基于風(fēng)險分析的流域優(yōu)先有機(jī)污染物篩查:方法構(gòu)建

卜慶偉，王東紅，王子健

1.中國礦業(yè)大學(xué)(北京)化學(xué)與環(huán)境工程學(xué)院，北京100083

2.中國科學(xué)院生態(tài)環(huán)境研究中心中國科學(xué)院飲用水科學(xué)與技術(shù)重點實驗室，北京100085

3.中國科學(xué)院生態(tài)環(huán)境研究中心環(huán)境水質(zhì)學(xué)國家重點實驗室，北京100085

基于風(fēng)險分析的流域優(yōu)先有機(jī)污染物篩查:方法構(gòu)建

卜慶偉1,3，王東紅2,*，王子健3

1.中國礦業(yè)大學(xué)(北京)化學(xué)與環(huán)境工程學(xué)院，北京100083

2.中國科學(xué)院生態(tài)環(huán)境研究中心中國科學(xué)院飲用水科學(xué)與技術(shù)重點實驗室，北京100085

3.中國科學(xué)院生態(tài)環(huán)境研究中心環(huán)境水質(zhì)學(xué)國家重點實驗室，北京100085

化學(xué)品的大量使用和排放進(jìn)入水環(huán)境,對水生態(tài)系統(tǒng)產(chǎn)生諸多不利影響。因此,流域環(huán)境管理的重點之一就是如何篩查具有潛在風(fēng)險的優(yōu)先污染物。對于流域環(huán)境介質(zhì)中污染物篩查而言,難點和關(guān)鍵是如何建立高效的分析方法來盡可能多的獲取環(huán)境介質(zhì)中的污染物信息,進(jìn)而對其危害及風(fēng)險水平進(jìn)行判斷與篩查。對在流域環(huán)境介質(zhì)中污染物篩查方面具有潛在應(yīng)用可能性的環(huán)境分析方法進(jìn)行了綜述,提出了以高通量分析方法為基礎(chǔ)的基于概率風(fēng)險分析的流域優(yōu)先有機(jī)污染物篩查方法體系,并對體系中涉及的篩查基準(zhǔn)、數(shù)據(jù)選擇等關(guān)鍵問題進(jìn)行了討論。

高通量分析方法；流域優(yōu)先污染物；概率風(fēng)險；篩查基準(zhǔn)；物種敏感度分布

據(jù)統(tǒng)計,目前商業(yè)化的化學(xué)品已經(jīng)超過8 400 000種,其中在美國《化學(xué)文摘》登記的有機(jī)化學(xué)品也有240 000種之多[1]。歐洲的現(xiàn)有商業(yè)化學(xué)品名錄對1971年到1981年間在歐洲市場上流通過并仍在使用的化學(xué)品登記發(fā)現(xiàn),其總數(shù)已超過100 000種[2]。如此眾多的化學(xué)品進(jìn)入環(huán)境后均會成為環(huán)境污染物,其中部分可通過介質(zhì)間遷移、食物鏈傳遞等過程進(jìn)入生物機(jī)體,損害機(jī)體的組織器官且可能在組織與器官內(nèi)發(fā)生生物化學(xué)或物理化學(xué)作用,破壞機(jī)體的正常生理功能?；瘜W(xué)品的環(huán)境污染已經(jīng)對生態(tài)系統(tǒng)和人體健康造成了巨大的威脅[3-6],亟需對其導(dǎo)致的風(fēng)險進(jìn)行科學(xué)評估。但是,由于人力物力等資源條件的限制,對環(huán)境中存在的全部化學(xué)品進(jìn)行全面風(fēng)險控制代價巨大。因此,如何對眾多化學(xué)品或潛在環(huán)境污染物進(jìn)行分類和排序,有針對性的篩查出需要優(yōu)先管理和控制的具有潛在風(fēng)險的物質(zhì),一直是環(huán)境學(xué)領(lǐng)域研究的熱點和難點。

經(jīng)過幾十年的發(fā)展和完善,污染物的篩查方法體系已從早期的僅考慮產(chǎn)量、持久性、生物富集性的簡單體系[7]發(fā)展到當(dāng)前篩查水平的風(fēng)險評體系[8]。我們在前期的綜述文章中已對不同的篩查方法體系的新近進(jìn)展進(jìn)行了全面的歸納和評述[9]。從管理的角度而言,現(xiàn)有的篩查體系多數(shù)是為了化學(xué)品管理而設(shè)計研發(fā),通常是從已有的化學(xué)品數(shù)據(jù)庫出發(fā),估算化學(xué)品可能的環(huán)境危害、生態(tài)及健康風(fēng)險,進(jìn)而得到需要優(yōu)先管理或替代的化學(xué)品；另一種篩查體系是針對特定流域或者區(qū)域的真實環(huán)境介質(zhì),綜合考慮生態(tài)毒性、健康效應(yīng)和暴露劑量而開發(fā)的優(yōu)先污染物篩查方法,隨著近年來流域污染問題的突出而引起關(guān)注。

對于服務(wù)于化學(xué)品管理的篩查方法體系,目前已有較多的綜述,對方法體系中涉及的關(guān)鍵問題也有較為詳細(xì)的闡述[9]。但是,針對化學(xué)品管理的篩查體系并不能準(zhǔn)確評估其環(huán)境風(fēng)險。同時,針對流域優(yōu)先污染物篩查能夠準(zhǔn)確反映實際環(huán)境污染狀況,但對相關(guān)方法的評述則較少。對流域環(huán)境而言,其難點和關(guān)鍵是如何建立高通量的分析方法來盡可能多的獲取環(huán)境介質(zhì)中的數(shù)以萬計污染物信息,以便建立相應(yīng)的污染物數(shù)據(jù)庫,進(jìn)而對其危害及風(fēng)險水平進(jìn)行判斷。本文首先對環(huán)境中優(yōu)先污染物的研究進(jìn)行簡要概述,綜述了在流域優(yōu)先污染物篩查方面具有潛在應(yīng)用可能性的環(huán)境分析方法；基于此,提出基于風(fēng)險分析的流域優(yōu)先污染物篩查體系,為環(huán)境管理者進(jìn)行流域特征污染物的管控提供技術(shù)支持。

1 環(huán)境優(yōu)先污染物(Environmental priority pollutants)

最早提出優(yōu)先污染物一詞的是美國,并于20世紀(jì)70年代開始開展優(yōu)先污染物監(jiān)測項目。例如美國在1977年頒布的“清潔水法”中提出129種環(huán)境優(yōu)先污染物；在1982年頒布的“安全飲用水水法”中,提出299種需要優(yōu)先控制的污染物。日本的相關(guān)研究基本與美國同期開始,經(jīng)過十余年的努力,提出了日本國內(nèi)需要優(yōu)先關(guān)注的189種優(yōu)先污染物。同時,歐共體也在1975年提出了環(huán)境優(yōu)先污染物的“黑名單”和“灰名單”[10]。

我國在環(huán)境優(yōu)先污染物篩查方法及清單方面的工作起步較晚,但后期進(jìn)展較快。我國第一批環(huán)境優(yōu)先污染物包括68種污染物,其中有機(jī)毒物為56種。近年來,各地方結(jié)合國家提出的優(yōu)先污染物及地方實際,制定了具有地方特色的優(yōu)先污染物黑名單,為地方的環(huán)境管理工作提供了依據(jù)。例如浙江省的“浙江省第一批環(huán)境優(yōu)先污染物黑名單(43種)”[11]；北京提出“北京市優(yōu)先控制的有毒化學(xué)品名單(33種)”[12]；天津市也提出“天津市水體中最優(yōu)先有機(jī)污染物(10類24種)”[13]。

2 環(huán)境介質(zhì)中污染物識別方法 (Identification method)

目前針對流域優(yōu)先污染物的篩查方法體系尚不成熟,究其原因,主要是當(dāng)前可用于環(huán)境介質(zhì)中的大量污染物同時分析的方法十分有限。傳統(tǒng)的分析方法主要建立在分類測定的基礎(chǔ)上,隨著質(zhì)譜技術(shù)的發(fā)展,已經(jīng)涵蓋了從多環(huán)芳烴到新興污染物(如抗生素、個人護(hù)理品等),前人已對該方面研究做了大量的綜述[14-17]。按照污染物分類測定的傳統(tǒng)標(biāo)準(zhǔn)分析方法具有高準(zhǔn)確度和重現(xiàn)度,但是通常前處理步驟繁瑣、操作耗時費力等缺點,難以用于大量污染物同時分析。同時,上述分析方法多屬于目標(biāo)分析(target analysis)方法,在識別未知污染物方面存在較大缺陷。因此,現(xiàn)有的篩查體系中,僅有為數(shù)不多的體系考慮了環(huán)境實測數(shù)據(jù),且數(shù)據(jù)均取自文獻(xiàn)報道或日常監(jiān)測積累[9]。

日常監(jiān)測積累的數(shù)據(jù),其時間跨度一般較大,在篩查優(yōu)先污染物方面可以反映其動態(tài)變化,具有較大的應(yīng)用潛能?？赡艽嬖诘膯栴}是日常監(jiān)測數(shù)據(jù)通常是根據(jù)現(xiàn)有標(biāo)準(zhǔn)進(jìn)行例行監(jiān)測,尤其是在我國,例行監(jiān)測的目標(biāo)物涵蓋數(shù)目及種類較少。因此,常規(guī)監(jiān)測手段忽略了多數(shù)工業(yè)化學(xué)品、藥物及化妝品、新型農(nóng)藥及這些污染物的降解產(chǎn)物。這種針對已知污染物的篩查評估體系與篩查未知潛在風(fēng)險污染物的出發(fā)點相悖。此外,日常監(jiān)測積累的數(shù)據(jù)還可來源于文獻(xiàn)報道,分析對象物質(zhì)多數(shù)是跟蹤國外熱點,并沒有考慮我國現(xiàn)階段產(chǎn)業(yè)格局特點,在針對我國特定流域的優(yōu)先污染物篩查方面存在適應(yīng)性差的問題。

隨著分析科學(xué)的發(fā)展和高級分析技術(shù)在環(huán)境監(jiān)測中的深入應(yīng)用,與污染物濃度、歸趨及其行為相關(guān)的數(shù)據(jù)獲取較以往變得更加容易。在各種分析方法中,污染物多殘留、同時分析的方法在優(yōu)先污染物識別和篩查方面展現(xiàn)出良好的應(yīng)用前景,可為更深入的認(rèn)識污染物在環(huán)境中的賦存狀況提供快速工具,已有大量的綜述對該類方法進(jìn)行匯總與闡述[18-21]。表1匯總了能夠同時分析50種以上有機(jī)污染物的多殘留分析方法,目標(biāo)物涵蓋殺蟲劑(如有機(jī)氯農(nóng)藥,含氮、含磷、含氯殺蟲劑)及其代謝物、藥品及個人護(hù)理品、多氯聯(lián)苯(PCBs)、多環(huán)芳烴(PAHs)、多溴聯(lián)苯醚(PBDEs)和多氯代二苯并二噁英或呋喃(PCDD/Fs)等,涉及的環(huán)境介質(zhì)包括天然水、污水、沉積物、土壤、動物飼料、牛奶、谷物及動物纖維等。多殘留分析方法在篩查體系中應(yīng)用的優(yōu)勢在于其涵蓋的污染物種類和數(shù)目較多,且一套方法一般涉及一類污染物,在特殊污染物場地的污染物識別與篩查中具有較強(qiáng)的專門性和針對性。但是,其專門性和針對性所帶來的弊端則是涵蓋的種類仍不夠,如需對多種類污染物同時分析,仍然存在耗時費力等缺點,難以達(dá)到污染物快速篩查的目的。

表1 環(huán)境介質(zhì)中有機(jī)污染物的多殘留同時分析方法(污染物≥50種)Table 1 Summary of multi-residual analysis method developed for environmental matrices

近年來,高通量分析方法得益于非目標(biāo)分析的提出而獲得飛速發(fā)展,是目前污染物篩查分析方面較為活躍的研究領(lǐng)域。零星的研究包括:Bruchet等[35]針對污水及天然水中的內(nèi)分泌干擾物、藥品及個人護(hù)理品建立了一套高通量的分析方法；Gómez等[36-37]先后針對廢水和天然水分別建立了400種和934種污染物同時分析的高通量方法；Helbling等[38]建立了針對環(huán)境微污染物的微生物降解產(chǎn)物的高通量識別方法。

針對高通量分析方法開發(fā)進(jìn)行了較為系統(tǒng)研究的包括日本的Kadokami教授課題組以及中科院生態(tài)中心的生態(tài)毒理課題組。Kadokami課題組在高通量分析方法開發(fā)方面做了一些工作,其建立的高通量篩查方法主要針對半揮發(fā)有機(jī)物,已在日本、越南等地進(jìn)行了案例應(yīng)用研究[39-43]。生態(tài)中心生態(tài)毒理課題組圍繞不同環(huán)境介質(zhì)中污染物的篩查做了大量的工作[44-50],比如建立了針對水體中酚類污染物的篩查方法,并將其成功應(yīng)用于太湖水體中酚類的篩查[47]；建立了地表水中1 093種污染物的定性篩查方法,并在丹江口水庫成功應(yīng)用[46]；上述方法在污染物的定性篩查方面具有較大的優(yōu)勢,但其定量方式多為采用一種內(nèi)標(biāo)物對所有物質(zhì)進(jìn)行定量,會導(dǎo)致較大的估計誤差。鑒于此,我們在近期研究中通過使用一系列定量內(nèi)標(biāo),采取“一種定量一類”的半定量思路,對該方法的定量方式進(jìn)行了改進(jìn),經(jīng)驗證表明半定量結(jié)果能夠滿足初級層次的風(fēng)險篩查需求[45],結(jié)合優(yōu)先序列污染物的定量風(fēng)險評估,可用于構(gòu)建流域環(huán)境介質(zhì)中優(yōu)先污染物篩查體系。

3 基于風(fēng)險分析的流域優(yōu)先污染物篩查體系(Risk-based screening approach for priority contaminants at the watershed scale)

污染物的高通量及多殘留同時分析方法從根本上為流域尺度的優(yōu)先污染物篩查體系構(gòu)建提供了可能性。污染物在環(huán)境中的風(fēng)險由其環(huán)境濃度和毒性效應(yīng)共同決定[51],越來越多的研究開始將污染物的風(fēng)險水平作為優(yōu)先污染物排序的依據(jù)。但是,仍有一些問題需要進(jìn)行深入的探討。首先,在暴露表征方面,尤其對流域尺度的暴露表征,多數(shù)研究采用濃度水平的95或90百分位點[52],部分研究采用濃度的均值或者中位數(shù)值作為生態(tài)受體的暴露濃度。在流域尺度上,考慮污染物濃度的區(qū)域空間分布更為合理；其次,在效應(yīng)表征方面,多數(shù)研究采用單一的預(yù)測環(huán)境無效應(yīng)濃度(PNEC)值,PNEC一般采用某單一物種的毒性數(shù)據(jù)推算。流域生態(tài)風(fēng)險表征一般采用商值法,商值法是一個非黑即白的判斷,存在一些不足[53]。對于某些化學(xué)物質(zhì),其毒性數(shù)據(jù)已相對豐富,這種情況下考慮采用概率風(fēng)險則更為合理；最后,危害評估作為污染物固有屬性的反映,在基于風(fēng)險的篩查體系中是否仍需考慮,也存在一定的爭議。

基于此,本文提出的篩查體系主要考慮2類指標(biāo):一、危害評估,即持久性和生物累積性；二、生態(tài)風(fēng)險水平,并將導(dǎo)致生態(tài)風(fēng)險發(fā)生的概率作為判斷污染物優(yōu)先性的依據(jù)。污染物的持久性和生物累積性是反映污染物在時間維度和空間維度(食物鏈傳遞)遷移和傳遞的重要指標(biāo),對于判斷其影響的時空尺度具有不可替代的作用,因此本文仍將持久性和生物累積性納入新構(gòu)建的篩查方法體系。圖1為本文提出的用于流域管理目標(biāo)識別的環(huán)境優(yōu)先污染物篩查方法體系。

3.1 危害評估-篩查基準(zhǔn)設(shè)定

持久性和生物累積性是衡量特定污染物危害屬性的常用指標(biāo),一直用作篩查新的持久性有機(jī)污染物的標(biāo)準(zhǔn)[54]。持久性是衡量污染物在環(huán)境中“存活”時間的標(biāo)準(zhǔn),通常用降解半衰期(t1/2)來表示。生物累積性則反映污染物進(jìn)入生物體并發(fā)生累積與傳遞的可能性,常用生物累積因子(BAF)或者生物濃縮因子(BCF)表示。表2和表3分別匯總了不同篩查體系中對于持久性和生物累積性的篩查基準(zhǔn)。

表2 不同篩查體系的持久性篩查基準(zhǔn)Table 2 Screening benchmarks for persistence from different studies

表3 生物累積性篩查基準(zhǔn)匯總Table 3 Screening benchmarks for bioaccumulation from different studies

危害評估中篩查出的初步優(yōu)先污染物還將經(jīng)過進(jìn)一步風(fēng)險評估,以確定其是否進(jìn)入最終的優(yōu)先污染物清單。因此,為了避免假陰性的結(jié)果,本研究所建立的體系采取保守的基準(zhǔn)進(jìn)行危害評估。在綜述已有篩查基準(zhǔn)的基礎(chǔ)上,將污染物的危害屬性分為低、中、高3個等級,具體基準(zhǔn)值匯總與表4之中。持久性和生物累積性同時判定為低的污染物不再進(jìn)行下一步評價,否則繼續(xù)進(jìn)行風(fēng)險評估以判斷其是否應(yīng)該被優(yōu)先關(guān)注(圖1)。

3.2 概率生態(tài)風(fēng)險評估要點

對于流域尺度的暴露表征,考慮污染物濃度的空間分布形式,模擬其在整個流域的暴露分布曲線(ECD)；效應(yīng)表征則視毒性數(shù)據(jù)的多寡程度,構(gòu)建物種敏感度分布曲線(SSD),或者采用最敏感的毒性終點,利用評價因子法計算PNEC值。

圖1 基于風(fēng)險分析的流域優(yōu)先污染物篩查方法體系Fig.1 Framework of the risk-based screening system for identifying priority pollutants in watershed

表4 篩查體系采用的危害屬性的篩查基準(zhǔn)Table 4 Screening benchmarks selected in the present study

在選擇毒性數(shù)據(jù)時,所有毒性數(shù)據(jù)都應(yīng)該有明確的測試終點、效應(yīng)終點、測試時間以及對測試階段的描述。數(shù)據(jù)選擇應(yīng)該選用可靠性高的文獻(xiàn)來源或者符合良好實驗室規(guī)范(GLP)操作規(guī)程下獲取的實驗結(jié)果。隨著檢測技術(shù)的不斷進(jìn)步,毒性數(shù)據(jù)的測量手段和表征方法也在不斷提高和完善,所以盡量選擇近期發(fā)表的數(shù)據(jù),并且考慮測試物種應(yīng)該在研究區(qū)域存在。

本方法體系推薦將概率風(fēng)險作為判斷污染物是否為流域優(yōu)先污染物的依據(jù)。概率風(fēng)險評價是傳統(tǒng)風(fēng)險評價的外延,它能夠把可能發(fā)生的風(fēng)險采用統(tǒng)計模型以概率的形式表達(dá)出來。對于毒性數(shù)據(jù)足夠構(gòu)建物種敏感度分布曲線的污染物,其環(huán)境效應(yīng)商(EEQ)的分布為:

對于毒性效應(yīng)數(shù)據(jù)不足以構(gòu)建物種敏感度分布曲線的污染物,僅考慮濃度的空間分布模擬[60-61],計算超過PNEC的概率或頻度。

本文在綜述多殘留及高通量分析方法的基礎(chǔ)上,提出以高通量分析方法為基礎(chǔ)的流域優(yōu)先污染物篩查方法體系。該體系考慮有機(jī)污染物在流域尺度的空間分布特性,分析概率風(fēng)險,將污染物導(dǎo)致風(fēng)險的概率作為優(yōu)先污染物篩查的主要依據(jù)；同時提出了危害評估的篩查基準(zhǔn)?；陲L(fēng)險分析的流域優(yōu)先污染物篩查方法可為不同研究之間提供統(tǒng)一的方法學(xué)參考,也可為我國流域管理中識別優(yōu)先管控的污染物提供科學(xué)依據(jù)。

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A Risk-based Screening Approach for Priority Organic Contaminants at the Watershed Scale:Method Development

Bu Qingwei1,3,Wang Donghong2,*,Wang Zijian3
1.School of Chemical&Environmental Engineering,China University of Mining&Technology-Beijing,Beijing 100083,China
2.Key Laboratory of Drinking Water Science and Technology,Research Center for Eco-Environmental Sciences,Chinese Academy of Sciences,Beijing 100085,China
3.State Key Laboratory of Environmental Aquatic Chemistry,Research Center for Eco-Environmental Sciences,Chinese Academy of Sciences,Beijing 100085,China

15 April 2015 accepted 11 June 2015

Massive chemical substances enter the aquatic environment due to their wide uses and emissions,causing adverse effects on the aquatic ecology.Thus the key issue of watershed management is to identify organic pollutants with potential risks.For the environmental matrix,the challenge lies in how to develop a high throughout screening method to gain a picture of the organic pollutants.In the present study,we reviewed the possible method that can be used in the screening analysis,and put forward a risk-based screening system that incorporated the high throughout analytical method.Setting of screening benchmark and selection procedure of data were also discussed.

high throughout analytical method;priority pollutants;probability risk;screening benchmark;species sensitivity distribution

2015-04-15 錄用日期:2015-06-11

1673-5897(2016)1-061-09

X171.5

A

10.7524/AJE.1673-5897.20150415007

卜慶偉,王東紅,王子健.基于風(fēng)險分析的流域優(yōu)先有機(jī)污染物篩查:方法構(gòu)建[J].生態(tài)毒理學(xué)報,2016,11(1):61-69

Bu Q W,Wang D H,Wang Z J.A risk-based screening approach for priority organic contaminants at the watershed scale:Method development[J].Asian Journal of Ecotoxicology,2016,11(1):61-69(in Chinese)

國家自然科學(xué)基金青年基金(21307068)；國家自然科學(xué)基金(51290283)；國家高技術(shù)研究發(fā)展計劃(863計劃)(2014AA06A506)

卜慶偉(1983-),男,博士,研究方向為水生態(tài)毒理學(xué)及生態(tài)風(fēng)險評價,E-mail:qingwei.bu@cumtb.edu.cn

),E-mail:dhwang@rcees.ac.cn

簡介:王東紅(1968—)，女，副研究員，主要研究天飲用水和地表水中持久性有機(jī)污染物的賦存形態(tài)和潛在風(fēng)險污染物的篩查研究和風(fēng)險評價。