王 睿, 林 錕, 王江濤, 譚麗菊

渤海多溴二苯醚的分布特征及其風(fēng)險(xiǎn)評(píng)價(jià)

王 睿, 林 錕, 王江濤, 譚麗菊

(中國(guó)海洋大學(xué)海洋化學(xué)理論與技術(shù)教育部重點(diǎn)實(shí)驗(yàn)室, 山東 青島 266100)

多溴二苯醚(PBDEs)屬于新興污染物, 是一種性能優(yōu)良的阻燃劑, 在各種工業(yè)產(chǎn)品中廣泛應(yīng)用, 而且存在于世界各地的海洋環(huán)境中。PBDEs還有持久性、遠(yuǎn)距離遷移性、生物累積性等特點(diǎn), 對(duì)海洋生態(tài)系統(tǒng)和人類造成嚴(yán)重危害。與此同時(shí)渤海又是我國(guó)唯一一個(gè)半封閉型的內(nèi)海, 有較差的自凈能力以及與外界海水交換的能力, 因此渤海區(qū)域PBDEs的研究在近十幾年來受到了極大的關(guān)注。本文綜述了PBDEs在渤海區(qū)域內(nèi)的污染特征以及在海水、沉積物和生物介質(zhì)中的含量水平與分布特征, 并對(duì)與PBDEs相關(guān)的生態(tài)環(huán)境風(fēng)險(xiǎn)評(píng)價(jià)方式進(jìn)行了總結(jié), 以期使讀者深入了解渤海區(qū)域內(nèi)PBDEs的污染現(xiàn)狀及其危害, 為以后此區(qū)域進(jìn)行多溴二苯醚的污染防治和渤海生態(tài)環(huán)境治理等方面的工作提供可以借鑒的資料。

多溴二苯醚; 渤海; 含量; 分布; 生態(tài)環(huán)境風(fēng)險(xiǎn)

多溴二苯醚(PBDEs)可以用來制作各種阻燃劑(BFRs)并在近二十幾年來廣泛用于建筑建材、家具行業(yè)、電子產(chǎn)品和一些基于泡沫材料的工業(yè)產(chǎn)品中。PBDEs的化學(xué)式一般用C12H(0-9)Br(1-10)O來表示, 根據(jù)每種同系物含Br的個(gè)數(shù)不同, 總計(jì)有209種同系物。常見的由PBDEs制作的阻燃劑有3種配方: 一種是十溴二苯醚產(chǎn)品(DBDE), 主要由十溴二苯醚(BDE-209)組成; 一種是八溴二苯醚產(chǎn)品(OBDE), 由六溴二苯醚、七溴二苯醚和八溴二苯醚組成; 還有一種五溴二苯醚產(chǎn)品(PeBDE), 主要由五溴二苯醚(BDE-99)和四溴二苯醚(BDE-47)組成[1-2], 這些都屬于商業(yè)混合物。1979年, 十溴二苯醚第一次在美國(guó)一個(gè)專門生產(chǎn)PBDEs廠房的附近被檢出[3]。在此之后, 隨著BFRs的普遍使用, 近十幾年在不同的環(huán)境介質(zhì)中和生物體中都檢測(cè)到了PBDEs, 這些介質(zhì)包括但不限于水環(huán)境、土壤、水中顆粒物、沉積物、生物體和人體血液等[4-8]。研究發(fā)現(xiàn), PBDEs具有環(huán)境持久性、生物累積性, 對(duì)各種水生生物具有一定的毒性作用。排放到環(huán)境中的PBDEs會(huì)進(jìn)行遷移擴(kuò)散并會(huì)在生物(人類)體內(nèi)富集, 當(dāng)人體內(nèi)的PBDEs到達(dá)一定濃度時(shí)會(huì)干擾內(nèi)分泌系統(tǒng)、影響生育能力、危害神經(jīng)系統(tǒng)以及對(duì)人的部分重要器官產(chǎn)生毒性[9-10]。所以說環(huán)境中的PBDEs是影響人類健康的一個(gè)重要因素。

多溴二苯醚除了可以通過多種途徑釋放到空氣中[11], 水體是PBDEs發(fā)生遷移轉(zhuǎn)化的重要環(huán)境介質(zhì), PBDEs在水環(huán)境中的溶解度很低, 初排放進(jìn)海洋環(huán)境中的PBDEs大多數(shù)會(huì)吸附顆粒物, 在海洋中遷徙, 最終到沉積物中[12]。渤海是我國(guó)唯一一個(gè)半封閉型內(nèi)海, 海域面積約7.7×104km2, 是世界上典型的半封閉海之一[13]。在近些年來, 環(huán)渤海地區(qū)經(jīng)濟(jì)快速發(fā)展、人口日益密集、海上航運(yùn)發(fā)達(dá), 使渤海飽受陸源和海源污染之困, 又因此區(qū)域海水交換和自凈能力差, 導(dǎo)致渤海灣PBDEs的污染形勢(shì)極為嚴(yán)峻。本文概述了近年來渤海區(qū)域PBDEs的污染現(xiàn)狀及其分布, 并對(duì)與PBDEs相關(guān)的生態(tài)環(huán)境安全風(fēng)險(xiǎn)評(píng)價(jià)方式進(jìn)行了總結(jié), 以期為以后此區(qū)域多溴二苯醚的污染防治和渤海生態(tài)環(huán)境治理等方面的工作提供可借鑒的資料。

1 渤海地區(qū)PBDEs的研究進(jìn)程概況

根據(jù)目前對(duì)渤海范圍內(nèi)PBDEs含量水平的調(diào)查結(jié)果顯示, 在渤海大部分區(qū)域的3種介質(zhì)中都有PBDEs被檢出, 這里把渤海劃分成5個(gè)部分, 分別是渤海灣、遼東灣、萊州灣、渤海中部及渤海海峽。其中在渤海入海河流中PBDEs的檢出率和含量都要比海洋中高, 據(jù)先前的研究, 渤海入海河流樣品中主要污染物之一BDE-209的最高濃度出現(xiàn)在靠近溴代阻燃劑(BFRs)生產(chǎn)園區(qū)的彌河[14]。Mou等[15]在2015年4和11月萊州灣調(diào)查得到, PBDEs主要吸附在顆粒相之上, 這些PBDEs主要來源于商業(yè)十溴二苯醚產(chǎn)品(DBDE)的地表徑流輸入。呂楊等[16]從渤海灣區(qū)域內(nèi)采集了沉積物和魚類(鯽魚)樣品, 得到沉積物中PBDEs的含量遠(yuǎn)遠(yuǎn)小于魚體中PBDEs含量(以干重計(jì)), 其中相對(duì)含量較高的PBDEs單體為三溴二苯醚(BDE-28)和四溴二苯醚(BDE-47)。Yao等[17]在2016年報(bào)道了渤海近岸PBDEs沉積物的污染主要是陸源污染, 其采集的柱狀樣中PBDEs的濃度隨深度的增加而明顯減小, 且淤泥區(qū)中PBDEs的濃度較高。據(jù)Wang等[18]的調(diào)查, PBDEs在渤海近岸海域的濃度較高, 遠(yuǎn)岸海域的濃度較低, 這顯示出人的生產(chǎn)生活、近岸局部的沖刷和地表徑流的輸入對(duì)渤海地區(qū)PBDEs的含量都有非常重要的影響。因PBDEs在渤海沉積物、生物體及水體中都有檢出, 所以在現(xiàn)階段探究PBDEs在不同介質(zhì)中的賦存狀態(tài)及含量對(duì)全面理解其在渤海中的環(huán)境行為、風(fēng)險(xiǎn)和歸趨有重要的價(jià)值。

2 渤海PBDEs在海水、沉積物和生物介質(zhì)中分布狀況

2.1 渤海水體中PBDEs的污染現(xiàn)狀

水環(huán)境是溴代阻燃劑(BFRs)遷移和擴(kuò)散的主要媒介, 陸地上很小比例的BFRs會(huì)揮發(fā)至空氣中[11], 通過降雨等方式進(jìn)入海洋, 大部分的 BFRs會(huì)從垃圾填埋場(chǎng)或廢舊電子處理廠等通過雨水沖刷及地表徑流等途徑進(jìn)入下水管道和入海河流之中, 然后遷移至海洋環(huán)境中被顆粒物吸附, 最后沉降到沉積物中或被海洋中魚類、藻類等動(dòng)植物吸收富集[19], 進(jìn)而通過食物鏈進(jìn)入人體之中。

PBDEs有較高的辛醇-水分配系數(shù)(lgow)[20], 所以大部分PBDEs在海洋水體中的濃度很低, 有關(guān)其在渤海水體中含量的報(bào)道也較少。PBDEs在水中的溶解度一般還與溴原子個(gè)數(shù)有關(guān), 而且高溴代PBDEs會(huì)分解為低溴代PBDEs[21], 因此高溴代PBDEs在海洋水體環(huán)境中的檢出率很低, 但高溴代的BDE-209是應(yīng)用最廣的一種BFRs的原料, 有可能因?yàn)槠鋵?duì)海洋環(huán)境的持續(xù)輸入而被檢出。表1為渤海萊州灣及渤海海峽北部旅順養(yǎng)殖區(qū)海水中PBDEs的污染情況[15]。在渤海海峽北部養(yǎng)殖區(qū)附近海域水體中PBDEs含量為15.4~65.5 ng·L–1[22], 此結(jié)果比Chen和Luo等在珠江口測(cè)得的濃度要高[23], 其中PBDEs同系物BDE-47在渤海環(huán)境中檢出率較高。除渤海區(qū)域外, Guan等在8條珠江入海支流采集水樣, 對(duì)樣品中PBDEs的17種PBDEs進(jìn)行了測(cè)定和分析, 水平范圍在0.34~68 ng·L–1[24], 主要成分為BDE-47、BDE-99和BDE-209, 其中BDE-47和BDE-99是BFRs中五溴二苯醚(PeBDE)配方的主要成分, 這與珠江入海口水體中PBDEs的成分大致相同, 這也與渤海區(qū)域主要的PBDEs相符, 不僅說明了兩區(qū)域使用的BFRs種類是大致相同的, 還說明了PBDEs在陸地上進(jìn)行一系列的遷移后, 會(huì)在河流入?？趨R聚成點(diǎn)源, 最后進(jìn)入到整個(gè)海洋環(huán)境中。總的來說, 渤海不同區(qū)域水體中PBDEs的含量水平變化較大, 以渤海旅順為例可能因?yàn)椴蓸狱c(diǎn)受點(diǎn)源污染輸出導(dǎo)致臨近水域濃度較高, 平均約為30.5± 13.5 ng·L–1(含BDE-209)[22], 萊州灣區(qū)域在2015年11月測(cè)得的濃度約為0.07~0.28 ng·L–1[15], 而中國(guó)海洋水體中PBDEs的平均水平大致<0.1 ng·L–1[25], 所以渤海區(qū)域PBDEs的含量還是處于較高水平, 和Pan等[26]先前的研究相比, 萊州灣區(qū)域PBDEs的濃度是顯著下降的。

表1 渤海水體中PBDEs的含量水平

2.2 渤海沉積物中PBDEs的污染現(xiàn)狀

PBDEs極易吸附在顆粒物上而沉降于水底, 沉積物是PBDEs主要的歸宿之一, 殘留在沉積物中的PBDEs又可以擴(kuò)散出來進(jìn)入水環(huán)境中[27], 造成海洋環(huán)境中PBDEs的再次污染并且對(duì)海洋動(dòng)植物有著潛在的威脅, 因此PBDEs在海洋沉積物中的賦存狀態(tài)和釋放方式是以后需要探究的重點(diǎn)。萊州灣附近有亞洲最大的溴化阻燃劑(BFRs)生產(chǎn)基地, 因此此區(qū)域沉積物中PBDEs的濃度較渤海灣其他區(qū)域高[26], 還因?yàn)椴煌瑓^(qū)域的河口處輸入PBDEs的量各不相同, 所以渤海海洋沉積物中PBDEs的含量水平會(huì)因研究區(qū)域的不同而存在差異。

表2是渤海及其附近海域沉積物中PBDEs的含量水平, Lin等[28]最早研究了環(huán)渤海主要河流入?？趨^(qū)域的表層沉積物發(fā)現(xiàn)PBDEs主要以BDE-209為主, ∑PBDEs(不含BDE-209) 的含量較少且分布差異較大。渤海整個(gè)區(qū)域PBDEs的含量整體呈上升趨勢(shì), 部分區(qū)域濃度因所調(diào)查范圍的不同而變化較大, 因?yàn)槿R州灣附近的濰坊工業(yè)園區(qū)有我國(guó)最大的BFRs廠商與供貨商[29], 其中電子制造業(yè)和BFRs生產(chǎn)業(yè)都是政府支持的高新技術(shù)產(chǎn)業(yè), 給渤海造成了很大的負(fù)擔(dān)。渤海作為一個(gè)半封閉型的內(nèi)海, 與黃海的水交換程度較小, 隨著渤海經(jīng)濟(jì)圈的迅速發(fā)展, 大部分的污染物會(huì)從陸地排放進(jìn)渤海[13], 使渤海區(qū)域的污染負(fù)擔(dān)加重, 環(huán)渤海區(qū)域沉積物中檢測(cè)出的PBDEs在河口處含量較高[30], 顯示出渤海周邊區(qū)域的工廠排放和河流徑流是影響渤海沉積物中PBDEs含量的主要因素, 基本上, 在所有站位中BDE-209的濃度要遠(yuǎn)高于其他PBDEs的濃度[31], 因?yàn)锽DE-209是DBDE的主要成分且DBDE是目前使用最廣泛的BFRs。

表2 渤海及其附近海域沉積物中PBDEs的含量水平/[ng·(g dw)–1]

注: ND為未檢出, dw為干重

值得注意的是渤海近岸海域受人類影響較大, 渤海區(qū)域共有約50多條入海河流, 渤海中的PBDEs主要是源于沿岸污水口的排放和地表徑流的輸入。在渤海入海35條河口的沉積物樣品中, BDE-209是所測(cè)PBDEs的主要組成[14]。BDE-209的均值濃度要比此區(qū)域∑PBDEs的濃度高大約一個(gè)數(shù)量級(jí), 最大值出現(xiàn)在萊州灣西部的彌河, 這可能是因?yàn)槿R州灣區(qū)域有溴代阻燃劑的生產(chǎn)工廠[34], 而且DBDE是一種常用的BFRs, BDE-209是DBDE產(chǎn)品的主要成分[1-2], 因此在渤海沉積物中占很高的比例, 最大值為1.77 ng·g–1。渤海的入海河流沉積物中PBDEs的最大值為4.08 ng·g–1[35]。

從圖1中BDE-209在渤海中的空間分布得出: BDE-209在萊州灣及附近海域的濃度較高, 在遼東灣和渤海海峽濃度較低; BDE-209總體上呈由近岸高遠(yuǎn)岸低, 渤海南部高北部低的特點(diǎn); 圖2所示, ∑PBDEs與BDE-209的分布類似, 其在萊州灣的濃度較高, 但BDE-209主要集中在萊州灣西部的彌河入?？趨^(qū)域, 而∑PBDEs卻集中在萊州灣東部, 而且在萊州灣東側(cè)王河和界河中∑PBDEs的濃度并不高, 這可能是兩個(gè)原因造成的, 一是由于BDE-209在輸入至海洋中后會(huì)降解為低溴的PBDEs, 然后受渤海沿岸流的影響向東遷移, 二可能是由于在兩條河流下游有工廠污水和/或含BFRs廢料的物品直接排放至萊州灣東部海域所導(dǎo)致的[14], 因此水動(dòng)力與陸源因素可能是導(dǎo)致此區(qū)域∑PBDEs與BDE-209的分布有差異的原因。

圖1 渤海及35條河流樣品中BDE-209空間分布(單位: pg·g–1)[35]

渤海灣區(qū)域沉積物中PBDEs的分布情況較為復(fù)雜, 部分區(qū)域的濃度較低, 部分區(qū)域的濃度則很高, 濃度高的區(qū)域可能是受附近點(diǎn)源污染的影響, 渤海中部PBDEs的濃度居中, 遼東灣和渤海海峽的濃度較低, 但遼東灣邊界處的PBDEs濃度要比灣內(nèi)高, 這可能是此區(qū)域有傾廢區(qū)(綏中發(fā)電廠二期工程配套碼頭項(xiàng)目臨時(shí)性海洋傾倒區(qū), 39°59′0.00″N, 120°5′60.00″E[13])和一系列綏中油氣平臺(tái)(綏中36-1EA/B/C/CEP-D/E/F/J/旅大5-2平臺(tái))的原因, 使得遼東灣邊界地區(qū)受污染的程度較灣內(nèi)嚴(yán)重?？傮w而言, 渤海區(qū)域的BDE-209與∑PBDEs的分布整體上有較好的相關(guān)性, 這也變相的說明了渤海區(qū)域內(nèi)的BDE-209可能會(huì)分解為低溴PBDEs。

2.3 渤海海洋生物中PBDEs的污染現(xiàn)狀

水生生物是反映環(huán)境污染的良好的生物指示物[36], 它們可以通過水及攝取海洋中的各類食物來富集環(huán)境中的PBDEs[37], 在渤海某些水生生物中同樣也檢測(cè)到了PBDEs, 如表3所示。根據(jù)現(xiàn)有的研究, PBDEs在渤海海洋生物中的污染較普遍, 它們?cè)诤Ｑ笊矬w內(nèi)的含量高低除了與環(huán)境污染狀況、動(dòng)植物的種類和不同部位的組織有關(guān)[38], 還與其捕食習(xí)性和代謝潛力有關(guān)[39]。除了未轉(zhuǎn)化的PBDEs, 羥基化(OH-)和甲氧基化(MeO-)的PBDEs在生物中也廣泛存在。但目前對(duì)它們的營(yíng)養(yǎng)級(jí)放大和人體中暴露水平的了解還很少, Liu等[40]研究了渤海沿岸城市大連的生物群, 通過食用海產(chǎn)品對(duì)OH- PBDEs(0.4 ng·kg–1·d–1)和MeO-PBDEs(0.8 ng·kg–1·d–1)的膳食攝入量的評(píng)估表明, 沿海居民通過大量食用海產(chǎn)品接觸OH-PBDEs和MeO-PBDEs的風(fēng)險(xiǎn)更高。

在萊州灣海域的生物體中PBDEs的濃度較高, PBDEs在此區(qū)域沉積物中的污染狀況相似, 可以推斷出海洋中的底棲生物的攝食習(xí)性及生存環(huán)境中污染物的暴露水平對(duì)底棲生物體中PBDEs的賦存有很大的影響[17]。在渤海海峽南部周邊海域生物體中PBDEs的濃度高于萊州灣, 這可能與渤海海域的沿岸流[41-42]有關(guān), 導(dǎo)致低溴的PBDEs遷移到渤海海峽的南部, 最終被水生生物所富集[43], 這同時(shí)體現(xiàn)出高溴的PBDEs受海流的影響較小, 很可能會(huì)附著在懸浮顆粒上而沉降[31]。

圖2 渤海及 35 條河流樣品中∑PBDEs(BDE-209除外)的空間分布(單位: pg·g–1)[35]

表3 渤海不同區(qū)域不同底棲生物中PBDEs的含量(單位: ng·g–1)[43]

BDE-209雖然近年來在某些魚/貝類中的檢出率和檢出濃度有上升趨勢(shì)[44], 但其在生物體中的檢出率相對(duì)來說還是很低, 這和沉積物中PBDEs分布方式不同, 主要有兩方面的原因, 一是因?yàn)锽DE-209在所有PBDEs同系物中的分子量最大, 很難透過細(xì)胞膜[45], 另一方面可能是生物體內(nèi)部會(huì)對(duì)高溴代PBDEs單體進(jìn)行一系列的代謝和轉(zhuǎn)化作用, 所以很難富集高溴代的PBDEs[46-47]。BDE-47/BDE-99的比值可以很好的反映出生物體降解PBDEs的能力[48], 這兩種PBDEs同系物是五溴二苯醚商業(yè)產(chǎn)品的主要成分, BDE-47/BDE-99的比例約為0.8至1.0[2, 49]。無脊椎動(dòng)物中BDE-47/99的比率為0.5至2.5, 魚類為2.4至22之間, BDE-99所占比例的減少可以用其在生物體內(nèi)降解為BDE-47來解釋[50]。魚類的這一比值相對(duì)高于無脊椎動(dòng)物樣本, 表明魚類的代謝能力更為發(fā)達(dá)。BDE-47/BDE-99的比值還可與營(yíng)養(yǎng)級(jí)相關(guān)聯(lián), 并有研究發(fā)現(xiàn)這一比值隨營(yíng)養(yǎng)級(jí)增加而增加[51]。He等[52]發(fā)現(xiàn)在同種生物體內(nèi)內(nèi)臟組織中含有的PBDEs明顯高于肌肉組織中的PBDEs, 這與LYU等[16]在渤海灣鯽魚體內(nèi)∑PBDEs在肌肉組織(6.81~20.00 ng·g–1)中的含量小于內(nèi)臟組織(8.10~ 35.50 ng·g–1)的結(jié)果一致。Zheng等[53]發(fā)現(xiàn)渤海沿岸滄州濕地的珩科鳥體內(nèi)的PBDEs等鹵代化合物還會(huì)選擇性地從母體轉(zhuǎn)移到卵中。

3 渤海PBDEs的生態(tài)環(huán)境安全風(fēng)險(xiǎn)評(píng)價(jià)

3.1 PBDEs在海水中的生態(tài)風(fēng)險(xiǎn)評(píng)價(jià)

現(xiàn)常用風(fēng)險(xiǎn)商值(RQ)來對(duì)水體中的PBDEs進(jìn)行生態(tài)風(fēng)險(xiǎn)評(píng)價(jià)[54]。風(fēng)險(xiǎn)商值基于美國(guó)環(huán)境保護(hù)署的規(guī)定和低等水生生物毒理學(xué)數(shù)據(jù), 來確定水體中不同BFRs產(chǎn)品的無效應(yīng)濃度(MSNOEC)分別是0.053 μg·L–1(五溴二苯醚)和0.017 μg·L–1(八溴二苯醚), 十溴二苯醚的毒性數(shù)據(jù)目前還沒有[55]。水體中的濃度(measured environmental concentration, MEC)為暴露水平, 公式如下:

RQ=MEC/MSNOEC, (1)

當(dāng)RQ≥1(高風(fēng)險(xiǎn)), 0.1≤RQ<1(中等風(fēng)險(xiǎn)), 0.01≤RQ<0.1(低風(fēng)險(xiǎn)), RQ<0.01(無風(fēng)險(xiǎn))。

3.2 PBDEs在沉積物中的生態(tài)風(fēng)險(xiǎn)評(píng)價(jià)

這里也可以采用風(fēng)險(xiǎn)商值(RQ)來對(duì)渤海灣PBDEs沉積物進(jìn)行生態(tài)風(fēng)險(xiǎn)評(píng)價(jià), 公式如下:

C是沉積物中PBDEs的濃度[56],si是PBDEs的標(biāo)準(zhǔn)濃度值[57], 標(biāo)準(zhǔn)濃度值依據(jù)加拿大環(huán)境部(EC)規(guī)定的沉積物質(zhì)量準(zhǔn)則[58]。C,si需經(jīng)1%TOC歸一化得到。

3.3 海洋生物食用健康風(fēng)險(xiǎn)評(píng)價(jià)

3.3.1 PBDEs在海洋生物中的富集研究

PBDEs通常具有親脂和難降解的特性, 當(dāng)某種化學(xué)物質(zhì)的生物富集因子(BCF)>5 000時(shí), 便認(rèn)為該化學(xué)物質(zhì)存在著生物富集性[59]。對(duì)于PBDEs, 其通過細(xì)胞膜的能力是影響PBDEs生物累積程度的重要因素, 而且高溴PBDEs比低溴PBDEs在海洋食物鏈中的生物累積性低[60]。生物沉積物富集因子(BSAF)也可以用來評(píng)估海洋中PBDEs的生物富集效應(yīng), 海洋生物對(duì)PBDEs的吸收富集能力的大小與其富集的種類和生存的環(huán)境有關(guān)[61]。相對(duì)來說, 底棲動(dòng)物對(duì)PBDEs有高的富集能力和敏感性, 常被用來指示海洋污染的程度[62], 海洋中魚類的富集能力一般要比浮游生物和貝類生物高, 主要是因?yàn)轸~類處于較高的營(yíng)養(yǎng)級(jí), 在渤海灣區(qū)域, 魚類體內(nèi)以低溴PBDEs (BDE-28/47/99)為主[51]。

3.3.2 生物沉積物富集因子

生物對(duì)沉積物中PBDEs的富集能力可以用下式表示:

BSAF=C/C, (3)

C是生物體中 PBDEs 的脂肪歸一化濃度;C是沉積物中 PBDEs 的TOC歸一化濃度[41]。

3.3.3 食用健康風(fēng)險(xiǎn)評(píng)價(jià)方式

1) 每日最大允許海產(chǎn)品攝入量

因?yàn)镻BDEs可能有致癌性的風(fēng)險(xiǎn), 也可能有非致癌性的風(fēng)險(xiǎn), 因此, 兩種風(fēng)險(xiǎn)都需要進(jìn)行分析。美國(guó)環(huán)境保護(hù)機(jī)構(gòu)(U.S. EPA)給出了每日允許海產(chǎn)品最大攝入量的計(jì)算公式[63-65]:

CRlim是由式(4): 特定某種海鮮產(chǎn)品中 PBDEs 的致癌性健康風(fēng)險(xiǎn)、式(5): 特定某種海鮮產(chǎn)品中 PBDEs的非致癌性健康風(fēng)險(xiǎn)計(jì)算得出的最高海鮮產(chǎn)品的攝入量, 單位: g·d–1; BW是體重(kg), 取男女體重的平均值 58.55 kg[65]; ARL是在可承受范圍內(nèi)最高的致癌風(fēng)險(xiǎn), 一般取10–6(即致癌率=1/106)[65];C是海產(chǎn)品中PBDEs的濃度, 單位: pg·g–1; CSF是海產(chǎn)品中PBDEs 致癌斜率因子, 取0.007 (mg·kg bw–1·d–1)–1[67]; RfD是參考劑量, 單位: mg·kg–1·d–1。

2) 日暴露量

對(duì)污染物進(jìn)行人體暴露評(píng)估是健康風(fēng)險(xiǎn)評(píng)估的前提條件, 人體暴露評(píng)估常用日攝入量來表示。在這里可以利用PBDEs的濃度來進(jìn)行評(píng)價(jià), 即認(rèn)為PBDEs進(jìn)入人體后會(huì)被全部吸收, 則日暴露量EDI的值可以用以下公式計(jì)算:

EDI是人體每天通過食用魚產(chǎn)品, 人每千克的體重?cái)z入污染物的量, 單位: pg·(kg bw)–1·d–1; IR是食物攝入率, 單位: g·d–1, 我國(guó)所在地區(qū)(采用G區(qū): 東南亞地區(qū))每人每天所食用不同海鮮產(chǎn)品量的標(biāo)準(zhǔn)為: 魚類9.4 g、甲殼類3.6 g、頭足類7.5 g和貝類7.5 g, 總海鮮產(chǎn)品的平均攝入量取45.0 g[68]; BW同式(5);C是生物體中PBDEs的濃度, 單位: pg·g–1。

3.4 渤海PBDEs的生態(tài)環(huán)境安全風(fēng)險(xiǎn)狀況

Mou等[15]對(duì)萊州灣區(qū)域海水中的PBDEs(除十溴二苯醚外)生態(tài)風(fēng)險(xiǎn)評(píng)價(jià)顯示其0.01≤RQ<0.1, 為中等生態(tài)風(fēng)險(xiǎn)。Wang等[74]對(duì)渤海中部表層沉積物中的PBDEs的生態(tài)風(fēng)險(xiǎn)評(píng)價(jià)表示五溴二苯醚(RQ>0.1 )和十溴二苯醚 (RQ>0.1)可能對(duì)底棲生物有潛在的威脅。在萊州灣東部區(qū)域沉積物中三、四、六和十溴二苯醚的RQ<0.01, 無生態(tài)風(fēng)險(xiǎn), 五溴二苯醚的0.1≤RQ<1, 為中等生態(tài)風(fēng)險(xiǎn)[15]。因此渤海灣不同區(qū)域不同介質(zhì)中PBDEs所產(chǎn)生的生態(tài)風(fēng)險(xiǎn)有明顯的差異。Wang等[30]還發(fā)現(xiàn)在環(huán)渤海近岸生物體中PBDEs的生物沉積物富集因子(BSAF)值與它們的lgow密切相關(guān)。Yao等[17]在環(huán)渤海近岸所計(jì)算PBDEs的BSAF值為菲律賓蛤仔(0.43~4.06)>紫怡貝(0.34~2.86)>四角蛤蜊(0.17~1.95)>麻蛤(0.13~2.33)>牡蠣(0.09~120), 此結(jié)果較Wang等[30]所測(cè)的結(jié)果偏低。渤海區(qū)域CRlim的最小值為15.82 kg·d–1[17], 超出美國(guó)環(huán)境保護(hù)機(jī)構(gòu)所給出的值(0.142 kg·d–1)約2個(gè)數(shù)量級(jí), 所以食用渤海周邊的海鮮是完全沒有問題的。據(jù)Liu等[75]的研究, 渤海的周邊城市(以大連為例), 此區(qū)域居民通過不同海產(chǎn)品消費(fèi)所攝入的MeO-PBDEs [0.8 ng·(kg bw)–1·d–1] 和PBDEs[0.8 ng·(kg bw)–1·d–1]均是OH-PBDEs [0.4 ng·(kg·bw)–1·d–1] 攝入量的2倍。由于所選取的海產(chǎn)品的不同, Yao等在大連所測(cè)得的PBDEs的攝入量為5 ng·(kg bw)–1·d–1。Eguchi等[76]人發(fā)現(xiàn)沿海居民血清中的OH-PBDEs和MeO-PBDEs的濃度要高于內(nèi)地的電子垃圾回收工作者, 說明了海鮮可能是沿海居民體內(nèi)OH-PBDEs 或 MeO-PBDEs的主要來源。由于缺乏關(guān)于人的準(zhǔn)確毒性數(shù)據(jù)以及PBDEs, OH-PBDEs和MeO-PBDEs的健康風(fēng)險(xiǎn)評(píng)估標(biāo)準(zhǔn), 因此難以通過食用海鮮定量評(píng)估PBDEs及其衍生物在人體的暴露風(fēng)險(xiǎn)。

4 結(jié)論和展望

本文系統(tǒng)地綜述了渤海區(qū)域PBDEs在沉積物, 水體及生物體中的污染現(xiàn)狀及其生態(tài)環(huán)境風(fēng)險(xiǎn)評(píng)價(jià)方式, 雖然目前關(guān)于PBDEs的研究已經(jīng)取得了一定的進(jìn)展, 但是PBDEs作為一種長(zhǎng)期污染物對(duì)于環(huán)境的持續(xù)影響和人類的安全依舊是潛在的威脅, 而且目前PBDEs在不同環(huán)境介質(zhì)中的濃度限定標(biāo)準(zhǔn)還沒有規(guī)范化, 因此亟需制定一套適合我國(guó)的PBDEs濃度標(biāo)準(zhǔn)。關(guān)于PBDEs在人體暴露的評(píng)估, 大多數(shù)是基于日常攝取食物來進(jìn)行評(píng)價(jià), 既沒有考慮PBDEs通過人的皮膚和呼吸攝入這兩個(gè)過程[72], 也沒有考慮PBDEs在人體內(nèi)的吸收率[73], 因此需要進(jìn)行更全面的研究, 把日常攝入, 呼吸和皮膚接觸這3種暴露途徑以及在人體內(nèi)的吸收率全部考慮在內(nèi)。而且, 由于在實(shí)際的海洋環(huán)境中PBDEs會(huì)受各種因素互相影響, PBDEs會(huì)發(fā)生各種反應(yīng), 如PBDEs的轉(zhuǎn)化(羥基化及巰基化等)、其反應(yīng)所產(chǎn)生的毒性物質(zhì)之間會(huì)存在哪些聯(lián)合作用(拮抗作用及協(xié)同作用等), 對(duì)于PBDEs的這些環(huán)境行為和毒理學(xué)效應(yīng)還需要進(jìn)一步的研究。

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Distribution and risk assessment of polybrominated diphenyl ethers in the Bohai Sea

WANG Rui, LIN Kun, WANG Jiang-tao, TAN Li-ju

(Key Laboratory of Marine Chemistry Theory and Technology/Ministry of Education, Ocean University of China, Qingdao 266100, China)

In the past few decades polybrominated diphenyl ethers(PBDEs) have emerged as a new class of persistent organic pollutants (POPs) owing to their accumulation in the marine environments all across the globe. PBDEs are widely used as a flame-retardant and are fount to exist is in a variety of industrial products including textiles, paints, rugs, automobiles, and airplanes. The characteristics of persistence, bioaccumulation, and long-range transportation make PBDEs a serious threat to marine ecosystems and human health. The Bohai Sea is the only semi-enclosed inland sea in China. Its poor ability of self-purification and exchange water with the outside of Bohai Sea has been found to be associated with the high pollution load present in this waterbody. Evaluation of PBDEs accumulation in the Bohai Sea region has received a significant attention in the recent decades. The current study aimed to provide an overview of the pollution status of the Bohai Sea and evaluate the harmful effects of the accumulated PBDEs. With a view to provide an overview of the pollution status of the Bohai Sea and the harmful effects of the accumulated PBDEs, the present work describes in detail the pollution characteristics and concentration levels of PBDEs in sea water, sediments and biological media of the Bohai Sea, methods used for ecological and environmental risk assessment, and distributions of PBDEs in water and sediment. The information thus obtained will be helpful in the prevention and control of pollution arising due to PBDEs accumulation which will further maintain the ecological and environmental serenity/balance of the Bohai Sea in the near future.

polybrominated diphenyl ethers; Bohai Sea; concentration; distribution; eco-environmental risk

Jul. 17, 2020

X145

A

1000-3096(2021)04-0189-12

10.11759/hykx20200717001

2020-07-17;

2020-08-16

國(guó)家重點(diǎn)研發(fā)計(jì)劃項(xiàng)目(2019YFC1407802)

[National Key Research and Development Project of China, No.2019YFC1407802]

王睿(1995—), 男, 山東省濟(jì)南市人, 主要從事海洋污染生態(tài)化學(xué)研究, E-mail: wangrui-ouc@foxmail.com; 王江濤(1967—),通信作者, 男, 河北省承德市人, 教授, 主要從事海洋化學(xué)和生態(tài)學(xué)研究, E-mail: jtwang@ouc.edu.cn

(本文編輯: 趙衛(wèi)紅)