何 佳,時 迪,王貝貝,馮承蓮,蘇海磊,王 穎,3,秦 寧,4*

10種典型重金屬在八大流域的生態(tài)風(fēng)險及水質(zhì)標(biāo)準(zhǔn)評價

何 佳1,2,時 迪1,王貝貝1,馮承蓮1,蘇海磊1,王 穎1,3,秦 寧1,4*

(1.中國環(huán)境科學(xué)研究院環(huán)境基準(zhǔn)與風(fēng)險評估國家重點(diǎn)實(shí)驗(yàn)室,北京 100012；2.北京師范大學(xué)水科學(xué)研究院,北京 100875；3.北京航空航天大學(xué)空間與環(huán)境學(xué)院,北京 102206；4.北京科技大學(xué)能源與環(huán)境工程學(xué)院,北京 100083)

收集了10種典型重金屬在我國八大流域水體中的暴露濃度和對水生生物的急性和慢性毒性數(shù)據(jù),分別應(yīng)用概率密度重疊面積法和聯(lián)合概率分布法對重金屬在各流域水體中的生態(tài)風(fēng)險進(jìn)行評估,并與現(xiàn)行水質(zhì)標(biāo)準(zhǔn)的評估結(jié)果進(jìn)行對比.結(jié)果顯示,Cu和Zn在各流域水體中生態(tài)風(fēng)險均較高,現(xiàn)行水質(zhì)標(biāo)準(zhǔn)對水生生物Cu、Zn的暴露不能實(shí)施有效的保護(hù);Hg和Ni現(xiàn)行標(biāo)準(zhǔn)對水生生物存在過保護(hù)的現(xiàn)象;Se、As和Sb在各流域水體中生態(tài)風(fēng)險均較低,現(xiàn)行標(biāo)準(zhǔn)對水生生物保護(hù)程度適中.建議對現(xiàn)行水質(zhì)標(biāo)準(zhǔn)適度修改,同時增強(qiáng)高風(fēng)險重金屬監(jiān)測水平,以合理有效的保護(hù)我國水生態(tài)系統(tǒng)安全.

重金屬；生態(tài)風(fēng)險評估；水質(zhì)標(biāo)準(zhǔn)；概率密度重疊面積法；聯(lián)合概率分布法

近些年,我國重金屬污染事件頻發(fā),對我國流域水生態(tài)安全造成極大的威脅[1].我國目前現(xiàn)行《地表水環(huán)境質(zhì)量標(biāo)準(zhǔn)GB3838-2002》[2],同時兼顧保護(hù)人體健康和水生生物安全雙重作用,導(dǎo)致不同的保護(hù)對象存在“欠保護(hù)”和“過保護(hù)”的問題[3].因此,準(zhǔn)確評估各大水體的重金屬生態(tài)風(fēng)險,不僅可為污染物控制提供基礎(chǔ)數(shù)據(jù),還能夠?yàn)樗|(zhì)標(biāo)準(zhǔn)的制定和修改提供基科學(xué)依據(jù),為國家環(huán)境管理提供技術(shù)支撐,具有重要的研究意義.

物種敏感度方法(Species sensitivity distribution)在毒理學(xué)的角度構(gòu)建了污染物與物種之間的劑量-效應(yīng)關(guān)系,是國內(nèi)外評估生態(tài)風(fēng)險和制定環(huán)境基準(zhǔn)的主流方法[4].我國已經(jīng)逐步開展應(yīng)用該方法的主要流域金屬風(fēng)險評估工作[5-8].然而現(xiàn)有研究仍然存在局限.首先,研究區(qū)域上,已有的研究報道多是針對某一具體區(qū)域的風(fēng)險研究,缺乏大尺度大流域的整體研究;此外,研究方法上,評價方式往往針對單一濃度的點(diǎn)估計風(fēng)險表征,往往忽視了環(huán)境濃度的差異[9].

本研究收集我國八大主要流域水體內(nèi)10種典型重金屬暴露濃度及急、慢性毒性效應(yīng)濃度數(shù)據(jù),在流域的尺度上對重金屬的風(fēng)險進(jìn)行表征.并對現(xiàn)行水質(zhì)標(biāo)準(zhǔn)進(jìn)行評估.方法上,本研究利用概率風(fēng)險評價[9-10],從概率角度分析重金屬污染的急、慢生態(tài)風(fēng)險以及現(xiàn)行水質(zhì)標(biāo)準(zhǔn)的超標(biāo)率情況,估計暴露于污染物的生物負(fù)效應(yīng)的可能或程度,同時考慮生物耐受性和污染物濃度兩方面的變異,可以對污染物的生態(tài)風(fēng)險做出整體評估[11-12].研究結(jié)果旨在對水質(zhì)標(biāo)準(zhǔn)的合理性提供修訂建議,為我國重金屬污染監(jiān)測和水生態(tài)系統(tǒng)保護(hù)提供參考.

1 材料與方法

1.1 數(shù)據(jù)來源

10種典型重金屬(Cu、Zn、Ni、As、Pb、Hg、Cd、Sb、Se、Cr)在我國八大流域(長江流域、黃河流域、松花江流域、淮河流域、海河流域、遼河流域、珠江流域、太湖流域)水體中的暴露濃度數(shù)據(jù)來源于近100篇國內(nèi)外公開發(fā)表的中文核心期刊及SCI文獻(xiàn),以中國知網(wǎng)和Web of science為文獻(xiàn)檢索來源.其中長江流域數(shù)據(jù)不包含太湖.數(shù)據(jù)的篩選原則:(1)選取近10a時間范圍內(nèi)暴露濃度數(shù)據(jù);(2)數(shù)據(jù)來源為各流域內(nèi)干流、支流及湖泊;(3)測定暴露濃度為重金屬總濃度,單位為μg/L;(4)重金屬測定方法為國家標(biāo)準(zhǔn)方法或美國環(huán)保署標(biāo)準(zhǔn)方法.10種重金屬在八大流域水體中的暴露濃度范圍統(tǒng)計數(shù)據(jù)見表1.

表1 2006~2017年中國八大流域s水體中10種典型重金屬暴露濃度統(tǒng)計數(shù)據(jù)(μg/L)

續(xù)表1

注:Range:樣品濃度范圍;GM:濃度數(shù)據(jù)幾何均值;SD:濃度數(shù)據(jù)標(biāo)準(zhǔn)差;N:樣品量;NA:無可用數(shù)據(jù).

10種重金屬對淡水水生生物的急性和慢性毒性數(shù)據(jù)來源于美國EPA Ecotox毒理數(shù)據(jù)庫(http: //www.epa.gov/ecotox/)以及國內(nèi)外公開發(fā)表的中文核心期刊和SCI文獻(xiàn).毒性數(shù)據(jù)的選擇按以下原則:(1)盡量選擇中國本土物種,引進(jìn)物種及世界廣布物種;(2)物種至少涵蓋3個營養(yǎng)級;水生植物/初級生產(chǎn)者、無脊椎動物/初級消費(fèi)者、脊椎動物/次級消費(fèi)者;(3)對于毒性測試時間的選擇,魚類和甲殼類動物的急性毒性盡量選擇96h的LC50或EC50,大型溞類等浮游動物的毒性盡量選擇48h的LC50或EC50.水生生物的慢性毒性盡量選擇21d以上測試時間的LOEC、NOEC或MATC數(shù)據(jù);(4)優(yōu)先選取流水式試驗(yàn)獲得的重金屬毒性數(shù)據(jù),其次選取半靜態(tài)或靜態(tài)實(shí)驗(yàn)數(shù)據(jù).同一物種的多個毒性數(shù)據(jù)取其幾何平均值.

1.2 風(fēng)險評價方法

本研究使用概率密度重疊面積法和聯(lián)合概率曲線法對各流域的重金屬生態(tài)風(fēng)險進(jìn)行評估.概率密度重疊面積法將暴露濃度和毒性數(shù)據(jù)分別作為獨(dú)立的觀測值,在此基礎(chǔ)上考慮其概率統(tǒng)計意義.概率密度重疊面積法將表征污染物的暴露濃度和毒性數(shù)據(jù)的概率密度曲線置于同一坐標(biāo)體系下,位于最大環(huán)境暴露濃度和對污染物最敏感生物的毒性數(shù)據(jù)之間的重疊部分的面積即可以反映污染物的生態(tài)風(fēng)險[9].重疊面積的大小反映不同污染風(fēng)險的大小關(guān)系,面積越大,表示污染物對水生生物風(fēng)險越高,反之則越小.采用MATLAB(R2014a)軟件對暴露濃度和毒性數(shù)據(jù)的重疊面積進(jìn)行計算.

聯(lián)合概率分布法是將表征污染物的暴露濃度和效應(yīng)濃度的累積概率曲線置于同一坐標(biāo)體系下,并通過概率單位轉(zhuǎn)換對概率曲線進(jìn)行直線轉(zhuǎn)換[9].聯(lián)合概率分布法反映了各損害水平下暴露濃度超過安全閾值的概率.本研究計算了在95%物種不受損害的水平下(HC5),各重金屬在不同流域水體中的暴露濃度超過HC5值的概率,體現(xiàn)暴露狀況和風(fēng)險水平之間的關(guān)系;計算各重金屬在八大流域水體中對現(xiàn)行水質(zhì)標(biāo)準(zhǔn)《地表水水質(zhì)標(biāo)準(zhǔn)GB3838-2002》[2]的超標(biāo)率情況,評估當(dāng)前流域重金屬的污染現(xiàn)狀.采用OriginPro 8軟件對暴露濃度分布和毒性數(shù)據(jù)分布相對位置作圖分析.

2 結(jié)果與討論

2.1 各大流域重金屬含量及現(xiàn)狀

如表1所示,相比于國外,我國10種典型重金屬在各流域水體中暴露濃度平均值普遍較高,Cu在松花江流域水體中暴露濃度均值高達(dá)527.77μg/L,在淮河流域暴露濃度均值為131.31μg/L,遼河流域平均濃度最低為6.35μg/L,而Cu在萊茵河和密西西比河流域水體中平均暴露濃度分別為3.4μg/L[34]和2μg/L[51],Cu在全球河流平均暴露濃度僅為3μg/L[51],松花江流域Cu平均濃度超出全球平均100余倍[51]; Zn在黃河水體中暴露濃度均值為360.07μg/L,最高檢出濃度為1132μg/L,在長江和松花江流域平均暴露濃度分別為74.55,46.43μg/L,最高檢出濃度均超過600μg/L,Zn在萊茵河流域暴露濃度均值為33μg/L[34],與我國遼河和太湖流域相近;Ni在長江水體中暴露濃度均值為168.14μg/L,其中最高采樣點(diǎn)檢出濃度為480μg/L,超出萊茵河平均濃度80余倍[34],在海河和珠江流域平均暴露濃度相對較低,分別為11.11,15.87μg/L.Pb在淮河流域水體中暴露濃度均值高達(dá)658.13μg/L,在松花江流域平均濃度也達(dá)到414.20μg/L,而密西西比河和全球河流平均值僅為0.2,3μg/L[51];其余金屬Hg在珠江、Cd在太湖、Cr在松花江以及As在海河流域中平均暴露濃度均較高,Se和Sb在各流域水體中暴露濃度相對較低.

我國流域水體中重金屬平均含量普遍高于國外流域,我國實(shí)施《重金屬污染綜合防止“十二五”規(guī)劃》[1]以前,涉及重金屬行業(yè)生產(chǎn)工藝/污染治理水平較低,重金屬污染物排放量逐年增加,一些污染物排放量增幅較大.再加上部分企業(yè)偷排漏排等問題突出,重金屬污染事件頻發(fā).規(guī)劃實(shí)施以來,盡管已在全國范圍內(nèi)淘汰了4000多家涉重企業(yè),行業(yè)集中度和技術(shù)水平也有明顯提高,但部分地區(qū)的重金屬污染排放量依然呈現(xiàn)較快增長的趨勢,重點(diǎn)監(jiān)控的重金屬企業(yè)排放達(dá)標(biāo)率僅為77.2%[1].

2.2 重金屬生態(tài)風(fēng)險評估

2.2.1 概率密度重疊面積法 如圖1,Cu和Zn慢性毒性效應(yīng)與各流域水體中暴露濃度間重疊面積均越大,說明Cu和Zn在水體中對水生生物的影響程度越高.Sb僅有長江流域暴露濃度數(shù)據(jù),信息量較少,未給出概率密度重疊面積圖.

由圖1可知,水生生物在海河、長江、松花江、珠江和黃河流域中受Cu污染的慢性生態(tài)風(fēng)險程度均超過50%,其中海河流域慢性毒性影響程度高達(dá)77.8%,遼河流域慢性影響程度最低,仍對近20%的水生生物存在影響.水生生物在松花江和淮河流域中受Cu污染的急性生態(tài)風(fēng)險概率均超過50%;Zn污染在黃河流域中對水生生物造成不利慢性影響的概率為65.2%,急性影響概率也高達(dá)37.6%,在遼河和淮河流域中受慢性影響較低,生態(tài)風(fēng)險概率分別為11.6%和16.3%;水生生物受長江流域中Ni污染的慢性影響風(fēng)險為65.8%,急性影響風(fēng)險也高達(dá)33.6%;珠江流域中Hg污染對水生生物造成不利慢性影響的概率也接近50%,急性影響風(fēng)險較低為11%;Pb污染除對珠江流域影響較低外,對黃河、長江、松花江和淮河流域水生生物的不利慢性影響均在40%左右,以松花江污染風(fēng)險概率最高,但Pb在各流域中對水生生物的急性風(fēng)險概率較低,最低僅為1.3%;Cd和Cr污染對黃河流域水生生物慢性影響概率分別為40.3%和25.6%;As、Se和Sb對水生生物的慢性影響和急性風(fēng)險均較低.

圖1 9種典型重金屬在八大流域水體中的暴露濃度和急性、慢性毒性的概率密度

由此可見,我國流域水生生物受重金屬污染造成的生態(tài)風(fēng)險較高,而礦業(yè)開采是造成我國流域重金屬污染的主要原因,我國作為礦產(chǎn)資源大國,Cd、Sb等金屬儲量列世界第一[90],我國近10a來Cd、Pb、Cu、Hg和Zn的產(chǎn)量增長了1倍[91-101],其中2016年Cu、Zn和Pb的產(chǎn)量均達(dá)到百萬t以上,Zn最高年產(chǎn)量高到493萬t.我國在持有豐富礦產(chǎn)資源的同時,也面臨著巨大的環(huán)境安全隱患.例如,2012年廣西龍江Cd污染事件,泄露量約20t,波及河段約300km[102].2015年甘肅隴南Sb污染事件,尾礦庫尾砂泄露造成嘉陵江及西漢水300多km水域Sb超標(biāo),污染涉及甘陜川三省,影響巨大[103].

根據(jù)風(fēng)險表征結(jié)果,得出各流域水生生物受重金屬污染慢性影響的生態(tài)風(fēng)險排序(圖2),以長江、黃河和松花江為例,水生生物在長江流域中受重金屬慢性影響的生態(tài)風(fēng)險排序?yàn)?Cu>Ni>Pb>Zn> Hg>Cd>Cr>As>Sb>Se;在黃河流域中受慢性影響的風(fēng)險排序?yàn)?Zn>Cu>Cd>Pb>Cr>As;在松花江流域中受慢性影響的風(fēng)險排序?yàn)?Cu>Pb>Zn>Cd> Cr>Se>As.水生生物在長江流域的急性風(fēng)險排序?yàn)?Cu>Ni>Zn>Pb>Hg>Cd>Cr>As>Sb>Se;在黃河流域中的急性風(fēng)險排序?yàn)?Zn>Cu>Pb>Cr>Cd>As;在松花江流域的急性風(fēng)險排序?yàn)?Cu>Pb>Zn> Cr>Cd> As>Se.以上結(jié)果可以看出,Cu和Zn在各流域水體中生態(tài)風(fēng)險較大,Cu和Zn雖為人體必需元素,相對于人體對水生動物具有較大的毒性危害[104].

圖2 八大流域水體中10種典型重金屬的慢性生態(tài)風(fēng)險

2.2.2 聯(lián)合概率分布法生態(tài)風(fēng)險評估 應(yīng)用聯(lián)合概率分布法,計算了10種典型重金屬在八大流域水體中的暴露濃度超過保護(hù)95%生物不受影響的急性和慢性HC5值的超標(biāo)率,Sb僅有長江流域暴露濃度數(shù)據(jù),信息量較少,未給出聯(lián)合概率分布.如圖3所示,暴露濃度對應(yīng)的累積概率值越小,超標(biāo)情況越嚴(yán)重,重金屬污染對水生生物造成的生態(tài)風(fēng)險越嚴(yán)重.與重疊面積法表征生態(tài)風(fēng)險結(jié)果一致,Cu和Zn對慢性毒性HC5的超標(biāo)率在各流域水體均較高,相比于人體對水生生物的更敏感性[105].

圖3表明,Cu在海河流域中對慢性HC5值超標(biāo)率高達(dá)88.7%,除太湖超標(biāo)為43.2%外,其他流域均超過60%.Cu在海河、長江和松花江流域中對急性HC5值的超標(biāo)率均超過50%,說明Cu污染在我國流域水體中對水生生物存在極大的安全隱患.遼河超標(biāo)率較低是暴露數(shù)據(jù)采樣點(diǎn)均來自東遼河地區(qū),且暴露濃度相近,多數(shù)采樣點(diǎn)為5μg/L,而急性HC5值為11.83μg/L,因此造成遼河急性超標(biāo)率較低;Zn在黃河和長江流域中對慢性HC5值超標(biāo)率分別為64.4%和41.1%,其余流域中超標(biāo)率均在30%左右.Zn在黃河流域中對急性HC5超標(biāo)率為38%,其余流域均超標(biāo)率低或不超標(biāo);Ni除在長江流域中對慢性和急性HC5超標(biāo)率分別高達(dá)68.4%和47.7%外,其余流域急、慢性HC5超標(biāo)率均較低;Hg在珠江流域中慢性HC5超標(biāo)率較高為49.6%;Pb在淮河流域慢性HC5超標(biāo)率高達(dá)65.5%,在黃河、長江和太湖慢性HC5超標(biāo)均超過40%;Cd和Cr對慢性HC5超標(biāo)率最高的流域均為黃河流域,分別為55.8%和38%;Se、Sb和As對慢性HC5均表現(xiàn)為較低超標(biāo)和不超標(biāo);Hg、Pb、Cd、Cr、Se、Sb和As對急性HC5均表現(xiàn)為較低超標(biāo)和不超標(biāo)的情況.

各流域水體中超標(biāo)率的排序情況,以黃河、長江和松花江流域?yàn)槔?在黃河流域中各金屬對慢性HC5超標(biāo)排序?yàn)?Zn>Cu>Cd>Pb>Cr>As,對急性HC5超標(biāo)率排序?yàn)?Cu>Zn>Pb>Cr>Cd>As;在長江流域中各金屬對慢性HC5超標(biāo)排序?yàn)?Cu>Ni>Pb>Zn> Cd>Hg>As>Sb>Se,對急性HC5超標(biāo)率排序?yàn)?Cu> Ni>Zn>Pb>Hg>Cd>Cr>As>Sb>Se;在松花江流域中各金屬對慢性HC5超標(biāo)排序?yàn)?Cu>Pb>Cd>Zn> Cr>Se>As,對急性HC5超標(biāo)率排序?yàn)?Cu>Pb>Zn> Cr>Cd>Se>As.與重疊面積法結(jié)論基本一致,Cu和Zn這兩種金屬在各流域中超標(biāo)率情況均較嚴(yán)重,對水生生物存在嚴(yán)重安全隱患.

圖3 9種典型重金屬在八大流域水體中的暴露濃度和急/慢性毒性的聯(lián)合概率分布

2.3 現(xiàn)行水質(zhì)標(biāo)準(zhǔn)修訂建議

2.3.1 重金屬水體暴露濃度對水質(zhì)標(biāo)準(zhǔn)的超標(biāo)率 基于聯(lián)合概率分布法,計算了8大流域水體中重金屬暴露濃度對我國現(xiàn)行《地表水水質(zhì)標(biāo)準(zhǔn)GB3838-2002》的超標(biāo)率情況,如表2所示,各流域中Cu對Ⅰ類水質(zhì)標(biāo)準(zhǔn)超標(biāo)情況嚴(yán)重,淮河水體中Cu對Ⅰ類水質(zhì)標(biāo)準(zhǔn)超標(biāo)率為86.6%,長江和松花江水體中Cu對Ⅰ類水超標(biāo)率也均超過50%,但各流域水體中Cu的暴露濃度對Ⅱ~Ⅴ類水質(zhì)標(biāo)準(zhǔn)基本均處于不超標(biāo)狀態(tài);Zn、Cd與Cu的情況相似,Zn和Cd在各流域水體中對Ⅰ類水質(zhì)標(biāo)準(zhǔn)普遍存在超標(biāo)情況,其中黃河水體中Zn和Cd超標(biāo)率最為嚴(yán)重,分別超Ⅰ類水質(zhì)標(biāo)準(zhǔn)59.9%和41.9%,超Ⅱ類、Ⅲ類水質(zhì)標(biāo)準(zhǔn)16%和11.3%.Pb、Hg和Cr在各流域水體中含量均對Ⅰ類~Ⅲ類水質(zhì)標(biāo)準(zhǔn)存在超標(biāo)現(xiàn)象,其中淮河水體中Pb對Ⅰ類和Ⅱ類水超標(biāo)率為66.4%,遼河和珠江水體中Hg含量均超Ⅰ類和Ⅱ類水質(zhì)標(biāo)準(zhǔn)50%以上,黃河、長江和松花江水體中Cr含量均超Ⅰ類和Ⅱ類水質(zhì)標(biāo)準(zhǔn)50%以上,黃河水體中Cr暴露濃度對Ⅰ類水超標(biāo)率高達(dá)70.7%.其余金屬如Ni在長江水體中含量超現(xiàn)行標(biāo)準(zhǔn)70%以上,As和Se在各流域水體中含量對現(xiàn)行標(biāo)準(zhǔn)未存在顯著性超標(biāo).

現(xiàn)行水質(zhì)標(biāo)準(zhǔn)和HC5超標(biāo)率評估均采用聯(lián)合概率分布法,現(xiàn)行水質(zhì)標(biāo)準(zhǔn)選用現(xiàn)行五類水標(biāo)準(zhǔn)作為特定臨界濃度,表示10種典型重金屬暴露濃度對于現(xiàn)行水質(zhì)標(biāo)準(zhǔn)的超標(biāo)率情況.現(xiàn)行地表水五類水質(zhì)標(biāo)準(zhǔn)中,Ⅰ類~Ⅲ類水標(biāo)準(zhǔn)涉及保護(hù)水生生物,主要研究以上3類水質(zhì)標(biāo)準(zhǔn).HC5超標(biāo)率評估采用保護(hù)95%水生生物不受影響或不致死的急、慢性HC5值作為特定臨界濃度,表示10種典型重金屬暴露濃度對保護(hù)95%水生生物不受影響或不致死的超標(biāo)率情況.水質(zhì)標(biāo)準(zhǔn)的制定基于慢性毒性,主要對比慢性HC5超標(biāo)率.對比以上兩類超標(biāo)率結(jié)果,若結(jié)果一致,說明現(xiàn)行標(biāo)準(zhǔn)適中;若水質(zhì)標(biāo)準(zhǔn)超標(biāo)率較低,HC5超標(biāo)率較高,說明現(xiàn)行水質(zhì)標(biāo)準(zhǔn)對水生生物存在“欠保護(hù)”現(xiàn)象,應(yīng)適度加嚴(yán);若水質(zhì)標(biāo)準(zhǔn)超標(biāo)率較高,HC5超標(biāo)率較低,說明現(xiàn)行水質(zhì)標(biāo)準(zhǔn)對水生生物存在“過保護(hù)”現(xiàn)象,應(yīng)適度放寬.

表2 重金屬水體中暴露濃度對水質(zhì)標(biāo)準(zhǔn)的超標(biāo)率

續(xù)表2

注:Ni和Sb水質(zhì)標(biāo)準(zhǔn)不分Ⅰ類~Ⅴ類水,僅有一個標(biāo)準(zhǔn)限值.

2.3.2 基于風(fēng)險評估法的現(xiàn)行水質(zhì)標(biāo)準(zhǔn)評價 表2結(jié)果表明,Cu在各流域水體中對現(xiàn)行Ⅰ類水質(zhì)標(biāo)準(zhǔn)均超標(biāo),例如黃河流域Ⅰ類水超標(biāo)率為48.1%,但Ⅱ~Ⅲ類水標(biāo)準(zhǔn)超標(biāo)率極低甚至不超標(biāo),最高為6.7%,最低為0.Cu在黃河流域?qū)Π踩撝礖C5的超標(biāo)率為62.8%,其他流域情況與黃河一致,超標(biāo)率在43.2%~88.7%,屬于水質(zhì)標(biāo)準(zhǔn)超標(biāo)率較低,HC5超標(biāo)率較高,由此可以說明,Cu的現(xiàn)行水質(zhì)標(biāo)準(zhǔn)對保護(hù)水生生物過松,建議適度加嚴(yán);Zn和Cd與Cu情況類似,例如,Zn在黃河流域中Ⅰ類水超標(biāo)率為59.9%, Ⅱ~Ⅴ類水超標(biāo)較低或不超標(biāo),最高超標(biāo)率為16%,最低為0.Zn在黃河流域中對安全閾值HC5的超標(biāo)率為64.4%,其他流域情況與黃河一致,HC5超標(biāo)率均較高,Zn的現(xiàn)行標(biāo)準(zhǔn)不足以保護(hù)水生生物的生態(tài)安全,現(xiàn)行水質(zhì)標(biāo)準(zhǔn)過松,建議適度加嚴(yán);Cd與Zn和Cu情況一致,建議適度加嚴(yán);Hg和Ni的情況與Cu、Zn和Cd相反,Hg在各流域水體中對Ⅰ類和Ⅱ類水標(biāo)準(zhǔn)超標(biāo)較嚴(yán)重,超標(biāo)范圍在34.9%~55.6%之間.但Hg對各流域安全閾值的超標(biāo)率為26%~49.6%之間,各流域超標(biāo)率均低于Ⅰ類和Ⅱ類水標(biāo)準(zhǔn)超標(biāo)率,主要因?yàn)镠g對人體健康影響較大,Hg具有極強(qiáng)的生物富集作用[106],在水環(huán)境中不易降解,現(xiàn)行水質(zhì)標(biāo)準(zhǔn)考慮人體健康因素較多,對水生生物存在“過保護(hù)”現(xiàn)象,非飲用水源地等水體可建議適度放寬.Hg的Ⅲ類水標(biāo)準(zhǔn)超標(biāo)率與安全閾值超標(biāo)率一致,現(xiàn)行標(biāo)準(zhǔn)適中.Ni在長江、珠江、太湖和海河的水質(zhì)標(biāo)準(zhǔn)限值的超標(biāo)率也均高于安全閾值HC5在各流域的超標(biāo)率,與Hg一致現(xiàn)行標(biāo)準(zhǔn)存在“過保護(hù)”現(xiàn)象,建議適度放寬.As、Pb、Cr、Se、Sb對各流域水體中現(xiàn)行標(biāo)準(zhǔn)超標(biāo)率與安全閾值超標(biāo)率結(jié)果一致,現(xiàn)行標(biāo)準(zhǔn)適中.

2.3.3 現(xiàn)行水質(zhì)標(biāo)準(zhǔn)不確定性分析 現(xiàn)行水質(zhì)標(biāo)準(zhǔn)按照水體的功能等級分類,對于水生生物和人體健康的針對對象不明確,對人體健康考慮較多,而許多污染物,例如Cu和Zn,水生生物對這兩類金屬更為敏感.近些年我國水生態(tài)系統(tǒng)問題嚴(yán)重,生物多樣性呈銳減下降趨勢,應(yīng)明確保護(hù)對象,加強(qiáng)對水生態(tài)系統(tǒng)的保護(hù).以Cu和Zn為例,二者均是有機(jī)體維持生命所必需的微量營養(yǎng)元素,但當(dāng)其濃度超過生物體所需量時,就會變成有毒物質(zhì),產(chǎn)生毒性效應(yīng)[107].美國環(huán)保局2009年發(fā)布Zn的保護(hù)淡水水生生物水質(zhì)基準(zhǔn)值為120μg/L[108],而保護(hù)人體健康基準(zhǔn)值為26000μg/L[109],可以看出水生生物對Zn的敏感性遠(yuǎn)遠(yuǎn)高于人體.Cu對哺乳類動物的毒性一般很少考慮,經(jīng)過測試的大多數(shù)哺乳動物在飲食中能夠承受高濃度的Cu.Cu對哺乳動物的無毒性作用主要是由于兩方面原因:第一,哺乳動物的肝和腎擁有一套能夠解毒的生化系統(tǒng).第二,由于Cu能被有機(jī)物固定,因此在很多食物中Cu的可利用性較低.而Cu對水生生物的敏感性是哺乳動物的10~100倍,藻類更是大1000倍[110].對于魚類,Cu與魚體內(nèi)的巰基結(jié)合,阻斷生物分子的基本生物官能團(tuán),抑制生命元素鈣和鎂的攝入,修飾生物分子的活性構(gòu)象,造成魚類的毒性效應(yīng).

3 結(jié)論

3.1 概率密度重疊面積法表征生態(tài)風(fēng)險結(jié)果表明,水生生物受重金屬污染造成慢性影響的生態(tài)風(fēng)險中,Cu和Zn在各流域水體的生態(tài)風(fēng)險均較高,其中Cu在海河流域中風(fēng)險概率最高為77.8%,在遼河流域中風(fēng)險最低為19%.Zn在黃河流域中概率最高,在遼河流域中最低,分別為65.2%和11.6%.Ni在長江流域、Hg在珠江流域、Cd在黃河流域以及Cr在海河流域風(fēng)險最高分別為65.8%、52.7%、40.3%和26%.Se、As和Sb在各流域中生態(tài)風(fēng)險均較低.

3.2 聯(lián)合概率分布法評估重金屬在各流域水體中超過安全閾值HC5(慢性毒性)的概率結(jié)果表明,Cu、Zn、Ni、Pb、Cd、Hg、Cr的在各流域水體中超標(biāo)率均較高,其中Cu和Zn對水生生物最為敏感,Cu在海河流域中超標(biāo)率高達(dá)88.7%,Zn在黃河流域中超標(biāo)率達(dá)到64.4%.Se、As和Sb在各流域中超標(biāo)情況均較低.

3.3 聯(lián)合概率分布法評估現(xiàn)行水質(zhì)標(biāo)準(zhǔn)和安全閾值HC5超標(biāo)率情況,比較結(jié)果發(fā)現(xiàn)Cu、Zn和Cd在各流域水體中生態(tài)風(fēng)險較高,但Ⅱ類和Ⅲ類水質(zhì)標(biāo)準(zhǔn)超標(biāo)率較低或不超標(biāo),現(xiàn)行標(biāo)準(zhǔn)存在“欠保護(hù)”現(xiàn)象,建議水質(zhì)標(biāo)準(zhǔn)適度加嚴(yán),增強(qiáng)對水生生物生態(tài)安全的保護(hù).其余金屬,As、Pb、Cr、Se、Sb的現(xiàn)行標(biāo)準(zhǔn)適中,Hg和Ni的水質(zhì)標(biāo)準(zhǔn)建議適度放寬.

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Ecological risk assessment and water quality standard evaluation of 10typical metals in eight basins in China.

HE Jia1,2, SHI Di1, WANG Bei-bei1, FENG Cheng-lian1, SU Hai-lei1, WANG Ying1,3, QIN Ning1,4*

(1.State Key Laboratory of Environmental Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012, China；2.College of Water Sciences, Beijing Normal university, Beijing 100875, China；3.School of Space and Environment, Beihang University, Beijing 102206, China；4.School of Energy and Environmental Engineering, University of Science and Technology Beijing, Beijing 100083, China )., 2019,39(7)：2970~2982

Concentrations of 10 priority metals were compiled for eight major river basins in China. In addition, toxicology data of metals were collected and validated. The overlapping area and joint probability curve methods were adopted to characterize ecological risk and results were compared to current water quality standards. Copper and zinc were identified as the elements exhibiting the greatest potential to cause adverse effects to aquatic organisms. Current water quality criteria might not be sufficiently protective of aquatic organisms. Conversely, the water quality standards for mercury and nickel were deemed sufficient or even slightly over-protective of aquatic organisms. The ecological risks of selenium, arsenic and antimony were relatively low. Water quality standards were moderately protective for these three elements. It is suggested that current water quality standards should be revised and monitoring should be strengthened in order to provide effective protection for the aquatic ecosystem safety in China.

heavy metal；ecological risk assessment；water quality standard；overlapping area method；joint probability curve method

X50

A

1000-6923(2019)07-2970-13

何 佳(1987-),女,吉林長春人,講師,博士,主要從事水質(zhì)基準(zhǔn)與標(biāo)準(zhǔn),生態(tài)風(fēng)險評估,預(yù)測毒理學(xué)研究.發(fā)表論文15篇.

2018-12-07

國家自然科學(xué)基金青年基金項(xiàng)目(41603113,41503104);創(chuàng)新研究群體項(xiàng)目(41521003);博士后科學(xué)基金面上項(xiàng)目(2016M591227);中央高?；究蒲袠I(yè)務(wù)費(fèi)專項(xiàng)資金資助項(xiàng)目(FRF-TP-18-071A1)

* 責(zé)任作者, 講師, qinning@ustb.edu.cn