中华预防医学杂志
中華預防醫學雜誌
중화예방의학잡지
CHINESE JOURNAL OF
2013年
7期
641-647
,共7页
刘红河%毛丽莎%康莉%刘桂华%彭朝琼
劉紅河%毛麗莎%康莉%劉桂華%彭朝瓊
류홍하%모려사%강리%류계화%팽조경
色谱法,液相%色谱法,高压液相%三聚氰胺%三聚氰酸%水%尿
色譜法,液相%色譜法,高壓液相%三聚氰胺%三聚氰痠%水%尿
색보법,액상%색보법,고압액상%삼취청알%삼취청산%수%뇨
Chromatography,liquid%Chromatography,high pressure liquid%Melamine%Cyanuric acid%Water%Urine
目的 建立固相萃取结合亲水作用液相色谱-串联质谱联用法测定各种水体和尿中三聚氰胺及三聚氰酸的方法,并对采自全国的501份水样和216份尿样中三聚氰胺和三聚氰酸的含量进行调查.方法 取100 ml水样或10 ml尿样,用浓盐酸调节pH至3.0,加入15N3-三聚氰胺和15N3-13C3-三聚氰酸混合内标溶液,再于水样中加入100 ml乙腈(尿样加10 ml乙腈),混匀后用MCT固相萃取柱净化,用3 ml甲醇洗脱一次,然后采用2.5 ml含体积分数为5％氨水的甲醇溶液洗脱两次,收集流出液,于40℃下用氮气吹干,加入含体积分数为90％乙腈的2 mmol/L乙酸铵水溶液,漩涡振荡,充分溶解,用0.22 μm有机滤膜过滤,滤液采用液相色谱-串联四极杆质谱联用仪测定,采用内标法定量,并对方法的检测限、精密度和准确度进行评价.并用此法检测了501份水祥和216份尿样中三聚氰胺和三聚氰酸的含量.结果 分别采用15N3-三聚氰胺和15N3-13C3-三聚氰酸作为内标物,测得三聚氰胺和三聚氰酸在2.0～1000.0 g/L范围内线性关系良好(r值分别为0.9998和0.9997).水中三聚氰胺、三聚氰酸方法检出限分别为0.4、0.3 ng/L,尿中三聚氰胺、三聚氰酸方法检出限分别为4.0、3.0 ng/L.水、尿样在3个添加水平范围内的平均回收率为95.3％ ～ 100.1％,RSD＜4.02％.在501份水样中,19.9％(100/501)水样中检出三聚氰胺,5.2％(26/501)水样中检出三聚氰酸,含量在0.03～5.00 g/L之间,24.5％(53/216)的尿样中检出三聚氰胺或三聚氰酸,含量在0.01～1.00 g/L之间.结论 建立的MCT固相萃取结合亲水作用液相色谱-电喷雾串联质谱联用测定法可以满足各种水体和尿液中三聚氰胺和三聚氰酸的检测要求.同时,这两种物质在我国环境水体和人群中存在较为广泛的污染.
目的 建立固相萃取結閤親水作用液相色譜-串聯質譜聯用法測定各種水體和尿中三聚氰胺及三聚氰痠的方法,併對採自全國的501份水樣和216份尿樣中三聚氰胺和三聚氰痠的含量進行調查.方法 取100 ml水樣或10 ml尿樣,用濃鹽痠調節pH至3.0,加入15N3-三聚氰胺和15N3-13C3-三聚氰痠混閤內標溶液,再于水樣中加入100 ml乙腈(尿樣加10 ml乙腈),混勻後用MCT固相萃取柱淨化,用3 ml甲醇洗脫一次,然後採用2.5 ml含體積分數為5％氨水的甲醇溶液洗脫兩次,收集流齣液,于40℃下用氮氣吹榦,加入含體積分數為90％乙腈的2 mmol/L乙痠銨水溶液,漩渦振盪,充分溶解,用0.22 μm有機濾膜過濾,濾液採用液相色譜-串聯四極桿質譜聯用儀測定,採用內標法定量,併對方法的檢測限、精密度和準確度進行評價.併用此法檢測瞭501份水祥和216份尿樣中三聚氰胺和三聚氰痠的含量.結果 分彆採用15N3-三聚氰胺和15N3-13C3-三聚氰痠作為內標物,測得三聚氰胺和三聚氰痠在2.0～1000.0 g/L範圍內線性關繫良好(r值分彆為0.9998和0.9997).水中三聚氰胺、三聚氰痠方法檢齣限分彆為0.4、0.3 ng/L,尿中三聚氰胺、三聚氰痠方法檢齣限分彆為4.0、3.0 ng/L.水、尿樣在3箇添加水平範圍內的平均迴收率為95.3％ ～ 100.1％,RSD＜4.02％.在501份水樣中,19.9％(100/501)水樣中檢齣三聚氰胺,5.2％(26/501)水樣中檢齣三聚氰痠,含量在0.03～5.00 g/L之間,24.5％(53/216)的尿樣中檢齣三聚氰胺或三聚氰痠,含量在0.01～1.00 g/L之間.結論 建立的MCT固相萃取結閤親水作用液相色譜-電噴霧串聯質譜聯用測定法可以滿足各種水體和尿液中三聚氰胺和三聚氰痠的檢測要求.同時,這兩種物質在我國環境水體和人群中存在較為廣汎的汙染.
목적 건립고상췌취결합친수작용액상색보-천련질보련용법측정각충수체화뇨중삼취청알급삼취청산적방법,병대채자전국적501빈수양화216빈뇨양중삼취청알화삼취청산적함량진행조사.방법 취100 ml수양혹10 ml뇨양,용농염산조절pH지3.0,가입15N3-삼취청알화15N3-13C3-삼취청산혼합내표용액,재우수양중가입100 ml을정(뇨양가10 ml을정),혼균후용MCT고상췌취주정화,용3 ml갑순세탈일차,연후채용2.5 ml함체적분수위5％안수적갑순용액세탈량차,수집류출액,우40℃하용담기취간,가입함체적분수위90％을정적2 mmol/L을산안수용액,선와진탕,충분용해,용0.22 μm유궤려막과려,려액채용액상색보-천련사겁간질보련용의측정,채용내표법정량,병대방법적검측한、정밀도화준학도진행평개.병용차법검측료501빈수상화216빈뇨양중삼취청알화삼취청산적함량.결과 분별채용15N3-삼취청알화15N3-13C3-삼취청산작위내표물,측득삼취청알화삼취청산재2.0～1000.0 g/L범위내선성관계량호(r치분별위0.9998화0.9997).수중삼취청알、삼취청산방법검출한분별위0.4、0.3 ng/L,뇨중삼취청알、삼취청산방법검출한분별위4.0、3.0 ng/L.수、뇨양재3개첨가수평범위내적평균회수솔위95.3％ ～ 100.1％,RSD＜4.02％.재501빈수양중,19.9％(100/501)수양중검출삼취청알,5.2％(26/501)수양중검출삼취청산,함량재0.03～5.00 g/L지간,24.5％(53/216)적뇨양중검출삼취청알혹삼취청산,함량재0.01～1.00 g/L지간.결론 건립적MCT고상췌취결합친수작용액상색보-전분무천련질보련용측정법가이만족각충수체화뇨액중삼취청알화삼취청산적검측요구.동시,저량충물질재아국배경수체화인군중존재교위엄범적오염.
Objective We aimed to establish a sensitive quantified method for the simultaneous determination of melamine and cyanuric acid residues in water and urine by hydrophilic interaction liquid chromatography coupled with electrospray tandem mass spectrometry (HILIC-ESI-MS/MS) with the pretreatment of hydrophilic functional silica gel and cation exchange resin mixed solid phase extraction column(MCT),and to investigate the melamine and cyanuric acid residues in 501 water and 216 urine from several province and city.Methods About 100 ml water (or 10 ml urine) was adjusted to pH 3.0 with concentrated hydrochloric acid,and then mixed with the internal standard solution (15 N3-melamine and 15N3-13C3-cyanuric acid) and 100 ml acetonitrile (10 ml for urine).The solution was cleaned with MCT solid-phase extraction column,and eluted once by 3 ml methanol and twice by 2.5 ml methanol (containing 5％ ammonia water).The effluent was collected and dried by N2 flow at 40 ℃,and then diluted to 2 mmol/L ammonium acetate containing 90％ volume fraction acetonitrile.The completely dissolved solution was then filtered with 0.22 μm organic membrane; and the filtrate was detected by high performance liquid chromatography-tandem mass spectrometry and quantified with internal standards.The repeatability and sensitivity of the assay were evaluated.Then we detected the melamine and cyanuric acid residues in 501 water and 216 urine samples collected from several province and city.Results By the quantification of internal standard 15N3-melamine and 15N3-13C3-cyanuric acid,the melamine and cyanuric acid were linear in the range of 2.0-1000.0 μg/L with correlation coefficient of 0.9998 and 0.9997.The detection limits of the method were separately 0.4 ng/L (melamine) and 0.3 ng/L (cyanuric acid) for water,and 4.0 ng/L (melamine) and 3.0 ng/L (cyanuric acid) for urine.The average recovery rate was around 95.3％-100.1％ with the relative standard deviation(RSD) was ＜4.02％.Out of the 501 water samples,melamine was detected out in 19.9％ (100/501) and cyanuric acid was detected out in 5.2％ (26/501).The content was around 0.03-5.00 g/L Melamine or cyanuric acid was detected out in 24.5％ of the urine samples (53/216),with the content around 0.01-1.00 g/L.Conclusion The established method of solid phase extraction-hydrophilic interaction liquid chromatography-electrospray tandem mass spectrometry can satisfy the requirement for detection of melamine and cyanuric acid residues in all sorts of water and urine.Meanwhile,the two sustances widely existed in water and Chinese population.
