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《長(zhǎng)三角生態(tài)綠色一體化發(fā)展示范區(qū)揮發(fā)性有機(jī)物走航監(jiān)測(cè)技術(shù)規(guī)范》編制說(shuō)明編制組二〇二〇年十一月

目錄TOC\o"1-2"\h\z\u1.背景情況和起草過(guò)程

《長(zhǎng)三角生態(tài)綠色一體化發(fā)展示范區(qū)揮發(fā)性有機(jī)物走航監(jiān)測(cè)技術(shù)規(guī)范》編制說(shuō)明1.背景情況和起草過(guò)程1.1背景情況為貫徹《中華人民共和國(guó)環(huán)境保護(hù)法》、《中華人民共和國(guó)大氣污染防治法》和中共中央、國(guó)務(wù)院《長(zhǎng)江三角洲區(qū)域一體化發(fā)展規(guī)劃綱要》,實(shí)現(xiàn)長(zhǎng)三角區(qū)域標(biāo)準(zhǔn)統(tǒng)一,上海、江蘇、浙江三省生態(tài)環(huán)境局(廳)聯(lián)合三地市場(chǎng)監(jiān)督管理局下達(dá)任務(wù),編制針對(duì)長(zhǎng)三角一體化示范區(qū)的《長(zhǎng)三角生態(tài)綠色一體化發(fā)展示范區(qū)揮發(fā)性有機(jī)物走航監(jiān)測(cè)技術(shù)規(guī)范》。標(biāo)準(zhǔn)編制任務(wù)由上海市環(huán)境監(jiān)測(cè)中心、江蘇省環(huán)境監(jiān)測(cè)中心、浙江省生態(tài)環(huán)境監(jiān)測(cè)中心、浙江省生態(tài)環(huán)境科學(xué)設(shè)計(jì)研究院承擔(dān)。1.2必要性說(shuō)明(1)政策將走航監(jiān)測(cè)作為VOCs管控重要手段國(guó)家和地方相關(guān)政策都將走航監(jiān)測(cè)作為VOCs污染問(wèn)題排查的重要手段。2019年生態(tài)環(huán)境部印發(fā)的關(guān)于《重點(diǎn)行業(yè)揮發(fā)性有機(jī)物綜合治理方案》(環(huán)大氣〔2019〕53號(hào))的通知中,首次提出了開(kāi)展走航監(jiān)測(cè)的要求?!斗桨浮诽岢黾哟蠊I(yè)園區(qū)和產(chǎn)業(yè)集群VOCs綜合治理,提升工業(yè)園區(qū)和產(chǎn)業(yè)集群監(jiān)測(cè)監(jiān)控能力,加快推進(jìn)重點(diǎn)工業(yè)園區(qū)和產(chǎn)業(yè)集群環(huán)境空氣質(zhì)量VOCs監(jiān)測(cè)工作。“石化、化工類工業(yè)園區(qū)應(yīng)建設(shè)監(jiān)測(cè)預(yù)警監(jiān)控體系,具備條件的,開(kāi)展走航監(jiān)測(cè)、網(wǎng)格化監(jiān)測(cè)以及溯源分析等工作”。2020年6月,生態(tài)環(huán)境部印發(fā)的《2020年揮發(fā)性有機(jī)物治理攻堅(jiān)方案》(環(huán)大氣〔2020〕33號(hào))中提出了由生態(tài)環(huán)境部組織重點(diǎn)區(qū)域各省(市)對(duì)重點(diǎn)工業(yè)園區(qū)和企業(yè)集群開(kāi)展走航監(jiān)測(cè),排查突出問(wèn)題,評(píng)估VOCs整治效果。地方層面上,上海市生態(tài)環(huán)境局《關(guān)于開(kāi)展本市重點(diǎn)行業(yè)揮發(fā)性有機(jī)物綜合治理工作的通知》(滬環(huán)氣〔2020〕41號(hào))中明確要求工業(yè)園區(qū)應(yīng)采用走航監(jiān)測(cè)、蘇瑪罐采樣監(jiān)測(cè)等手段動(dòng)態(tài)監(jiān)控園區(qū)周界及內(nèi)部VOCs排放情況。長(zhǎng)三角化工園區(qū)密集,走航監(jiān)測(cè)作為VOCs監(jiān)管的重要手段,亟需出臺(tái)相關(guān)技術(shù)規(guī)范指導(dǎo)工作開(kāi)展,更好地服務(wù)于管理需求。(2)相關(guān)環(huán)保標(biāo)準(zhǔn)和環(huán)保工作的需要環(huán)境治理,監(jiān)測(cè)先行。揮發(fā)性有機(jī)物(VOCs)在大氣中參與一系列復(fù)雜的光化學(xué)反應(yīng),是重要的臭氧前體物,以《大氣污染物綜合排放標(biāo)準(zhǔn)》為代表的多項(xiàng)綜合及行業(yè)排放標(biāo)準(zhǔn)都對(duì)多種典型揮發(fā)性有機(jī)物的廠界排放濃度進(jìn)行了規(guī)定。然而揮發(fā)性有機(jī)物來(lái)源廣泛、組成復(fù)雜,基于傳統(tǒng)手工采樣實(shí)驗(yàn)室分析的方法難以對(duì)企業(yè)廠界排放濃度實(shí)現(xiàn)持續(xù)監(jiān)控,揮發(fā)性有機(jī)物惡臭(異味)引起的大氣環(huán)境投訴及信訪十分突出。近年來(lái),以氣相色譜方法為代表的在線監(jiān)測(cè)技術(shù)取得了長(zhǎng)足進(jìn)步,長(zhǎng)三角區(qū)域內(nèi)多個(gè)大型工業(yè)區(qū)均建立起了在線監(jiān)測(cè)網(wǎng)絡(luò),對(duì)園區(qū)揮發(fā)性有機(jī)物排放開(kāi)展了實(shí)時(shí)監(jiān)控,初步掌握了園區(qū)VOCs時(shí)空變化特征。為進(jìn)一步實(shí)現(xiàn)VOCs精細(xì)化管控、精準(zhǔn)污染溯源,勢(shì)必需要加強(qiáng)對(duì)在線監(jiān)測(cè)網(wǎng)絡(luò)空白點(diǎn)以及次一級(jí)規(guī)模工業(yè)地塊的監(jiān)控。揮發(fā)性有機(jī)物走航監(jiān)測(cè),指利用車(chē)載快速質(zhì)譜技術(shù),調(diào)查一定區(qū)域范圍揮發(fā)性有機(jī)物時(shí)空分布及趨勢(shì),同步識(shí)別潛在排放源。相比固定站點(diǎn)在線監(jiān)測(cè),走航監(jiān)測(cè)機(jī)動(dòng)性強(qiáng),能夠快速掌握VOCs的動(dòng)態(tài)空間分布及其污染特征,是對(duì)排放源的環(huán)境空氣影響進(jìn)行跟蹤溯源的重要技術(shù)手段,也是環(huán)境空氣固定站自動(dòng)監(jiān)測(cè)技術(shù)和污染源在線監(jiān)測(cè)技術(shù)在管理需求數(shù)據(jù)支持上不足的一種技術(shù)手段補(bǔ)充。目前應(yīng)用在工業(yè)區(qū)環(huán)境空氣VOCs連續(xù)監(jiān)測(cè)中,彌補(bǔ)了固定站自動(dòng)監(jiān)測(cè)數(shù)據(jù)空間局限性問(wèn)題,應(yīng)用于排放源異常排放或者突發(fā)環(huán)境事件的應(yīng)急偵檢中,在時(shí)間上和空間上顯示了技術(shù)方法的快速、靈活的特點(diǎn)。該方法技術(shù)推廣應(yīng)用可以直接為大氣VOCs的精細(xì)化管控、精準(zhǔn)環(huán)境執(zhí)法提供技術(shù)支撐。(3)目前走航監(jiān)測(cè)實(shí)施情況和存在問(wèn)題近年來(lái),長(zhǎng)三角多個(gè)城市已開(kāi)展了揮發(fā)性有機(jī)物走航監(jiān)測(cè),積累了較豐富的應(yīng)用經(jīng)驗(yàn)。以上海為例,上海市環(huán)境監(jiān)測(cè)中心已連續(xù)三年開(kāi)展揮發(fā)性有機(jī)物走航監(jiān)測(cè),積累了豐富的實(shí)戰(zhàn)經(jīng)驗(yàn),2019年至今在長(zhǎng)三角區(qū)域共50多個(gè)工業(yè)園區(qū)走航監(jiān)測(cè),發(fā)現(xiàn)問(wèn)題點(diǎn)位100余個(gè),開(kāi)展監(jiān)測(cè)執(zhí)法聯(lián)動(dòng)13次,并在金山-平湖開(kāi)展了兩地聯(lián)合監(jiān)測(cè)執(zhí)法,有效實(shí)現(xiàn)VOCs排放精準(zhǔn)管控;在重大活動(dòng)空氣質(zhì)量保障、臭氧污染治理工作中,走航監(jiān)測(cè)服務(wù)管理及時(shí)提供了數(shù)據(jù)支持,發(fā)揮了走航方法本身的檢測(cè)技術(shù)優(yōu)勢(shì)。2019年至今,飛行時(shí)間質(zhì)譜走航監(jiān)測(cè)技術(shù)已經(jīng)在江蘇13個(gè)地級(jí)市,50多個(gè)工業(yè)園區(qū)開(kāi)展了實(shí)際應(yīng)用,參與監(jiān)測(cè)執(zhí)法聯(lián)動(dòng)50余次,開(kāi)展異味調(diào)查溯源20余次,共計(jì)發(fā)現(xiàn)問(wèn)題點(diǎn)位400余個(gè)。浙江省生態(tài)環(huán)境監(jiān)測(cè)中心已開(kāi)展了多次揮發(fā)性有機(jī)物走航監(jiān)測(cè),其中在舟山綠色石化基地、麗水市工業(yè)園區(qū)走航監(jiān)測(cè)過(guò)程中,發(fā)現(xiàn)問(wèn)題點(diǎn)位50余個(gè),為環(huán)境管理提供了數(shù)據(jù)支持;在磐安溴乙烷泄露事故、溫嶺槽罐車(chē)爆炸事故應(yīng)急監(jiān)測(cè)中,走航車(chē)在確定污染范圍過(guò)程中作用明顯,發(fā)揮了走航快速、高效的技術(shù)優(yōu)勢(shì)。隨著認(rèn)識(shí)逐漸深入,發(fā)現(xiàn)走航監(jiān)測(cè)還存在一系列問(wèn)題。由于缺乏設(shè)備統(tǒng)一的技術(shù)規(guī)范和相關(guān)方法標(biāo)準(zhǔn),不同品牌設(shè)備原理特點(diǎn)差異較大、監(jiān)測(cè)質(zhì)量控制和質(zhì)量保證不到位,數(shù)據(jù)可比性較差,數(shù)據(jù)準(zhǔn)確性也尚未得到系統(tǒng)驗(yàn)證,為此大量的不同區(qū)域走航數(shù)據(jù),系統(tǒng)和關(guān)聯(lián)性分析難以成為體系,目前應(yīng)用更多的局限于較為分散的、對(duì)區(qū)域污染排放線索定性“偵查”,區(qū)域性VOCs排放研究和更精準(zhǔn)的服務(wù)管理由于數(shù)據(jù)質(zhì)量問(wèn)題受到限制。具體為:由于缺乏統(tǒng)一的質(zhì)量控制方法和要求,不同走航設(shè)備在同一時(shí)間、同一地點(diǎn),分析結(jié)果存在較大差異,設(shè)備的定量準(zhǔn)確性亟待改善。且因沒(méi)有相關(guān)標(biāo)準(zhǔn),定量數(shù)據(jù)無(wú)法用作污染物超標(biāo)判定依據(jù)。受設(shè)備原理和性能所限,多個(gè)監(jiān)測(cè)污染物因子存在干擾,在較復(fù)雜污染情況下,儀器可能出現(xiàn)定性錯(cuò)誤,仍需借助人工經(jīng)驗(yàn)判斷和其他參考信息,這對(duì)監(jiān)測(cè)執(zhí)法聯(lián)動(dòng)時(shí)判斷污染來(lái)源帶來(lái)一定困難;走航監(jiān)測(cè)實(shí)施方案不一致,難以實(shí)現(xiàn)執(zhí)法口徑統(tǒng)一。同一型號(hào)不同設(shè)備之間數(shù)據(jù)一致性尚待驗(yàn)證,多次走航監(jiān)測(cè)任務(wù)形成的區(qū)域污染分布狀況難以進(jìn)行對(duì)比和綜合分析,難以利用多套設(shè)備在短時(shí)間內(nèi)得到大范圍的污染時(shí)空分布。因此,將先進(jìn)的監(jiān)測(cè)技術(shù)有效精準(zhǔn)直接服務(wù)于科研與管理,實(shí)現(xiàn)精準(zhǔn)溯源、聯(lián)合執(zhí)法,是走航監(jiān)測(cè)亟需解決的問(wèn)題。1.3起草過(guò)程(1)前期準(zhǔn)備2020年6月,上海市環(huán)境監(jiān)測(cè)中心接受任務(wù)后,會(huì)同江蘇省環(huán)境監(jiān)測(cè)中心、浙江省生態(tài)環(huán)境監(jiān)測(cè)中心、浙江省生態(tài)環(huán)境科學(xué)設(shè)計(jì)研究院,成立了編制組,收集并分析了國(guó)內(nèi)外各儀器廠家的情況資料以及走航監(jiān)測(cè)方法的相關(guān)文獻(xiàn)。編制組起草了《長(zhǎng)三角生態(tài)綠色一體化發(fā)展示范區(qū)揮發(fā)性有機(jī)物走航監(jiān)測(cè)技術(shù)規(guī)范》(以下簡(jiǎn)稱《規(guī)范》)文本,并對(duì)草案的框架和內(nèi)容進(jìn)行了多次內(nèi)部討論。6月23日,編制組內(nèi)部共反饋草案修改意見(jiàn)29條,編制組根據(jù)討論征集的意見(jiàn)進(jìn)行了修改,形成內(nèi)部討論稿(第一稿)。7月2日,召開(kāi)會(huì)議修改內(nèi)部討論稿(第一稿),共反饋意見(jiàn)9條,確定了規(guī)范驗(yàn)證實(shí)驗(yàn)方案。編制組根據(jù)討論征集的意見(jiàn)進(jìn)行了修改,形成內(nèi)部討論稿(第二稿),同時(shí)組織開(kāi)展規(guī)范驗(yàn)證實(shí)驗(yàn)。2020年8-10月,完成《規(guī)范》文本(2)規(guī)范立項(xiàng)2020年11月,《規(guī)范》獲批立項(xiàng)。編制組提交《規(guī)范》征求意見(jiàn)稿。(3)征求意見(jiàn)2020年11月16日,上海市市場(chǎng)監(jiān)督管理局對(duì)《規(guī)范》公開(kāi)征求意見(jiàn),其他省也同步開(kāi)展征求意見(jiàn)工作。公開(kāi)征求時(shí)間為11月16日至12月15日。2.國(guó)內(nèi)外走航監(jiān)測(cè)技術(shù)研究進(jìn)展近年來(lái),走航監(jiān)測(cè)技術(shù)作為在環(huán)境空氣監(jiān)測(cè)領(lǐng)域一種新技術(shù)手段已越來(lái)越受到關(guān)注,技術(shù)研發(fā)和探索應(yīng)用不斷拓展。針對(duì)常態(tài)污染指標(biāo)顆粒物監(jiān)測(cè)仍主要沿用光學(xué)原理的設(shè)備監(jiān)測(cè),對(duì)特征污染物VOCs監(jiān)測(cè)主要基于質(zhì)譜方法。國(guó)內(nèi)商品化開(kāi)發(fā)設(shè)備,比較成熟的技術(shù)為單光子電離-飛行時(shí)間質(zhì)譜(SPI-TOFMS)、氣相色譜-質(zhì)譜聯(lián)用技術(shù)(GC-MS)以及質(zhì)子轉(zhuǎn)移反應(yīng)質(zhì)譜法(PTR-MS)原理,供應(yīng)商截止目前已知有6家。編制組在前期走航監(jiān)測(cè)探索階段采用較多的設(shè)備主要是廣州禾信儀器股份有限公司生產(chǎn)的SPI-TOFMS。其余各品牌走航監(jiān)測(cè)設(shè)備均有接觸。據(jù)不完全文獻(xiàn)檢索分析,國(guó)外的快速質(zhì)譜主要以科研原理研究為主,SPI-TOFMS科研單位主要有德國(guó)國(guó)立環(huán)境與健康院、東京大學(xué)環(huán)境科學(xué)中心等。在科研領(lǐng)域,國(guó)內(nèi)的中國(guó)科學(xué)院大連化學(xué)物理研究所和生態(tài)環(huán)境研究中心等科研單位也一直在從事SPI-TOFMS的研究。國(guó)內(nèi)已有基于SPI-TOFMS和GC-MS的走航監(jiān)測(cè)案例報(bào)道。3.制定基本原則和技術(shù)路線3.1基本原則編制組本著科學(xué)性、先進(jìn)性和可操作性為原則,以HJ168《環(huán)境監(jiān)測(cè)分析方法標(biāo)準(zhǔn)制修訂技術(shù)指導(dǎo)原則》為依據(jù),廣泛了解行業(yè)現(xiàn)狀,在長(zhǎng)三角區(qū)域應(yīng)用現(xiàn)狀及工作需求的基礎(chǔ)上,不斷深入研究和完善,保證本標(biāo)準(zhǔn)的先進(jìn)性和適用性。確保標(biāo)準(zhǔn)規(guī)定的儀器性能指標(biāo)及技術(shù)要求滿足相關(guān)環(huán)境標(biāo)準(zhǔn)和環(huán)保管理工作的需求。3.2技術(shù)路線圖1規(guī)范制定技術(shù)路線

4.主要條款說(shuō)明4.1內(nèi)容框架本文件包括:前言、適用范圍、規(guī)范性引用文件、術(shù)語(yǔ)和定義、方法原理、試劑和材料、儀器和設(shè)備、實(shí)施方法、結(jié)果計(jì)算與表示、質(zhì)量控制與質(zhì)量保證、附錄共十一個(gè)部分。4.2范圍本規(guī)范規(guī)定了利用走航監(jiān)測(cè)技術(shù)測(cè)定環(huán)境空氣、無(wú)組織排放廢氣中揮發(fā)性有機(jī)物濃度,結(jié)合地理位置信息顯示揮發(fā)性有機(jī)物濃度空間分布的方法原理、儀器性能要求、監(jiān)測(cè)實(shí)施方法及質(zhì)量控制方法。本規(guī)范適用于長(zhǎng)三角生態(tài)綠色一體化發(fā)展示范區(qū),長(zhǎng)三角其它區(qū)域執(zhí)行本規(guī)范由各省(市)人民政府批準(zhǔn)實(shí)施。本規(guī)范目的在于為揮發(fā)性有機(jī)物排放監(jiān)控提供支持。走航監(jiān)測(cè)主要在城市道路、工業(yè)園區(qū)邊界及內(nèi)部道路、工業(yè)企業(yè)邊界和內(nèi)部道路開(kāi)展,監(jiān)測(cè)對(duì)象主要是環(huán)境空氣(城市、園區(qū)內(nèi)部、廠界)及無(wú)組織排放廢氣。本規(guī)范規(guī)定的技術(shù)內(nèi)容不因地域改變,但在其他區(qū)域?qū)嵤?,需由各?。ㄊ校┤嗣裾鷾?zhǔn)。4.3術(shù)語(yǔ)和定義本規(guī)范采用的術(shù)語(yǔ)和定義包括揮發(fā)性有機(jī)物、總揮發(fā)性有機(jī)物、走航監(jiān)測(cè)。目前尚無(wú)揮發(fā)性有機(jī)物的統(tǒng)一定義,各標(biāo)準(zhǔn)著眼點(diǎn)不同,對(duì)揮發(fā)性有機(jī)物的定義各有側(cè)重??紤]到走航監(jiān)測(cè)工作難以預(yù)測(cè)高值點(diǎn)位企業(yè),難以完全掌握區(qū)域所有監(jiān)測(cè)目標(biāo)所屬行業(yè),且設(shè)備可監(jiān)測(cè)的揮發(fā)性有機(jī)物不完全一致,本規(guī)范采用的揮發(fā)性有機(jī)物定義綜合參考GB37822-2019以及DB31/933-2015,主要以物理性質(zhì)對(duì)揮發(fā)性有機(jī)物進(jìn)行規(guī)定??倱]發(fā)性有機(jī)物(TVOC)濃度為走航監(jiān)測(cè)的主要結(jié)果指標(biāo),本規(guī)范中也牽涉到TVOC的計(jì)算。本規(guī)范中對(duì)TVOC的定義參考GB37822-2019制定。由于設(shè)備原理存在差別,各設(shè)備所能監(jiān)測(cè)到揮發(fā)性有機(jī)物范圍不同,TVOC在各設(shè)備上的實(shí)際污染物范圍不一致,在應(yīng)用時(shí)需要明確。本規(guī)范采用的走航監(jiān)測(cè)定義系根據(jù)工作實(shí)際情況規(guī)定。走航監(jiān)測(cè)區(qū)別于一般移動(dòng)監(jiān)測(cè)車(chē)或移動(dòng)實(shí)驗(yàn)室最重要的特點(diǎn)在于實(shí)時(shí)連續(xù)并基于地理位置信息連續(xù)顯示污染空間分布。在實(shí)際工作中,為確認(rèn)污染特征和來(lái)源,行進(jìn)時(shí)連續(xù)監(jiān)測(cè)和定點(diǎn)監(jiān)測(cè)結(jié)合開(kāi)展,通過(guò)高值點(diǎn)定點(diǎn)監(jiān)測(cè)是確認(rèn)污染點(diǎn)位、取得精確定性、定量數(shù)據(jù)的必要手段。4.4方法原理本規(guī)范第四章規(guī)定了走航監(jiān)測(cè)的方法原理。本規(guī)范所指的“快速監(jiān)測(cè)設(shè)備”目前主要指快速質(zhì)譜方法,主要出于如下兩點(diǎn)原因:從走航監(jiān)測(cè)工作目的與方式來(lái)看,分析周期必須盡可能的短,行進(jìn)時(shí)不經(jīng)氣相色譜模塊,直接利用質(zhì)譜如飛行時(shí)間質(zhì)譜得到污染物定性定量結(jié)果是目前較普遍的走航監(jiān)測(cè)方式。經(jīng)氣相色譜儀對(duì)污染物進(jìn)行全分析的方法可視為對(duì)走航監(jiān)測(cè)的有力補(bǔ)充。從技術(shù)現(xiàn)狀與發(fā)展趨勢(shì)角度出發(fā),市場(chǎng)上部分利用氣相色譜-質(zhì)譜聯(lián)用的走航監(jiān)測(cè)設(shè)備,在車(chē)輛行進(jìn)時(shí)環(huán)境空氣不進(jìn)入色譜模塊,僅在質(zhì)譜模塊得到響應(yīng)信號(hào),但損失污染物定性信息。但根據(jù)編制組調(diào)查,已有設(shè)備生產(chǎn)商推出分析周期更短、走航時(shí)兼顧物質(zhì)定性能力的基于氣相色譜-質(zhì)譜聯(lián)用原理的走航監(jiān)測(cè)設(shè)備。本標(biāo)準(zhǔn)希望兼顧市場(chǎng)現(xiàn)狀與發(fā)展趨勢(shì),盡量避免對(duì)某種質(zhì)譜技術(shù)或品牌的指向性。目前市場(chǎng)上未見(jiàn)成熟的基于光學(xué)原理的揮發(fā)性有機(jī)物走航監(jiān)測(cè)設(shè)備。抽取式紫外差分分析儀可實(shí)現(xiàn)行進(jìn)中的VOCs物種監(jiān)測(cè),但監(jiān)測(cè)物種范圍較窄,僅監(jiān)測(cè)苯系物(苯、甲苯、二甲苯),難以滿足滿足工業(yè)園區(qū)復(fù)雜污染的監(jiān)測(cè)需求。抽取式/被動(dòng)式傅里葉變換紅外光譜分析儀可實(shí)現(xiàn)行進(jìn)中VOCs監(jiān)測(cè),檢測(cè)限較高不適于環(huán)境空氣監(jiān)測(cè),且存在數(shù)據(jù)間隔時(shí)間長(zhǎng)、譜圖庫(kù)相對(duì)有限、自動(dòng)解析能力不足導(dǎo)致干擾物難以判別等問(wèn)題。4.5試劑和材料本標(biāo)準(zhǔn)5.2節(jié)規(guī)定了使用116種組分揮發(fā)性有機(jī)物標(biāo)準(zhǔn)氣體。目前,走航監(jiān)測(cè)設(shè)備主要應(yīng)用PAMS及TO-14對(duì)設(shè)備進(jìn)行校準(zhǔn),部分廠家還選用有機(jī)硫化物標(biāo)準(zhǔn)氣體進(jìn)行校準(zhǔn)。為盡量擴(kuò)大走航監(jiān)測(cè)的可定量污染物范圍,提升走航監(jiān)測(cè)在惡臭異味排查中的作用,本規(guī)范要求按照116種組分揮發(fā)性有機(jī)物標(biāo)準(zhǔn)氣體進(jìn)行測(cè)試,監(jiān)測(cè)盡可能多的污染物以滿足管理需求。本規(guī)范利用PMAS、TO-15及有機(jī)硫?qū)υO(shè)備進(jìn)行測(cè)試,和116種組分揮發(fā)性有機(jī)物標(biāo)準(zhǔn)氣體組成大部分重合。4.6儀器和設(shè)備(1)質(zhì)譜儀目前由于走航的質(zhì)譜儀,進(jìn)樣方式主要分三種:直接進(jìn)入質(zhì)譜儀、經(jīng)PDMS膜滲透進(jìn)入質(zhì)譜儀、經(jīng)氣相色譜分離后進(jìn)入色譜儀。一般而言,為追求更短的分析周期,主要采用前兩種方式。也存在第一、第三種進(jìn)樣方式組合的走航監(jiān)測(cè)設(shè)備,車(chē)輛在行進(jìn)時(shí)采取第一種,定點(diǎn)監(jiān)測(cè)時(shí)采取第三種。無(wú)論選擇何種進(jìn)樣方式,都需存在進(jìn)樣系統(tǒng),穩(wěn)定進(jìn)樣體積。目前用于走航的質(zhì)譜儀,離子源主要分三種:?jiǎn)喂庾与婋x(SPI),電子轟擊(EI)和質(zhì)子轉(zhuǎn)移反應(yīng)(PTR)。質(zhì)量分析器主要有兩種:飛行時(shí)間質(zhì)譜(TOF)與離子阱(IonTrap)。為兼顧市場(chǎng)上現(xiàn)有設(shè)備的技術(shù)原理,本標(biāo)準(zhǔn)不限離子源和質(zhì)量分析器的類型。數(shù)據(jù)分析與展示部分,根據(jù)工作需求規(guī)定。(2)車(chē)載式大氣采樣系統(tǒng)本規(guī)范中對(duì)大氣采樣系統(tǒng)的規(guī)定主要參考HJ654制定,顆粒物過(guò)濾、保溫、防水要求是為了防止設(shè)備故障,減少測(cè)值受濕度的影響。車(chē)輛本身具有一定高度(一般在1.5米以上),過(guò)高的采樣管高度將影響車(chē)輛在部分限高路段的通過(guò)性能,只要滿足車(chē)頂周邊無(wú)明顯障礙物阻擋的高度即可,本規(guī)范要求“高于車(chē)頂0.2米以上,且不受車(chē)輛尾氣排放干擾”。(3)供電設(shè)備根據(jù)工作需求,電池組至少需提供約300W輸出功率,單次走航監(jiān)測(cè)一般耗時(shí)3h以上,本規(guī)范取能完成單次走航監(jiān)測(cè)的最低要求。實(shí)際工作中,建議有條件的至少滿足走航監(jiān)測(cè)設(shè)備8h以上供電。(4)車(chē)載衛(wèi)星定位系統(tǒng)及電子地圖行進(jìn)時(shí)同時(shí)顯示污染物濃度變化和地理位置變化是走航監(jiān)測(cè)的主要特點(diǎn)之一,因此對(duì)定位精度、時(shí)延有一定要求。一般而言,民用級(jí)別車(chē)載衛(wèi)星定位系統(tǒng)精度(3m以內(nèi))即可滿足工作需求,可選用北斗、GPS等導(dǎo)航系統(tǒng)。時(shí)延受環(huán)境條件影響,本規(guī)范不做特別要求。常見(jiàn)電子地圖有百度地圖、高德地圖、騰訊地圖等,各設(shè)備廠商可自行選擇,本規(guī)范不指定具體品牌。(5)其他設(shè)備為進(jìn)一步發(fā)揮走航監(jiān)測(cè)作用,可依據(jù)工作目的,對(duì)走航監(jiān)測(cè)車(chē)的設(shè)備進(jìn)行擴(kuò)展。如在走航監(jiān)測(cè)發(fā)現(xiàn)高值點(diǎn)位時(shí)開(kāi)展定點(diǎn)監(jiān)測(cè)與蘇瑪罐采樣,利用手持風(fēng)向風(fēng)速儀輔助判斷污染擴(kuò)散來(lái)源;針對(duì)光化學(xué)污染監(jiān)測(cè)的,可配備常規(guī)污染監(jiān)測(cè)設(shè)備,與走航監(jiān)測(cè)的揮發(fā)性有機(jī)物進(jìn)行綜合分析;針對(duì)環(huán)境執(zhí)法、應(yīng)急監(jiān)測(cè)的,可配備便攜式GC-MS,精準(zhǔn)判斷污染物的種類與濃度,對(duì)走航監(jiān)測(cè)數(shù)據(jù)進(jìn)行補(bǔ)充。4.7監(jiān)測(cè)方法4.7.1儀器準(zhǔn)備(1)方法檢出限、重復(fù)性本規(guī)范7.1.2節(jié)對(duì)重復(fù)性和方法檢出限進(jìn)行了規(guī)定:連續(xù)通入10nmol/mol標(biāo)準(zhǔn)氣體2min,取最后連續(xù)7組檢測(cè)數(shù)據(jù),參照HJ168規(guī)定計(jì)算相對(duì)標(biāo)準(zhǔn)偏差及方法檢出限。相對(duì)標(biāo)準(zhǔn)偏差及方法檢出限結(jié)果應(yīng)作為附表,列在走航監(jiān)測(cè)結(jié)果報(bào)告中。要求附錄A中所規(guī)定的揮發(fā)性有機(jī)物相對(duì)標(biāo)準(zhǔn)偏差≤20.0%,方法檢出限≤10nmol/mol。重復(fù)性表征了設(shè)備響應(yīng)的穩(wěn)定性,較好的重復(fù)性,即較低的RSD,能保證連續(xù)分析數(shù)據(jù)的再現(xiàn)性。從實(shí)際工作角度出發(fā),重復(fù)性越好,方法檢出限越低。由于各監(jiān)測(cè)設(shè)備可定性、定量分析的污染物不完全相同,本標(biāo)準(zhǔn)未對(duì)應(yīng)滿足檢出限的可監(jiān)測(cè)組分?jǐn)?shù)量做強(qiáng)制規(guī)定,但要求至少附錄A中的污染物滿足一定要求。根據(jù)規(guī)范驗(yàn)證實(shí)驗(yàn)結(jié)果,在本規(guī)范規(guī)定的測(cè)試條件下,參與規(guī)范驗(yàn)證各設(shè)備重復(fù)性以及方法檢出限,詳見(jiàn)附件。圖2給出了三套參與規(guī)范驗(yàn)證的走航監(jiān)測(cè)設(shè)備對(duì)PAMS、TO-14/TO-15、有機(jī)硫標(biāo)準(zhǔn)氣體的重復(fù)性測(cè)試結(jié)果分布。設(shè)備A、B、C分別有83%、97%、95%的可監(jiān)測(cè)組分(設(shè)備上有響應(yīng)的污染物)相對(duì)標(biāo)準(zhǔn)偏差(RSD)小于20%。三套設(shè)備分別有44、38、40種RSD>20%或無(wú)響應(yīng)的物質(zhì)。僅一套設(shè)備正己烷的RSD>20%,根據(jù)設(shè)備上反饋,該指標(biāo)仍有改善空間。其余附錄A的物質(zhì),三套設(shè)備均滿足規(guī)范要求。因此,規(guī)范要求的重復(fù)性指標(biāo)可實(shí)現(xiàn)。根據(jù)驗(yàn)證測(cè)試結(jié)果,根據(jù)實(shí)際應(yīng)用情況,兼顧HJ168-2010附錄A的相關(guān)要求,使各物質(zhì)方法檢出限盡量落在3~5倍測(cè)試范圍濃度,選取10nmol/mol作為本標(biāo)準(zhǔn)方法檢出限測(cè)試濃度。圖3給出了三套參與設(shè)備規(guī)范驗(yàn)證的走航監(jiān)測(cè)設(shè)備對(duì)PAMS、TO-14/TO-15、有機(jī)硫標(biāo)準(zhǔn)氣體組分的方法檢出限分布情況。設(shè)備A、B、C分別有93%、97%、97%的可監(jiān)測(cè)組分方法檢出限小于10nmol/mol。三套設(shè)備附錄A物質(zhì)均滿足本規(guī)范對(duì)方法檢出限的要求。圖2參與規(guī)范驗(yàn)證設(shè)備重復(fù)性分布柱狀圖圖3參與規(guī)范驗(yàn)證設(shè)備方法檢出限分布柱狀圖(2)準(zhǔn)確度本規(guī)范7.1.3節(jié)對(duì)準(zhǔn)確度的規(guī)定為:連續(xù)通入40nmol/mol標(biāo)準(zhǔn)氣體2min,取最后連續(xù)7組檢測(cè)數(shù)據(jù),參照HJ168規(guī)定,計(jì)算與理論濃度的相對(duì)誤差。要求附錄A中所規(guī)定的揮發(fā)性有機(jī)物相對(duì)誤差小于30%。設(shè)備無(wú)法區(qū)分的一組分子量相同或相近的有機(jī)物,理論濃度為所用標(biāo)準(zhǔn)氣體組分中所有分子量相同或相近成分的濃度數(shù)學(xué)加和。準(zhǔn)確度表征了設(shè)備在工作條件下對(duì)環(huán)境空氣監(jiān)測(cè)結(jié)果貼近實(shí)際濃度的程度。相對(duì)誤差越低,定量結(jié)果越準(zhǔn)確。根據(jù)規(guī)范驗(yàn)證實(shí)驗(yàn)結(jié)果,在本規(guī)范規(guī)定的測(cè)試條件下,參與規(guī)范驗(yàn)證各設(shè)備準(zhǔn)確性,詳見(jiàn)附件。圖4給出了三套參與設(shè)備規(guī)范驗(yàn)證的走航監(jiān)測(cè)設(shè)備對(duì)PAMS、TO-14/TO-15、有機(jī)硫標(biāo)準(zhǔn)氣體組分的準(zhǔn)確度分布情況。參與規(guī)范驗(yàn)證的三套設(shè)備,在規(guī)范規(guī)定的測(cè)試條件下分別有98%、94%、100%的可監(jiān)測(cè)物質(zhì)相對(duì)誤差小于30%。三套設(shè)備分別有34、39、37種相對(duì)誤差>50%或無(wú)響應(yīng)的不可監(jiān)測(cè)物質(zhì)。三套設(shè)備附錄A物質(zhì)均滿足本規(guī)范對(duì)準(zhǔn)確度的要求。圖4參與規(guī)范驗(yàn)證設(shè)備準(zhǔn)確度分布柱狀圖4.7.2監(jiān)測(cè)方案制定和樣品采集分析本規(guī)范第七章還對(duì)走航監(jiān)測(cè)方案制定和樣品采集分析工作進(jìn)行了要求。7.2.1節(jié)規(guī)定了走航監(jiān)測(cè)開(kāi)展的適宜天氣條件。根據(jù)實(shí)踐經(jīng)驗(yàn),風(fēng)力4級(jí)以上或降雨天氣,大氣稀釋作用較強(qiáng),走航車(chē)在一般道路上不易監(jiān)測(cè)到污染物濃度高值。晴朗、無(wú)風(fēng)、高溫低氣壓環(huán)境,污染物擴(kuò)散較慢,易在局部地區(qū)累積,走航監(jiān)測(cè)較易發(fā)現(xiàn)高濃度點(diǎn)位。7.2.3節(jié)規(guī)定內(nèi)容是發(fā)揮走航監(jiān)測(cè)污染溯源作用的關(guān)鍵。由于走航監(jiān)測(cè)設(shè)備無(wú)法監(jiān)測(cè)所有工業(yè)排放的揮發(fā)性有機(jī)物,且基于快速質(zhì)譜的走航設(shè)備在定性方面存在干擾物種,如不了解目標(biāo)區(qū)域、企業(yè)的所處行業(yè)以及生產(chǎn)涉及揮發(fā)性有機(jī)物,難以在走航監(jiān)測(cè)現(xiàn)場(chǎng)快速判斷污染來(lái)源。通過(guò)污染物特征判斷污染來(lái)源對(duì)監(jiān)測(cè)人員的知識(shí)結(jié)構(gòu)及經(jīng)驗(yàn)要求較高。4.8附錄附錄A為規(guī)范性附錄,揮發(fā)性有機(jī)物走航監(jiān)測(cè)設(shè)備必須監(jiān)測(cè)附錄A中的污染物,且需滿足7.1.2節(jié)及7.1.3節(jié)所規(guī)定的重復(fù)性、方法檢出限和準(zhǔn)確度指標(biāo)。通過(guò)附錄的方式對(duì)這些污染物進(jìn)行統(tǒng)一規(guī)定,可提升數(shù)據(jù)的可比性,有助示范區(qū)的區(qū)域數(shù)據(jù)互認(rèn)和跨區(qū)域統(tǒng)一評(píng)估與管控。需要特別說(shuō)明的是,由于設(shè)備原理或性能所限,附錄A中的同分異構(gòu)體或同分子量污染物(如鄰-、間-、對(duì)-二甲苯之間,或二甲苯及乙苯)可能無(wú)法實(shí)現(xiàn)完全分離,不要求附錄A中的所有污染物在結(jié)果中單獨(dú)列出。在測(cè)試或?qū)嶋H監(jiān)測(cè)時(shí),允許將同類別污染視為一個(gè)整體,監(jiān)測(cè)到其中一個(gè)污染物時(shí),可視為同時(shí)監(jiān)測(cè)到它的同分異構(gòu)體或同分子量污染物,濃度結(jié)果視為同分異構(gòu)體或同分子量污染物濃度的數(shù)學(xué)加和。附錄A物質(zhì)的選取出于以下三個(gè)考慮:一是考慮大氣綜排中有排放限值的,常見(jiàn)的主要污染物。如苯系物等。二是考慮市場(chǎng)上各設(shè)備的監(jiān)測(cè)能力。從工作需求出發(fā),走航污染物監(jiān)測(cè)范圍越廣越好。但規(guī)范的目的在于指導(dǎo)各用戶規(guī)范性地開(kāi)展揮發(fā)性有機(jī)物走航監(jiān)測(cè)工作,規(guī)范制定過(guò)程中盡量避免設(shè)備品牌的指向性。因此取“最大公約數(shù)”,選取監(jiān)測(cè)難度相對(duì)較低,可供不同設(shè)備、不同用戶單位間相互比較的污染物。三是考慮管理需求和技術(shù)發(fā)展趨勢(shì),充分發(fā)揮走航監(jiān)測(cè)的優(yōu)勢(shì)。各設(shè)備品牌實(shí)際上可監(jiān)測(cè)的污染物遠(yuǎn)多于附錄A中所規(guī)定的,為鼓勵(lì)走航監(jiān)測(cè)設(shè)備和服務(wù)的發(fā)展,進(jìn)一步挖掘工業(yè)區(qū)復(fù)雜污染特征,選取氯苯和三氯乙烯作為鹵代烴的代表,2-丁酮作為含氧揮發(fā)性有機(jī)物(OVOCs)和極性化合物的代表,推動(dòng)走航監(jiān)測(cè)技術(shù)提升對(duì)衍生物、極性揮發(fā)性有機(jī)物的監(jiān)測(cè)能力進(jìn)步。5.先進(jìn)性說(shuō)明目前尚無(wú)針對(duì)揮發(fā)性有機(jī)物走航監(jiān)測(cè)的國(guó)家、地方標(biāo)準(zhǔn)或規(guī)范,本規(guī)范為首個(gè)針對(duì)揮發(fā)性有機(jī)物走航監(jiān)測(cè)的標(biāo)準(zhǔn)文件。本規(guī)范對(duì)揮發(fā)性有機(jī)物走航監(jiān)測(cè)工作的全流程進(jìn)行了要求,特別是針對(duì)市場(chǎng)上品牌眾多、缺乏統(tǒng)一質(zhì)量控制要求的局面,基于實(shí)驗(yàn)數(shù)據(jù),兼顧技術(shù)現(xiàn)狀和發(fā)展趨勢(shì),規(guī)定了可落地的設(shè)備性能指標(biāo)和質(zhì)控要求。通過(guò)附錄的方式確定了基本污染物,對(duì)這些污染物在儀器上的定量準(zhǔn)確性進(jìn)行統(tǒng)一規(guī)定,可提升數(shù)據(jù)的可比性,有助不同品牌設(shè)備數(shù)據(jù)的可比性、一致性提升,有助示范區(qū)數(shù)據(jù)互認(rèn)和跨區(qū)域統(tǒng)一評(píng)估與管控。

附件一規(guī)范驗(yàn)證實(shí)驗(yàn)結(jié)果1.規(guī)范驗(yàn)證方案本方案主要用于指導(dǎo)長(zhǎng)三角生態(tài)綠色一體化發(fā)展示范區(qū)揮發(fā)性有機(jī)物走航監(jiān)測(cè)技術(shù)規(guī)范驗(yàn)證工作,驗(yàn)證工作由上海市環(huán)境監(jiān)測(cè)中心組織,廣州禾信質(zhì)譜技術(shù)有限公司、杭州譜育科技技術(shù)有限公司、聚光(杭州)環(huán)??萍加邢薰境袚?dān),對(duì)走航監(jiān)測(cè)設(shè)備設(shè)備進(jìn)行驗(yàn)證。本次編制規(guī)范驗(yàn)證的方案使用各型號(hào)揮發(fā)性有機(jī)物走航監(jiān)測(cè)設(shè)備,根據(jù)規(guī)范規(guī)定的設(shè)備性能檢查方法中的性能指標(biāo),逐一進(jìn)行相關(guān)測(cè)試,匯總分析測(cè)試結(jié)果并同編制規(guī)范中的技術(shù)指標(biāo)要求進(jìn)行比較評(píng)判,驗(yàn)證編制標(biāo)準(zhǔn)中各性能指標(biāo)的科學(xué)性和合理性。參與技術(shù)指標(biāo)驗(yàn)證的揮發(fā)性有機(jī)物走航監(jiān)測(cè)設(shè)備基本信息如下:表1參與技術(shù)指標(biāo)驗(yàn)證的揮發(fā)性有機(jī)物走航監(jiān)測(cè)設(shè)備信息表品牌型號(hào)進(jìn)樣系統(tǒng)離子源質(zhì)量分析器質(zhì)量分辨率譜育科技EXPEC3500Plus10m×0.1mm×0.4μmDB-1msLTM色譜柱EI(70eV)三維離子阱<0.50amu禾信儀器SPI-MS2000顆粒物過(guò)濾器,PDMS膜進(jìn)樣SPI(10.6eV)TOF800(FWHM)聚光科技TOFMS-100顆粒物過(guò)濾器,直接進(jìn)樣SPI(10.78eV)TOF900(FWHM)2.規(guī)范驗(yàn)證結(jié)果2.1重復(fù)性附表1統(tǒng)計(jì)了三套參與規(guī)范驗(yàn)證設(shè)備在10ppb、40ppb測(cè)試條件下,相對(duì)標(biāo)準(zhǔn)偏差的分布結(jié)果,各物質(zhì)的規(guī)范測(cè)試結(jié)果詳見(jiàn)表2、表3。10ppb測(cè)試條件下,三套設(shè)備相對(duì)標(biāo)準(zhǔn)偏差(RSD)大于10%的物質(zhì)明顯多于40ppb測(cè)試條件,RSD大于10%的物質(zhì)個(gè)數(shù)占可監(jiān)測(cè)物質(zhì)的比例分別為31%、14%、50%,而在40ppb測(cè)試條件下,這一比例分別為15%、12%、2%。在本標(biāo)準(zhǔn)規(guī)定的40ppb測(cè)試條件下,設(shè)備A、B、C分別有85%、88%、98%的可監(jiān)測(cè)組分相對(duì)標(biāo)準(zhǔn)偏差小于10%,基本滿足本標(biāo)準(zhǔn)對(duì)重復(fù)性的要求。由表2、表3可知,三套設(shè)備監(jiān)測(cè)苯系物時(shí)RSD較低,長(zhǎng)鏈烷烴、含氧及含氯有機(jī)物RSD較高或無(wú)響應(yīng)。走航監(jiān)測(cè)設(shè)備相對(duì)更適于較高濃度的VOCs,符合走航實(shí)際工作需求。表1不同測(cè)試條件下的RSD分布ABC10ppb40ppb10ppb40ppb10ppb40ppb0-2%30443771052%-5%1943381810405%-10%2981434159>10%35171412522無(wú)響應(yīng)252635343532表2重復(fù)性驗(yàn)證結(jié)果(10nmol/mol)物種名稱平均值重復(fù)性(相對(duì)標(biāo)準(zhǔn)偏差)ABCABC乙烷乙烯丙烷丙烯乙炔1-丁烯9.2610.05%順-2-丁烯9.2610.959.8410.05%2.54%9.34%反-2-丁烯9.2610.9510.05%2.54%正丁烷12.032.15%異丁烷12.032.15%異戊二烯9.3611.31%1-戊烯9.3710.345.28%3.26%順-2-戊烯9.3710.585.28%7.67%反-2-戊烯9.3710.495.28%9.60%環(huán)戊烷9.3710.6610.245.28%2.18%9.26%正戊烷11.909.521.84%14.88%異戊烷11.901.84%苯9.4111.049.028.31%1.38%18.06%環(huán)己烷9.7711.066.92%1.88%甲基環(huán)戊烷9.7711.0610.736.92%1.88%10.75%1-己烯9.7710.6712.026.92%3.95%9.35%正己烷5.5711.6410.2747.59%3.07%14.80%3-甲基戊烷5.5711.649.9447.59%3.07%7.15%2-甲基戊烷5.5711.6410.0247.59%3.07%11.88%2,2-二甲基丁烷5.5711.6447.59%3.07%2,3-二甲基丁烷5.5711.6416.0347.59%3.07%12.15%甲苯9.9111.0217.413.16%1.64%16.37%甲基環(huán)己烷9.4412.2211.6912.03%4.77%6.51%正庚烷9.0513.8610.3314.52%18.30%9.83%3-甲基己烷9.0513.8615.9014.52%18.30%20.09%2-甲基己烷9.0513.8613.9514.52%18.30%8.80%2,3-二甲基戊烷9.0513.8611.5614.52%18.30%12.45%2,4-二甲基戊烷9.0513.8613.2314.52%18.30%13.17%苯乙烯10.2712.0011.161.22%1.38%2.94%對(duì)-二甲苯10.1111.5515.191.20%0.86%16.33%間-二甲苯10.1111.5515.191.20%0.86%16.33%鄰二甲苯10.1111.5515.231.20%0.86%15.93%乙苯10.1111.5513.051.20%0.86%9.75%正辛烷9.4318.0411.236.09%9.73%6.68%2,2,4-三甲基戊烷9.4318.0410.586.09%9.73%15.97%2,3,4-三甲基戊烷9.4318.0410.826.09%9.73%17.78%3-甲基庚烷9.4318.0411.826.09%9.73%6.79%2-甲基庚烷9.4318.0411.366.09%9.73%10.74%4-乙基甲苯10.6412.2311.650.43%0.63%3.35%2-乙基甲苯10.6412.2312.840.43%0.63%12.40%3-乙基甲苯10.6412.239.850.43%0.63%7.64%正壬烷10.464.5710.979.29%11.25%5.07%1,2,3-三甲苯10.6412.2310.770.43%0.63%8.26%1,2,4-三甲苯10.6412.239.330.43%0.63%12.19%1,3,5-三甲苯10.6412.2310.640.43%0.63%5.51%異丙基苯10.6412.2310.840.43%0.63%3.02%正丙基苯10.6412.2311.200.43%0.63%3.42%正癸烷10.545.5613.416.59%264.58%22.57%間二乙苯10.7913.4211.851.69%1.05%15.87%對(duì)二乙苯10.7913.4210.701.69%1.05%5.26%十一烷11.290.0010.536.04%8.13%十二烷11.464.1910.846.87%127.98%8.80%丙烯9.985.44%乙醇14.3724.31%1,3-丁二烯0.479.33171.77%3.00%丙烯醛/10.261.23%丙酮12.609.739.6416.49%1.85%10.01%丙醇11.235.91%氯乙烯10.577.99%氯乙烷丁酮12.6610.3512.468.06%2.50%5.96%四氫呋喃12.6610.3713.838.06%2.46%7.92%二硫化碳10.6010.0416.2931.21%2.85%11.39%苯11.1710.4710.685.08%2.09%17.13%環(huán)己烷9.9511.3911.9826.06%3.86%5.00%乙酸乙烯酯8.2510.30/12.63%2.80%/正己烷7.1410.3013.4829.23%2.80%9.74%甲基叔丁基醚12.8610.3210.747.59%2.61%17.44%1,4-二惡烷8.6010.7212.7060.29%2.74%14.34%乙酸乙酯12.6610.728.0873.03%2.74%9.65%甲苯11.5610.8210.954.71%1.99%4.12%溴甲烷25.3510.179.8629.23%8.99%8.32%順-1,2-二氯乙烯10.553.70%1,1-二氯乙烯10.559.873.70%9.04%反-1,2-二氯乙烯10.5511.243.70%8.02%1,2-二氯乙烷10.4116.685.82%16.08%1,1-二氯乙烷10.419.465.82%14.28%甲基丙烯酸甲酯12.0110.0511.004.70%4.68%5.52%甲基異丁酮12.0110.0511.064.70%4.68%4.77%2-己酮12.0110.0511.114.70%4.68%2.78%正庚烷12.0110.0512.744.70%4.68%3.62%苯乙烯13.3910.5211.781.95%1.85%15.33%乙苯12.6310.599.480.74%1.11%6.31%對(duì)-二甲苯12.6310.5916.970.74%1.11%16.41%間-二甲苯12.6310.5916.970.74%1.11%16.41%鄰-二甲苯12.6310.5916.880.74%1.11%13.33%順-1,3-二氯丙烯10.9818.9816.493.19%16.72%16.79%反-1,3-二氯丙烯10.9818.9816.483.19%16.72%17.01%1,2-二氯丙烷11.9410.383.00%14.24%氯苯11.9410.5012.893.00%1.97%12.22%1,4-二氯苯14.7010.2713.930.87%1.49%9.61%1,3-二氯苯14.7010.2712.470.87%1.49%11.15%1,2-二氯苯14.7010.2715.850.87%1.49%12.26%1,2,4-三氯苯17.4111.078.761.30%5.72%5.59%氯仿8.7111.05%4-乙基甲苯13.1910.4411.241.01%1.20%7.15%1,3,5-三甲苯13.1910.4411.541.01%1.20%8.13%1,2,4-三甲苯13.1910.4415.471.01%1.20%13.87%二氯二氟甲烷13.191.01%芐基氯13.449.5212.531.71%3.87%7.89%萘16.4410.621.21%5.62%三氯乙烯12.0710.4811.076.88%2.67%6.46%1,1,1-三氯乙烷12.6116.534.84%17.93%1,1,2-三氯乙烷12.6110.974.84%3.39%1,1,2-三氟三氯乙烷9.3310.12%三氯一氟甲烷27.7310.0128.06%8.56%四氯化碳42.0010.6425.69%13.90%溴二氯甲烷11.4318.207.59%10.75%四氯乙烯11.779.9110.736.72%4.01%5.62%四氯乙烯11.779.9110.736.72%4.01%5.62%1,1,2,2-四氯乙烷11.9310.976.23%11.25%二氯四氟乙烷11.4222.09%三氯三氟乙烷11.7137.33%1,2-二溴乙烷11.625.82%二溴氯甲烷14.6216.20%溴仿4.5211.3158.25%12.19%六氯-1,3-丁二烯14.568.8610.562.96%6.12%10.15%丙烯腈9.488.00%二氯甲烷9.959.7626.06%9.31%3-氯丙烯10.029.81%甲硫醇9.119.687.9740.44%3.80%86.44%乙硫醇12.7810.229.4311.13%3.56%49.69%二甲基硫12.7811.13%丙硫醇11.058.8011.91%13.56%二硫化碳11.0512.2111.91%12.86%二乙基硫(乙硫醚)11.539.597.933.77%2.62%20.57%丁硫醇11.539.593.77%2.62%二甲基二硫醚15.699.769.133.02%3.25%3.45%己硫醇17.5914.077.19%13.54%甲硫醚10.2210.123.56%12.43%噻吩9.961.83%硫酸二甲酯9.926.55%戊硫醇11.6214.84%

表3重復(fù)性驗(yàn)證結(jié)果(40nmol/mol)物種名稱平均值(ppb)重復(fù)性(相對(duì)標(biāo)準(zhǔn)偏差)ABCABC乙烷乙烯丙烷丙烯乙炔1-丁烯41.3640.402.5%0.6%順-2-丁烯41.3640.4038.722.5%0.6%7.1%反-2-丁烯41.3640.402.5%0.6%正丁烷39.170.9%異丁烷39.170.9%異戊二烯41.162.2%1-戊烯41.3638.733.2%0.7%順-2-戊烯41.3638.7340.823.2%0.7%8.5%反-2-戊烯41.3638.7339.013.2%0.7%4.9%環(huán)戊烷41.3639.5642.813.2%1.0%5.1%正戊烷39.2136.951.4%6.4%異戊烷39.211.4%苯41.7739.2640.502.0%0.6%5.9%環(huán)己烷42.2939.212.1%1.1%甲基環(huán)戊烷42.2939.2136.832.1%1.1%4.8%1-己烯42.2938.2342.192.1%1.1%6.9%正己烷43.7338.9338.9613.2%1.2%8.3%3-甲基戊烷43.7338.9338.8713.2%1.2%8.1%2-甲基戊烷43.7338.9340.4913.2%1.2%8.2%2,2-二甲基丁烷43.7338.9313.2%1.2%2,3-二甲基丁烷43.7338.9341.0413.2%1.2%2.4%甲苯42.9338.6242.170.6%0.6%6.0%甲基環(huán)己烷42.3440.5637.831.5%2.6%2.9%正庚烷42.7537.6037.578.0%10.9%4.7%3-甲基己烷42.7537.6036.918.0%10.9%6.5%2-甲基己烷42.7537.6043.808.0%10.9%7.4%2,3-二甲基戊烷42.7537.6042.248.0%10.9%8.1%2,4-二甲基戊烷42.7537.6044.998.0%10.9%6.7%苯乙烯44.0938.9938.491.2%0.9%3.9%對(duì)-二甲苯43.5838.1242.390.6%0.3%7.4%間-二甲苯43.5838.1242.390.6%0.3%7.4%鄰二甲苯43.5838.1243.960.6%0.3%7.8%乙苯43.5838.1239.060.6%0.3%8.2%正辛烷43.6436.6836.982.1%4.9%3.5%2,2,4-三甲基戊烷43.6436.6838.832.1%4.9%3.6%2,3,4-三甲基戊烷43.6436.6836.692.1%4.9%2.6%3-甲基庚烷43.6436.6843.222.1%4.9%3.3%2-甲基庚烷43.6436.6837.492.1%4.9%4.2%4-乙基甲苯44.6338.8338.700.3%0.1%7.1%2-乙基甲苯44.6338.8341.550.3%0.1%4.4%3-乙基甲苯44.6338.8341.310.3%0.1%6.0%正壬烷43.9724.3139.563.8%13.0%4.6%1,2,3-三甲苯44.6338.8343.240.3%0.1%6.5%1,2,4-三甲苯44.6338.8338.150.3%0.1%4.3%1,3,5-三甲苯44.6338.8337.110.3%0.1%3.7%異丙基苯44.6338.8340.310.3%0.1%5.9%正丙基苯44.6338.8336.950.3%0.1%5.0%正癸烷45.9740.1239.822.5%45.3%7.7%間二乙苯45.1038.5038.850.6%0.6%3.9%對(duì)二乙苯45.1038.5040.060.6%0.6%1.6%十一烷46.0923.8840.112.1%96.0%1.3%十二烷43.2314.7940.092.9%74.9%1.1%丙烯36.613.4%乙醇36.1611.7%1,3-丁二烯31.7739.7110.2%0.8%丙烯醛38.494.0%丙酮41.7639.4337.486.6%1.1%6.2%丙醇40.953.2%氯乙烯41.490.9%氯乙烷丁酮39.8840.1137.534.3%2.1%8.4%四氫呋喃39.8840.1442.734.3%2.4%6.8%二硫化碳45.2140.8938.3521.9%1.2%4.1%苯39.9639.8740.842.4%0.9%4.4%環(huán)己烷37.3642.9840.245.2%1.6%6.1%乙酸乙烯酯37.3239.7610.9%1.9%正己烷37.3239.7641.7210.9%1.9%5.8%甲基叔丁基醚39.7140.0744.093.1%1.6%2.8%1,4-二惡烷45.9541.0844.6916.1%1.3%5.1%乙酸乙酯45.9541.0839.3916.1%1.3%3.9%甲苯40.4040.5641.771.7%1.2%3.7%溴甲烷44.8543.3938.0625.8%3.2%4.9%順-1,2-二氯乙烯40.2140.032.1%5.0%1,1-二氯乙烯40.2135.822.1%7.9%反-1,2-二氯乙烯40.2137.942.1%4.5%1,2-二氯乙烷40.4142.543.4%7.9%1,1-二氯乙烷40.4137.813.4%7.5%甲基丙烯酸甲酯41.3240.1239.171.4%2.2%3.8%甲基異丁酮41.3240.1240.261.4%2.2%3.2%2-己酮41.3240.1238.441.4%2.2%2.4%正庚烷41.3240.1243.961.4%2.2%5.0%苯乙烯41.3640.2839.170.6%0.8%5.3%乙苯41.1539.2038.670.4%0.5%4.4%對(duì)-二甲苯41.1539.2044.600.4%0.5%5.3%間-二甲苯41.1539.2044.600.4%0.5%5.3%鄰-二甲苯41.1539.2044.600.4%0.5%5.3%順-1,3-二氯丙烯40.5031.9643.381.6%11.1%6.3%反-1,3-二氯丙烯40.5031.9641.951.6%11.1%5.9%1,2-二氯丙烷40.9437.371.5%4.5%氯苯40.9440.1339.961.5%1.2%8.1%1,4-二氯苯40.8938.7140.500.8%0.6%5.8%1,3-二氯苯40.8938.7140.610.8%0.6%5.0%1,2-二氯苯40.8938.7140.210.8%0.6%5.6%1,2,4-三氯苯38.5136.0642.491.1%2.8%7.6%氯仿43.214.4%4-乙基甲苯41.0139.5143.110.7%0.6%6.0%1,3,5-三甲苯41.0139.5141.430.7%0.6%4.9%1,2,4-三甲苯41.0139.5140.550.7%0.6%6.4%二氯二氟甲烷41.010.7%芐基氯39.7439.8939.781.4%1.7%4.9%萘38.2745.590.5%6.4%三氯乙烯40.5641.2239.382.5%0.8%5.4%1,1,1-三氯乙烷40.8539.114.5%7.7%1,1,2-三氯乙烷40.8539.534.5%3.4%1,1,2-三氟三氯乙烷40.153.7%三氯一氟甲烷40.0337.0626.1%6.9%四氯化碳32.0338.8434.2%7.3%溴二氯甲烷41.6639.892.3%8.6%四氯乙烯41.7440.8236.361.8%0.7%2.6%四氯乙烯35.001.0%1,1,2,2-四氯乙烷41.0143.273.1%4.7%二氯四氟乙烷38.5710.2%三氯三氟乙烷40.0312.7%1,2-二溴乙烷40.685.9%二溴氯甲烷41.877.7%溴仿18.8447.9422.0%6.0%六氯-1,3-丁二烯39.8937.9240.202.1%1.7%2.8%丙烯腈33.173.6%二氯甲烷37.3639.705.2%3.0%3-氯丙烯35.473.0%甲硫醇37.5337.5935.972.5%1.2%18.1%乙硫醇38.9337.5539.153.3%0.8%12.7%二甲基硫38.933.3%丙硫醇36.3335.363.3%5.1%二硫化碳36.3332.933.3%4.8%二乙基硫(乙硫醚)39.7737.2936.591.9%1.3%6.4%丁硫醇39.7737.291.9%1.3%二甲基二硫醚43.1335.9239.082.6%1.9%1.8%己硫醇50.4133.534.6%6.9%甲硫醚37.5535.670.8%5.6%噻吩37.630.7%硫酸二甲酯50.223.1%戊硫醇30.618.8%2.2方法檢出限表4統(tǒng)計(jì)了三套參與規(guī)范驗(yàn)證設(shè)備在10ppb、40ppb條件下的方法檢出限分布。具體各物質(zhì)的方法檢出限見(jiàn)表5。根據(jù)驗(yàn)證測(cè)試結(jié)果,在標(biāo)準(zhǔn)規(guī)定的測(cè)試條件下,多數(shù)可監(jiān)測(cè)物質(zhì)的方法檢出限小于5ppb。由于個(gè)別物質(zhì)重復(fù)性較差,方法檢出限>10ppb。表4不同測(cè)試條件下的方法檢出限分布ABC10ppb40ppb10ppb40ppb10ppb40ppb檢出限<2ppb613879631922ppb-5ppb324372152245ppb-10ppb1191493061檢出限>10ppb822311317

表5各物質(zhì)方法檢出限物種名稱方法檢出限(10ppb測(cè)試)方法檢出限(40ppb測(cè)試)ABCABC乙烷乙烯丙烷丙烯乙炔1-丁烯2.920.873.250.76順-2-丁烯2.922.893.258.64反-2-丁烯2.923.25正丁烷0.811.06異丁烷異戊二烯3.331.514.102.852.485.641-戊烯1.564.15順-2-戊烯1.561.062.554.150.7910.87反-2-戊烯1.561.063.174.150.795.98環(huán)戊烷1.560.732.984.151.226.85正戊烷0.694.451.677.38異戊烷0.691.67苯2.460.485.122.640.767.56環(huán)己烷2.130.652.781.35甲基環(huán)戊烷2.130.653.622.781.355.601-己烯2.131.323.532.781.289.09正己烷8.331.124.7818.181.4610.132,2-二甲基丁烷8.331.1218.181.462,3-二甲基丁烷8.331.126.1218.181.463.123-甲基戊烷8.331.122.2318.181.469.942-甲基戊烷8.331.123.7418.181.4610.442-4-二甲基戊烷4.137.965.4810.7612.819.472-3-二甲基戊烷4.137.964.5210.7612.8110.70甲苯0.980.578.960.790.757.97甲基環(huán)己烷3.571.832.391.953.353.49正庚烷4.137.963.1910.7612.815.543-甲基己烷4.137.9610.0410.7612.817.552-甲基己烷4.137.963.8610.7612.8110.17苯乙烯0.390.521.031.681.164.76對(duì)-二甲苯0.380.317.800.760.349.90間-二甲苯0.380.317.800.760.349.90鄰-二甲苯0.380.317.620.760.3410.81乙苯0.380.314.000.760.3410.11正辛烷1.815.512.362.885.624.092,3,4-三甲基戊烷1.815.516.052.885.622.972,2,4-三甲基戊烷1.815.515.312.885.624.343-甲基庚烷1.815.512.522.885.624.432-甲基庚烷1.815.513.832.885.624.971,2,4-三甲苯0.140.243.580.430.145.141,2,3-三甲苯0.140.242.800.430.148.851,3,5-三甲苯0.140.241.840.430.144.344-乙基甲苯0.140.241.230.430.148.612-乙基甲苯0.140.245.000.430.145.743-乙基甲苯0.140.242.360.430.147.84正丙基苯0.140.241.200.430.145.84異丙基苯0.140.241.030.430.147.50正壬烷3.051.611.755.189.915.72間二乙苯0.570.445.910.850.734.71對(duì)二乙苯0.570.441.770.850.732.02正癸烷2.1846.209.513.6757.129.68十一烷2.140.002.693.0572.001.62十二烷2.4716.833.003.9934.801.42丙烯1.703.85乙醇10.9713.27氯甲烷1,3-丁二烯2.550.8810.190.94丙烯醛0.404.87丙酮6.530.873.038.710.767.36異丙醇2.084.14氯乙烯2.651.17氯乙烷丁酮3.200.812.345.412.649.94四氫呋喃3.200.803.445.413.049.19二硫化碳10.400.905.8331.181.524.93苯1.780.695.753.021.115.70環(huán)己烷8.151.381.886.122.137.66二氯甲烷8.152.866.123.72乙酸乙烯酯3.270.9012.752.40正己烷6.560.904.1312.752.407.66甲基叔丁基醚3.070.845.893.912.003.851,4-二惡烷16.300.925.7323.281.717.17乙酸乙酯29.060.922.4523.281.714.86甲苯1.710.681.422.171.514.84對(duì)-二甲苯0.300.378.750.520.607.47間-二甲苯0.300.378.750.520.607.47鄰-二甲苯0.300.377.070.520.609.901,3,5-三甲苯0.420.392.950.870.726.321,2,4-三甲苯0.420.396.740.870.728.154-乙基甲苯0.420.392.520.870.728.15溴甲烷23.292.872.5836.434.425.88順-1,2-二氯乙烯1.235.502.696.351,1-二氯乙烯1.232.802.698.89反-1,2-二氯乙烯1.232.832.695.331,2-二氯乙烷1.908.434.2610.621,1二氯乙烷1.904.244.268.93甲基丙烯酸甲酯1.771.481.911.802.804.74甲基異丁酮1.771.481.661.802.804.112-己酮1.771.480.971.802.802.94正庚烷1.771.481.451.802.806.97苯乙烯0.820.615.670.791.006.47乙苯0.300.371.880.520.605.32順-1,3-二氯丙烯1.109.968.712.0611.178.56反-1,3-二氯丙烯1.109.968.812.0611.177.751,2-二氯丙烷1.134.651.955.29氯苯1.130.654.951.951.4710.181,4-二氯苯0.400.484.211.060.767.431,3-二氯苯0.400.484.371.060.766.441,2-二氯苯0.400.486.101.060.767.051,2,4-三氯苯0.711.991.541.293.1910.09氯仿3.035.99二氯二氟甲烷0.420.87芐基氯0.721.163.111.772.136.18萘0.621.870.659.23三氯乙烯2.610.882.253.161.016.641,1,1-三氯乙烷1.929.325.779.501,1,2-三氯乙烷1.921.175.774.251,1,2-三氟三氯乙烷2.974.72四氯化碳33.924.6534.478.89一溴二氯甲烷2.736.153.0610.82四氯乙烯2.491.251.892.360.923.01四氯乙烯0.711.061,1,2,2-四氯乙烷2.343.883.956.35二氯四氟乙烷7.9312.33三氯三氟乙烷13.7416.001,2-二溴乙烷2.127.50二溴氯甲烷7.4410.19溴仿8.284.3313.029.02六氯-1,3-丁二烯1.361.703.372.651.973.51丙烯腈2.383.70三氯一氟甲烷24.462.6932.828.033-氯丙烯3.093.32甲硫醇11.591.1621.642.941.3868.03乙硫醇4.471.1414.724.090.9946.27二甲基硫4.474.09丙硫醇4.143.753.745.71二硫化碳4.144.933.7415.50二乙基硫(乙硫醚)1.370.795.132.431.5716.12丁硫醇1.370.792.431.57二甲基二硫醚1.491.000.993.562.163.11己硫醇3.975.987.317.30甲硫醚1.143.950.9912.42噻吩0.570.87硫酸二甲酯2.044.94戊硫醇5.418.432.3準(zhǔn)確度表6統(tǒng)計(jì)了三套規(guī)范驗(yàn)證設(shè)備在10、40、80ppb測(cè)試條件下的準(zhǔn)確度分布,以與理論濃度的相對(duì)誤差表示。各物質(zhì)在不同測(cè)試條件下的具體準(zhǔn)確度見(jiàn)表7。由表6可見(jiàn),B設(shè)備在40ppb測(cè)試條件下準(zhǔn)確度最佳,相對(duì)誤差<10%的物質(zhì)個(gè)數(shù)最多,A、C兩套設(shè)備在80ppb條件下最優(yōu)。但從分布來(lái)看,三套設(shè)備在40ppb測(cè)試條件下,相對(duì)誤差小于10%物質(zhì)數(shù)量占所有可監(jiān)測(cè)物質(zhì)的比例分別為85%、89%、98%,已滿足實(shí)際工作需求;標(biāo)準(zhǔn)規(guī)定的測(cè)試條件下分別有98%、94%、100%的可監(jiān)測(cè)物質(zhì)相對(duì)誤差小于20%。三套設(shè)備分別有34、39、37種相對(duì)誤差>50%或無(wú)響應(yīng)的不可監(jiān)測(cè)物質(zhì)。表6不同測(cè)試條件下的準(zhǔn)確度分布ABC10ppb40ppb80ppb10ppb40ppb80ppb10ppb40ppb80ppb<5%145678346859943805%-10%37342521222340582110%-20%1414628512492220%-50%3327966400>50%或無(wú)響應(yīng)423424483940383737表7各物質(zhì)在不同測(cè)試條件下的準(zhǔn)確度物種名稱準(zhǔn)確度(10ppb測(cè)試)準(zhǔn)確度(40ppb測(cè)試)準(zhǔn)確度(80ppb測(cè)試)ABCABCABC乙烷/////////乙烯/////////丙烷/////////丙烯/////////乙炔/////////1-丁烯-7.4%7.8%/3.4%1.01%/-2.3%0.32%/順-2-丁烯-7.4%/9.3%3.4%/7.10%-2.3%/2.76%反-2-丁烯-7.4%//3.4%//-1.9%//正丁烷/15.2%//2.08%/-1.9%0.40%/異丁烷//////-0.7%//2-甲基-1,3-丁二烯-6.4%//2.9%//-0.4%//1-戊烯-6.3%2.4%/3.4%3.18%/-0.4%0.11%/順-2-戊烯-6.3%/7.7%3.4%/8.47%-0.4%/4.47%反-2-戊烯-6.3%/9.6%3.4%/4.88%-0.4%/3.48%環(huán)戊烷-6.3%4.6%9.3%3.4%1.10%5.09%-6.7%1.24%2.97%正戊烷/15.1%14.9%/1.98%6.36%-6.7%0.54%3.50%異戊烷//////0.7%//苯-5.9%6.3%18.1%4.4%1.86%5.94%0.9%0.18%3.27%環(huán)己烷-2.3%6.7%/5.7%1.99%/0.9%0.33%/甲基環(huán)戊烷-2.3%6.7%10.7%5.7%1.99%4.84%0.9%0.33%4.66%1-己烯-2.3%6.0%9.4%5.7%4.42%6.85%-2.8%3.64%5.88%正己烷-44.3%12.9%14.8%9.3%2.67%8.27%-2.8%1.97%4.50%2,2-二甲基丁烷-44.3%12.9%/9.3%2.67%/-2.8%1.97%/2,3-二甲基丁烷-44.3%12.9%12.1%9.3%2.67%2.42%-2.8%1.97%2.67%3-甲基戊烷-44.3%12.9%7.1%9.3%2.67%8.14%-2.8%1.97%3.64%2-甲基戊烷-44.3%12.9%11.9%9.3%2.67%8.21%2.4%1.97%4.66%2-4-二甲基戊烷-9.5%35.8%13.2%6.9%6.00%6.70%2.2%4.37%4.87%2-3-二甲基戊烷-9.5%35.8%12.4%6.9%6.00%8.06%2.2%4.37%4.23%2,3,4-三甲基戊烷-5.7%80.0%17.8%9.1%8.30%2.58%1.5%10.59%1.68%2,2,4-三甲基戊烷-5.7%80.0%16.0%9.1%8.30%3.56%7.5%10.59%2.67%甲苯-0.9%7.7%16.4%7.3%3.45%6.01%3.3%2.01%5.72%對(duì)-二甲苯1.1%12.4%16.3%8.9%4.71%7.43%4.9%2.73%6.37%間-二甲苯1.1%12.4%16.3%8.9%4.71%7.43%4.9%2.73%6.37%鄰-二甲苯1.1%12.4%15.9%8.9%4.71%7.83%4.9%2.73%3.42%1,2,4-三甲苯6.4%17.2%12.2%11.6%2.92%4.29%7.5%1.68%3.61%4-乙基甲苯6.4%17.2%3.3%11.6%2.92%7.08%7.5%1.68%1.81%1,2,3-三甲苯6.4%17.2%8.3%11.6%2.92%6.52%7.5%1.68%2.21%2-乙基甲苯6.4%2.9%12.4%11.6%2.92%4.39%7.5%1.68%2.58%3-乙基甲苯6.4%17.2%7.6%11.6%2.92%6.04%7.5%1.68%3.64%1,3,5-三甲苯6.4%17.2%5.5%11.6%2.92%3.72%5.4%1.68%2.99%甲基環(huán)己烷-5.6%16.6%6.5%5.9%1.40%2.93%2.2%4.79%3.25%正庚烷-9.5%35.8%9.8%6.9%6.00%4.69%6.1%4.37%4.49%3-甲基己烷-9.5%35.8%20.1%6.9%6.00%6.51%2.2%4.37%4.58%2-甲基己烷-9.5%35.8%8.8%6.9%6.00%7.39%2.2%4.37%2.54%苯乙烯2.7%16.4%2.9%10.2%2.52%3.94%4.9%1.75%3.29%乙苯1.1%12.4%9.7%8.9%4.71%8.23%1.5%2.73%2.24%正辛烷-5.7%80.0%6.7%9.1%8.30%3.51%1.5%10.59%3.81%3-甲基庚烷-5.7%80.0%6.8%9.1%8.30%3.26%1.5%10.59%6.07%2-甲基庚烷-5.7%80.0%10.7%9.1%8.30%4.22%1.5%10.59%2.27%正丙基苯6.4%17.2%3.4%11.6%2.92%5.03%7.5%1.68%2.18%異丙基苯6.4%17.2%3.0%11.6%2.92%5.92%7.5%1.68%3.04%正壬烷4.6%52.6%5.1%9.9%39.23%4.60%8.7%49.29%3.25%間-二乙苯7.9%25.7%15.9%12.8%3.74%3.85%8.7%3.42%4.41%對(duì)-二乙苯7.9%25.7%5.3%12.8%3.74%1.60%8.8%3.42%5.07%正癸烷5.4%44.1%22.6%14.9%0.30%7.73%9.5%14.97%2.66%十一烷12.9%100.0%8.1%15.2%40.31%1.28%8.6%12.58%3.21%十二烷14.6%75.0%8.8%8.1%63.02%1.12%8.1%######4.77%異戊二烯/7.2%11.4%/3.89%4.57%/1.53%6.24%丙烯/0.8%//8.47%//0.57%/乙醇/21.2%//9.61%//4.89%/氯甲烷/////////1,3-丁二烯/9.1%/-20.6%0.72%/0.2%0.58%/丙烯醛/3.7%//3.78%//7.23%/丙酮26.0%0.6%10.0%4.4%1.43%6.24%-1.8%5.90%9.59%異丙醇/13.9%//2.38%//4.27%/氯乙烯/8.7%//3.73%//0.96%/氯乙烷/////////2-丁酮26.6%2.1%6.0%-0.3%0.27%8.43%-2.0%7.44%3.99%四氫呋喃26.6%4.3%7.9%-0.3%0.34%6.85%-2.0%8.03%4.37%二硫化碳/1.9%11.4%13.0%2.23%4.09%14.0%0.88%4.43%苯11.7%4.6%17.1%-0.1%0.32%4.44%-2.4%4.36%3.89%環(huán)己烷-0.5%15.6%5.0%-6.6%7.44%6.06%-0.3%5.87%2.49%二氯甲烷-0.5%/9.3%-6.6%/2.98%-0.3%/4.32%乙酸乙烯酯/1.8%/-6.7%0.60%/-43.1%8.66%/正己烷-28.6%1.8%9.7%-6.7%0.60%5.84%-43.1%8.66%4.36%甲基叔丁基醚28.6%4.1%17.4%-0.7%0.18%2.78%2.9%6.04%5.71%1,4-二惡烷/5.0%14.3%/2.70%5.11%18.4%/6.30%乙酸乙酯/5.0%9.6%/2.70%3.92%18.4%7.01%6.75%甲苯15.6%10.0%4.1%1.0%1.40%3.68%-0.2%5.25%2.86%溴甲烷/3.4%8.3%/8.48%4.92%-30.8%2.61%2.34%順-1,2-二氯乙烯5.5%/16.5%0.5%/5.04%-2.7%/6.01%1,1-二氯乙烯5.5%/9.0%0.5%/7.89%-2.7%/3.39%反-1,2-二氯乙烯5.5%/8.0%0.5%/4.47%-2.7%/4.14%1,2-二氯乙烷4.1%/16.1%1.0%/7.94%-1.5%/4.31%1,1-二氯乙烷4.1%/14.3%1.0%/7.51%-1.5%/3.49%甲基丙烯酸甲酯20.1%0.6%5.5%3.3%0.29%3.85%-0.1%3.73%3.46%甲基異丁酮20.1%0.6%4.8%3.3%0.29%3.25%-0.1%3.73%2.29%2-己酮20.1%0.6%2.8%3.3%0.29%2.43%-0.1%3.73%1.52%正庚烷20.1%0.6%3.6%3.3%0.29%0.29%-0.1%3.73%4.99%苯乙烯33.9%4.7%15.3%3.4%0.70%5.26%2.3%5.49%4.01%乙苯26.3%8.5%6.3%2.9%2.00%4.38%0.5%4.78%2.78%對(duì)-二甲苯26.3%8.5%16.4%2.9%2.00%5.33%0.5%4.78%2.34%間-二甲苯26.3%8.5%16.4%2.9%2.00%5.33%0.5%4.78%2.34%鄰二甲苯26.3%8.5%13.3%2.9%2.00%7.51%0.5%4.78%4.57%順-1,3-二氯丙烯9.8%99.7%16.8%1.3%20.11%6.28%-0.8%26.10%4.04%反-1,3-二氯丙烯9.8%99.7%17.0%1.3%20.11%5.88%-0.8%26.10%4.99%1,2-二氯丙烷19.4%/14.2%2.3%/4.51%-43.2%/3.40%氯苯19.4%6.7%12.2%2.3%0.33%8.10%-43.2%5.07%3.58%1,4-二氯苯47.0%4.1%9.6%2.2%3.22%5.84%4.7%8.78%5.13%1,3-二氯苯47.0%4.1%11.1%2.2%3.22%5.04%4.7%8.78%5.25%1,2-二氯苯47.0%4.1%12.3%2.2%3.22%5.58%4.7%8.78%2.86%1,2,4-三氯苯74.1%14.3%5.6%-3.7%9.85%7.55%7.8%20.10%4.69%氯仿//11.0%//4.41%//2.17%1,3,5-三甲苯31.9%3.9%8.1%2.5%1.23%4.85%2.3%5.68%3.83%1,2,4-三甲苯31.9%3.9%13.9%2.5%1.23%6.40%2.3%5.68%7.91%4-乙基甲苯31.9%3.9%7.1%2.5%1.23%6.02%2.3%5.68%5.13%二氯二氟甲烷31.9%//2.5

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