水質(zhì)多環(huán)芳烴的測(cè)定液液萃取和固相萃取高效液相色譜法HJ478-2009方法證實(shí)記錄

水質(zhì)多環(huán)芳烴的測(cè)定液液萃取和固相萃取高效液相色譜法HJ478-2009方法證實(shí)記錄一、方法原理用二氯甲烷萃取水中多環(huán)芳烽（PAHs），萃取液經(jīng)弗羅里硅土柱凈化，用二氯甲烷和正己烷的混合溶劑洗脫，洗脫液經(jīng)濃縮后，用具有紫外檢測(cè)器的高效液相色譜儀分離檢測(cè)。二、試劑乙月青：SIGMA-ALDRICH，液相色譜純甲醇：Fisher，液相色譜純二氯甲烷：天津致遠(yuǎn)，色譜純正己烷：SIMARK，液相色譜純無(wú)水硫酸鈉：天津光復(fù)，優(yōu)級(jí)純，400℃烘烤2h氯化鈉：天津北聯(lián)，優(yōu)級(jí)純，400℃烘烤2h多環(huán)芳烽標(biāo)準(zhǔn)溶液：SITAER，甲醇中16種多環(huán)芳烽混標(biāo)（編號(hào)：301702F55）弗羅里硅土柱：100mg/6mL三、主要儀器設(shè)備液相色譜儀：Thermo,M-3000,配有紫外檢測(cè)器色譜柱：AcclaimTM120 C185Am120A（4.6X250mm）分液漏斗：2000mL，活塞不加凡士林層析柱旋轉(zhuǎn)蒸發(fā)儀四、方法步驟樣品預(yù)處理萃取搖勻水樣，量取1000mL水樣，倒入2000mL分液漏斗中，加入30g氯化鈉，再加入50mL二氯甲烷，振搖5min，靜置分層，收集有機(jī)相，放入250mL接收瓶中，重復(fù)萃取兩遍，合并有機(jī)相，加入無(wú)水硫酸鈉至有流動(dòng)的無(wú)水硫酸鈉存在。放置30min，脫水干燥。濃縮用旋轉(zhuǎn)蒸發(fā)儀濃縮至1mL,加入正己烷至5mL，重復(fù)濃縮3次，最后濃縮至1mL，待凈化。凈化用1g弗羅里硅土柱凈化：先用4mL淋洗液（二氯甲烷：正己烷=1:1）沖洗凈化柱，再用10mL正己烷平衡凈化柱。將濃縮后的樣品加到柱上，再用3mL正己烷分3次洗滌裝樣品的容器，一并加到柱上，棄去流出的溶劑。用10mL淋洗液洗滌凈化柱，收集洗脫液于濃縮瓶中，濃縮至0.5~1.0mL后加入3mL乙月青，濃縮至0.5mL，最后用乙月青定容至1.0mL。色譜條件色譜條件0-15min,乙月青：水=60:40；15-30min，乙月青：水變化至100:0；30-39min，乙月青：水=100:0；39-40min，乙月青：水變化至60:40；40-42min,乙月青：水=60:40檢測(cè)器檢測(cè)器類(lèi)型：紫外檢測(cè)器。檢測(cè)波長(zhǎng)：220nm。五、標(biāo)準(zhǔn)曲線標(biāo)準(zhǔn)系列的制備取一定量多環(huán)芳烴標(biāo)準(zhǔn)溶液，用乙月青稀釋至少5個(gè)濃度點(diǎn)的標(biāo)準(zhǔn)系列U：0.5、1.0、2.0、4.0、5.0、10.0Hg/mL。標(biāo)準(zhǔn)曲線的測(cè)定通過(guò)自動(dòng)進(jìn)樣器移取10uL標(biāo)準(zhǔn)系列注入液相色譜儀，得到不同濃度的多環(huán)芳烴的色譜圖，以峰面積為縱坐標(biāo)，濃度為橫坐標(biāo)，繪制標(biāo)準(zhǔn)曲線。六、方法檢出限檢出限的2?5倍法。（采用曲線點(diǎn)0.04ug/mL測(cè)量7次得到萃取液檢出限，再根據(jù)水樣體積和萃取液定容體積，算出方法檢出限）七、精密度實(shí)驗(yàn)室內(nèi)相對(duì)標(biāo)準(zhǔn)偏差：標(biāo)準(zhǔn)曲線點(diǎn)測(cè)定法。（對(duì)3組不同濃度的標(biāo)準(zhǔn)曲線點(diǎn)各測(cè)定6次，得到3組結(jié)果）八、準(zhǔn)確度樣品加標(biāo)法。（分別對(duì)6個(gè)平行樣品加標(biāo)0.5mg/L,得到6個(gè)加標(biāo)結(jié)果）九、結(jié)論方法的線性為0.9986~0.9999；檢出限為0.001Ug/L-0.010ug/L,均等于或優(yōu)于方法檢出限；精密度為0.08%~2.01%；加標(biāo)回收率為63.3%~97.1%,均滿足方法要求。附表1方法檢出限、測(cè)定下限測(cè)試數(shù)據(jù)表平行樣品編號(hào)試樣1（萘）試樣2（二氫危）試樣3（苊）備注測(cè)定結(jié)果（Hg/L）10.03810.03790.0376濃 度0.04日g/mL20.03700.03690.035530.03710.03640.032640.03720.03850.037450.03710.03690.036260.03700.03680.035270.03770.03730.0358平均值京（咫/L）0.03730.03720.0358標(biāo)準(zhǔn)偏差SiRg/L）0.000420.00070.00167t值3.1433.1433.143檢出限（Hg/L）0.0010.0020.005測(cè)定下限（Hg/L）0.0050.0090.021

方法檢出限、測(cè)定下限測(cè)試數(shù)據(jù)表平行樣品編號(hào)試樣1（笏）試樣2（菲）試樣3（蒽）備注測(cè)定結(jié)果（Hg/L）10.04130.03760.0385濃度0.04ug/mL20.04580.03690.036530.04280.03610.038440.03550.03510.038050.04130.03610.038360.04320.03610.036270.04200.0.3720.0393平均值京 Rg/L）0.04170.03640.0379標(biāo)準(zhǔn)偏差SiRg/L）0.00310.00080.0011t值3.1433.1433.143檢出限（聞/L）0.0100.0030.004測(cè)定下限（聞/L）0.0390.0110.014方法檢出限、測(cè)定下限測(cè)試數(shù)據(jù)表平行樣品編號(hào)試樣1（熒蒽）試樣2（芘）試樣3（苯并［a］蒽）備注測(cè)定結(jié)果（Hg/L）10.03960.03830.0396濃度0.04ug/mL20.03870.03750.040230.03820.03800.039440.03840.03740.039550.03840.03700.039560.03830.03730.039970.03820.03670.0400平均值京 Rg/L）0.03850.03750.0397標(biāo)準(zhǔn)偏差SiRg/L）0.00050.00060.0003t值3.1433.1433.143檢出限（M/L）0.0020.0020.001測(cè)定下限（Hg/L）0.0060.0070.004

方法檢出限、測(cè)定下限測(cè)試數(shù)據(jù)表平行樣品編號(hào)試樣1（篇）試樣2（苯并［b］熒蒽）試樣3（苯并［k］熒蒽）備注測(cè)定結(jié)果（Hg/L）10.04060.03610.0365濃度0.04ug/mL20.03900.03670.038830.04020.03670.038540.03960.03610.038750.03990.03650.038560.03930.03620.038470.03950.03620.0385平均值京 Rg/L）0.03970.03640.0383標(biāo)準(zhǔn)偏差SiRg/L）0.00050.00030.0008t值3.1433.1433.143檢出限（聞/L）0.0020.0010.002測(cè)定下限（聞/L）0.0070.0030.010方法檢出限、測(cè)定下限測(cè)試數(shù)據(jù)表平行樣品編號(hào)試樣1（苯并［a］芘）試樣2（二苯并［a,h］蒽）試樣3（苯并［g,h,i］花）備注測(cè)定結(jié)果（Hg/L）10.04440.04880.0416濃度0.04ug/mL20.04210.04610.038630.04280.04730.038940.04400.04700.039150.04400.04810.038860.04230.04620.038870.04210.04860.0385平均值京 Rg/L）0.04310.04740.0392標(biāo)準(zhǔn)偏差SiRg/L）0.00100.0110.0011t值3.1433.1433.143檢出限（Hg/L）0.0030.0030.003測(cè)定下限（Hg/L）0.0130.0140.014

方法檢出限、測(cè)定下限測(cè)試數(shù)據(jù)表平行樣品編號(hào)試樣1(茚并[1,2,3,-c?)試樣2()試樣3()備注測(cè)定結(jié)果(4/L)10.0394濃度0.04〃g/mL20.038630.038740.038650.038860.038470.0383平均值京(4/L)0.0387標(biāo)準(zhǔn)偏差5](Ag/L)0.0004t值3.143檢出限(華兒)0.001測(cè)定下限(Ag/L)0.004附表2方法精密度測(cè)試數(shù)據(jù)表平行樣品編號(hào)試樣1(1.00mg/L)試樣2(2.00mg/L)試樣3(5.00mg/L)備注萘測(cè)定結(jié)果(mg/L)11.01842.01535.078721.03092.01645.078731.02902.01685.083541.03352.00045.075551.03422.00025.079761.03492.00535.0677平均值纂(mg/L)1.03022.00915.0773標(biāo)準(zhǔn)偏差5](mg/L)0.00620.00800.0054相對(duì)標(biāo)準(zhǔn)偏差RSD.%0.600.400.11

方法精密度測(cè)試數(shù)據(jù)表平行樣品編號(hào)試樣1（1.00mg/L）試樣2（2.00mg/L）試樣3（5.00mg/L）備注苊測(cè)定結(jié)果（mg/L）11.00872.00875.090020.02232.01095.092931.02122.01065.098441.02611.99445.096051.02611.99285.102461.02701.99875.0952平均值纂（mg/L）1.02192.00275.0958標(biāo)準(zhǔn)偏差Si（mg/L）0.00620.00830.0043相對(duì)標(biāo)準(zhǔn)偏差RSD.%0.600.420.08方法精密度測(cè)試數(shù)據(jù)表平行樣品編號(hào)試樣1（1.00mg/L）試樣2（2.00mg/L）試樣3（5.00mg/L）備注笏測(cè)定結(jié)果（mg/L）10.96581.93515.049120.97331.94635.046130.98421.96364.982940.97921.94794.957850.98221.89434.897060.97191.90075.0241平均值K （mg/L）0.97611.93134.9928標(biāo)準(zhǔn)偏差Si（mg/L）0.00700.02780.0591相對(duì)標(biāo)準(zhǔn)偏差RSD.%0.721.441.18

方法精密度測(cè)試數(shù)據(jù)表平行樣品編號(hào)試樣1（1.00mg/L）試樣2（2.00mg/L）試樣3（5.00mg/L）備注二氫苊測(cè)定結(jié)果（mg/L）11.00912.01975.124721.02452.01925.127031.02012.01395.146141.02741.99915.099351.02702.00905.120461.02982.01305.1262平均值纂（mg/L）1.02302.01235.1240標(biāo)準(zhǔn)偏差Si（mg/L）0.00760.00760.0150相對(duì)標(biāo)準(zhǔn)偏差RSD.%0.740.380.29方法精密度測(cè)試數(shù)據(jù)表平行樣品編號(hào)試樣1（1.00mg/L）試樣2（2.00mg/L）試樣3（5.00mg/L）備注非測(cè)定結(jié)果（mg/L）10.98481.95985.156220.99611.96295.160030.99431.96145.163140.99991.94564.959651.00111.94354.961760.99951.94945.1322平均值拓 （mg/L）0.99601.95385.0888標(biāo)準(zhǔn)偏差Si（mg/L）0.00600.00860.0999相對(duì)標(biāo)準(zhǔn)偏差RSD.%0.610.441.96

方法精密度測(cè)試數(shù)據(jù)表平行樣品編號(hào)試樣1（1.00mg/L）試樣2（2.00mg/L）試樣3（5.00mg/L）備注蒽測(cè)定結(jié)果（mg/L）10.95571.93395.186920.97681.93305.173730.97641.93145.179440.98001.91444.903550.98021.91534.908960.98341.91735.1399平均值纂（mg/L）0.97541.92425.0820標(biāo)準(zhǔn)偏差Si（mg/L）0.01000.00940.1372相對(duì)標(biāo)準(zhǔn)偏差RSD.%1.020.492.70方法精密度測(cè)試數(shù)據(jù)表平行樣品編號(hào)試樣1（1.00mg/L）試樣2（2.00mg/L）試樣3（5.00mg/L）備注熒蒽測(cè)定結(jié)果（mg/L）10.98591.97145.164120.99951.97285.165130.99861.97095.169141.00331.95445.053951.00341.96815.059361.00491.95895.1354平均值拓 （mg/L）0.99931.96615.1245標(biāo)準(zhǔn)偏差Si（mg/L）0.00700.00760.0540相對(duì)標(biāo)準(zhǔn)偏差RSD.%0.700.391.05

方法精密度測(cè)試數(shù)據(jù)表平行樣品編號(hào)試樣1（1.00mg/L）試樣2（2.00mg/L）試樣3（5.00mg/L）備注芘測(cè)定結(jié)果（mg/L）10.95971.93865.247720.97331.94035.231330.97151.93575.225740.97561.89985.050750.97642.00775.048760.97821.90285.1701平均值纂（mg/L）0.97241.93755.1624標(biāo)準(zhǔn)偏差Si（mg/L）0.00670.03890.0911相對(duì)標(biāo)準(zhǔn)偏差RSD.%0.692.011.76方法精密度測(cè)試數(shù)據(jù)表平行樣品編號(hào)試樣1(1.00mg/L)試樣2(2.00mg/L)試樣3(5.00mg/L)備注窟測(cè)定結(jié)果（mg/L）10.99562.00115.165721.01361.98915.139531.02751.99885.152441.01722.00115.088351.01982.03225.109961.02051.98255.1373平均值拓 （mg/L）1.01572.00085.1322標(biāo)準(zhǔn)偏差Si（mg/L）0.01090.01710.0284相對(duì)標(biāo)準(zhǔn)偏差RSD.%1.070.850.55

方法精密度測(cè)試數(shù)據(jù)表平行樣品編號(hào)試樣1（1.00mg/L）試樣2（2.00mg/L）試樣3（5.00mg/L）備注苯并［a］蒽測(cè)定結(jié)果（mg/L）10.99192.01245.108821.01141.99085.124131.02701.98185.118441.01352.00485.087451.01492.01985.083561.01321.97125.0807平均值纂（mg/L）1.01201.99685.1005標(biāo)準(zhǔn)偏差Si（mg/L）1.01130.01870.0190相對(duì)標(biāo)準(zhǔn)偏差RSD.%1.120.940.37方法精密度測(cè)試數(shù)據(jù)表平行樣品編號(hào)試樣1（1.00mg/L）試樣2（2.00mg/L）試樣3（5.00mg/L）備注苯并［b］熒蒽測(cè)定結(jié)果（mg/L）10.98221.97245.077220.99431.95285.076431.00541.95665.076940.99791.95944.997950.99731.96345.001260.99821.94185.0204平均值拓 （mg/L）0.99591.95775.0417標(biāo)準(zhǔn)偏差Si（mg/L）0.00760.01030.0393相對(duì)標(biāo)準(zhǔn)偏差RSD.%0.770.530.78

方法精密度測(cè)試數(shù)據(jù)表平行樣品編號(hào)試樣1（1.00mg/L）試樣2（2.00mg/L）試樣3（5.00mg/L）備注苯并［k］熒蒽測(cè)定結(jié)果（mg/L）11.00641.99455.102021.01282.00395.096131.00992.00285.101941.01681.98615.065151.01621.98405.066361.01711.98415.0674平均值纂（mg/L）1.01321.99265.0831標(biāo)準(zhǔn)偏差Si（mg/L）0.00430.00920.0186相對(duì)標(biāo)準(zhǔn)偏差RSD.%0.430.460.37方法精密度測(cè)試數(shù)據(jù)表平行樣品編號(hào)試樣1（1.00mg/L）試樣2（2.00mg/L）試樣3（5.00mg/L）備注苯并［a］芘測(cè)定結(jié)果（mg/L）10.97011.98275.136920.99302.00005.140730.98871.99625.140040.99451.98035.024050.99821.98045.024460.99551.97075.0237平均值拓 （mg/L）0.99001.98505.0816標(biāo)準(zhǔn)偏差Si（mg/L）0.01020.01100.0631相對(duì)標(biāo)準(zhǔn)偏差RSD.%1.030.551.24

方法精密度測(cè)試數(shù)據(jù)表平行樣品編號(hào)試樣1（1.00mg/L）試樣2（2.00mg/L）試樣3（5.00mg/L）備注二苯并［a,h］蒽測(cè)定結(jié)果（mg/L）10.97361.99215.002321.00012.00414.984731.00251.99724.991240.99651.97334.983751.01701.97454.980661.01191.98444.9757平均值纂（mg/L）1.00021.98764.9864標(biāo)準(zhǔn)偏差Si（mg/L）0.01510.01240.0093相對(duì)標(biāo)準(zhǔn)偏差RSD.%1.510.620.19方法精密度測(cè)試數(shù)據(jù)表平行樣品編號(hào)試樣1(1.00mg/L)試樣2(2.00mg/L)試樣3(5.00mg/L)備注苯并［ghi］花測(cè)定結(jié)果（mg/L）11.00922.01115.091621.02172.01355.091031.01902.01165.093241.02411.99485.087051.02491.99295.089661.02251.99855.0810平均值拓 （mg/L）1.02022.00375.0889標(biāo)準(zhǔn)偏差Si（mg/L）0.00580.00930.0044相對(duì)標(biāo)準(zhǔn)偏差RSD.%0.570.470.09

方法精密度測(cè)試數(shù)據(jù)表平行樣品編號(hào)試樣1（1.00mg/L）試樣2（2.00mg/L）試樣3（5.00mg/L）備注茚并[1,2,3-c,d]芘測(cè)定結(jié)果（mg/L）11.00632.01225.097521.02152.01335.094731.01892.01225.098941.02731.99545.092551.02461.99425.094961.02401.99985.0854平均值纂（mg/L）1.02042.00455.0940標(biāo)準(zhǔn)偏差Si（mg/L）0.00750.00900.0048相對(duì)標(biāo)準(zhǔn)偏差RSD.%0.730.450.09附表4方法準(zhǔn)確度測(cè)試數(shù)據(jù)表（實(shí)際樣品加標(biāo)測(cè)試數(shù)據(jù)）平行樣品編號(hào)有證標(biāo)準(zhǔn)樣品備注試樣1萘試樣2苊試樣3笏樣品加標(biāo)樣品樣品加標(biāo)樣品樣品加標(biāo)樣品測(cè)定結(jié)果（Hg/L）10.17130.487300.483000.468020.16860.488800.482200.466330.17160.487100.482100.461040.17130.487400.483500.475350.17240.487800.482200.465860.17300.489900.485400.4605平均值公立（Hg/L）0.17140.488000.483100.4662加標(biāo)量〃（Hg/L）0.50.50.5加標(biāo)回收率Pi（%）63.396.693.2

方法準(zhǔn)確度測(cè)試數(shù)據(jù)表（實(shí)際樣品加標(biāo)測(cè)試數(shù)據(jù)）平行樣品編號(hào)有證標(biāo)準(zhǔn)樣品備注試樣1一氫苊試樣2菲試樣3蒽樣品加標(biāo)樣品樣品加標(biāo)樣品樣品加標(biāo)樣品測(cè)定結(jié)果（Hg/L）100.484700.473600.4595200.485100.471500.4611300.484900.471500.4601400.483100.471300.4614500.485500.471400.4607600.488900.468500.4633平均值二工（Hg/L）00.485400.471300.4610力口標(biāo)量四（Hg/L）0.50.50.5加標(biāo)回收率Pi（%）97.194.392.2方法準(zhǔn)確度測(cè)試數(shù)據(jù)表（實(shí)際樣品加標(biāo)測(cè)試數(shù)據(jù)）平行樣品編號(hào)有證標(biāo)準(zhǔn)樣品備注試樣1熒蒽試樣2芘試樣3窟樣品加標(biāo)樣品樣品加標(biāo)樣品樣品加標(biāo)樣品測(cè)定結(jié)果（Hg/L）100.474200.461600.4766200.474500.461300.4796300.473600.461600.4776400.47430