SHOUJIQIAOTAOSHIDUISHOUJIWAIGUANJINXINGBAOHUHUOZHUANGSHIDEZHUANGSHIPIN,JUYOUFANGHUA、FANGZHEN、FANGGUA、FANGSHUAI、NAIMO、MEIGUANDENGTEDIAN。YOUYUSHOUJIPINPAIHEGONGNENGBUTONG,SHOUJIQIAOTAODEZHONGLEIDUOZHONGDUOYANG,ANQICAIZHIKEFENWEIJUTANSUANZHIQIAO、JULVYIXIQIAO、TPU SUJIAOQIAO、ABS QIAO、JUBINGXIQIAO、PIGEQIAO、GUIJIAOQIAO、BULIAOQIAO、JINSHUGANGHUABOLIQIAO、RONGZHIQIAO、CHOUZHIQIAODENG。
JUGUOWAIMEITIBAODAO,2018 NIANQUANQIUZHINENGSHOUJIGONGXIAOSHOU14.98 YIBU,SHOUJITAODEYONGLIANGYEYURIJUZENG。SHOUJIQIAOTAOZHONGDEKEQIANYIYOUHAIYUANSUZHUYAOYOUQIAN、GE、GE、GONG、TI、SHEN、XI、BEI、XI、XIN、GU、TONG、MENG、NIE、SI、FANDENG,ZHEIXIEKERONGXINGYUANSUJINGRENTISHOUSHANGDEHANYE、LIANBUYOUZHIHUOZHEYINGYOUERKENYAOSHIDETUOYEQIANYIZHIRENTINEI,DUIRENTIZAOCHENGWEIHAI。LIRUQIANKEDUIRENTIMIANYIXITONG、SHENJINGXITONG、SHENGZHIXITONG、XIAOHUAXITONGDENGZAOCHENGWEIHAI,DUICHUYUSHENGZHANGFAYUSHIQIDEERTONG,KEYINQIDUOXITONGSUNSHANG。BUFENFANHUAHEWUDUIYANJINGHEPIFUJUYOUCIJIZUOYONG,DUIHUXIDAO、XIAOHUADAO、XUEYE、SHENJINGDENGJUYOUDUXING。GUOLIANGDEXINBUJINHUIYIZHIJITIDEZHENGCHANGSHENGZHANGFAYU,JIANGDIJITIMIANYIGONGNENG,HAIHUIYINQIXIONGXINGDONGWUDEBUYU。MENGKEYIZHIJIEJINRURENTIDANAOCHANSHENGSHENJINGDUXING,HAIHUIFUJIYUGANZANG,ZAOCHENGGANSUNSHANG。GUOLIANGHANGEHUAHEWUKEYINQISHENZANGSUNSHANG,ZAOCHENGSHENGONGNENGJINIAOZHONGMEIHEDANBAIHANLIANGDEGAIBIAN,YANZHONGSHIKENENGDAOZHISHENZANGHUAISI。YINCIJIANLISHOUJIQIAOTAOZHONGDUOZHONGKEQIANYIYOUHAIYUANSUHANLIANGDECEDINGFANGFAJUYOUZHONGYAOYIYI。
DIANGANOUHEDENGLIZITIZHIPU (ICP–MS) FAJUYOULINGMINDUGAO、XIANXINGFANWEIGUANG、DINGLIANGZHUNQUE、DUOYUANSUTONGSHICEDINGDENGTEDIAN,YIGUANGFANYINGYONGYUSHIPIN、HUANJING、DIZHIDENGLINGYUZHONGHENLIANGJICHAOHENLIANGYUANSUDEJIANCE。MUQIANSHANGWUSHOUJIQIAOTAOZHONGDUOZHONGKEQIANYIYOUHAIYUANSUTONGSHIJIANCEDEGUOJIAHUOXINGYEBIAOZHUN,YEZANWUXIANGGUANWENXIANBAODAO。BIZHETONGGUORENGONGMONIHANYESHIYANFANGFA,JIANLILEDIANGANOUHEDENGLIZITIZHIPUFACEDINGSHOUJIQIAOTAOZHONG14 ZHONGKEQIANYIYUANSUHANLIANGDEFANGFA,WEITIGAOHEKONGZHISHOUJIQIAOTAOCHANPINZHILIANGTIGONGYIDINGDEJISHUZHICHI。
1 实验部分
1.1 主要仪器与试剂
DIANGANOUHEDENGLIZITIZHIPUYI:NEXION 300 XING;
WEIBOXIAOJIEYI:ETHOS UP XING;
GANSUANYI:YKM–36 XING
CHAOCHUNSHUIJI:Milli-Q Reference XING;
DIANZITIANPING:AL204XING,GANLIANGWEI0.000 1 g;
HENGWENSHUIYUGUO:HH.S21–8 XING;
JINGMI pH JI:PHS–3C XING;
FAN、SHEN、QIAN、GONG、GE、GE、NIE、MENG、SI、BEI、TONG、XINDANYUANSUBIAOZHUNRONGYE:ZHILIANGNONGDUJUNWEI 1 000 μg/mL,BIANHAOFEN BIE WEI GSB G 62016–90,GSB G 62028–90,GSB G62071–90,GSB G 62069–90,GSB G 62017–90,GSB G 62040–90,GSB G 62022–90,GSB G 62019–90,GSB G 62031–90,GSB G 62046–90,GSB G 62024–90 HE GSB G 62025–90;
XI、TIDANYUANSUBIAOZHUNRONGYE:ZHILIANGNONGDUJUNWEI 500 μg/mL,BIANHAOFENBIEWEI GSB G 62042–90 HE GSB G 62043–90;
ZHE、YIN、LAI、LAODANYUANSUNEIBIAOBIAOZHUNRONGYE:ZHILIANGNONGDUJUNWEI 1 000 μg/mL,BIANHAOFENBIEWEI GSB G 62073–90,GSB G 62041–90,GSB G 62064–90,GSB G 62037–90;
ZHIPUYIDIAOXIERONGYE:HANPI、SHI、TIE、YIN、LI、MEI、QIAN、YOUYUANSU,ZHILIANGNONGDUJUNWEI 1 μg/mL;
NIAOSU:FENXICHUN;
LVHUANA、ANSHUI:FENXICHUN;
DL– RUSUAN:FENXICHUN;
XIAOSUAN:YOUJICHUN;
YAQI、HAIQI:CHUNDUJUNWEI 99.999%;
SHOUJIQIAOTAOYANGPIN:GONG 12 PICI,GOUZIWANGSHANGSHANGCHENG、CHAOSHIHEDITAN,CAIZHIFENBIEWEIGUIJIAO、JUTANSUANZHI、JULVYIXI、BULIAO、PIGE、GANGHUABOLIJINGMIAN;
SHIYANYONGSHUIWEICHAOCHUNSHUI。
1.2 溶液配制
XIAOSUANRONGYE:TIJIFENSHUWEI 2%,ZHUNQUEYIQU 20 mL XIAOSUANYU 1 000 mL RONGLIANGPINGZHONG,YONGCHAOCHUNSHUIDINGRONGZHIBIAOXIAN,YAOYUN,BEIYONG。
ANSHUIRONGYE:TIJIFENSHUWEI 2.5%,LIANGQU 103 mL ANSHUIYU 1 000 mL RONGLIANGPINGZHONG,YONGCHAOCHUNSHUIDINGRONGZHIBIAOXIAN,YAOYUN,BEIYONG。
MENG、TONG、XIN、SI、BEIHUNHEBIAOZHUNCHUBEIRONGYE:5 μg/mL,FENBIEYIQU 0.5 mL MENG、TONG、XIN、SI、BEIDANYUANSUBIAOZHUNRONGYEYU 100 mL RONGLIANGPINGZHONG,YONG 2% XIAOSUANRONGYEDINGRONGZHIBIAOXIAN,YAOYUN。
FAN、GE、NIE、SHEN、XI、GE、QIANHUNHEBIAOZHUNCHUBEIRONGYE:500 ng/mL,FENBIEYIQU 0.05 mL FAN、GE、NIE、SHEN、GE、QIANHE 0.1 mL XIDANYUANSUBIAOZHUNRONGYEYU 100 mL RONGLIANGPINGZHONG,YONG 2% XIAOSUANRONGYEDINGRONGZHIBIAOXIAN,YAOYUN。
GONG、TIHUNHEBIAOZHUNCHUBEIRONGYE:5 μg/mL,FENBIEYIQU 0.5 mL GONGHE 1 mL TIDANYUANSUBIAOZHUNRONGYEYU 100 mLRONGLIANGPINGZHONG,YONG 2% XIAOSUANRONGYEDINGRONGZHIBIAOXIAN,YAOYUN。
GONG、TIHUNHEBIAOZHUNZHONGJIANYE:50 ng/mL,YIQU 1 mLGONG、TIHUNHEBIAOZHUNCHUBEIRONGYEYU 100 mL RONGLIANGPINGZHONG,YONG 2%XIAOSUANRONGYEDINGRONGZHIBIAOXIAN,YAOYUN。
14 ZHONGYUANSUHUNHEBIAOZHUNGONGZUORONGYE:FENBIEYIQU 0,0.2, 1,2,5,10 mL MENG、TONG、XIN、SI、BEIHUNHEBIAOZHUNCHUBEIRONGYEHEFAN、GE、NIE、SHEN、XI、GE、QIANHUNHEBIAOZHUNCHUBEIRONGYEYIJIGONG、TIHUNHEBIAOZHUNZHONGJIANYEYU 6 ZHI 100 mL RONGLIANGPINGZHONG,YONG 2%XIAOSUANRONGYEXISHIBINGDINGRONGZHIBIAOXIAN,YAOYUN,PEIZHICHENGMENG、TONG、XIN、SI、BEIDEZHILIANGNONGDUJUNFENBIEWEI 0,10,50,100,250,500 μg/L,FAN、GE、NIE、SHEN、XI、GE、QIANDEZHILIANGNONGDUJUNFENBIE 0,1,5,10,25,50 μg/L,GONG、TIDEZHILIANGNONGDUJUNFENBIEWEI 0,0.1,0.5,1,2.5,5 μg/L XILIEHUNHEBIAOZHUNGONGZUORONGYE。
ZHE、YIN、LAI、LAOHUNHENEIBIAOGONGZUORONGYE:FENBIEYIQU 0.25 mL ZHE、YIN、LAI、LAO 4 ZHONGDANYUANSUNEIBIAOBIAOZHUNRONGYEYU 500 mL RONGLIANGPINGZHONG,YONG 2% XIAOSUANRONGYEDINGRONGZHIBIAOXIAN,YAOYUN,PEIZHICHENGZHE、YIN、LAI、LAOZHILIANGNONGDUJUNWEI 500 μg/L DEHUNHENEIBIAOGONGZUORONGYE。
MONIHANYERONGYE:YIQU 900 mL SHUIYU 1 000 mL SHAOBEIZHONG,JIARU 5 g NIAOSU、1 g LVHUANAHE 1 g DL– RUSUAN,JIAOBANZHISUOYOUSHIJIWANQUANRONGJIE,ZAIQINGQINGJIAOBANXIAZHUDIJIARU2.5% ANSHUIRONGYE,DIAOJIERONGYE pH ZHIZHI (4.4±0.1)。JIANGRONGYEZHUANYIZHI 1 000 mL RONGLIANGPINGZHONG,JIARUSHUIDINGRONGZHIBIAOXIAN,YAOYUN。
1.3 仪器工作条件
DENGLIZITISHEPINGONGLV:1 300 W ;LENGQUEQI:YAQI,LIULIANGWEI 15 L/min ;FUZHUQI:YAQI,LIULIANGWEI 1.2 L/min ;WUHUAQI:YAQI,LIULIANGWEI 1.0 L/min ;CEDINGMOSHI:HAIMOSHI;SIJIGANZHENKONGDU:8.9×10–6 Pa ;WUHUASHIWENDU:3℃;RUDONGBENGZHUANSU:24 r/min ;JINYANGSHIJIAN:30 s ;FENGXINGXUANZE:3 DIAN;JIANCEZHONGFUCISHU:3 CI;SHUJUCAIJIFANGSHI:TIAOFENG。
1.4 样品处理
JIANGYANGPINJIANSUI,CHENGQUYUE 1.0 g YANGPINZHIYUZHUIXINGPINGZHONG,JIARU 50 mL MONIHANYERONGYE,ZAI (37±2)℃HENGWENSHUIYUZHENDANGYAOCHUANGZHONGYI 60 CI/min DEPINLVZHENDANG 1 h,GUOLV,ZHIDEYANGPINJINPAOYE。LIANGQU 10 mL YANGPINJINPAOYEYUXIAOJIEGUANZHONG,JIARU 5 mL NONGXIAOSUAN,ZHIYUWEIBOXIAOJIEYIZHONGXIAOJIE,XIAOJIEYEYONGGANSUANYIJIARENONGSUOZHIYUE 1 mL,LENGQUEHOUZHUANYIZHI25 mL RONGLIANGPINGZHONG,YONGSHUIDINGRONGZHIBIAOXIAN,YAOYUN,JIWEIYANGPINXIAOJIEYE。ANXIANGTONGFANGFATONGSHIZUOKONGBAISHIYANG。
2 结果与讨论
2.1 样品前处理方法选择
FENBIEKAOCHAZHIJIECEDINGJINPAOYEHEJINPAOYEJINGWEIBOXIAOJIEHOUCEDINGLIANGZHONGYANGPINCHULIFANGFADUICEDINGJIEGUODEYINGXIANG。JIEGUOFAXIAN,ZHIJIECEDINGJINPAOYESHI,CEDINGJIEGUODEXIANGDUIBIAOZHUNPIANCHADAYU 10%,YUANYINKENENGSHISHOUJIQIAOTAOBIAOMIANZHANYOUTUOMOJIHUOQINGXIJI,ZHEIXIEWUZHIDUOWEIYOUJIJUHEWU,ZAIJINPAOGUOCHENGZHONGZHUANYIZHIJINPAOYEZHONG,DUIJIANCEJIEGUOCHANSHENGJITIGANRAO,ERTONGGUOWEIBOXIAOJIEKEYIJIAOHAODIJIEJUESHANGSHUWENTI,JINPAOYEJINGWEIBOXIAOJIEHOUCEDINGJIEGUODEXIANGDUIBIAOZHUNPIANCHAXIAOYU 10%。
2.2 干扰及消除
DIANGANOUHEDENGLIZITIZHIPUFACEDINGSHIDEGANRAOZHUYAOYOUZHIPUGANRAOHEFEIZHIPUGANRAOLIANGLEI。ZHIPUGANRAOZHUYAOBAOKUOTONGLIANGYIWEISUGANRAO、DUOYUANZILIZIGANRAO、YANGHUAWUHESHUANGDIANHEGANRAODENG,BIAOXIANWEIZHIPUFENGZHONGDIE。FEIZHIPUGANRAOZHUYAOBAOKUOJITIYIZHIGANRAO、KONGJIANDIANHEXIAOYINGGANRAO、WULIXIAOYINGGANRAODENG。
TONGGUOXUANZEBUSHOUTONGLIANGYIWEISUGANRAODEDAICEYUANSUTONGWEISUCEDINGLAIXIAOCHUTONGLIANGYIWEISUGANRAO。14 ZHONGKEQIANYIYUANSUZHONG,55Mn HE 75As MEIYOUTONGWEISU,QITAYUANSUFENBIEXUANZE 51V,52Cr,60Ni,63Cu,66Zn,88Sr,118Sn,111Cd,137Ba,123Sb,200Hg,208Pb TONGWEISUJINXINGCEDING。
JIANGDAICEGEYUANSUFENBIEZAI He MOSHIHEPUTONGMOSHILIANGZHONGFENXIMOSHIXIAJINXINGKAOCHA,FAXIANDABUFENDAICEYUANSUZAI HeMOSHIXIADEBEIJINGDENGXIAONONGDUDAFUJIANGDI,YOUXIAOXIAOCHULEBEIJINGGANRAO,GUXUANZE He MOSHIXIAOCHUDUOYUANZILIZIGANRAO。
CAIYONGZHIPUYIDIAOXIERONGYEDUIYIQIJINXINGYOUHUADIAOXIEXIAOCHUYANGHUAWUHESHUANGDIANHEGANRAO。
CAIYONGNEIBIAOXIAOZHENGFAXIAOCHUFEIZHIPUXINGGANRAO。ANZHAONEIBIAOYUANSUTONGWEISUZHILIANGSHUYUDAICEYUANSUZHILIANGSHUXIANGJINDEYUANZEXUANZENEIBIAOYUANSU。51V,52Cr,55Mn,60Ni,63Cu,66Zn XUAN ZE 72Ge ZUONEIBIAO;75As,88Sr,111Cd XUANZE 103Rh ZUONEIBIAO;118Sn,123Sb,137Ba XUANZE 115In ZUONEIBIAO;200Hg,208Pb XUANZE185Re ZUONEIBIAO。
2.3 线性方程和检出限
ZAI 1.3 YIQIGONGZUOTIAOJIANXIA,DUIXILIEHUNHEBIAOZHUNGONGZUORONGYEJINXINGCEDING,YIDAICEYUANSUDEZHILIANGNONGDU (x) WEIHENGZUOBIAO,YIDAICEYUANSUYUNEIBIAOYUANSUXIANGYINGXINHAOZHIDEBIZHI (y)WEIZONGZUOBIAO,HUIZHIBIAOZHUNQUXIAN,JISUANXIANXINGFANGCHENGHEXIANGGUANXISHU。ZAI 1.3 YIQIGONGZUOTIAOJIANXIA,DUIKONGBAIRONGYEPINGXINGCEDING11 CI,YI 3 BEIBIAOZHUNPIANCHAZUOWEIFANGFAJIANCHUXIAN。GEYUANSUDEXIANXINGFANWEI、XIANXINGFANGCHENG、XIANGGUANXISHUJIJIANCHUXIANJIANBIAO 1。
YOUBIAO 1KE ZHI,14ZHONGYUANSUZAIGEZIDEZHILIANGNONGDUFANWEINEIJUYOULIANGHAODEXIANXINGGUANXI,XIANGGUANXISHUWEI0.999 2~0.999 9,FANGFAJIANCHUXIANWEI 0.004~0.400 μg/L。BIAOMINGGAIFANGFAMANZUCEDINGYAOQIU。
2.4 加标回收与精却度试验
ANRENGONGMONIHANYESHIYANFANGFA,XUANZEBENDIZHIJIAODIDEYANGPINJINPAOYE,FENBIETIANJIA 5,10,25 μg/L 3 GENONGDUSHUIPINGDEBIAOZHUNRONGYEJINXINGJIABIAOHUISHOUSHIYAN,JIEGUOJIANBIAO 2。
YOUBIAO 2 KEZHI,YANGPINJIABIAOHUISHOULVWEI 88.2%~99.5%,CEDINGJIEGUODEXIANGDUIBIAOZHUNPIANCHAWEI 2.5%~9.3%,BIAOMINGGAIFANGFAJUYOUJIAOHAODEZHUNQUEDUHEJINGMIDU。
2.5 实际样品测定
ANSUOJIANFANGFAFENBIEDUIGUIJIAO、JUTANSUANZHI、JULVYIXI、BULIAO、PIGE、JINSHUGANGHUABOLIJINGMIAN 6 ZHONGCAIZHIGELIANGGEPICI,GONGJI 12 PICIDESHOUJIQIAOTAOSHIJIYANGPINJINXINGCEDING,JIEGUOJIANBIAO 3。YOUBIAO 3 KEZHI,1 HAOSHOUJIQIAOTAOYANGPIN ( BOLIJINGMIANCAIZHI,YOUCAISETUAN ) ZHONGYOUFANJIANCHU,SHIYINWEIFANDEYANLEICHENGGEZHONGYANSE,FANHUAHEWUZUOWEIYANLIAOJIARUDAOYANGPINZHONG,ZHICHENGLECAISEYANGPIN;ER 2 HAOSHOUJIQIAOTAOYANGPIN ( BOLIJINGMIANCAIZHI,WUSE ) ZEMEIYOUJIANCHUFANYUANSU;GUIJIAOCAIZHIDESHOUJIQIAOTAOYANGPINZHONGXINHANLIANGPIANGAODEYUANYINKENENGSHIGUIJIAOZHIPINGAOWENCHENGXINGSHITIANJIALEYANGHUAXINZUOWEILIUHUAJI;MENGJIQIHUAHEWUCHANGYONGZUORANLIAO、YANLIAO、SULIAO、RENZAOSUJIAODENGDEYUANLIAO,YINCIYANSEXIANYANDESHOUJIQIAOTAOZHONGDEMENGHANLIANGHUISHAOWEIGAOXIE;JULVYIXICAIZHIDESHOUJIQIAOTAOZHONGXIHANLIANGPIANGAO,SHIYINWEISHENGCHANJULVYIXISHIJIARULELIUCHUNJIAJIXIZUOWEIREWENDINGJI;PIGECAIZHISHOUJIQIAOTAOZHONGDEGEHANLIANGBIQITACAIZHIDEHANLIANGGAO,SHIYINWEIZHONGGESUANYANTONGCHANGYONGZUOPIGEDEROULIAO。
3 结语
CAIYONGRENGONGMONIHANYERONGYEQIANYIDEMOSHICHULIYANGPIN,JIANLILEDIANGANOUHEDENGLIZITIZHIPUFACEDINGSHOUJIQIAOTAOZHONG14 ZHONGKEQIANYIYUANSUHANLIANGDEFENXIFANGFA。GAIFANGFACAOZUOJIANBIAN,GANRAOXIAO,LINGMINDUGAO,DINGLIANGZHUNQUE,SHIYONGYUSHOUJIQIAOTAOZHONG14 ZHONGKEQIANYIYUANSUHANLIANGDECEDING。