GB/T 5750.6生活饮用水标准检验方法 金属指标应用

智能文字提取功能测试中

摘要：本方法根据《GB/T 5750.6-2006 生活饮用水标准检验方法 金属指标》，采用RPIC-2017型离子色谱仪，在7分钟内即完成锂离子、钠离子、钾离子、镁离子与钙离子的洗脱。2000倍浓度范围内线性相关系数0.999907〜0.999993；同时样品的保留时间RSD＜0.5%，浓度RSD＜3%；加标回收率80%〜115%。可以满足水质样品中阳离子检测要求。色谱条件：离子色谱仪：RPIC-2017型离子色谱仪（青岛睿谱分析仪器有限公司）色谱柱：CS12A(4×250mm×9μm) （赛默飞）淋洗液：25mM MSA淋洗液（手动配置）流速：1.0mL/min抑制器：WLK-8C(4mm)免维护抑制器（青岛睿谱分析仪器有限公司）检测器：动态量程电导检测器进样体积：25mL温度：30℃ 空白溶液色谱曲线：图1 空白谱图空白谱图与曲线中最低点叠加图2 空白与标准溶液最低点谱图叠加色谱曲线叠加图：5个浓度点，每个浓度点6个平行样品的色谱图叠加，叠加图如下。图3 五个浓度点、每浓度点六针平行谱图叠加 外标曲线：根据表1中的浓度做标准曲线，并计算外标曲线方程及相关系数。表1 标准溶液浓度离子浓度Li+0.0150.030.3330Na+0.050.1110100K+0.1250.252.525250Mg2+0.020.040.4440Ca2+0.20.4440400图4 五个浓度点、每浓度点六针平行谱图叠加表2 检测离子及峰面积响应值离子浓度ppm峰面积μS·s（六针平行）std1Li+0.0150.77260.77680.7780.77580.7840.7806Na+0.050.86310.84820.8380.84850.8460.8413K+0.1251.33341.36591.28351.35211.35531.3605Mg2+0.020.28410.22450.27980.27840.26070.2459Ca2+0.24.93724.69664.54455.06774.87764.8276std2Li+0.031.58361.58481.58311.58671.58731.5926Na+0.11.71881.71761.71591.71651.71651.7108K+0.252.77152.77062.77022.76952.77712.7731Mg2+0.040.50660.50340.51850.50810.51460.518Ca2+0.48.69488.80548.59048.62138.71238.599std3Li+0.316.073516.096516.108416.103116.105716.1213Na+117.506217.517617.567317.518117.525217.578K+2.528.392928.384928.367628.480428.430428.4425Mg2+0.44.85164.85854.82654.85384.87494.8586Ca2+471.739172.508670.895772.543972.256972.2595std4Li+3160.3736160.6549160.7646160.866160.841161.9812Na+10175.278174.2236174.5549174.4763174.4325175.6831K+25287.4426287.6123287.9163288.1763289.6952288.3516Mg2+449.173449.1749.186749.087149.411549.1617Ca2+40740.0505740.624743.4776744.7966744.7249746.1407std5Li+301582.96911586.2251588.0591591.9391590.1211591.809Na+1001701.74841710.5081706.3051708.1811706.1571709.996K+2502760.3212766.2452769.072789.3242773.9492776.704Mg2+40539.8584543.0435543.2403543.6288543.2864544.1023Ca2+4007181.99367210.3577218.4697244.3917230.3587240.43 表3 阴离子与有机酸的外标曲线方程与相关系数离子外标曲线方程相关系数/rLi+Y=52.9378330239757X+0.5374915631059510.999993Na+Y=17.0636843111475X+1.078841096524620.999991K+Y=11.0826791085922X+2.746385206654350.99997Mg2+Y=13.5961763930835X-1.359980487298540.999907Ca2+Y=18.042191457432X+5.654658938482060.99998从表中可知阳离子在一定的浓度区间内与电导信号呈较好的一次线性关系。样品检测结果表4 样品检测结果及重复性数据样品离子保留时间(min)保留时间RSD含量(mg/L)含量RSD蓝瓶崂矿Li+2.402.402.402.402.402.400.05＜0.015＜0.015＜0.015＜0.015＜0.015＜0.015/Na+2.762.762.762.772.762.760.068.618.668.618.608.628.610.23K+3.683.683.673.683.673.670.070.340.340.330.330.340.330.84Mg2+4.554.554.554.554.554.550.065.145.135.145.145.155.150.18Ca2+5.425.435.425.435.425.420.0611.5511.5311.4911.5111.5611.540.23红瓶崂矿Li+2.402.402.402.402.402.410.070.020.020.020.020.020.022.77Na+2.782.782.782.782.782.780.0634.6134.5034.7334.5234.8334.540.38K+3.683.683.683.683.683.680.041.001.001.011.010.990.990.72Mg2+4.554.554.554.554.554.560.107.437.477.487.487.507.480.28Ca2+5.415.425.415.415.425.430.1018.9519.0419.0319.0118.9119.020.26伊刻活泉Li+2.412.402.402.402.402.400.140.040.040.040.040.040.041.55Na+2.782.762.762.762.762.760.3111.0111.0411.0411.0411.0511.040.12K+3.683.673.683.683.683.680.091.261.271.281.261.261.260.55Mg2+4.564.514.524.514.524.520.4038.5538.5438.6438.5738.8038.650.25Ca2+5.435.375.395.385.385.380.3620.6320.4320.5720.5020.5720.670.42屈臣氏Li+NANANANANANA/NANANANANANA/Na+2.752.752.752.752.752.750.03＜0.05＜0.05＜0.05＜0.05＜0.05＜0.05/K+3.683.683.673.673.683.670.035.245.255.275.255.255.250.19Mg2+4.544.534.534.534.534.540.0510.3810.7010.6810.7210.6510.821.40Ca2+NANANANANANA/NANANANANANA/悦活Li+2.402.402.402.402.402.400.090.040.040.040.040.040.040.79Na+2.762.762.762.762.762.760.078.428.418.418.428.428.420.07K+3.673.683.673.683.673.670.054.274.274.314.294.314.290.35Mg2+4.514.524.514.524.524.520.0811.0411.0211.0311.0411.0911.070.22Ca2+5.385.385.385.395.395.390.0710.1610.1310.0910.1610.1810.160.31木兰泉Li+2.412.402.402.402.402.400.13＜0.015＜0.015＜0.015＜0.015＜0.015＜0.015/Na+2.772.772.762.772.772.760.1015.9616.0516.0816.1416.0916.120.41K+3.693.683.683.683.683.680.161.141.141.141.151.141.140.50Mg2+4.504.504.504.504.504.510.0615.6715.8415.8215.7815.8115.860.43Ca2+5.365.355.355.355.355.360.0538.9239.1739.1539.1739.2339.210.29百岁山Li+2.402.402.402.402.402.400.05＜0.015＜0.015＜0.015＜0.015＜0.015＜0.015/Na+2.762.762.762.762.762.760.096.396.336.336.346.366.330.39K+3.683.683.683.683.683.690.062.302.302.302.302.312.300.23Mg2+4.544.544.544.534.544.540.042.082.092.092.092.092.100.32Ca2+5.415.415.425.415.415.410.058.568.578.698.618.638.630.58自来水Li+2.402.402.402.402.402.400.04＜0.015＜0.015＜0.015＜0.015＜0.015＜0.015/Na+2.792.782.782.782.782.780.1936.9837.9938.4538.6838.7638.861.86K+3.733.703.693.683.683.680.476.366.546.596.716.676.691.98Mg2+4.514.504.514.514.524.520.1330.9431.5931.8631.9732.0632.051.36Ca2+5.385.365.365.365.375.370.1248.3849.8650.2150.1550.4150.511.58雪水Li+NANANA//NANANA//Na+2.762.762.760.114.714.734.730.21K+3.683.683.680.050.060.060.062.99Mg2+4.544.544.550.071.401.411.410.38Ca2+5.425.435.430.107.627.787.821.40冷水江Li+2.402.402.40/0.02＜0.015＜0.015＜0.015//Na+2.762.762.760.056.126.146.160.27K+3.673.673.670.061.811.811.820.14Mg2+4.524.524.520.047.537.587.560.29Ca2+5.375.375.370.0336.2136.4336.570.49精密度：在已知的色谱条件下连续进样6次实际样品，结果如表4所示。从表中可知，阳离子的定量重复性均低于3.0%，说明仪器具有较高的稳定性。准确度将红瓶崂山矿泉水及蓝瓶崂山矿泉水分别加入标准样品，测试其回收率，结果如表5：表5 样品加标回收率样品离子加标回收率(%)平行1平行2平行3平行4平行5平行6蓝瓶崂矿Li+97.64101.1998.54101.32101.32101.50Na+101.71102.39102.04102.19102.15102.45K+103.41103.69103.89103.98103.96104.05Mg2+95.1696.5696.7296.8396.7397.10Ca2+105.02105.39105.84105.86106.15105.88红瓶崂矿Li+92.9893.2593.2593.4593.2593.18Na+90.7380.6080.6289.1884.2384.98K+102.77103.06103.24103.51103.53104.07Mg2+104.55103.15111.03114.64109.55103.75Ca2+104.93105.62106.52107.72106.11107.96  基线噪声、基线漂移与检测限：采集30分钟基线，在30分钟时注入系统0.2ppm的锂离子，切换进样阀至分析位，继续采集锂离子峰并记录谱图。图5 30分钟基线及0.2ppm锂离子数据图6 前30分钟基线噪声及漂移从图5及图6中可知，具有较低的噪声和漂移表6 基线噪声与漂移离子基线噪声基线漂移0.2ppm锂离子峰高检出限Li+0.00027μS/cm0.0049μS/cm1.7016μS/cm0.000317μg/g 结语：根据GB/T5750.6，使用RPIC-2017型离子色谱仪测定水质中的阳离子，基线噪声低，灵敏度高，线性、准确度、精密度较好。离子色谱报告 GB/T 5750.6生活饮用水标准检验方法金属指标应用报告 青岛睿谱分析仪器有限公司 摘要： 本方法根据《GB/T 5750.6-2006生活饮用水标准检验方法金属指标》，采用RPIC-2017型离子色谱仪，在7分钟内即完成锂离子、钠离子、钾离子、镁离子与钙离子的洗脱。2000倍浓度范围内线性相关系数 0.999907〜0.999993；同时样品的保留时间 RSD＜0.5%，浓度 RSD＜3%；加标回收率80%〜115%。可以满足水质样品中阳离子检测要求。 色谱条件： 离子色谱仪：RPIC-2017型离子色谱仪（青岛睿谱分析仪器有限公司） 色谱柱：CS12A(4×250mm×9μm) （赛默飞） 淋洗液：25mM MSA淋洗液（手动配置） 流速：1.0mL/min 抑制器：WLK-8C(4mm)免维护抑制器（青岛睿谱分析仪器有限公司） 检测器：动态量程电导检测器 进样体积：25L 温度：30℃ 空白溶液色谱曲线： 图 1空白谱图 空白谱图与曲线中最低点叠加 图 2空白与标准溶液最低点谱图叠加 色谱曲线叠加图： 5个浓度点，每个浓度点6个平行样品的色谱图叠加，叠加图如下。 图 3五个浓度点、每浓度点六针平行谱图叠加 外标曲线： 根据表1中的浓度做标准曲线，并计算外标曲线方程及相关系数。 表 1标准溶液浓度 离子 浓度 Li+ 0.015 0.03 0.3 3 30 Na+ 0.05 0.1 1 10 100 K+ 0.125 0.25 2.5 25 250 Mg2+ 0.02 0.04 0.4 4 40 Ca2+ 0.2 0.4 4 40 400 图 4五个浓度点、每浓度点六针平行谱图叠加 表2检测离子及峰面积响应值 离子 浓度 ppm 峰面积 μS·s（六针平行） std1 Li+ 0.015 0.7726 0.7768 0.778 0.7758 0.784 0.7806 Na+ 0.05 0.8631 0.8482 0.838 0.8485 0.846 0.8413 K+ 0.125 1.3334 1.3659 1.2835 1.3521 1.3553 1.3605 Mg2+ 0.02 0.2841 0.2245 0.2798 0.2784 0.2607 0.2459 Ca2+ 0.2 4.9372 4.6966 4.5445 5.0677 4.8776 4.8276 std2 Li+ 0.03 1.5836 1.5848 1.5831 1.5867 1.5873 1.5926 Na+ 0.1 1.7188 1.7176 1.7159 1.7165 1.7165 1.7108 K+ 0.25 2.7715 2.7706 2.7702 2.7695 2.7771 2.7731 Mg2+ 0.04 0.5066 0.5034 0.5185 0.5081 0.5146 0.518 Ca2+ 0.4 8.6948 8.8054 8.5904 8.6213 8.7123 8.599 std3 Li+ 0.3 16.0735 16.0965 16.1084 16.1031 16.1057 16.1213 Na+ 1 17.5062 17.5176 17.5673 17.5181 17.5252 17.578 K+ 2.5 28.3929 28.3849 28.3676 28.4804 28.4304 28.4425 Mg2+ 0.4 4.8516 4.8585 4.8265 4.8538 4.8749 4.8586 Ca2+ 4 71.7391 72.5086 70.8957 72.5439 72.2569 72.2595 std4 Li+ 3 160.3736 160.6549 160.7646 160.866 160.841 161.9812 Na+ 10 175.278 174.2236 174.5549 174.4763 174.4325 175.6831 K+ 25 287.4426 287.6123 287.9163 288.1763 289.6952 288.3516 Mg2+ 4 49.1734 49.17 49.1867 49.0871 49.4115 49.1617 Ca2+ 40 740.0505 740.624 743.4776 744.7966 744.7249 746.1407 std5 Li+ 30 1582.9691 1586.225 1588.059 1591.939 1590.121 1591.809 Na+ 100 1701.7484 1710.508 1706.305 1708.181 1706.157 1709.996 K+ 250 2760.321 2766.245 2769.07 2789.324 2773.949 2776.704 Mg2+ 40 539.8584 543.0435 543.2403 543.6288 543.2864 544.1023 Ca2+ 400 7181.9936 7210.357 7218.469 7244.391 7230.358 7240.43 表3阴离子与有机酸的外标曲线方程与相关系数 离子 外标曲线方程 相关系数/r Li+ Y=52.9378330239757X+0.537491563105951 0.999993 Na+ Y=17.0636843111475X+1.07884109652462 0.999991 K+ Y=11.0826791085922X+2.74638520665435 0.99997 Mg2+ Y=13.5961763930835X-1.35998048729854 0.999907 Ca2+ Y=18.042191457432X+5.65465893848206 0.99998 从表中可知阳离子在一定的浓度区间内与电导信号呈较好的一次线性关系。 样品检测结果 表4样品检测结果及重复性数据 样品 离子 保留时间(min) 保留时间 RSD 含量(mg/L) 含量RSD 蓝瓶崂矿 Li+ 2.40 2.40 2.40 2.40 2.40 2.40 0.05 ＜0.015 ＜0.015 ＜0.015 ＜0.015 ＜0.015 ＜0.015 / Na+ 2.76 2.76 2.76 2.77 2.76 2.76 0.06 8.61 8.66 8.61 8.60 8.62 8.61 0.23 K+ 3.68 3.68 3.67 3.68 3.67 3.67 0.07 0.34 0.34 0.33 0.33 0.34 0.33 0.84 Mg2+ 4.55 4.55 4.55 4.55 4.55 4.55 0.06 5.14 5.13 5.14 5.14 5.15 5.15 0.18 Ca2+ 5.42 5.43 5.42 5.43 5.42 5.42 0.06 11.55 11.53 11.49 11.51 11.56 11.54 0.23 红瓶崂矿 Li+ 2.40 2.40 2.40 2.40 2.40 2.41 0.07 0.02 0.02 0.02 0.02 0.02 0.02 2.77 Na+ 2.78 2.78 2.78 2.78 2.78 2.78 0.06 34.61 34.50 34.73 34.52 34.83 34.54 0.38 K+ 3.68 3.68 3.68 3.68 3.68 3.68 0.04 1.00 1.00 1.01 1.01 0.99 0.99 0.72 Mg2+ 4.55 4.55 4.55 4.55 4.55 4.56 0.10 7.43 7.47 7.48 7.48 7.50 7.48 0.28 Ca2+ 5.41 5.42 5.41 5.41 5.42 5.43 0.10 18.95 19.04 19.03 19.01 18.91 19.02 0.26 伊刻活泉 Li+ 2.41 2.40 2.40 2.40 2.40 2.40 0.14 0.04 0.04 0.04 0.04 0.04 0.04 1.55 Na+ 2.78 2.76 2.76 2.76 2.76 2.76 0.31 11.01 11.04 11.04 11.04 11.05 11.04 0.12 K+ 3.68 3.67 3.68 3.68 3.68 3.68 0.09 1.26 1.27 1.28 1.26 1.26 1.26 0.55 Mg2+ 4.56 4.51 4.52 4.51 4.52 4.52 0.40 38.55 38.54 38.64 38.57 38.80 38.65 0.25 Ca2+ 5.43 5.37 5.39 5.38 5.38 5.38 0.36 20.63 20.43 20.57 20.50 20.57 20.67 0.42 屈臣氏 Li+ NA NA NA NA NA NA / NA NA NA NA NA NA / Na+ 2.75 2.75 2.75 2.75 2.75 2.75 0.03 ＜0.05 ＜0.05 ＜0.05 ＜0.05 ＜0.05 ＜0.05 / K+ 3.68 3.68 3.67 3.67 3.68 3.67 0.03 5.24 5.25 5.27 5.25 5.25 5.25 0.19 Mg2+ 4.54 4.53 4.53 4.53 4.53 4.54 0.05 10.38 10.70 10.68 10.72 10.65 10.82 1.40 Ca2+ NA NA NA NA NA NA / NA NA NA NA NA NA / 悦活 Li+ 2.40 2.40 2.40 2.40 2.40 2.40 0.09 0.04 0.04 0.04 0.04 0.04 0.04 0.79 Na+ 2.76 2.76 2.76 2.76 2.76 2.76 0.07 8.42 8.41 8.41 8.42 8.42 8.42 0.07 K+ 3.67 3.68 3.67 3.68 3.67 3.67 0.05 4.27 4.27 4.31 4.29 4.31 4.29 0.35 Mg2+ 4.51 4.52 4.51 4.52 4.52 4.52 0.08 11.04 11.02 11.03 11.04 11.09 11.07 0.22 Ca2+ 5.38 5.38 5.38 5.39 5.39 5.39 0.07 10.16 10.13 10.09 10.16 10.18 10.16 0.31 木兰泉 Li+ 2.41 2.40 2.40 2.40 2.40 2.40 0.13 ＜0.015 ＜0.015 ＜0.015 ＜0.015 ＜0.015 ＜0.015 / Na+ 2.77 2.77 2.76 2.77 2.77 2.76 0.10 15.96 16.05 16.08 16.14 16.09 16.12 0.41 K+ 3.69 3.68 3.68 3.68 3.68 3.68 0.16 1.14 1.14 1.14 1.15 1.14 1.14 0.50 Mg2+ 4.50 4.50 4.50 4.50 4.50 4.51 0.06 15.67 15.84 15.82 15.78 15.81 15.86 0.43 Ca2+ 5.36 5.35 5.35 5.35 5.35 5.36 0.05 38.92 39.17 39.15 39.17 39.23 39.21 0.29 百岁山 Li+ 2.40 2.40 2.40 2.40 2.40 2.40 0.05 ＜0.015 ＜0.015 ＜0.015 ＜0.015 ＜0.015 ＜0.015 / Na+ 2.76 2.76 2.76 2.76 2.76 2.76 0.09 6.39 6.33 6.33 6.34 6.36 6.33 0.39 K+ 3.68 3.68 3.68 3.68 3.68 3.69 0.06 2.30 2.30 2.30 2.30 2.31 2.30 0.23 Mg2+ 4.54 4.54 4.54 4.53 4.54 4.54 0.04 2.08 2.09 2.09 2.09 2.09 2.10 0.32 Ca2+ 5.41 5.41 5.42 5.41 5.41 5.41 0.05 8.56 8.57 8.69 8.61 8.63 8.63 0.58 自来水 Li+ 2.40 2.40 2.40 2.40 2.40 2.40 0.04 ＜0.015 ＜0.015 ＜0.015 ＜0.015 ＜0.015 ＜0.015 / Na+ 2.79 2.78 2.78 2.78 2.78 2.78 0.19 36.98 37.99 38.45 38.68 38.76 38.86 1.86 K+ 3.73 3.70 3.69 3.68 3.68 3.68 0.47 6.36 6.54 6.59 6.71 6.67 6.69 1.98 Mg2+ 4.51 4.50 4.51 4.51 4.52 4.52 0.13 30.94 31.59 31.86 31.97 32.06 32.05 1.36 Ca2+ 5.38 5.36 5.36 5.36 5.37 5.37 0.12 48.38 49.86 50.21 50.15 50.41 50.51 1.58 雪水 Li+ NA NA NA / / NA NA NA / / Na+ 2.76 2.76 2.76 0.11 4.71 4.73 4.73 0.21 K+ 3.68 3.68 3.68 0.05 0.06 0.06 0.06 2.99 Mg2+ 4.54 4.54 4.55 0.07 1.40 1.41 1.41 0.38 Ca2+ 5.42 5.43 5.43 0.10 7.62 7.78 7.82 1.40 冷水江 Li+ 2.40 2.40 2.40 / 0.02 ＜0.015 ＜0.015 ＜0.015 / / Na+ 2.76 2.76 2.76 0.05 6.12 6.14 6.16 0.27 K+ 3.67 3.67 3.67 0.06 1.81 1.81 1.82 0.14 Mg2+ 4.52 4.52 4.52 0.04 7.53 7.58 7.56 0.29 Ca2+ 5.37 5.37 5.37 0.03 36.21 36.43 36.57 0.49 精密度： 在已知的色谱条件下连续进样6次实际样品，结果如表4所示。 从表中可知，阳离子的定量重复性均低于3.0%，说明仪器具有较高的稳定性。 准确度 将红瓶崂山矿泉水及蓝瓶崂山矿泉水分别加入标准样品，测试其回收率，结果如表5： 表5样品加标回收率 样品 离子 加标回收率(%) 平行 1 平行 2 平行 3 平行 4 平行 5 平行 6 蓝瓶崂矿 Li+ 97.64 101.19 98.54 101.32 101.32 101.50 Na+ 101.71 102.39 102.04 102.19 102.15 102.45 K+ 103.41 103.69 103.89 103.98 103.96 104.05 Mg2+ 95.16 96.56 96.72 96.83 96.73 97.10 Ca2+ 105.02 105.39 105.84 105.86 106.15 105.88 红瓶崂矿 Li+ 92.98 93.25 93.25 93.45 93.25 93.18 Na+ 90.73 80.60 80.62 89.18 84.23 84.98 K+ 102.77 103.06 103.24 103.51 103.53 104.07 Mg2+ 104.55 103.15 111.03 114.64 109.55 103.75 Ca2+ 104.93 105.62 106.52 107.72 106.11 107.96 基线噪声、基线漂移与检测限： 采集 30分钟基线，在 30分钟时注入系统 0.2ppm的锂离子，切换进样阀至分析位，继 续采集锂离子峰并记录谱图。 图 5 30分钟基线及 0.2ppm锂离子数据 图 6前 30分钟基线噪声及漂移 从图5及图6中可知，具有较低的噪声和漂移 表 6基线噪声与漂移 离子 基线噪声 基线漂移 0.2ppm锂离子峰高 检出限 Li+ 0.00027μS/cm 0.0049μS/cm 1.7016μS/cm 0.000317μg/g 结语： 根据 GB/T5750.6，使用 RPIC-2017型离子色谱仪测定水质中的阳离子，基线噪声低，灵敏度高，线性、准确度、精密度较好。