廢棄電子垃圾拆解地野生魚類鹵系阻燃劑殘留

吳江平,馮文露,吳思康,胡 鈺,麥碧嫻

廢棄電子垃圾拆解地野生魚類鹵系阻燃劑殘留

吳江平1*,馮文露1,吳思康1,胡 鈺1,麥碧嫻2

(1.安徽師范大學(xué)生態(tài)與環(huán)境學(xué)院,安徽 蕪湖 241002；2.中國(guó)科學(xué)院廣州地球化學(xué)研究所,廣東 廣州 510640)

為了解廢棄拆解地環(huán)境中電子垃圾相關(guān)污染物的含量水平及其生態(tài)風(fēng)險(xiǎn),本文測(cè)試了華南某廢棄電子垃圾拆解地野生鯪魚和鯽魚體內(nèi)多溴聯(lián)苯醚(PBDEs)、多溴聯(lián)苯(PBBs)、得克隆(DP)和替代型溴系阻燃劑(ABFRs)等鹵系阻燃劑(HFRs)的含量和組成,評(píng)估了這些污染物對(duì)于野生魚類及食魚野生動(dòng)物的生態(tài)風(fēng)險(xiǎn).電子垃圾拆解地鯪魚和鯽魚體內(nèi)∑HFRs的含量范圍分別為1230~1680和141~650ng/g,高于對(duì)照區(qū)1~2個(gè)數(shù)量級(jí),表明雖然粗獷的電子垃圾回收活動(dòng)已禁止多年,當(dāng)?shù)匾吧~類仍然受到HFRs嚴(yán)重污染.PBDEs是魚體內(nèi)最主要的HFRs,鯪魚和鯽魚體內(nèi)其分別占∑HFRs的96%和89%.鯪魚和鯽魚體內(nèi)HFRs含量和組成均存在顯著差異,可能與其生活習(xí)性、營(yíng)養(yǎng)級(jí)和脂肪含量不同有關(guān).風(fēng)險(xiǎn)評(píng)估結(jié)果顯示,PBDEs對(duì)野生魚類及食魚野生動(dòng)物均具有較大的生態(tài)風(fēng)險(xiǎn).

鹵系阻燃劑；多溴聯(lián)苯醚；電子垃圾；野生魚類；生態(tài)風(fēng)險(xiǎn)

鹵系阻燃劑(HFRs)是一類具有阻燃能力的含鹵素(主要為溴和氯)有機(jī)化合物,被廣泛添加于塑料、紡織品和電子電器等產(chǎn)品中以降低其發(fā)生火災(zāi)的風(fēng)險(xiǎn)[1].多溴聯(lián)苯(PBBs)、多溴聯(lián)苯醚(PBDEs)和得克隆(DP)是使用量較大的HFRs.由于這些化合物在環(huán)境中具有持久性、可生物蓄積性、長(zhǎng)距離遷移性和較強(qiáng)的生物毒性,PBBs和PBDEs已經(jīng)自動(dòng)退出生產(chǎn)或被政府(組織)禁用或限用,DP最近也被斯德哥爾摩公約持久性有機(jī)污染物(POPs)審查委員會(huì)認(rèn)定符合POPs標(biāo)準(zhǔn)[2].然而,這些化合物還將從已添加的產(chǎn)品及污染的環(huán)境介質(zhì)(土壤和沉積物等)中持續(xù)釋放到環(huán)境.此外,為了達(dá)到嚴(yán)格的消防標(biāo)準(zhǔn),生產(chǎn)廠家逐漸使用一些非PBDE類溴系阻燃劑替代已禁用的PBDEs[3].與PBDEs相似,這些替代型溴系阻燃劑(ABFRs)在產(chǎn)品的使用過(guò)程中和產(chǎn)品廢棄后處置不當(dāng)很容易釋放到環(huán)境[3],這些新型污染物對(duì)區(qū)域和全球環(huán)境的不利影響及其潛在的生態(tài)風(fēng)險(xiǎn)也引起了高度關(guān)注[3-4].

廢棄電子電器產(chǎn)品(電子垃圾)拆解地是HFRs典型污染地[5-6].由于嚴(yán)重的環(huán)境污染,我國(guó)在2010年前后開(kāi)始禁止酸洗和焚燒等粗獷的電子垃圾回收方式,并取締家庭作坊式手工拆解活動(dòng),許多電子垃圾拆解地被廢棄[6].然而,廢棄電子垃圾拆解地環(huán)境中HFRs含量仍然較高[6].野生魚類在食物網(wǎng)上既是捕食者,又是被捕食者,對(duì)于生態(tài)系統(tǒng)的物質(zhì)循環(huán)和能量流動(dòng)起著重要作用.PBDEs等HFRs暴露對(duì)野生魚類從個(gè)體和種群水平都可以產(chǎn)生不利影響[7-8],從而可能損害生態(tài)系統(tǒng)的正常功能[9].此外,野生魚體內(nèi)的HFRs可以通過(guò)食物鏈傳遞在食魚野生動(dòng)物體內(nèi)蓄積,并對(duì)這些野生生物產(chǎn)生毒害作用.最近的研究顯示,廢棄電子垃圾拆解地野生魚體內(nèi)HFRs含量較高[10-11],這些廢棄場(chǎng)地中野生魚類HFRs的含量、組成及暴露風(fēng)險(xiǎn)尚需深入研究.

廣東省清遠(yuǎn)市龍?zhí)伶?zhèn)是我國(guó)主要的電子垃圾拆解地之一.該地電子垃圾拆解活動(dòng)始于20世紀(jì)90年代初,高峰時(shí)期約有1300個(gè)手工作坊式拆解工廠,每年電子垃圾拆解量超過(guò)170萬(wàn)t,是我國(guó)最大的電子垃圾拆解地之一.由于嚴(yán)重的環(huán)境污染,當(dāng)?shù)卣?014年前后取締了粗獷的電子垃圾拆解活動(dòng).為了探尋電子垃圾拆取締后當(dāng)?shù)丨h(huán)境中HFRs殘留水平,本研究測(cè)試了該廢棄電子垃圾拆解地野生鯪魚和鯽魚體內(nèi)PBDEs、PBBs、DP和6種ABFRs(十溴二苯乙烷(DBDPE)、1,2-雙(2,4,6-三溴苯氧基)乙烷(BTBPE)、六溴苯(HBB)、五溴甲苯(PBT)、五溴乙苯(PBEB)和二甲基四溴苯(pTBX))等HFRs的含量與組成,并評(píng)估了這些污染物暴露對(duì)野生魚類及食魚野生動(dòng)物的生態(tài)風(fēng)險(xiǎn).

1 材料與方法

1.1 樣品采集

鯪魚(=10)和鯽魚(=10)于2015年采集于廣東省清遠(yuǎn)市龍?zhí)伶?zhèn)廢棄電子垃圾拆解地一自然池塘(23°36′N,113°04′E).所有魚類樣品的體長(zhǎng)均<15cm.同時(shí),在非電子垃圾拆解地(離該電子垃圾拆解地以北約100km)一自然池塘采集了大小相似的鯪魚(=6)和鯽魚(=6)作為對(duì)照樣品.樣品采集后冰袋保存,運(yùn)回實(shí)驗(yàn)室后置-20°C保存.

1.2 HFRs含量測(cè)定

樣品經(jīng)真空冷凍干燥48h后,每條整魚樣品用粉碎機(jī)粉碎、混勻.準(zhǔn)確稱取約2g混勻后樣品,用無(wú)水硫酸鈉研磨并添加回收率指示物(BDE-77、BDE-181和13C-BDE-209).樣品經(jīng)丙酮/正己烷混合溶劑(1/1,/)索氏抽提48h.抽提液濃縮至10mL,取1mL進(jìn)行脂肪含量測(cè)定(重量法).剩余9mL抽提液濃縮后經(jīng)凝膠滲透色譜柱去除脂肪,并經(jīng)多層硅膠氧化鋁色譜柱進(jìn)一步凈化.凈化后的抽提液旋轉(zhuǎn)蒸發(fā)濃縮后轉(zhuǎn)換溶劑為正己烷.氮吹至近干,用異辛烷定容至200μL,加入定量?jī)?nèi)標(biāo)(BDE-118和BDE- 128)后利用氣相色譜/質(zhì)譜(GC/MS)測(cè)試.樣品前處理具體過(guò)程參見(jiàn)文獻(xiàn)[12].

使用GC-MS-NCI(Agilent 7890A-5975MS)測(cè)定HFRs含量[10,12].采用DB-XLB毛細(xì)色譜柱(30m× 250mm i.d.×0.25μm;J&W Scientific)分離低溴代PBDE同系物(BDE-28、BDE-47、BDE-66、BDE- 99、BDE-100、BDE-138、BDE-153、BDE-154和BDE-183)、BB-153、BB-209、-DP、-DP、HBB、PBT和PBEB.高溴代PBDE同系物(BDE-196、BDE-197、BDE-202、BDE-203、BDE-206、BDE-207、BDE-208和BDE-209)、DBDPE和BTBPE采用DP-5HT毛細(xì)色譜柱(15m×0.25mm i.d.×0.10μm;J&W Scientific)分離.載氣為高純氦氣,反應(yīng)氣為甲烷.離子源壓力為2.4× 10-3Pa,離子源溫度為230℃,界面溫度280℃.采用無(wú)分流進(jìn)樣,進(jìn)樣量為1 μL,進(jìn)樣口溫度290℃.GC升溫程序參照文獻(xiàn)[10,12].MS采用選擇性離子模式(SIM),目標(biāo)化合物掃描離子荷質(zhì)比(/):DP為653.8和651.8,13C-BDE-209為486.7和488.7,其它目標(biāo)化合物為79和81.

1.3 質(zhì)量保證與質(zhì)量控制(QA/QC)

質(zhì)量控制和保證措施包括回收率指示物添加、程序空白、基質(zhì)加標(biāo)和樣品重復(fù)樣分析等.真實(shí)樣品中回收率指示物BDE-77、BDE-181和13C-BDE- 209的平均回收率分別為94.3%、98.9%和89.8%.基質(zhì)加標(biāo)(4種ABFRs、-DP、-DP和11個(gè)PBDE同系物)得到的加標(biāo)物的回收率范圍為75.9%~104%.每批11個(gè)樣品設(shè)置1個(gè)程序空白樣品.程序空白中檢測(cè)到DP和一些PBDE同系物,但含量低于真實(shí)樣品中該化合物含量的1%.樣品最終含量經(jīng)空白校正.3個(gè)鯪魚樣品重復(fù)樣中目標(biāo)化合物(除BDE-209)測(cè)定值的相對(duì)標(biāo)準(zhǔn)偏差(RSD)均<10%, BDE-209的RSD為28%.

目標(biāo)化合物的檢測(cè)限(LOD)按程序空白中的含量加3倍標(biāo)準(zhǔn)偏差計(jì)算.對(duì)于程序空白中未檢出的化合物,其LOD按5倍信噪比(S/N)計(jì)算.魚體樣品中PBDEs和PBBs、DPs和ABFRs的檢測(cè)限分別為0.04~0.11、0.01~0.05和0.01~0.11ng/g濕重.

2 結(jié)果與討論

2.1 魚體中HFRs含量

廢棄電子垃圾拆解地及對(duì)照區(qū)野生鯪魚和鯽魚樣品中∑PBDEs(17個(gè)PBDE同系物含量之和)、∑PBBs(BB-153和BB-209含量之和)、∑DPs(- DP和-DP含量之和)和∑ABFRs(DBDPE、BTBPE、HBB、PBT、PBEB和pTBX含量之和)含量見(jiàn)表1.電子垃圾拆解地魚類樣品中∑PBDEs、∑PBBs和∑DPs的含量高于對(duì)照區(qū)1~3個(gè)數(shù)量級(jí), ∑ABFRs含量也是對(duì)照區(qū)的2~3倍,表明當(dāng)?shù)匾吧~類已受到HFRs嚴(yán)重污染.鯪魚體內(nèi)∑PBDEs脂肪歸一化含量(均值:24.8μg/g)與2010年(整魚,32~ 39μg/g)[13]、2014年(肌肉,18μg/g)[11]和2016年(整魚,12μg/g)[10]采集于同一電子垃圾拆解地鯪魚體內(nèi)∑PBDEs含量相當(dāng).鯽魚體內(nèi)∑PBDEs脂肪歸一化含量(均值:22.3μg/g)和∑ABFRs含量(均值:430ng/g)也與2016年采集于該廢棄電子垃圾拆解地鯽魚體內(nèi)這些污染物含量(∑PBDEs:20.6μg/g,∑ABFRs: 130μg/g)[10]相近.然而,廢棄電子垃圾拆解地鯪魚體內(nèi)∑PBDEs、∑DPs和DBDPE脂肪歸一化含量高于華南非電子垃圾拆解地野生鯪魚體內(nèi)這些污染物的報(bào)道值(∑PBDEs:9.3~170ng/g,∑DPs:1.9~36ng/g, DBDPE:0.09~1.3ng/g)[11]1~4個(gè)數(shù)量級(jí).這些研究表明,盡管粗獷的電子垃圾拆解活動(dòng)已經(jīng)取締,當(dāng)?shù)匾吧~體中HFRs含量仍然極高.廢棄電子垃圾拆解地野生魚體內(nèi)較高的HFRs含量可能與下列因素有關(guān):(一)這些污染物在環(huán)境中的自然降解速度較慢;(二)早期電子垃圾拆解過(guò)程中隨意丟棄的塑料等不可回收部分在南方常年氣溫較高的條件下,這些廢棄物中HFRs等揮發(fā)性有機(jī)污染物很容易釋放到環(huán)境,從而在生物體內(nèi)蓄積;(三)已經(jīng)受到HFRs污染的環(huán)境介質(zhì)(如早期焚燒跡地土壤)是廢棄電子垃圾拆解地重要的污染源[6],這些介質(zhì)中的HFRs在合適條件下經(jīng)淋溶、揮發(fā)等方式再次進(jìn)入到環(huán)境并在野生魚體內(nèi)蓄積.電子垃圾拆解地廢棄后,當(dāng)?shù)貍鹘y(tǒng)的農(nóng)業(yè)生產(chǎn)活動(dòng)(如水產(chǎn)養(yǎng)殖和水稻種植等)仍在進(jìn)行,當(dāng)?shù)丨h(huán)境中極高的HFRs等電子垃圾相關(guān)污染物對(duì)野生生物及居民的健康影響應(yīng)引起高度關(guān)注.

表1 廢棄電子垃圾拆解地和對(duì)照區(qū)野生鯪魚和鯽魚脂肪(%)及HFRs含量(ng/g)

注:括號(hào)內(nèi)為范圍,括號(hào)外為均值.

*< 0.05, **< 0.0001

鯪魚體內(nèi)∑PBDEs、∑PBB和∑ABFRs等HFRs的含量均顯著高于鯽魚(檢驗(yàn),<0.05)(圖1(a)).鯪魚是一種底層魚類,主要以藻類、高等植物殘?bào)w及有機(jī)碎屑為食,攝食時(shí)喜用下頜在沉積物表面刮取著生藻類.HFRs是一類憎水性有機(jī)污染物,其在水體中主要分布于沉積物及有機(jī)顆粒物中[2-4],鯪魚獨(dú)特的生活和攝食習(xí)性可能導(dǎo)致了其體內(nèi)HFRs的高蓄積.此外,生物的脂肪含量也是影響HFRs等親脂性有機(jī)污染物生物蓄積的重要因素.本研究鯪魚體內(nèi)脂肪含量(5.8%)顯著高于鯽魚(1.5%)(圖1(b)),從而導(dǎo)致了鯪魚體內(nèi)HFRs含量較高.魚類的食量也影響其體內(nèi)HFRs等污染物的蓄積.鯽魚因腸道較細(xì)、腸壁較薄,其對(duì)食物的機(jī)械性消化能力及食量均低于鯪魚,也可能是鯽魚體內(nèi)HFRs較低的原因之一.然而,鯽魚體內(nèi)∑DPs含量卻顯著高于鯪魚(圖1(a)),可能與DP在水生食物鏈上具有較高的生物放大能力有關(guān). 前期關(guān)于淡水食物網(wǎng)上DPs的營(yíng)養(yǎng)級(jí)放大因子(TMF)研究發(fā)現(xiàn),-DP和-DP在本池塘食物網(wǎng)中具有較大的生物放大能力(TMF分別為11.3和6.5)[14],而鯽魚的營(yíng)養(yǎng)級(jí)(TL=3.30)高于鯪魚(TL= 3.07)[15].

2.2 魚體中HFRs組成

鯪魚和鯽魚體內(nèi)均以PBDEs為最主要的HFRs,兩種魚類PBDEs含量分別占∑HFRs含量(∑PBDEs、∑PBBs、∑DPs和∑ABFRs含量之和)的96.4%和88.7%(圖2).然而,鯽魚體內(nèi)DPs的相對(duì)含量(7.3%)顯著高于鯪魚(1.0%)(檢驗(yàn),< 0.0001),可能是由于鯽魚對(duì)DPs具有較大的生物放大能力.前期關(guān)于淡水食物網(wǎng)上DPs的營(yíng)養(yǎng)級(jí)放大因子(TMF)研究發(fā)現(xiàn),-DP和-DP在本池塘食物網(wǎng)中具有較大的生物放大能力(TMF分別為11.3和6.5)[14],而鯽魚的營(yíng)養(yǎng)級(jí)(TL = 3.30)高于鯪魚(TL = 3.07)[15].與對(duì)照區(qū)相比,廢棄電子垃圾拆解地魚體內(nèi)PBDEs相對(duì)含量較高,而ABFRs的相對(duì)含量較低(圖2),表明近年來(lái)ABFRs在華南地區(qū)已替代PBDEs大量使用,這與前人的研究結(jié)果相符[16].最近的研究顯示,ABFRs在全球范圍內(nèi)(如亞洲、歐洲和北美)廣泛檢出[17-20],其含量甚至超過(guò)了PBDEs,這類新型污染物的環(huán)境行為及其生態(tài)毒理學(xué)和健康效應(yīng)應(yīng)引起高度關(guān)注.

鯪魚和鯽魚均以BDE-28、BDE-47、BDE-100、BDE-153、BDE-154和BDE-209為主要的PBDE單體,這些單體的總含量約占∑PBDEs的97%(圖3).鯪魚和鯽魚體內(nèi)PBDEs組成模式與前期電子垃圾拆解地這些魚體內(nèi)PBDEs同系物組成報(bào)道相符[10-13].這種同系物組成模式與電子電器產(chǎn)品中添加的PBDE工業(yè)品同系物組成、PBDEs在環(huán)境及生物體內(nèi)的降解及PBDE單體的生物蓄積能力有關(guān)[10-13,15].與鯪魚相比,鯽魚體內(nèi)BDE-100和BDE-154的相對(duì)含量顯著升高(檢驗(yàn),<0.0001),而B(niǎo)DE-28的相對(duì)含量顯著降低(檢驗(yàn),<0.0001) (圖4),可能與BDE-100和BDE-154在鯽魚體內(nèi)的生物放大能力較高而B(niǎo)DE-28的生物放大能力較低有關(guān).前期研究證實(shí)[15],在本池塘水生生物食物網(wǎng)上, BDE-100和BDE-154的生物放大能力高于BDE-28.

圖2 研究區(qū)和對(duì)照區(qū)鯪魚和鯽魚體內(nèi)HFRs組成

圖3 研究區(qū)鯪魚和鯽魚體內(nèi)PBDEs同系物組成

**<0.0001

本文采用anti(-DP與∑DPs的含量比值)表征魚體內(nèi)DP的異構(gòu)體組成.廢棄電子垃圾拆解地鯪魚體內(nèi)的anti值(均值:0.81)顯著高于鯽魚(均值:0.68)(檢驗(yàn),<0.0001)(圖4),表明鯪魚較鯽魚對(duì)-DP具有更強(qiáng)的選擇性蓄積作用.鯪魚體內(nèi)較高的anti值可能與其獨(dú)特的生活習(xí)性及較低的營(yíng)養(yǎng)級(jí)有關(guān).前期研究證實(shí),-DP因具有較-DP更大的辛醇-水分配系數(shù)(OW)而在水體底泥中選擇性富集[21],鯪魚的底層生活習(xí)性導(dǎo)致了其體內(nèi)anti值相對(duì)較高.此外,我們的前期研究發(fā)現(xiàn),魚體內(nèi)anti值與其營(yíng)養(yǎng)級(jí)負(fù)相關(guān)[14],鯪魚較鯽魚相對(duì)較低的營(yíng)養(yǎng)級(jí)也可能是其體內(nèi)anti值較高的原因.與對(duì)照區(qū)相比,廢棄電子垃圾拆解地鯪魚體內(nèi)anti值顯著升高(檢驗(yàn),= 0.001),而鯽魚體內(nèi)anti值顯著降低(= 0.001).廢棄電子垃圾拆解地與對(duì)照區(qū)魚體內(nèi)anti值的差異可能與不同樣點(diǎn)魚體內(nèi)∑DPs含量有關(guān).anti值與∑DPs含量的相關(guān)分析結(jié)果顯示,鯪魚體內(nèi)anti值與∑DPs負(fù)相關(guān)(= -0.57,= 0.09),而鯽魚呈顯著的正相關(guān)關(guān)系(= 0.81,= 0.004)(圖5).電子垃圾拆解地魚體內(nèi)較高的DPs含量可能導(dǎo)致了該地鯪魚體內(nèi)較高的anti值和鯽魚體內(nèi)較低的anti值.前人的研究也發(fā)現(xiàn)魚類及鳥(niǎo)類體內(nèi)DP的anti值與∑DPs含量具有相關(guān)性[22–24],但不同物種及不同∑DPs含量范圍對(duì)anti值的影響不盡相同.

圖4 研究區(qū)和對(duì)照區(qū)鯪魚和鯽魚體內(nèi)anti-DP的相對(duì)含量(fanti)

**< 0.0001

魚體內(nèi)ABFRs以DBDPE、HBB和BTBPE為主,其含量之和占∑ABFRs含量的96%以上(圖6).前人的研究也發(fā)現(xiàn),DBDPE和BTBPE是電子垃圾拆解地生物體內(nèi)主要的ABFRs[10,25-26],可能與DBDPE和BTBPE是PBDEs的主要替代品有關(guān).兩種魚類對(duì)ABFRs的蓄積存在種間差異性:鯪魚體內(nèi)DBDBE相對(duì)含量顯著高于鯽魚(檢驗(yàn),<0.0001),而B(niǎo)TBPE和HBB的相對(duì)含量卻顯著低于鯽魚(檢驗(yàn),<0.05)(圖6).鯪魚和鯽魚對(duì)這些ABFRs的種間差異性蓄積可能與這兩種魚類不同的生活習(xí)性及營(yíng)養(yǎng)級(jí)有關(guān).DBDPE是一種極端憎水的有機(jī)物,其在水體中主要分布于沉積物中[4].鯪魚的水體底層生活習(xí)性使得其較鯽魚對(duì)DBDPE的高蓄積.BTBPE和HBB的logOW值分別為7.8和7.07[27],化合物在這一OW范圍通常具有較強(qiáng)的生物放大能力[15],從而導(dǎo)致較高營(yíng)養(yǎng)級(jí)的鯽魚體內(nèi)這些化合物的相對(duì)含量較高.

圖5 鯪魚和鯽魚的fanti值與DP總含量(CDPs)的相關(guān)性

圖6 廢棄電子垃圾拆解地鯪魚和鯽魚體內(nèi)ABFRs組成

*< 0.05, **<0.0001

2.3 生態(tài)風(fēng)險(xiǎn)評(píng)估

我國(guó)尚無(wú)野生魚類HFRs含量標(biāo)準(zhǔn).本文根據(jù)加拿大聯(lián)邦環(huán)境質(zhì)量指南(CFEQG)中關(guān)于野生魚體內(nèi)PBDEs含量標(biāo)準(zhǔn)及魚體內(nèi)PBDEs含量對(duì)食魚野生動(dòng)物產(chǎn)生危害的含量標(biāo)準(zhǔn)[28],計(jì)算了廢棄電子垃圾拆解地鯪魚和鯽魚體內(nèi)PBDEs中值含量和第95個(gè)百分位含量的危害熵值(HQ),評(píng)估PBDEs中值暴露和高值暴露對(duì)野生魚類及對(duì)食魚野生動(dòng)物的生態(tài)風(fēng)險(xiǎn).HQ按式(1)計(jì)算

HQ=BDE/FEGQBDE(1)

式中:BDE和FEGQBDE分別為魚體內(nèi)某PBDE單體含量和該化合物的含量標(biāo)準(zhǔn)(FEQG).當(dāng)HQ <1時(shí),表示風(fēng)險(xiǎn)較低;1< HQ < 10時(shí),表明有一定風(fēng)險(xiǎn);當(dāng)HQ >10時(shí),表明具有較高生態(tài)風(fēng)險(xiǎn).

表2 廢棄電子垃圾拆解地野生鯪魚和鯽魚PBDEs暴露的危害熵值(HQ)

表3 廢棄電子垃圾拆解地野生魚體內(nèi)PBDEs對(duì)食魚野生動(dòng)物的危害熵值(HQ)

結(jié)果顯示,廢棄電子垃圾拆解地野生鯪魚和鯽魚BDE-47和BDE-99暴露對(duì)魚體健康有一定風(fēng)險(xiǎn)(HQ:1.7~7.8),而B(niǎo)DE-100暴露具有較高生態(tài)風(fēng)險(xiǎn)(HQ:42~77)(表2).鯪魚體內(nèi)BDE-209含量對(duì)食魚野生動(dòng)物具有一定生態(tài)風(fēng)險(xiǎn)(中值暴露和高端暴露HQ分別為3.6和5.9),而B(niǎo)DE-47和BDE-153含量對(duì)食魚野生動(dòng)物具有較大生態(tài)風(fēng)險(xiǎn)(HQ值為10.5~23.5) (表3).鯽魚體內(nèi)BDE-47、BDE-99、BDE-153和BDE-209含量對(duì)食魚野生動(dòng)物均具有一定生態(tài)風(fēng)險(xiǎn)(HQ:1.1~7.4)(表3).

3 結(jié)論

3.1 廢棄電子垃圾拆解地野生鯪魚和鯽魚體內(nèi)HFRs的含量范圍分別為1230~1680和141~650ng/g,高于對(duì)照區(qū)1~2個(gè)數(shù)量級(jí).這一結(jié)果表明,盡管粗獷的電子垃圾回收活動(dòng)已禁止多年,當(dāng)?shù)匾吧~類仍然受到這些HFRs嚴(yán)重污染.

3.2 鯪魚體內(nèi)PBDEs、PBB和ABFRs含量均顯著高于鯽魚,但DPs含量顯著低于鯽魚.此外,兩種魚體內(nèi)PBDEs、DP及ABFRs組成不盡相同.HFRs在魚體內(nèi)的種間差異性蓄積與兩種魚類不同的生活習(xí)性、營(yíng)養(yǎng)級(jí)及脂肪含量不同有關(guān).

3.3 鯪魚和鯽魚體內(nèi)的BDE-47和BDE-100對(duì)魚類(HQ = 1.7~77)具有較高的生態(tài)風(fēng)險(xiǎn),魚體內(nèi)BDE-47、BDE-153和BDE-209對(duì)食魚野生動(dòng)物也具有較大生態(tài)風(fēng)險(xiǎn)(HQ = 1.2~23.5).這些廢棄場(chǎng)地的生態(tài)修復(fù)及管理應(yīng)引起關(guān)注.

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WU Jiang-ping1*, FENG Wen-lu1, WU Si-kang1, HU Yu1, MAI Bi-xian2

(1.School of Ecology and Environment, Anhui Normal University, Wuhu 241002, China；2.Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640, China)., 2021,41(4)：1886~1892

Due to its serious environmental pollution, crude e-waste dismantling has been banned in China, leaving many abandoned e-waste sites. However, the levels and the ecological risks of e-waste derived contaminants in these sites were not fully understood. In the present study, the concentrations of several halogenated flame retardants (HFRs), including polybrominated diphenyl ethers (PBDEs), polybrominated biphenyls (PBBs), Dechlorane Plus (DP) and alternative brominated flame retardants (ABFRs), were examined in wild mud carps and crucian carps collected from an abandoned e-waste site in South China. The concentrations of ∑HFRs in mud carps and crucian carps ranged from 1230 to 1680ng/g and from 141 to 650ng/g, respectively. These concentrations were 1~2 orders of magnitude higher than those detected in the same species from a reference site, suggesting heavy contamination of HFRs, despite of the fact that primitive e-waste recycling has been regulated for several years. Among the HFRs measured, PBDEs were detected at the highest concentrations contributing 96% and 89% to ∑HFRs in mud carp and crucian carp, respectively. There were significant differences in both the concentrations, and compositions of HFRs between mud carp and crucian carp, possibly resulting from the differences in the feeding habits, trophic level and lipid content between the two fish species. The result of risk assessment showed that PBDEs posed an important risk both for the fish and for piscivorous wildlife.

halogenated flame retardants；PBDEs；e-waste；wild fish；ecological risk

X503.225

A

1000-6923(2021)04-1886-07

吳江平(1976-),男,安徽南陵人,副教授,博士,主要從事持久性有毒物質(zhì)的環(huán)境化學(xué)行為及其生態(tài)毒理學(xué)效應(yīng)研究.發(fā)表論文50余篇.

2020-08-25

國(guó)家自然科學(xué)基金資助項(xiàng)目(22076002);安徽省自然科學(xué)基金資助項(xiàng)目(2008085MD123)

* 責(zé)任作者, 副教授, jpwu@ahnu.edu.cn