDND0.3910.9510.08mg/kg苊烯NDND0.3670.8480.09mg/kg苊NDND0.3680.8520.1mg/kg4-硝基苯酚NDND0.3831.0690.09mg/kg芴NDND0.3820.8520.08mg/kg菲NDND0.3810.8210.1mg/kg蒽NDND0.3980.8240.1mg/kg邻苯二甲酸二正丁酯NDND0.3870.7890.1mg/kg荧蒽NDND0.3930.8560.2mg/kg芘NDND0.3880.8540.1mg/kg苯并[a]蒽NDND0.3960.9110.1mg/kg屈NDND0.3670.7980.1mg/kg邻苯二甲酸二正辛酯NDND0.3240.8570.2mg/kg苯并[b]荧蒽NDND0.3170.8650.2mg/kg苯并[k]荧蒽NDND0.3350.9070.1mg/kg苯并[a]芘NDND0.3130.8550.1mg/kg茚并[1,2,3-cd]芘NDND0.2800.6640.1mg/kg二苯并[a,h]蒽NDND0.2750.7410.1mg/kg苯并[g,h,i]苝NDND0.2760.7410.1mg/kg8、结论从设备、环境条件、人员能力、标准物质及试剂，以及检出限、精密度和准确度的验证结果说明实验室已具备《土壤半挥发性有机物的测定气相色谱-质谱法HJ834-2017》方法的测试能力。9、附件（记录）附表检出限、精密度、准确度原始数据汇总表附件1新项目申请仪器设备验收表附件2环境监控记录表附件3质量考核结果评价表附件4标准物质证书复印件附件5方法验证原始谱图及记录编制批准日期日期附表检出限、精密度、准确度原始数据汇总表1、方法检出限、测定下限测试数据表1-1方法检出限、测定下限测试数据表平行样品编号苯酚苯胺2-氯酚2-甲酚4-甲酚硝基苯测定结果（mg/kg）10.2140.1780.1940.2150.2260.20620.2120.1780.1950.2130.2230.20030.2310.1940.2140.2350.2470.22440.1900.1550.1710.1900.2020.17850.2170.1770.1980.2200.2330.21260.2200.1870.2050.2250.2350.21170.2370.1930.2180.2390.2500.230平均值`xi（mg/kg）0.2170.1800.1990.2200.2310.209标准偏差Si（mg/kg）0.0140.0130.0150.0160.0160.017t值（无量纲）3.1433.1433.1433.1433.1433.143检出限（mg/kg）0.050.050.050.060.060.06标准方法检出限（mg/kg）0.10.10.060.090.090.09测定下限（mg/kg）0.200.200.200.240.240.24标准方法测定下限（mg/kg）40.360.360.36判定：验证结果满足标准要求平行样品编号2-硝基苯酚2,4-二甲酚萘2-甲基萘2,4,6-三氯酚2,4,5-三氯酚测定结果（mg/kg）10.2540.2640.1570.1850.2250.21020.2400.2500.1660.1850.2130.20230.2750.2840.1780.2040.2440.23940.2210.2290.1400.1620.1940.18650.2650.2710.1570.1880.2330.22160.2570.2670.1740.1950.2350.23170.2820.2910.1760.2040.2490.238平均值`xi（mg/kg）0.2560.2650.1640.1890.2280.218标准偏差Si（mg/kg）0.0210.0210.0140.0150.0190.020t值（无量纲）3.1433.1433.1433.1433.1433.143检出限（mg/kg）0.070.070.050.050.060.07标准方法检出限（mg/kg）0.080.10.10.20.10.1测定下限（mg/kg）0.280.280.200.200.240.28标准方法测定下限（mg/kg）0.30.40.4判定：验证结果满足标准要求表1-1方法检出限、测定下限测试数据表-续表平行样品编号2-硝基苯胺苊烯苊4-硝基苯酚芴菲测定结果（mg/kg）10.2290.1460.1680.2610.1630.16720.2250.1610.1760.2380.1750.18130.2530.1710.1910.2830.1890.19240.2000.1290.1470.2190.1460.14850.2350.1450.1680.2700.1630.16660.2380.1670.1850.2590.1830.18870.2560.1680.1910.2950.1850.193平均值`xi（mg/kg）0.2340.1550.1750.2610.1720.176标准偏差Si（mg/kg）0.0190.0160.0160.0260.0160.017t值（无量纲）3.1433.1433.1433.1433.1433.143检出限（mg/kg）0.060.050.050.090.050.06标准方法检出限（mg/kg）0.10.10.060.090.090.09测定下限（mg/kg）0.240.200.200.360.200.24标准方法测定下限（mg/kg）40.360.360.36判定：验证结果满足标准要求平行样品编号蒽邻苯二甲酸二正丁酯荧蒽芘苯并[a]蒽屈测定结果（mg/kg）10.1760.1300.1740.1880.2190.16420.1930.1560.1880.1970.2190.17130.2040.1570.2020.2150.2430.19140.1590.1200.1540.1640.1910.13650.1770.1280.1730.1890.2220.16660.2010.1650.1980.2080.2330.18370.2030.1550.2010.2150.2430.190平均值`xi（mg/kg）0.1880.1440.1840.1970.2240.171标准偏差Si（mg/kg）0.0170.0180.0180.0180.0180.019t值（无量纲）3.1433.1433.1433.1433.1433.143检出限（mg/kg）0.060.060.060.060.060.06标准方法检出限（mg/kg）0.080.10.10.20.10.1测定下限（mg/kg）0.240.240.240.240.240.24标准方法测定下限（mg/kg）0.30.40.4判定：验证结果满足标准要求表1-1方法检出限、测定下限测试数据表-续表平行样品编号邻苯二甲酸二正辛酯苯并[b]荧蒽苯并[k]荧蒽苯并[a]芘茚并[1,2,3-cd]芘二苯并[a,h]蒽测定结果（mg/kg）10.1410.1960.1810.1970.1910.18120.1570.1970.1940.1960.1840.17530.1690.2180.2110.2210.2100.20240.1230.1690.1630.1720.1590.15650.1390.1980.1790.2000.1980.18560.1690.2080.2040.2080.1970.18770.1660.2180.2100.2230.2180.207平均值`xi（mg/kg）0.1520.2010.1920.2030.1940.185标准偏差Si（mg/kg）0.0180.0170.0180.0170.0190.017t值（无量纲）3.1433.1433.1433.1433.1433.143检出限（mg/kg）0.060.050.060.050.060.05标准方法检出限（mg/kg）0.10.10.060.090.090.09测定下限（mg/kg）0.240.200.240.200.240.20标准方法测定下限（mg/kg）40.360.360.36判定：验证结果满足标准要求平行样品编号苯并[g,h,i]苝/////测定结果（mg/kg）10.170/////20.167/////30.192/////40.142/////50.172/////60.179/////70.196/////平均值`xi（mg/kg）0.174/////标准偏差Si（mg/kg）0.018/////t值（无量纲）3.143/////检出限（mg/kg）0.06/////标准方法检出限（mg/kg）0.08/////测定下限（mg/kg）0.24/////标准方法测定下限（mg/kg）0.32/////判定：验证结果满足标准要求2、方法精密度测试数据表2-1精密度测试数据平行样品编号苯酚苯胺2-氯酚2-甲酚备注ρ1ρ2ρ3ρ1ρ2ρ3ρ1ρ2ρ3ρ1ρ2ρ3测定结果（mg/kg）10.1940.3890.9470.1620.3490.8190.1760.3740.9200.1960.4020.95320.2150.3870.6640.1720.3260.5780.1950.3660.6360.2170.3940.66330.2210.3890.9780.1850.3270.8520.2020.3660.9510.2240.3950.98140.2420.3970.7320.1950.3350.6280.2210.3740.7010.2420.4010.73050.1970.4160.7300.1630.3650.6260.1780.3860.7020.1990.4240.72960.2170.4040.7240.1730.3610.6250.1960.3790.6980.2170.4120.717标准偏差Si（mg/kg）0.0170.0110.7960.0130.0170.1160.0170.0080.1320.0170.0110.135平均值`xi（mg/kg）0.2140.3970.1320.1750.3440.6880.1950.3740.7680.2160.4050.795相对标准偏差RSDi（%）8.12.916.67.54.916.98.62.117.37.92.817.0标准方法RSD(%)要求≤40≤40≤40≤40平行样品编号4-甲酚硝基苯2-硝基苯酚2,4-二甲酚备注ρ1ρ2ρ3ρ1ρ1ρ1ρ1ρ2ρ3ρ1ρ2ρ3测定结果（mg/kg）10.2070.4030.9410.1840.3690.8900.2280.3940.9740.2380.4290.95620.2280.4080.6790.2080.3580.6300.2620.4320.7060.2690.4450.68530.2350.4120.9610.2110.3620.9220.2560.4401.0250.2670.4420.99840.2540.4170.7400.2340.3680.6900.2910.4500.7840.2980.4570.75150.2100.4310.7400.1870.3800.6860.2320.4250.7740.2410.4570.74760.2300.4160.7360.2110.3750.6810.2650.4050.7740.2710.4380.740标准偏差Si（mg/kg）0.0170.0100.1200.0190.0080.1230.0230.0210.1280.0220.0110.130平均值`xi（mg/kg）0.2270.4150.8000.2060.3690.7500.2560.4240.8400.2640.4450.813相对标准偏差RSDi（%）7.62.315.09.02.316.49.05.015.38.42.516.0标准方法RSD(%)要求≤40≤40≤40≤40平行样品编号萘2-甲基萘2,4,6-三氯酚2,4,5-三氯酚备注ρ1ρ2ρ3ρ1ρ2ρ3ρ1ρ2ρ3ρ1ρ2ρ310.1450.3700.8460.1660.3820.8660.2040.3570.9070.1970.3810.90420.1540.2770.5870.1870.3220.6120.2260.3830.6630.2180.3800.69030.1720.2740.8740.1930.3220.8850.2330.3940.9570.2240.3941.00140.1770.2750.6430.2080.3230.6720.2540.3990.7450.2450.4020.76850.1470.3650.6340.1710.3790.6660.2070.3880.7390.1990.3740.74460.1510.3740.6270.1860.3810.6560.2280.3660.7270.2200.3540.759标准偏差Si（mg/kg）0.0130.0520.1240.0150.0320.1180.0180.0160.1150.0180.0160.117平均值`xi（mg/kg）0.1570.3230.7020.1850.3520.7260.2250.3810.7890.2170.3810.811相对标准偏差RSDi（%）8.516.017.78.29.116.28.24.314.68.24.314.4标准方法RSD(%)要求≤40≤40≤40≤40判定验证结果满足标准要求2、方法精密度测试数据表2-1精密度测试数据-续表平行样品编号2-硝基苯胺苊烯苊4-硝基苯酚备注ρ1ρ2ρ3ρ1ρ2ρ3ρ1ρ2ρ3ρ1ρ2ρ3测定结果（mg/kg）10.2090.3910.9510.1360.3670.8480.1550.3680.8520.2340.3831.06920.2330.4010.6990.1420.2650.5860.1650.2960.5970.2710.4710.78130.2380.4050.9880.1640.2640.8820.1830.2960.8830.2630.4731.02040.2600.4060.7740.1690.2590.6480.1910.2920.6580.3020.4840.88450.2110.4140.7780.1380.3560.6480.1570.3640.6560.2370.4370.87860.2350.4030.7660.1390.3650.6270.1640.3700.6390.2750.4080.867标准偏差Si（mg/kg）0.0190.0080.1160.0150.0550.1250.0150.0400.1210.0260.0410.107平均值`xi（mg/kg）0.2310.4030.8260.1480.3130.7070.1690.3310.7140.2640.4430.916相对标准偏差RSDi（%）8.31.914.09.817.617.78.612.017.09.89.211.7标准方法RSD(%)要求≤40≤40≤40≤40平行样品编号芴菲蒽邻苯二甲酸二正丁酯备注ρ1ρ2ρ3ρ1ρ1ρ1ρ1ρ2ρ3ρ1ρ2ρ3测定结果（mg/kg）10.1540.3820.8520.1560.3810.8210.1660.3980.8240.1380.3870.78920.1600.2880.5940.1620.2670.5840.1720.2790.5860.1330.2230.55130.1810.2880.8770.1860.2670.8270.1980.2780.8300.1610.2200.78540.1860.2830.6480.1900.2640.6270.2040.2710.6290.1520.2170.58650.1550.3690.6520.1580.3610.6190.1680.3770.6220.1430.3540.57960.1580.3800.6300.1590.3740.6020.1670.3910.6030.1370.3710.556标准偏差Si（mg/kg）0.0140.0500.1230.0160.0590.1120.0170.0620.1130.0110.0830.114平均值`xi（mg/kg）0.1660.3320.7090.1690.3190.6800.1790.3320.6820.1440.2950.641相对标准偏差RSDi（%）8.515.017.39.218.416.59.418.616.57.328.217.8标准方法RSD(%)要求≤40≤40≤40≤40平行样品编号荧蒽芘苯并[a]蒽屈备注ρ1ρ2ρ3ρ1ρ2ρ3ρ1ρ2ρ3ρ1ρ2ρ3测定结果（mg/kg）10.1630.3930.8560.1740.3880.8540.2050.3960.9110.1490.3670.79820.1690.2800.6050.1850.3040.6130.2190.3620.6500.1590.2640.56330.1940.2780.8640.2060.3020.8690.2320.3650.9340.1790.2610.83040.2000.2790.6530.2180.2990.6620.2460.3580.7140.1900.2620.62150.1660.3770.6470.1770.3830.6580.2070.4240.7180.1500.3400.61860.1650.3850.6280.1850.3830.6410.2190.3980.6970.1600.3620.597标准偏差Si（mg/kg）0.0170.0580.1180.0170.0450.1140.0160.0260.1210.0170.0520.113平均值`xi（mg/kg）0.1760.3320.7090.1910.3430.7160.2210.3840.7710.1640.3090.671相对标准偏差RSDi（%）9.417.616.79.013.215.97.16.815.610.116.916.8标准方法RSD(%)要求≤40≤40≤40≤40判定验证结果满足标准要求2、方法精密度测试数据表2-1精密度测试数据-续表平行样品编号邻苯二甲酸二正辛酯苯并[b]荧蒽苯并[k]荧蒽苯并[a]芘备注ρ1ρ2ρ3ρ1ρ2ρ3ρ1ρ2ρ3ρ1ρ2ρ3测定结果（mg/kg）10.1380.3240.8570.1790.3170.8650.1750.3350.9070.1800.3130.85520.1370.2160.5710.1950.2850.5940.1780.2720.6220.1970.2970.59230.1660.2120.9130.2060.2840.9260.2040.2670.9710.2070.2960.88340.1650.2080.6380.2240.2880.6630.2090.2640.6970.2260.2970.66450.1390.3110.6340.1810.3350.6670.1770.3400.6960.1820.3290.66960.1330.3260.6140.1920.3230.6500.1750.3360.6710.1960.3150.648标准偏差Si（mg/kg）0.0150.0590.1430.0170.0220.1340.0160.0380.1420.0170.0130.120平均值`xi（mg/kg）0.1460.2660.7050.1960.3050.7280.1860.3020.7610.1980.3080.718相对标准偏差RSDi（%）10.222.320.38.57.318.48.412.618.78.44.416.7标准方法RSD(%)要求≤40≤40≤40≤40平行样品编号茚并[1,2,3-cd]芘二苯并[a,h]蒽苯并[g,h,i]苝ρ1ρ2ρ3ρ1ρ1ρ1ρ1ρ2ρ3///测定结果（mg/kg）10.1780.2800.6640.1600.2750.7410.1490.2760.741///20.1920.2910.4860.1810.2850.5060.1680.2700.494///30.1920.3020.6580.1860.2960.7930.1750.2800.762///40.2210.3090.5400.2080.3010.5810.1950.2860.557///50.1700.2870.5150.1620.2770.5870.1520.2710.557///60.1930.2970.5020.1830.2850.5790.1720.2860.543///标准偏差Si（mg/kg）0.0180.0100.0800.0170.0100.1100.0170.0070.113///平均值`xi（mg/kg）0.1910.2940.5610.1800.2860.6310.1690.2780.609///相对标准偏差RSDi（%）9.23.514.29.73.517.510.02.518.5///标准方法RSD(%)要求≤40≤40≤40判定验证结果满足标准要求3、方法准确度测试数据表3-1加标测试数据平行样品编号苯酚加标量浓度1浓度2浓度3（mg/kg）样品加标样品样品加标样品样品加标样品低中高测定结果（mg/kg）10.000.1940.000.3890.000.9470.2790.5031.00320.000.2150.000.3870.000.6640.2800.5071.00430.000.2210.000.3890.000.9780.2800.5091.01340.000.2420.000.3970.000.7320.2880.5161.03450.000.1970.000.4160.000.7300.2840.5141.03060.000.2170.000.4040.000.7240.2810.5101.020平均值`xi、`yi（mg/kg）0.000.2140.000.3970.000.796加标回收率Pi（%）75.977.878.3标准方法要求（%）47~11947~11947~119平行样品编号苯胺加标量浓度1浓度2浓度3（mg/kg）样品加标样品样品加标样品样品加标样品低中高测定结果（mg/kg）10.000.1620.000.3490.000.8190.2790.5031.00320.000.1720.000.3260.000.5780.2800.5071.00430.000.1850.000.3270.000.8520.2800.5091.01340.000.1950.000.3350.000.6280.2880.5161.03450.000.1630.000.3650.000.6260.2840.5141.03060.000.1730.000.3610.000.6250.2810.5101.020平均值`xi、`yi（mg/kg）0.000.1750.000.3440.000.688加标回收率Pi（%）62.067.467.7标准方法要求（%）47~11947~11947~119平行样品编号2-氯酚加标量浓度1浓度2浓度3（mg/kg）样品加标样品样品加标样品样品加标样品低中高测定结果（mg/kg）10.000.1760.000.3740.000.9200.2790.5031.00320.000.1950.000.3660.000.6360.2800.5071.00430.000.2020.000.3660.000.9510.2800.5091.01340.000.2210.000.3740.000.7010.2880.5161.03450.000.1780.000.3860.000.7020.2840.5141.03060.000.1960.000.3790.000.6980.2810.5101.020平均值`xi、`yi（mg/kg）0.000.1950.000.3740.000.768加标回收率Pi（%）68.973.475.6标准方法要求（%）47~11947~11947~119判定验证结果满足标准要求续表平行样品编号2-甲酚加标量浓度1浓度2浓度3（mg/kg）样品加标样品样品加标样品样品加标样品低中高测定结果（mg/kg）10.000.1960.000.4020.000.9530.2790.5031.00320.000.2170.000.3940.000.6630.2800.5071.00430.000.2240.000.3950.000.9810.2800.5091.01340.000.2420.000.4010.000.7300.2880.5161.03450.000.1990.000.4240.000.7290.2840.5141.03060.000.2170.000.4120.000.7170.2810.5101.020平均值`xi、`yi（mg/kg）0.000.2160.000.4050.000.795加标回收率Pi（%）76.479.478.3标准方法要求（%）47~11947~11947~119平行样品编号4-甲酚加标量浓度1浓度2浓度3（mg/kg）样品加标样品样品加标样品样品加标样品低中高测定结果（mg/kg）10.000.2070.000.4030.000.9410.2790.5031.00320.000.2280.000.4080.000.6790.2800.5071.00430.000.2350.000.4120.000.9610.2800.5091.01340.000.2540.000.4170.000.7400.2880.5161.03450.000.2100.000.4310.000.7400.2840.5141.03060.000.2300.000.4160.000.7360.2810.5101.020平均值`xi、`yi（mg/kg）0.000.2270.000.41566.10.800加标回收率Pi（%）80.581.378.7标准方法要求（%）47~11947~11947~119平行样品编号硝基苯加标量浓度1浓度2浓度3（mg/kg）样品加标样品样品加标样品样品加标样品低中高测定结果（mg/kg）10.000.1840.000.3690.000.8900.2790.5031.00320.000.2080.000.3580.000.6300.2800.5071.00430.000.2110.000.3620.000.9220.2800.5091.01340.000.2340.000.3680.000.6900.2880.5161.03450.000.1870.000.3800.000.6860.2840.5141.03060.000.2110.000.3750.000.6810.2810.5101.020平均值`xi、`yi（mg/kg）0.000.2060.000.3690.000.750加标回收率Pi（%）72.972.373.8标准方法要求（%）47~11947~11947~119判定验证结果满足标准要求续表平行样品编号2-硝基苯酚加标量浓度1浓度2浓度3（mg/kg）样品加标样品样品加标样品样品加标样品低中高测定结果（mg/kg）10.000.2280.000.3940.000.9740.2790.5031.00320.000.2620.000.4320.000.7060.2800.5071.00430.000.2560.000.4400.001.0250.2800.5091.01340.000.2910.000.4500.000.7840.2880.5161.03450.000.2320.000.4250.000.7740.2840.5141.03060.000.2650.000.4050.000.7740.2810.5101.020平均值`xi、`yi（mg/kg）0.000.2565.90.4240.000.840加标回收率Pi（%）90.583.282.6标准方法要求（%）47~11947~11947~119平行样品编号2,4-二甲酚加标量浓度1浓度2浓度3（mg/kg）样品加标样品样品加标样品样品加标样品低中高测定结果（mg/kg）10.000.2380.000.4290.000.9560.2790.5031.00320.000.2690.000.4450.000.6850.2800.5071.00430.000.2670.000.4420.000.9980.2800.5091.01340.000.2980.000.4570.000.7510.2880.5161.03450.000.2410.000.4570.000.7470.2840.5141.03060.000.2710.000.4380.000.7400.2810.5101.020平均值`xi、`yi（mg/kg）0.000.2640.000.4450.000.813加标回收率Pi（%）93.587.280.0标准方法要求（%）47~11947~11947~119平行样品编号萘加标量浓度1浓度2浓度3（mg/kg）样品加标样品样品加标样品样品加标样品低中高测定结果（mg/kg）10.000.1450.000.3700.000.8460.2790.5031.00320.000.1540.000.2770.000.5870.2800.5071.00430.000.1720.000.2740.000.8740.2800.5091.01340.000.1770.000.2750.000.6430.2880.5161.03450.000.1470.000.3650.000.6340.2840.5141.03060.000.1510.000.3740.000.6270.2810.5101.020平均值`xi、`yi（mg/kg）0.000.1570.000.3230.000.702加标回收率Pi（%）55.863.369.1标准方法要求（%）47~11947~11947~119判定验证结果满足标准要求续表平行样品编号2-甲基萘加标量浓度1浓度2浓度3（mg/kg）样品加标样品样品加标样品样品加标样品低中高测定结果（mg/kg）10.000.1660.000.3820.000.8660.2790.5031.00320.000.1870.000.3220.000.6120.2800.5071.00430.000.1930.000.3220.000.8850.2800.5091.01340.000.2080.000.3230.000.6720.2880.5161.03450.000.1710.000.3790.000.6660.2840.5141.03060.000.1860.000.3810.000.6560.2810.5101.020平均值`xi、`yi（mg/kg）0.000.1850.000.3520.000.726加标回收率Pi（%）65.569.071.4标准方法要求（%）47~11947~11947~119平行样品编号2,4,6-三氯酚加标量浓度1浓度2浓度3（mg/kg）样品加标样品样品加标样品样品加标样品低中高测定结果（mg/kg）10.000.2040.000.3570.000.9070.2790.5031.00320.000.2260.000.3830.000.6630.2800.5071.00430.000.2330.000.3940.000.9570.2800.5091.01340.000.2540.000.3990.000.7450.2880.5161.03450.000.2070.000.3880.000.7390.2840.5141.03060.000.2280.000.3660.000.7270.2810.5101.020平均值`xi、`yi（mg/kg）0.000.2250.000.3810.000.789加标回收率Pi（%）79.874.777.7标准方法要求（%）47~11947~11947~119平行样品编号2,4,5-三氯酚加标量浓度1浓度2浓度3（mg/kg）样品加标样品样品加标样品样品加标样品低中高测定结果（mg/kg）10.000.1970.000.3810.000.9040.2790.5031.00320.000.2180.000.3800.000.6900.2800.5071.00430.000.2240.000.3940.001.0010.2800.5091.01340.000.2450.000.4020.000.7680.2880.5161.03450.000.1990.000.3740.000.7440.2840.5141.03060.000.2200.000.3540.000.7590.2810.5101.020平均值`xi、`yi（mg/kg）0.000.2170.000.3810.000.811加标回收率Pi（%）76.974.779.8标准方法要求（%）47~11947~11947~119判定验证结果满足标准要求续表平行样品编号2-硝基苯胺加标量浓度1浓度2浓度3（mg/kg）样品加标样品样品加标样品样品加标样品低中高测定结果（mg/kg）10.000.2090.000.3910.000.9510.2790.5031.00320.000.2330.000.4010.000.6990.2800.5071.00430.000.2380.000.4050.000.9880.2800.5091.01340.000.2600.000.4060.000.7740.2880.5161.03450.000.2110.000.4140.000.7780.2840.5141.03060.000.2350.000.4030.000.7660.2810.5101.020平均值`xi、`yi（mg/kg）0.000.2310.000.4030.000.826加标回收率Pi（%）81.779.181.2标准方法要求（%）47~11947~11947~119平行样品编号苊烯加标量浓度1浓度2浓度3（mg/kg）样品加标样品样品加标样品样品加标样品低中高测定结果（mg/kg）10.000.1360.000.3670.000.8480.2790.5031.00320.000.1420.000.2650.000.5860.2800.5071.00430.000.1640.000.2640.000.8820.2800.5091.01340.000.1690.000.2590.000.6480.2880.5161.03450.000.1380.000.3560.000.6480.2840.5141.03060.000.1390.000.3650.000.6270.2810.5101.020平均值`xi、`yi（mg/kg）0.000.1480.000.3130.000.707加标回收率Pi（%）52.461.369.5标准方法要求（%）47~11947~11947~119判定验证结果满足标准要求平行样品编号苊加标量浓度1浓度2浓度3（mg/kg）样品加标样品样品加标样品样品加标样品低中高测定结果（mg/kg）10.000.1550.000.3680.000.8520.2790.5031.00320.000.1650.000.2960.000.5970.2800.5071.00430.000.1830.000.2960.000.8830.2800.5091.01340.000.1910.000.2920.000.6580.2880.5161.03450.000.1570.000.3640.000.6560.2840.5141.03060.000.1640.000.3700.000.6390.2810.5101.020平均值`xi、`yi（mg/kg）0.000.1690.000.3310.000.714加标回收率Pi（%）59.964.970.2标准方法要求（%）47~11947~11947~119判定验证结果满足标准要求续表平行样品编号4-硝基苯酚加标量浓度1浓度2浓度3（mg/kg）样品加标样品样品加标样品样品加标样品低中高测定结果（mg/kg）10.000.2340.000.3830.001.0690.2790.5031.00320.000.2710.000.4710.000.7810.2800.5071.00430.000.2630.000.4730.001.0200.2800.5091.01340.000.3020.000.4840.000.8840.2880.5161.03450.000.2370.000.4370.000.8780.2840.5141.03060.000.2750.000.4080.000.8670.2810.5101.020平均值`xi、`yi（mg/kg）0.000.2640.000.4430.000.916加标回收率Pi（%）93.486.890.1标准方法要求（%）47~11947~11947~119平行样品编号芴加标量浓度1浓度2浓度3（mg/kg）样品加标样品样品加标样品样品加标样品低中高测定结果（mg/kg）10.000.1540.000.3820.000.8520.2790.5031.00320.000.1600.000.2880.000.5940.2800.5071.00430.000.1810.000.2880.000.8770.2800.5091.01340.000.1860.000.2830.000.6480.2880.5161.03450.000.1550.000.3690.000.6520.2840.5141.03060.000.1580.000.3800.000.6300.2810.5101.020平均值`xi、`yi（mg/kg）0.000.1660.000.3320.000.709加标回收率Pi（%）58.765.169.7标准方法要求（%）47~11947~11947~119判定验证结果满足标准要求平行样品编号菲加标量浓度1浓度2浓度3（mg/kg）样品加标样品样品加标样品样品加标样品低中高测定结果（mg/kg）10.000.1560.000.3810.000.8210.2790.5031.00320.000.1620.000.2670.000.5840.2800.5071.00430.000.1860.000.2670.000.8270.2800.5091.01340.000.1900.000.2640.000.6270.2880.5161.03450.000.1580.000.3610.000.6190.2840.5141.03060.000.1590.000.3740.000.6020.2810.5101.020平均值`xi、`yi（mg/kg）0.000.1690.000.3190.000.680加标回收率Pi（%）59.762.666.9标准方法要求（%）47~11947~11947~119判定验证结果满足标准要求续表平行样品编号蒽加标量浓度1浓度2浓度3（mg/kg）样品加标样品样品加标样品样品加标样品低中高测定结果（mg/kg）10.000.1660.000.3980.000.8240.2790.5031.00320.000.1720.000.2790.000.5860.2800.5071.00430.000.1980.000.2780.000.8300.2800.5091.01340.000.2040.000.2710.000.6290.2880.5161.03450.000.1680.000.3770.000.6220.2840.5141.03060.000.1670.000.3910.000.6030.2810.5101.020平均值`xi、`yi（mg/kg）0.000.1790.000.3320.000.682加标回收率Pi（%）63.465.267.1标准方法要求（%）47~11947~11947~119平行样品编号邻苯二甲酸二正丁酯加标量浓度1浓度2浓度3（mg/kg）样品加标样品样品加标样品样品加标样品低中高测定结果（mg/kg）10.000.1380.000.3870.000.7890.2790.5031.00320.000.1340.000.2230.000.5510.2800.5071.00430.000.1600.000.2200.000.7850.2800.5091.01340.000.1530.000.2170.000.5860.2880.5161.03450.000.1420.000.3540.000.5790.2840.5141.03060.000.1370.000.3710.000.5560.2810.5101.020平均值`xi、`yi（mg/kg）0.000.1440.000.2950.000.641加标回收率Pi（%）51.058.063.1标准方法要求（%）47~11947~11947~119判定验证结果满足标准要求平行样品编号荧蒽加标量浓度1浓度2浓度3（mg/kg）样品加标样品样品加标样品样品加标样品低中高测定结果（mg/kg）10.000.1630.000.3930.000.8560.2790.5031.00320.000.1690.000.2800.000.6050.2800.5071.00430.000.1940.000.2780.000.8640.2800.5091.01340.000.2000.000.2790.000.6530.2880.5161.03450.000.1660.000.3770.000.6470.2840.5141.03060.000.1650.000.3850.000.6280.2810.5101.020平均值`xi、`yi（mg/kg）0.000.1760.000.3320.000.709加标回收率Pi（%）62.465.169.7标准方法要求（%）47~11947~11947~119判定验证结果满足标准要求续表平行样品编号芘加标量浓度1浓度2浓度3（mg/kg）样品加标样品样品加标样品样品加标样品低中高测定结果（mg/kg）10.000.1740.000.3880.000.8540.2790.5031.00320.000.1850.000.3040.000.6130.2800.5071.00430.000.2060.000.3020.000.8690.2800.5091.01340.000.2180.000.2990.000.6620.2880.5161.03450.000.1770.000.3830.000.6580.2840.5141.03060.000.1850.000.3830.000.6410.2810.5101.020平均值`xi、`yi（mg/kg）0.000.1910.000.3430.000.716加标回收率Pi（%）67.667.370.5标准方法要求（%）47~11947~11947~119平行样品编号苯并[a]蒽加标量浓度1浓度2浓度3（mg/kg）样品加标样品样品加标样品样品加标样品低中高测定结果（mg/kg）10.000.2050.000.3960.000.9110.2790.5031.00320.000.2190.000.3620.000.6500.2800.5071.00430.000.2320.000.3650.000.9340.2800.5091.01340.000.2460.000.3580.000.7140.2880.5161.03450.000.2070.000.4240.000.7180.2840.5141.03060.000.2190.000.3980.000.6970.2810.5101.020平均值`xi、`yi（mg/kg）0.000.2210.000.3840.000.771加标回收率Pi（%）78.475.375.8标准方法要求（%）47~11947~11947~119判定验证结果满足标准要求平行样品编号屈加标量浓度1浓度2浓度3（mg/kg）样品加标样品样品加标样品样品加标样品低中高测定结果（mg/kg）10.000.1490.000.3670.000.7980.2790.5031.00320.000.1590.000.2640.000.5630.2800.5071.00430.000.1790.000.2610.000.8300.2800.5091.01340.000.1900.000.2620.000.6210.2880.5161.03450.000.1500.000.3400.000.6180.2840.5141.03060.000.1600.000.3620.000.5970.2810.5101.020平均值`xi、`yi（mg/kg）0.000.1640.000.3090.000.671加标回收率Pi（%）58.260.666.0标准方法要求（%）47~11947~11947~119判定验证结果满足标准要求续表平行样品编号邻苯二甲酸二正辛酯加标量浓度1浓度2浓度3（mg/kg）样品加标样品样品加标样品样品加标样品低中高测定结果（mg/kg）10.000.1380.000.3240.000.8570.2790.5031.00320.000.1370.000.2160.000.5710.2800.5071.00430.000.1660.000.2120.000.9130.2800.5091.01340.000.1650.000.2080.000.6380.2880.5161.03450.000.1390.000.3110.000.6340.2840.5141.0