本文關(guān)鍵詞：土壤和沉積物中草甘膦的檢測方法　出處：《南京理工大學(xué)》2017年碩士論文　論文類型：學(xué)位論文

  更多相關(guān)文章： 土壤/沉積物 草甘膦 高效液相色譜 熒光檢測 柱前衍生 理化性質(zhì) 方法驗證

【摘要】：草甘膦(Gly)自1974年推向市場以來,因為其具有較強的內(nèi)吸傳導(dǎo)性和廣譜的滅殺效果,已成為使用最為普遍、銷售量最大的除草劑。由于草甘膦的使用量越來越大,施藥范圍越來越廣,且其在土壤中具有中等的持留性(t1/2在1-174d),草甘膦在土壤環(huán)境中的污染也越發(fā)受到關(guān)注。我國的《土壤環(huán)境質(zhì)量標(biāo)準(zhǔn)》(修訂)(GB15618-2008)的征求意見稿中增加草甘膦為有機污染物之一。草甘膦的化學(xué)性質(zhì)使得對它的分析測定困難,草甘膦的極性和水溶性不利于對其進行提取,而且草甘膦缺少發(fā)色基團和熒光基團,在利用色譜法進行檢測前必須先進行衍生。尤其在土壤環(huán)境中,草甘膦極易被土壤顆粒吸附,并與土壤中有機質(zhì)、腐殖酸、金屬氧化物及重金屬離子等反應(yīng),所以對土壤中草甘膦的痕量檢測愈加困難。目前,我國還沒有土壤及沉積物中草甘膦的標(biāo)準(zhǔn)檢測方法,而之前報道過的分析方法,如采用氣相色譜串聯(lián)質(zhì)譜或液相色譜串聯(lián)質(zhì)譜法進行檢測,由于操作復(fù)雜,造價昂貴等原因,無法大范圍推廣。為了更好地監(jiān)測和分析草甘膦在土壤和沉積物中的污染狀況,迫切需要建立一套經(jīng)濟實惠,實施方便且準(zhǔn)確可靠的土壤及沉積物中草甘膦的標(biāo)準(zhǔn)檢測技術(shù)。本文建立了土壤和沉積物中草甘膦測定的標(biāo)準(zhǔn)檢測方法,并探究了土壤的不同理化性質(zhì)對草甘膦檢測的影響,并按照《環(huán)境監(jiān)測分析方法標(biāo)準(zhǔn)制修訂技術(shù)導(dǎo)則》(HJ 168)和《國家環(huán)境污染物監(jiān)測方法標(biāo)準(zhǔn)制修訂工作暫行要求》(環(huán)科函[2009]10號)的要求,對該標(biāo)準(zhǔn)方法進行了六家實驗室驗證。主要研究內(nèi)容和結(jié)果如下:(1)土壤及沉積物中草甘膦分析方法的建立:土壤樣品用0.03 mol/L磷酸鈉和0.01 mol/L的檸檬酸三鈉混合溶液提取,超聲提取后,用鹽酸(HC1)調(diào)節(jié)溶液pH至9,經(jīng)正己烷萃取凈化,萃取液與9-芴氯甲酸甲酯(FMOC-C1)進行衍生化反應(yīng),采用液相色譜-熒光檢測器,以乙腈/0.2%磷酸水溶液作為流動相,對樣品進行檢測。對樣品前處理方法進行優(yōu)化,通過磷酸鹽與草甘膦在土壤中競爭吸附位點,降低草甘膦的吸附量,并通過添加金屬離子絡(luò)合劑解除草甘膦與土壤中金屬離子的絡(luò)合,解決了土壤中草甘膦提取困難的難題。該分析方法操作簡單,靈敏度高,重現(xiàn)性好。在0.005～0.5 mg/L濃度范圍內(nèi),標(biāo)準(zhǔn)工作曲線的線性相關(guān)系數(shù)R20.999,土壤樣品平均回收率為75%-100%,相對標(biāo)準(zhǔn)偏差均15%。方法檢出限為0.01 mg/kg,測定下限為0.04mg/kg,添加回收率及檢出限均能滿足農(nóng)土壤環(huán)境質(zhì)量標(biāo)準(zhǔn)要求(0.5mg/kg)。(2)通過比較土壤腐殖酸含量,土壤pH值和七種重金屬離子對草甘膦回收率的影響,探究土壤理化性質(zhì)對草甘膦檢測的影響。結(jié)果表明:土壤中有機質(zhì)含量越高,對草甘膦的吸附越強,回收率越低;土壤pH值對草甘膦的回收率有重大影響。在酸性土壤中,草甘膦以分子形態(tài)存在,而在堿性條件下,大多是以陰離子的形態(tài)存在,與帶有負(fù)電荷的土壤顆粒相排斥,減少了草甘膦的吸附量;土壤中的重金屬離子(Cu~(2+),Fe~(2+),Fe3+,Zn~(2+),Ni~(2+))可以和草甘膦形成穩(wěn)定的絡(luò)合物,使回收率降低。而重金屬離子Co~(2+)和Mn~(2+)對草甘膦沒有影響;建立的土壤和沉積物中草甘膦的檢測方法能滿足各種類型的土壤和沉積物。其中磷酸鈉和檸檬酸三鈉提取液具有緩沖溶液的效果,可以適應(yīng)各種pH環(huán)境的土壤,而且檸檬酸三鈉可以去除土壤中大部分重金屬離子的干擾。(3)按照《環(huán)境監(jiān)測分析方法標(biāo)準(zhǔn)制修訂技術(shù)導(dǎo)則》(HJ 168)和《國家環(huán)境污染物監(jiān)測方法標(biāo)準(zhǔn)制修訂工作暫行要求》(環(huán)科函[2009]10號)的要求,組織了 6家有資質(zhì)的實驗室對該標(biāo)準(zhǔn)方法進行驗證。6家實驗室驗證結(jié)果表明,方法檢出限為0.011 mg/kg,測定下限為0.043 mg/kg。遠(yuǎn)低于我國環(huán)境質(zhì)量標(biāo)準(zhǔn)限值(0.5 mg/kg),所以本方法檢出限滿足現(xiàn)在及以后環(huán)保標(biāo)準(zhǔn)的要求。方法具有較好的重復(fù)性和再現(xiàn)性,湖南紅壤的重復(fù)性限為0.016mg/kg-0.134 mg/kg,再現(xiàn)性為0.034mg/kg-0.299 mg/kg,基質(zhì)加標(biāo)回收率最終值為 99.21%±11.75%-101.15%±9.60%;水稻土的重復(fù)性限為 0.015mg/kg-0.139mg/kg,再現(xiàn)性為0.027mg/kg-0.214mg/kg,基質(zhì)加標(biāo)回收率最終值為83.53%±5.96%-88.79%±4.11%;東北黑土的重復(fù)性限為 0.016mg/kg-0.147mg/kg,再現(xiàn)性為 0.020mg/kg-0.172mg/kg,基質(zhì)加標(biāo)回收率最終值為 79.96%±10.09%-83.66%±3.11%;前湖沉積物的重復(fù)性限為0.017 mg/kg-0.140 mg/kg,再現(xiàn)性為0.024 mg/kg-0.178 mg/kg,基質(zhì)加標(biāo)回收率最終值為75.31%±9.70%-80.62%±12.92%;秦淮河沉積物的重復(fù)性限為0.018 mg/kg-0.182 mg/kg,再現(xiàn)性為0.022 mg/kg-0.208 mg/kg,基質(zhì)加標(biāo)回收率最終值為79.26%±10.07%82.03%±10.14%。結(jié)果表明,該標(biāo)準(zhǔn)方法的各項特性指標(biāo)能達到預(yù)期要求。
[Abstract]:Glyphosate (Gly) since 1974 to the market, because of its strong absorption within the conduction and broad-spectrum killing effect, has become the most widely used, the largest sales due to the use of glyphosate herbicide. More and more big, more and more wide range of application, and in the soil with moderate retention (t1/2 in 1-174d), pollution of glyphosate in the soil environment is more and more attention. "Soil environmental quality standard in China" (Amendment) (GB15618-2008) draft increased glyphosate as organic pollutants. The chemical properties of glyphosate and makes analysis on it is difficult to determine the polarity and water solubility of glyphosate is not conducive to the extraction, and the lack of glyphosate chromophore and fluorophore, are must be derived before detection in the use of chromatography. Especially in the soil environment, glyphosate is easily adsorbed by soil, and And the organic matter in the soil, humic acid, metal oxides and heavy metal ions and other reactions, so more difficult to trace detection of glyphosate in soil. At present, no method for detection of glyphosate in soil and sediment in China, and the analysis methods reported before, such as the use of gas chromatography or liquid chromatography tandem mass spectrometry mass spectrometry detection, because of complex operation, high cost and other reasons, can not be extended. In order to pollution in soil and sediment in better monitoring and analysis of glyphosate, the urgent need to establish a set of economic benefits, the implementation of glyphosate in soil and sediment is convenient and accurate and reliable in the standard detection technology. This paper established detection method the standard Determination of glyphosate in soil and sediment, and to explore the effects of different soil physical and chemical properties of glyphosate detection, and in accordance with "environmental monitoring analysis method Technical guidelines for standard revision (HJ > 168) and "Interim National Environmental Monitoring Methods and standard system revision > (ring of letter [2009]10) requirements, the standard method for six lab experiments. The main research contents and results are as follows: (1) the establishment of soil and sediment in glyphosate analysis methods: the soil samples with three citric acid mixed solution of sodium 0.03 mol/L sodium phosphate and 0.01 mol/L extraction, ultrasonic extraction, using hydrochloric acid (HC1) solution was adjusted to pH 9 by n-hexane extraction purification, extract and 9- fluorene methyl chloroformate (FMOC-C1) derivatization reaction was carried out by liquid chromatography a fluorescence detector with acetonitrile /0.2% phosphoric acid water solution as mobile phase, detection of the sample. The sample preparation methods were optimized by phosphate and glyphosate competing adsorption sites in the soil, reduce the adsorption amount of glyphosate, and by adding metal ions Remove metal ion complexing agent sub complexation of glyphosate and soil, solve the difficult problem of glyphosate in soil extraction. This method has the advantages of simple operation, high sensitivity and good reproducibility. In 0.005 ~ 0.5 mg/L concentration range, the linear correlation coefficient R20.999 standard curve, soil samples the average recovery rate was 75%-100%, the relative standard deviation 15%. the detection limit was 0.01 mg/kg. The detection limit is 0.04mg/kg, recovery and detection limit can meet the requirements of agricultural soil environmental quality standard (0.5mg/kg). (2) through the comparison of soil humic acid content, soil pH value and seven kinds of heavy metal ions on recovery of glyphosate, explore the influence of soil the nature of glyphosate detection. The results show that the higher the content of organic matter in soil, the adsorption of glyphosate is stronger, the recovery rate is low; soil pH value of glyphosate recovery rate has a significant impact on the acid. In soil, glyphosate in molecular form, while in alkaline conditions, mostly in the form of anion repulsion, and soil particles with negative charge, reduce the adsorption of glyphosate in soil; heavy metal ions (Cu~ (2+), Fe~ (2+), Fe3+, Zn~ (2+). Ni~ (2+)) and Glyphosate can form a stable complex, the recovery rate decreased. And the heavy metal ion Co~ (2+) and Mn~ (2+) had no effect on glyphosate; detection method of glyphosate in soil and sediment can meet various types of soil and sediment. The effect of sodium phosphate and citric acid three sodium extract with buffer solution, pH can adapt to various environment and soil disturbance, citric acid three sodium ions can remove most of the heavy metals in soil. (3) according to the "technical guidelines for environmental monitoring and analysis methods of the revision of the standard (HJ > 168) and" national environmental pollutants monitoring The interim law revision of the standard system > (ring of letter [2009]10) requirements, the organization of the standard methods for 6 qualified laboratory validation of.6 laboratory verification results show that the detection limit was 0.011 mg/kg, the detection limit is 0.043 mg/kg. far below the national environmental quality standard limits (0.5 mg/kg) so, the detection limit of the method meet the current and future environmental standards. The method has better repeatability and reproducibility, repeatability limit for 0.016mg/kg-0.134 mg/kg in Hunan red soil, the reproducibility was 0.034mg/kg-0.299 mg/kg, average recovery matrix final value is 99.21% + 11.75%-101.15% + 9.60%; repeatability limit of paddy soil is 0.015mg/kg-0.139mg/kg. The reproducibility of 0.027mg/kg-0.214mg/kg matrix, the recovery rate of final value is 83.53% + 5.96%-88.79% + 4.11%; repeatability limit of black soil in Northeast China 0.016mg/kg-0.147mg/kg, reproducibility was 0 .020mg/kg-0.172mg/kg matrix, recovery of the final value of 79.96% + 10.09%-83.66% + 3.11%; repeatability limit before the lake sediment is 0.017 mg/kg-0.140 mg/kg 0.024 mg/kg-0.178 mg/kg, reproducibility, matrix recoveries of the final value of 75.31% + 9.70%-80.62% + 12.92%; repeatability limit the Qinhuai River sediment was 0.018 mg/kg-0.182 mg/kg, reproducibility was 0.022 mg/kg-0.208 mg/kg, the matrix recoveries of final values indicate that the 79.26% + 10.07%82.03% + 10.14%. results, the characteristic index of the standard method can achieve the desired requirements.

【學(xué)位授予單位】：南京理工大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：X839.2

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