土壤有效硼的测定 编制说明

1《土壤有效硼的测定（征求意见稿）》标准编制说明一、工作简况，包括任务来源、制定背景、起草过程等（一）任务来源家标准计划及相关标准外文版计划的通知》（国标委发〔2023〕582和螯合态硼的数量比水溶态硼大得多，可占全硼的15-91%，但与作（三）起草过程本标准由农业农村部耕地质量监测保护中心主持成立标准编写30农业农村部耕地质量监测1农业农村部肥料质量检验2四川省农业科学院农业资3456所789华中农业大学资源与环境农业农村部肥料质量检验谱尼测试集团股份有限公司4二、国家标准编制原则、主要内容及其确定依据，修订国家标准时，还包括修订前后技术内容的对比（一）标准编制原则5制标准的规范性。（二）主要内容本标准规定了使用聚四氟乙烯消煮管在多孔石墨消煮炉上加热合等离子体发射光谱法和电感耦合等离子体质谱法测定土壤中有效使用聚四氟乙烯消煮管在多孔石墨消煮炉上加热的方式提取土（三）主要内容确定依据6加热提取法和微波提取法等。国内测定土壤有效硼的标准有NY/T149-1990（姜黄素比色法）、NY/T1121.8-2006（甲亚胺比色法）、感耦合等离子体质谱法，天津市地方标准），前四个标准均是采用不利于批量化操作，且煮沸过程中的沸腾强度也存在因人而异的现7文研究表明水浴加热法还存在测定结果略低于沸水回流提取法的问8不确定度时间时间时间时间时间时间NSA-4NSA-21.3.2聚四氟乙烯消煮管：聚四氟乙烯材料的器皿存在无硼污9质和有参考推荐值的参比物质开展加热温度试验研究，结果见表3。质编号不确定度NSA-41NSA-2加热40分钟，至加热结束微沸时间不至加热结束无肉眼可见加热后期有加热后期大量水蒸气逸）（四川省农业科学研究院农业资源与环境研究所（单位编号2）、四川进行2次平行测定，提取后的土壤硼采用ICP-OES法（波长249.773nm）进行定量检测，同时观察记录加热前后土液重量变化，1单位编号100281准确性，但需严格控制在无水条件下显色，操作复杂费时，一些测11镍6Li/72Ge1进行分析，结果表明，208.8nm、208.9nm谱线灵敏度相对较低，干扰较小，无需进行干扰的校正。但若提取液中铁的含量超过硼的150倍，就需要校正铁对测定硼元素的质谱干扰影响。故本标准选择B三、试验验证的分析、综述报告，技术经济论证，预期的经济效益、社会效益和生态效益（一）试验验证的分析、综述报告（GB/T27417-2017）《测量方法与结果的准确度(正确度与精密度)》1四川省农业科学研究院农业资源与环境研究所（单位编号2）、四川室进行了方法检出限/定量下限的研究，结果见表8，同时组织其他试验（样品空白试验用石英砂代替土壤样品，石英砂纯度和规格为），为：0.12mg/kg，定量下限为：0.27mg/kg；姜黄素比色法0.02mg/kg，定量下限为：0.05mg/kg；ICP-MS法方法检出限为：0.02mg/kg，定量下限为：0.04mg/1测定方法甲亚胺比色法姜黄素比色法ICP-OES法ICP-MS法单位编号128128128128测定结果（mg/kg）10.03560.09000.04100.03340.15000.03700.01120.01600.00480.02040.02700.006720.02430.05000.01800.03540.13000.05200.01100.01400.01020.01900.02200.010030.09060.06000.10100.03260.19000.04200.00820.01800.00540.01680.02300.005240.08600.07000.03700.02860.16000.07900.01520.01400.00760.01600.01800.007950.03790.07000.01300.02060.16000.01800.01480.01800.00620.01390.02100.007460.06120.08000.04400.02660.12000.07200.00640.01200.01050.01440.01700.009070.02710.07000.06500.03940.13000.03200.00540.01400.00610.01380.01700.003480.05180.09000.10200.03090.12000.04500.01030.01200.00660.01630.01600.006390.04320.08000.02900.02790.17000.01400.02200.01200.00830.02070.01500.00810.02820.06000.07200.03080.16000.10100.02440.01200.00940.01360.01400.0059平均值x(mg/kg)0.0490.0600.0520.0310.1500.0490.0130.0140.0080.0160.0190.007标准偏差S0.0240.0100.0300.0050.0200.0260.0060.0020.0020.0030.0040.002方法检出限MDL(mg/kg)0.1200.0900.1400.0460.2100.1300.0320.0210.0130.0250.0310.012方法定量限MQL(mg/kg)0.2870.1600.3600.0820.3500.3100.0760.0380.0270.0440.0610.025平均方法检出限MDL(mg/kg)0.120.130.020.02平均方法定量限MQL(mg/kg)0.270.250.050.041选择7个土壤样品进行测试，每个样品采用同样的前处理方式、6379.4-2006）给出的方法对测定方法进行偏法的正确度。再按照《测量方法与结果的准确度(正确度与精密度)》（GB/T6379.2-2004）给出的方法，计算重复性限r和再现性限R；西红壤GBW(E)070357(ASA-12a)、山东棕壤GBW(E)07西藏土壤（XZ-07），国家标准物质和实际土壤均涵盖高、中、低浓2单位编号GBW(E)070357GBW(E)070358GBW(E)070352GBW07459aSC-06GX-08XZ-071/0.962.287.690.4712.02/1.252.128.430.5611.96/1.151.878.880.5912.05/1.231.888.290.4812.27/1.071.787.970.5411.76/1.131.978.460.5112.3320.462.367.220.5712.310.442.187.790.5512.820.441.907.840.5813.290.472.398.020.6012.410.462.537.170.5612.820.442.526.930.6412.9030.370.350.370.330.340.3540.370.810.918.590.7813.900.360.810.868.550.5315.100.340.780.918.620.529.780.310.800.847.840.599.400.360.800.908.650.5812.600.340.800.888.590.5412.5050.349.490.5613.600.369.880.5613.50单位编号GBW(E)070357GBW(E)070358GBW(E)070352GBW07459aSC-06GX-08XZ-070.359.440.6012.300.359.350.5912.100.349.510.6212.200.349.350.5912.3060.581.242.600.6012.900.361.022.450.7410.300.461.252.520.9011.800.211.522.480.6610.300.371.112.590.5410.400.341.392.690.6911.607///7.480.5711.00///7.910.5711.02///7.680.5810.72///8.440.615.78///8.100.566.00///7.980.5110.8680.410.908.310.419.780.370.887.330.469.970.330.828.350.519.670.390.867.440.4410.600.380.857.720.4210.000.370.868.070.4610.2090.320.752.010.7515.100.300.780.7214.600.320.760.8415.300.300.782.060.7214.900.310.760.814.900.290.740.7615.20单位编号GBW(E)070357GBW(E)070358GBW(E)070352GBW07459aSC-06GX-08XZ-070.402.159.440.6913.920.382.329.400.6614.200.392.229.870.6713.970.382.279.150.6914.000.402.259.440.7013.160.412.329.600.6513.280.421.043.3811.310.5620.200.310.933.2511.480.4819.340.350.883.3711.870.510.8419.310.350.893.8013.370.490.9022.140.400.834.0713.050.480.8919.950.370.843.9012.980.5721.620.412.509.490.7713.400.362.549.770.8313.400.422.519.170.8513.600.362.348.880.8913.500.360.972.248.990.8513.900.342.289.630.8014.300.310.869.930.7817.000.380.892.249.970.772.0817.500.330.962.0310.100.7317.700.322.109.880.792.0217.900.350.852.1510.500.782.1617.800.350.972.089.560.732.1017.60注：共71组426个实验室数据参与统计分析，另离群剔除16组数据、4组缺失数据，其中加粗斜体数据为离群剔除数据，“/”为验证实验室未提交验证结果。单位编号GBW(E)070357GBW(E)070358GBW(E)070352GBW07459aSC-06GX-08XZ-071/0.837.870.5712.17/0.776.930.5412.81/0.857.670.5012.37/0.878.370.6212.09/0.858.530.5711.07/0.858.450.6211.9920.341.987.360.5010.580.360.842.708.250.4710.400.370.861.898.310.4912.070.320.902.078.550.4910.700.352.227.840.5011.410.340.931.957.660.5510.40340.380.922.016.190.660.9010.600.160.962.016.190.620.9312.300.282.007.040.650.9212.400.380.982.017.070.670.9812.500.432.027.070.680.9617.700.432.027.070.670.9815.7050.352.2210.400.4713.300.370.982.1510.400.4712.80单位编号GBW(E)070357GBW(E)070358GBW(E)070352GBW07459aSC-06GX-08XZ-070.350.992.0110.600.4712.900.400.9810.600.5012.800.380.9910.600.5012.800.370.9810.600.5312.8060.360.7810.300.441.7811.200.360.8410.300.561.3011.100.400.8910.300.531.8710.400.460.899.780.441.2811.300.400.849.660.481.9111.600.400.839.440.571.8711.107///7.190.491.3913.61///8.170.61.1613.86///7.110.561.1212.51///8.500.541.0213.77///8.190.500.8913.98///7.730.361.0913.8780.282.089.020.380.9213.900.322.119.560.4614.300.270.959.100.340.8514.400.270.892.0410.400.460.9513.600.250.972.109.480.480.8814.000.300.912.0410.000.410.9914.8090.330.862.3912.900.6416.700.340.812.4911.700.8416.800.340.962.4713.100.8115.900.322.7011.800.6616.700.350.922.6011.900.6816.200.332.5412.200.6616.80单位编号GBW(E)070357GBW(E)070358GBW(E)070352GBW07459aSC-06GX-08XZ-070.302.279.760.5512.780.350.982.409.150.5613.230.312.259.680.5213.870.322.359.820.5714.070.342.509.870.5512.790.302.539.500.5113.270.332.6510.920.7813.800.362.5610.220.8113.480.422.479.960.820.9214.120.332.0510.600.820.9215.200.280.942.2710.100.6714.680.290.992.2411.060.720.9315.260.460.972.129.690.8215.100.432.319.990.6813.300.350.992.038.810.6514.200.332.078.690.8013.700.350.952.038.460.8115.400.392.149.050.6915.200.330.872.418.640.782.0817.400.332.268.970.742.1717.700.380.932.1310.000.762.1417.200.320.952.5410.900.792.1217.300.360.982.3210.500.732.0617.700.340.932.149.850.7517.90注：共81组486个实验室数据参与统计分析，另离群剔除6组数据、4组缺失数据，其中加粗斜体数据为离群剔除数据，“/”为验证实验室未提交验证结果。2单位编号GBW(E)070357GBW(E)070358GBW(E)070352GBW07459aSC-06GX-08XZ-071/0.862.048.630.4812.11/0.852.099.090.4312.79/0.902.009.290.4512.71/0.869.460.4512.22/0.872.018.980.4312.15/0.899.330.4612.5320.290.942.108.260.4912.220.280.952.008.380.4911.900.280.968.360.4912.380.290.952.028.380.4811.660.280.912.158.240.4912.260.280.912.098.340.4912.2630.300.872.119.420.4810.300.300.792.328.630.490.8910.100.310.872.289.840.530.9611.500.350.872.158.580.450.9311.700.350.872.288.430.4911.200.330.922.108.870.5611.2040.389.040.6716.400.388.850.6113.700.380.972.049.270.6414.600.320.998.760.6214.600.339.040.5415.400.380.989.070.6515.6050.310.852.0011.700.390.9211.50单位编号GBW(E)070357GBW(E)070358GBW(E)070352GBW07459aSC-06GX-08XZ-070.300.8111.100.5111.700.330.7810.800.390.9211.800.330.8011.100.5011.300.320.7910.800.420.9811.600.370.7810.800.510.9711.0060.250.822.0510.340.4312.500.230.802.0010.400.5313.400.210.812.1110.660.5312.500.220.802.0710.120.5513.100.200.842.0410.400.4613.300.210.842.0710.200.6012.707///9.200.572.0514.00///9.120.572.0012.92///9.670.582.0812.26///8.230.612.1513.66///8.990.562.1114.37///8.890.512.11/80.310.878.590.4611.500.290.908.660.5212.000.300.918.840.5111.600.290.862.138.930.4511.100.330.842.028.970.4911.100.280.949.060.4710.8090.302.4211.200.7715.300.302.5211.000.6915.000.312.6411.000.6614.900.290.992.5511.500.7215.800.292.5810.600.6814.800.292.6511.400.7515.60单位编号GBW(E)070357GBW(E)070358GBW(E)070352GBW07459aSC-06GX-08XZ-070.322.319.420.6013.400.312.319.170.6013.290.312.419.210.6113.390.322.399.050.5913.410.322.379.460.5813.120.312.369.150.5713.430.270.942.2711.860.4515.180.250.942.3111.100.4814.920.270.932.3010.840.4814.760.280.892.3911.080.4815.820.270.752.4011.800.450.9815.400.270.792.4011.220.4414.920.232.799.750.7715.000.202.509.630.7715.500.212.509.240.6915.900.212.498.710.6214.500.192.469.330.7115.700.202.359.460.8015.300.360.892.3810.600.712.2119.100.360.982.1410.100.712.1418.300.330.942.229.690.672.1619.200.330.981.9810.200.712.2018.100.340.981.989.830.712.3018.500.340.981.979.500.682.3218.20注：共78组468个实验室数据参与统计分析，另离群剔除9组数据、4组缺失数据，其中加粗斜体数据为离群剔除数据，“/”为验证实验室未提交验证结果。21///////////2340.510.610.600.520.580.493560.260.420.250.500.220.520.230.530.210.450.210.587///12.78///13.43///13.50///6.44///6.11///13.53890.210.770.200.780.210.760.200.680.200.530.200.562.350.7016.501.970.7015.002.020.6214.902.160.6913.801.900.6515.402.060.8114.50332.2正确度分析：异常结果剔除后，以13家验证单位的4个国家95%置信区间，若置信区间包含0，则测定方法的偏倚在水平α=5%GBW(E)070357(ASA-12a)GBW(E)070358(ASA-13a)GBW(E)070352(ASA-20a)GBW07459a(ASA-8a)参考值（mg/kg）0.340.932.209.70胺比色法总体平均值（mg/kg）0.370.932.149.25置信区间0~0.053-0.068~0.077-0.231~0.108-1.210~0.317偏倚估计不显著不显著不显著不显著姜黄素比色法总体平均（mg/kg）0.340.962.089.35置信区间-0.016~0.025-0.016~0.068-0.278~0.046-1.130~0.432偏倚估计不显著不显著不显著不显著ICP-OES法总体平均（mg/kg）0.320.932.149.67置信区间-0.034~-0.001-0.050~0.054-0.196~0.074-0.567~0.507偏倚估计不显著不显著不显著不显著ICP-MS法总体平均（mg/kg）0.320.922.129.47置信区间-0.034~-0.002-0.053~0.039-0.189~0.035-0.842~0.389偏倚估计不显著不显著不显著不显著2.3.1重复性限和再现性限的确定：依据获得的表9～12基础数33单位编号SiSiSiSiSiSiSi1//////8.290.410.530.050.0512.070.2120.450.010.03//7.500.440.580.030.0512.760.363//0.910.032.070.049.600.180.570.020.0310.650.1640.350.020.800.01//8.470.31//0.06//50.350.010.020.039.500.200.590.020.0212.670.696////2.560.0911.050.65//0.10//7//////7.930.330.570.030.02//80.380.030.860.030.067.870.440.450.040.0610.040.3390.310.010.760.020.1012.030.240.770.050.0615.000.250.390.010.032.260.069.480.240.680.020.0213.760.430.370.04//////0.520.040.970.10//0.380.030.042.400.139.320.360.830.040.1113.680.350.340.030.920.062.090.109.990.310.760.032.050.0817.580.323统计水平参数///Sr2（重复性方差）SL2（实验室间方差）sR（标准差）R（再现性限）范围或水平m重复性限r再现性限Rr=0.0853m+0.0513注：精密度依据GB/T6379.2-2004，由13个实验室对7个有效硼含量水平的样品进行试验得到，71组426个实验数据参与统3根据实验数据统计分析，姜黄素比色法测定土壤中有效硼重复性限r为0.072mg/kg～1.162mg/GBW(E)070357GBW(E)070358GBW(E)070352GBW07459aSC-06GX-08XZ-07SiSiSiSiSiSiSi1//0.840.030.147.970.610.570.050.0812.090.5820.350.020.930.08//8.000.450.500.030.0410.930.6730.330.010.880.030.099.620.460.560.030.0110.770.104//0.062.010.016.770.450.660.020.950.03//50.370.020.990.012.030.1310.530.100.490.020.0812.900.2060.400.030.840.040.039.960.380.50///11.127//////7.820.570.510.08//13.600.5580.280.020.970.072.060.059.590.530.420.050.940.0714.170.4290.340.010.940.102.530.1112.270.600.720.090.0616.520.380.320.020.042.380.129.630.270.540.020.1013.340.540.340.050.09//10.480.450.770.060.1014.420.740.390.050.062.120.119.120.600.740.080.1214.480.880.340.020.940.052.300.169.810.870.760.022.090.0717.530.273统计水平参数///Sr2（重复性方差）SL2（实验室间方差）sR（标准差）R（再现性限）范围或水平m重复性限r再现性限Rr=0.0829m+0.044注：精密度依据GB/T6379.2-2004，由13个实验室对7个有效硼含量水平的样品进行试验得到，81组486个实验数据参与统3根据实验数据统计分析，ICP-OES法测定土壤中有效硼重复性限r为0.064mg/kg～1.191mg/kg，再表20平均值与标准偏差统计分析表—ICP-OE单位编号GBW(E)070357GBW(E)070358GBW(E)070352GBW07459aSC-06GX-08XZ-07SiSiSiSiSiSiSi//0.870.020.089.130.300.450.020.0512.420.300.280.010.940.022.050.078.330.060.490.000.0212.110.270.320.020.870.042.210.108.960.550.500.040.0811.000.650.360.030.030.099.010.180.620.050.04//0.330.020.800.030.0311.050.350.450.060.980.0611.480.29//0.820.022.060.0410.350.190.520.060.0512.920.40//////9.020.470.570.032.080.05//0.300.020.890.040.118.840.180.480.030.0711.350.430.300.010.032.560.0911.120.330.710.040.0615.230.400.320.010.012.360.049.240.160.590.010.0213.340.12////2.350.0611.320.420.460.020.0915.170.39//0.02//9.350.370.730.070.0815.320.510.340.010.960.04//9.990.400.700.022.220.0718.570.474表21精密度相关参数计算结果表—ICP-OE统计水平参数///Sr2（重复性方差）SL2（实验室间方差）sR（标准差）R（再现性限）表22土壤中有效硼含量的精密度—I范围或水平m重复性限r再现性限Rr=0.0853m+0.0365注：精密度依据GB/T6379.2-2004，由13个实验室对7个有效硼含量水平的样品进行试验得到，78组468个实验数据参与统4根据实验数据统计分析，ICP-MS法测定土壤中有效硼重复性限r为0.071mg/kg～1.082mg/kg，再现性限R为表23平均值与标准偏差统计分析表—ICP-MSSiSiSiSiSiSiSi1//0.810.010.097.920.330.410.010.0512.320.3520.300.000.930.022.100.068.080.190.500.020.0311.570.2030.320.010.810.022.110.088.650.230.500.020.0811.250.5840.300.020.880.040.049.660.28//0.0713.550.5450.340.010.920.020.0210.550.240.470.010.920.0310.100.066//0.810.042.340.1010.520.56//0.0712.220.417//////8.660.600.610.040.11//80.290.020.990.032.100.099.330.320.510.020.0712.580.3390.320.010.022.410.0512.020.290.780.030.0616.020.320.320.010.970.022.120.089.380.270.560.010.0313.760.25////2.090.109.930.430.310.020.560.0313.960.310.370.020.06//8.680.48//0.09//0.360.010.960.052.400.099.770.400.720.012.340.0818.530.214表24精密度相关参数计算结果表—ICP-MS统计水平参数GBW(E)070357GBW(E)070358GBW(E)070352GBW07459aSC-06GX-08XZ-070.34±0.60.93±0.142.2±0.49.7±1.2SL2（实验室间方差）r（重复性限）R（再现性限）m（含量平均值）表25土壤中有效硼含量的精密度—I范围或水平m重复性限r再现性限Rr=0.0829m+0.044注：精密度依据GB/T6379.2-2004，由13个实验室对7个有效硼含量水平的样品进行试验得到，78组463个实验数据参与统4有效硼含量≥0.5mg/kg时，四种检测方法的临界相对相差基本小于4单位编号甲亚胺比色法姜黄素比色法ICP-OES法ICP-MS法GBW(E)070357(ASA-12a)GBW(E)070358(ASA-13a)GBW(E)070352(ASA-20a)GBW07459a(ASA-8a)GBW(E)070357(ASA-12a)GBW(E)070358(ASA-13a)GBW(E)070352(ASA-20a)GBW07459a(ASA-8a)GBW(E)070357(ASA-12a)GBW(E)070358(ASA-13a)GBW(E)070352(ASA-20a)GBW07459a(ASA-8a)GBW(E)070357(ASA-12a)GBW(E)070358(ASA-13a)GBW(E)070352(ASA-20a)GBW07459a(ASA-8a)0.34±0.60.93±0.142.2±0.49.7±1.20.34±0.60.93±0.142.2±0.49.7±1.20.34±0.60.93±0.142.2±0.49.7±1.20.34±0.60.93±0.142.2±0.49.7±1.21///0.41/0.030.140.61/0.020.080.30/0.010.090.3320.010.03/0.440.020.08/0.450.010.020.070.060.000.020.060.193/0.030.040.180.010.030.090.460.020.040.100.550.010.020.080.2340.020.01/0.31/0.060.010.450.030.030.090.180.020.040.040.2850.010.020.030.200.020.010.130.100.020.030.030.350.010.020.020.246//0.090.650.030.040.030.38/0.020.040.19/0.040.100.567///0.33///0.57///0.47///0.6080.030.030.060.440.020.070.050.530.020.040.110.180.020.030.090.3290.010.020.100.240.010.100.110.600.010.030.090.330.010.020.050.290.010.030.060.240.020.040.120.270.010.010.040.160.010.020.080.270.04///0.050.09/0.45//0.060.42//0.100.430.030.040.130.360.050.060.110.60/0.02/0.370.020.06/0.480.030.060.100.310.020.050.160.870.010.04/0.400.010.050.090.40标准差平均值0.020.030.080.340.030.060.090.490.020.030.070.300.010.030.070.35两平行临界相差0.060.080.210.960.070.160.260.040.07