劉建超,胡雍容

聚氯乙烯和橡膠中化學(xué)成分的浸出行為及生態(tài)毒性

劉建超*,胡雍容

(河海大學(xué)環(huán)境學(xué)院,淺水湖泊綜合治理與資源開(kāi)發(fā)教育部重點(diǎn)實(shí)驗(yàn)室,江蘇 南京 210098)

為探究塑料中化學(xué)成分的浸出行為及其生態(tài)毒性,以環(huán)境中廣泛存在的聚氯乙烯(PVC)和橡膠(CTR)為研究對(duì)象,篩選25種有機(jī)塑化劑和15種金屬作為目標(biāo)物質(zhì),分析其在PVC和CTR材料中的浸出潛能,利用大型溞的急性致死效應(yīng)和慢性亞致死效應(yīng)(心率、胸肢跳動(dòng)和游泳活性)表征了PVC和CTR浸出液的生態(tài)毒性效應(yīng).結(jié)果表明,PVC和CTR浸出液中共檢出21種化學(xué)成分,其中鄰苯二甲酸二異丁酯(DiBP)、鄰苯二甲酸二(2-甲氧基)乙酯(DMEP)、雙酚A(BPA)、雙酚F(BPF)、Ca和Zn的浸出濃度較高.CTR中浸出的塑化劑和金屬總濃度分別是PVC的8.8倍和1.2倍,且CTR中浸出的新型塑化劑BPF濃度達(dá)到3.51 μg/g,顯著高于BPA的浸出濃度.對(duì)比不同條件下浸出的物質(zhì)量差異,發(fā)現(xiàn)光照能夠加速PVC和CTR中DiBP、Zn和Ca等物質(zhì)的釋放,其賦存狀態(tài)還受到細(xì)菌作用的干擾.CTR浸出液對(duì)大型溞的急性致死效應(yīng)明顯,48h半數(shù)致死濃度(LC50)為浸出原液的19.1%.慢性暴露條件下,PVC浸出液對(duì)大型溞心率、胸肢跳動(dòng)和游泳活性產(chǎn)生明顯抑制作用,并造成大型溞肢體肥大.PVC和CTR等塑料顆粒不斷排放,并在環(huán)境中累積,其生物毒害效應(yīng)不容忽視.

聚氯乙烯；橡膠；浸出液；大型溞；生態(tài)毒性

塑料廣泛應(yīng)用于人類(lèi)的日常生活與生產(chǎn)中[1],在全球海洋、淡水、土壤等環(huán)境介質(zhì)中大量賦存[2],并不斷破碎形成微塑料,釋放添加劑,對(duì)全球生態(tài)系統(tǒng)健康產(chǎn)生潛在負(fù)面影響[3].聚氯乙烯(PVC)作為全球年產(chǎn)量最高的塑料之一,廣泛應(yīng)用于管道、工業(yè)配件、電纜等產(chǎn)品制造工業(yè)[4].2020年,我國(guó)PVC的年產(chǎn)量已達(dá)到2000萬(wàn)t[5].PVC為不可降解塑料,其化學(xué)法回收工藝復(fù)雜、成本較高,用焚燒法處理時(shí)會(huì)向空氣中釋放二噁英和氯化氫等有害氣體[6],造成空氣污染[7].橡膠(CTR)作為三大高分子材料之一,含鄰苯二甲酸酯類(lèi)、脂肪二元酸酯類(lèi)增塑劑,在輪胎、床墊、體育設(shè)施中使用廣泛.輪胎等產(chǎn)品在使用過(guò)程中磨損速度快,微粒形成量大.這2類(lèi)材料在環(huán)境殘留高、不斷老化形成微粒,隨降雨徑流進(jìn)入河湖系后與其它污染物形成復(fù)合污染效應(yīng)[8],對(duì)水生態(tài)系統(tǒng)安全產(chǎn)生負(fù)面影響.

在PVC和CTR等高分子材料生產(chǎn)過(guò)程中會(huì)添加增塑劑、緩凝劑、粘合劑和活化劑等,這些物質(zhì)在材料自然老化過(guò)程中不斷被釋放[9-10].研究發(fā)現(xiàn), PVC和CTR能夠浸出雙酚A(BPA)和鄰苯二甲酸鹽(PAEs)等物質(zhì)[11],這些物質(zhì)釋放到環(huán)境后對(duì)水生生物和人類(lèi)產(chǎn)生不利影響[12].Wei等[13]發(fā)現(xiàn)鄰苯二甲酸(2-乙基)己酯(DEHP)會(huì)降低大型溞的抗氧化能力,對(duì)大型溞的24h-LC50為0.83mg/L.BPA和DEHP被人類(lèi)攝取后也會(huì)干擾其內(nèi)分泌代謝,并對(duì)人類(lèi)健康產(chǎn)生不利影響[14].Al-Odaini等[15]在淡水和海水環(huán)境中發(fā)現(xiàn)了阻燃劑(六溴環(huán)十二烷(HBCD))的存在,其在聚苯乙烯泡沫(EPS)使用過(guò)程中隨著材料的老化不斷從內(nèi)部向表面遷移,并溶出到環(huán)境[16-17].PVC和CTR不僅能浸出塑化劑等有機(jī)物,還能釋放Zn等多種金屬物質(zhì)[18],高濃度的鋅能夠抑制生物的乙酰膽堿酯酶活性[19],并對(duì)水生生物的存活和繁殖產(chǎn)生不利影響[20].現(xiàn)有研究缺乏對(duì)PVC和CTR浸出液中PAEs、BPs及金屬單體成分及濃度分析,浸出物質(zhì)對(duì)水生生物的毒性效應(yīng)仍需進(jìn)一步開(kāi)展.

本研究以水環(huán)境中檢出率較高的25種塑化劑和15種金屬為目標(biāo)物,分析PVC和CTR材料在水環(huán)境中的浸出成分,探究不同稀釋程度下浸出液對(duì)大型溞的急、慢性毒理效應(yīng),分析毒理效應(yīng)與浸出物之間的關(guān)系,以期為生物種群資源保護(hù)和塑料的污染防控提供基礎(chǔ)數(shù)據(jù).

1 材料與方法

1.1 試劑與儀器

橡膠顆粒(粒徑2.0mm),為汽車(chē)輪胎,購(gòu)自于華益橡膠公司;PVC顆粒(粒徑2.0mm),為硬質(zhì)PVC飲用水管,來(lái)自于市場(chǎng)五金店,人工破碎;甲醇和二氯甲烷等試劑購(gòu)自于Merk公司,純度高于99%;內(nèi)標(biāo)物質(zhì)103Rh、115In,購(gòu)自美國(guó)Agilent公司:質(zhì)量濃度均為100mg/L.

混合標(biāo)準(zhǔn)溶液包括16種鄰苯二甲酸酯類(lèi)(PAEs):鄰苯二甲酸二甲酯(DMP)、鄰苯二甲酸二乙酯(DEP)、鄰苯二甲酸二異丁酯(DiBP)、鄰苯二甲酸二正丁酯(DnBP)、鄰苯二甲酸二(2-甲氧基)乙酯(DMEP)、鄰苯二甲酸丁基卞酯(BBP)、鄰苯二甲酸二(4-甲基-2-戊基)酯(BMPP)、鄰苯二甲酸二正辛酯(DNOP)、鄰苯二甲酸二壬酯(DNP)、鄰苯二甲酸二烯丙酯(DAP)、鄰苯二甲酸二異癸酯(DPHP)、鄰苯二甲酸二環(huán)己酯(DCHP)、鄰苯二甲酸二(2-丁氧基)乙酯(DBEP)、DEHP、鄰苯二甲酸二(2-乙氧基)乙酯(DEEP)、鄰苯二甲酸二己酯(DHXP);9種雙酚類(lèi)物質(zhì)(BPs):雙酚(BPF)、BPA、雙酚S(BPS)、雙酚AF(BPAF)、聚氧乙烯醚(BPE)、雙酚Z(BPZ)、雙酚AP(BPAP)、雙酚B(BPB)、四溴雙酚A(TBBPA);15種金屬:Mg、Ca、Cr、Mn、Fe、Ni、Cu、Zn、As、Se、Mo、Cd、Sn、Hg和Pb,購(gòu)自百靈威科技有限公司.

1.2 PVC和CTR塑料浸出實(shí)驗(yàn)

實(shí)驗(yàn)所用水樣取自南京某生態(tài)公園塘水,該公園生態(tài)塘無(wú)污染源排放,不與外界河流連通,水質(zhì)優(yōu)良.水樣品取完立即送回實(shí)驗(yàn)室,用砂濾和1.2μm的玻璃纖維濾膜進(jìn)行真空過(guò)濾,去除水樣中顆粒性雜質(zhì).過(guò)濾后的水樣分成2份,一份進(jìn)行高溫滅菌處理,一份不做處理.

表1 暴露組設(shè)置情況

將PVC和CTR顆粒過(guò)篩,用清水清洗并干燥后分別稱取5.0g樣品,放入250mL錐形瓶中,每個(gè)錐形瓶加入200mL預(yù)處理后的水樣,并設(shè)置塘水對(duì)照組,每組設(shè)置3個(gè)平行,實(shí)驗(yàn)組別設(shè)計(jì)見(jiàn)表1.為模擬河底黑暗環(huán)境,設(shè)置黑暗實(shí)驗(yàn)組,該組用錫紙把錐形瓶包裹起來(lái)(不留空隙),且用錫紙封住瓶口,以免雜質(zhì)進(jìn)入.然后將所有的錐形瓶放到振蕩培養(yǎng)箱中進(jìn)行浸出實(shí)驗(yàn).振蕩培養(yǎng)箱的具體參數(shù)設(shè)置為:溫度25℃;振蕩速度125r/min;光照強(qiáng)度2000lx.浸出42d后,從錐形瓶中用移液管移取10mL浸出液放入玻璃試管以備液-液萃取.對(duì)水樣進(jìn)行處理提取塑化劑參考Capolupo等[19]的方法,具體步驟如下:從10mL浸出液中取5mL樣液加入2mL的二氯甲烷(DCM),渦旋1min,然后離心2min(轉(zhuǎn)速2000r/min).離心后,用針管吸取下層水樣放入干凈試管中,重復(fù)上述步驟2次.在水樣試管中再加入2mL的正己烷,渦旋1min,離心2min(轉(zhuǎn)速2000r/min),再重復(fù)操作2次.然后合并4次提取溶液,加入1g無(wú)水硫酸鈉(Na2SO4)干燥24h,取上清液放入棕色玻璃瓶并氮吹至0.5mL,然后用0.22μm濾膜過(guò)濾,以備液質(zhì)聯(lián)用儀檢測(cè)分析.剩余的5mL浸出液直接放入棕色玻璃瓶用于金屬組分濃度的測(cè)定.

1.3 儀器檢測(cè)與分析

1.3.1 16種PAEs和9種BPs的檢測(cè)方法 PAEs和BPs均采用超高效液相色譜-三重四級(jí)桿串聯(lián)質(zhì)譜聯(lián)用儀(型號(hào):Waters ACQUITY UPLC Xevo TQ)進(jìn)行定性定量分析,該系統(tǒng)配有電噴霧離子源.采用規(guī)格為2.1mm×100mm×1.7μm的ACQUITY BEH C18色譜柱,柱溫設(shè)定為40℃.PAEs流動(dòng)相:A為水:甲醇 (98:2)+0.05% FA(甲酸),B為乙腈,流動(dòng)相梯度見(jiàn)表2.樣品進(jìn)樣體積為5μL,流速0.4mL/min.質(zhì)譜條件:采用離子電噴霧正離子(ESI+),多反應(yīng)離子監(jiān)測(cè)(MRM)模式.設(shè)定離子源溫度為150℃,毛細(xì)血管電壓3.5kV;BPs流動(dòng)相:A為0.01%(體積比)的氨水溶液,B為乙腈,流動(dòng)相梯度見(jiàn)表2.樣品進(jìn)樣體積為5μL,流速為0.3mL/min.質(zhì)譜條件:采用離子電噴霧負(fù)離子(ESI-),多反應(yīng)離子監(jiān)測(cè)(MRM)模式;設(shè)定離子源溫度為150℃,毛細(xì)管電壓3.0kV.

表2 PAEs和BPs流動(dòng)相梯度

1.3.2 金屬物質(zhì)的測(cè)定 將浸出液用超純水稀釋,然后加入103Rh和115In作為內(nèi)標(biāo).金屬采用電感耦合等離子體質(zhì)譜儀(型號(hào):Thermofish iCAPQ)進(jìn)行定性、定量分析.儀器條件設(shè)置為:檢測(cè)模式(KED),射頻功率1543W,載氣流速1.038L/min,氦氣流量4.88L/min,采樣深度5mm,蠕動(dòng)泵轉(zhuǎn)速40r/min,重復(fù)取樣3次,霧化器壓力3.418bar,霧化室溫度2.7℃.

1.3.3 質(zhì)量控制與保證 整個(gè)前處理和分析過(guò)程中進(jìn)行嚴(yán)格的質(zhì)量控制程序,設(shè)置溶劑空白、清水空白、方法空白.標(biāo)準(zhǔn)曲線的濃度范圍為0.1～200μg/L,線性相關(guān)系數(shù)R2>0.99,以3倍信噪比(=3)確定方法檢出限(LOD),以10倍信噪比(=10)確定方法定量限(LOQ),塑化劑和金屬的檢出限(LOD)和檢測(cè)限(LOQ)結(jié)果如表3、表4所示.通過(guò)10,100μg/L的PAE和BPs加標(biāo)回收實(shí)驗(yàn)發(fā)現(xiàn),16種PAEs和9種BPs的前處理方法平均回收率為79.8%～118.2%,相對(duì)標(biāo)準(zhǔn)偏差(RSD)為0.9%～10.2%,空白樣品中目標(biāo)物成分未檢出或低于檢測(cè)線,滿足檢測(cè)的基本要求.

表3 塑化劑的檢出限LOD及檢測(cè)限LOQ(ng/L)

表4 金屬物質(zhì)的定量限LOD(μg/L)

1.4 大型溞毒性實(shí)驗(yàn)

1.4.1 受試動(dòng)物 大型溞()由中國(guó)科學(xué)院武漢水生生物研究所提供.實(shí)驗(yàn)開(kāi)始前,大型溞在實(shí)驗(yàn)室馴化3代,馴化介質(zhì)為曝氣24h的純凈水.環(huán)境條件為溫度:(20±1)℃;光暗周期:16h:8h;光照強(qiáng)度2000lx.大型溞每天定時(shí)喂食斜生柵藻()濃縮液,投喂密度為5.0× 104cell/mL.

1.4.2 實(shí)驗(yàn)方法 毒性暴露濃度設(shè)置:選擇PVC和CTR濃度較高的黑暗殺菌環(huán)境浸出液為暴露溶液,黑暗殺菌塘水組為溶劑對(duì)照,清水作為空白對(duì)照.實(shí)驗(yàn)開(kāi)始前對(duì)浸出液進(jìn)行過(guò)濾(玻璃濾膜規(guī)格為:0.45μm),去除浸出液中的雜質(zhì),避免塑料微粒干擾實(shí)驗(yàn)結(jié)果.試驗(yàn)稀釋水均為曝氣純凈水.實(shí)驗(yàn)共設(shè)有PVC和CTR不同稀釋程度浸出液10組(P0～P4和C0～C4)對(duì)照組分別為黑暗殺菌溶劑對(duì)照(D0～D4)和空白對(duì)照(W)具體情況見(jiàn)表5.

表5 暴露組中濃度設(shè)置

急性實(shí)驗(yàn):參照OECD 211標(biāo)準(zhǔn)方法進(jìn)行[21].取6～24h的幼溞進(jìn)行急性暴露實(shí)驗(yàn).在100mL燒杯中加入50mL稀釋好的浸出液,隨機(jī)加入5只溞齡在6～24h的健康幼溞,每個(gè)濃度設(shè)置4個(gè)平行,將燒杯放入人工光照培養(yǎng)箱進(jìn)行培養(yǎng),溫度保持在(20.0±1)℃,光暗比16h:8h,設(shè)置光照強(qiáng)度為2000lx.急性毒性實(shí)驗(yàn)周期為48h,分別在第24,48h記錄大型溞受抑制情況(振蕩試驗(yàn)溶液,在15s內(nèi)無(wú)反應(yīng),即為受抑制)和死亡率.實(shí)驗(yàn)過(guò)程中不喂食,不換液.

慢性實(shí)驗(yàn):參照OECD211標(biāo)準(zhǔn)方法進(jìn)行[21].在急性毒性實(shí)驗(yàn)的基礎(chǔ)上進(jìn)行7d慢性毒性實(shí)驗(yàn),每天喂食斜生柵藻,喂食密度為5.0×104cell/mL,每隔24h記錄大型溞存活情況.暴露7d結(jié)束,進(jìn)行心率、胸肢跳動(dòng)、游速和體長(zhǎng)等指標(biāo)測(cè)定.

1.4.3 測(cè)定項(xiàng)目 心率和胸肢跳動(dòng):利用體式顯微鏡對(duì)大型溞進(jìn)行1min左右的錄像,然后使用計(jì)數(shù)器對(duì)大型溞胸肢、心臟跳動(dòng)次數(shù)進(jìn)行計(jì)數(shù),每組計(jì)3次,結(jié)果換算成“次/min”[22-23].

體長(zhǎng):在顯微鏡下用目微尺測(cè)量母溞體長(zhǎng),母溞身體與刻度尺平行,記錄其對(duì)應(yīng)的刻度(包括尾刺)[24].

游速:參考郭婧穎等[25]的方法,將大型溞放入培養(yǎng)皿,加入剛好沒(méi)過(guò)大型溞身體的水量,使其只能水平游動(dòng),錄制其游動(dòng)的視頻,再將視頻導(dǎo)入tracker軟件測(cè)量游泳軌跡、速度和加速度.

1.5 數(shù)據(jù)統(tǒng)計(jì)方法

使用Excel2016對(duì)實(shí)驗(yàn)數(shù)據(jù)進(jìn)行整理,用SPSS計(jì)算各組均值及標(biāo)準(zhǔn)偏差,并進(jìn)行單因素方差分析,用Origin2017進(jìn)行繪圖,并計(jì)算半致死濃度LC50及95%置信區(qū)間.

2 結(jié)果與討論

2.1 PVC和CTR浸出液的主要成分檢測(cè)

在PVC和CTR顆粒浸出液中共檢測(cè)了40種化學(xué)成分,其中21種化學(xué)成分在PVC浸出液中被檢出,包括7種PAEs(DMP、DEP、DiBP、DnBP、DMEP、DNOP和DNP)、4種BPs(BPF、BPA、BPS和BPAF)和10種金屬(Ca、Cr、Mn、Fe、Ni、Cu、Zn、Se、Mo和Sn),其他5種金屬(Mg、As、Cd、Hg、Pb)檢出含量低于檢出限或未檢出,忽略不計(jì).以實(shí)驗(yàn)組C1～C4為塘水污染物背景值,各浸出實(shí)驗(yàn)組扣除背景值后發(fā)現(xiàn),PVC浸出的總塑化劑量為0.46～ 2.73μg/g,其中DMP(最大浸出濃度0.61μg/g)、DEP(0.52μg/g)、DiBP(2.71μg/g)、DMEP(1.16μg/g)和BPA(0.89μg/g)的浸出量較高.PVC浸出液中金屬總質(zhì)量為0.89～1066.07μg/g,其中Ca和Zn的浸出含量較高,分別為953.79μg/g和4.54μg/g.

在CTR浸出液中共檢出19種化學(xué)成分,包括7種PAEs(DMP、DEP、DiBP、DnBP、DMEP、DNOP和DNP)、4種BPs(BPF、BPA、BPS和BPAF)和8種金屬(Ca、Cr、Mn、Ni、Cu、Zn、Se和Mo),其他7種金屬(Mg、As、Cd、Hg、Pb、Fe、Sn)檢出含量遠(yuǎn)低于檢出限或未檢出,忽略不計(jì).CTR浸出的總塑化劑量為10.34～17.68μg/g,其中DMEP和BPF的浸出量較高,最高浸出濃度分別達(dá)到13.22μg/g和3.51μg/g.CTR浸出的金屬質(zhì)量在35.50～1127.89μg/g之間,其中Ca和Zn的浸出含量仍然較高,分別為898.77,102.79μg/g.本實(shí)驗(yàn)中PVC和CRT浸出的PAEs、BPs和金屬的種類(lèi)與Marco等[26]進(jìn)行的PVC和CTR浸出實(shí)驗(yàn)結(jié)果相似.PVC和CTR中Ca、Zn的檢出濃度較高,可能與PVC和CTR制備過(guò)程中投加了大量用于提高材料熱穩(wěn)定性的鈣鋅穩(wěn)定劑有關(guān)[27].DiBP和BPA是PVC浸出液中最主要的塑化劑,而CTR浸出液中的塑化劑成分主要是DMEP、BPF和BPA,這些物質(zhì)都是水環(huán)境中廣泛檢出的高濃度新污染物.在對(duì)我國(guó)多處水系進(jìn)行PAEs測(cè)定發(fā)現(xiàn),部分地表水體中的DiBP濃度已經(jīng)達(dá)到了μg/L級(jí)別[28],如九龍江的DiBP濃度范圍高達(dá)2.28～ 3.81mg/L[29].BPF作為BPA的替代品,在塑料制品中廣泛使用,我國(guó)太湖水體中BPF平均濃度已達(dá)到140ng/L[30].塑化劑在水體環(huán)境中廣泛分布,其環(huán)境賦存特征與塑料污染的關(guān)系研究仍需進(jìn)一步開(kāi)展.

圖1 PVC和CTR中浸出的塑化劑(A)、金屬(B)種類(lèi)和濃度

對(duì)比PVC和CTR浸出液中有機(jī)塑化劑成分,發(fā)現(xiàn)2種材料浸出的塑化劑組分基本一致,但CTR浸出的總塑化劑量明顯高于PVC,每克CTR塑化劑浸出總量約為PVC的8.81倍.從塑化劑單體來(lái)看CTR浸出液中明顯增加的塑化劑是DMEP、BPF、BPA和BPAF,平均浸出量分別是PVC組的29.14倍、50.08倍、4.01倍和2.37倍.從金屬成分來(lái)看,PVC浸出液中檢出10種金屬,而CTR浸出液中僅檢出8種,未發(fā)現(xiàn)Fe和Sn,但CTR浸出的總金屬量高于PVC,每克CTR浸出的總金屬量約為PVC的1.20倍.Zn和Mn在CTR浸出液中的含量明顯高于PVC組,Zn和Mn在CTR浸出液中的平均含量是PVC組的21.34倍和30.84倍.CTR在光照殺菌組浸出的Zn質(zhì)量最高達(dá)129.77μg/g(濃度為3.24mg/L),浸出液中Zn濃度是《地表水環(huán)境質(zhì)量標(biāo)準(zhǔn)》[31]V類(lèi)水標(biāo)準(zhǔn)的1.62倍.Tetu等[32]在探究微塑料浸出液對(duì)綠球藻的毒性效應(yīng)時(shí),發(fā)現(xiàn)在50g/L的PVC塑料溶液中Zn的浸出濃度達(dá)到6.28mg/L(質(zhì)量比為125.6μg/g),Zn在所有檢出的金屬成分中濃度最高(該研究未檢測(cè)Ca成分),這與本研究結(jié)果相一致.對(duì)比2種材質(zhì)發(fā)現(xiàn),由于CTR顆粒表面多孔疏松,比表面積大,同等浸泡條件下其浸出污染物的能力明顯高于PVC.從工藝的角度上,PVC和CTR屬于性質(zhì)不同的2種物質(zhì),其組成成分存在較大差異,塑料以高分子合成樹(shù)脂為主要組分,CTR以橡膠烴為主要成分,2種材料浸出的化學(xué)成分濃度也存在較大區(qū)別[33-34],在水環(huán)境中CTR產(chǎn)生的復(fù)合污染效應(yīng)可能更加明顯.

2.2 不同環(huán)境條件下PVC和CTR的浸出差異

2.2.1 光照對(duì)浸出的影響 對(duì)比殺菌條件下光暗環(huán)境對(duì)PVC溶出效應(yīng)影響,發(fā)現(xiàn)光照能夠增加PVC浸出液中總塑化劑的含量,尤其是BPA和DiBP(圖2A).光照條件對(duì)CTR浸出液中總塑化劑濃度無(wú)明顯影響,只有DiBP含量有增加趨勢(shì),而B(niǎo)PA、BPF和DMEP含量略有降低.光照條件下PVC和CTR浸出液中DiBP濃度對(duì)比黑暗條件下分別增加了52%和77%.此外,光照條件能夠加速PVC和CTR材料中金屬物質(zhì)的溶出,金屬總?cè)艹隽糠謩e達(dá)到957.11μg/g和1002.30μg/g,是黑暗條件下的9.92倍和5.88倍(圖2B).其中,PVC和CTR材料中Ca溶出量占到了金屬總質(zhì)量的99%和90%,光照條件下PVC和CTR浸出液中Ca的濃度分別是黑暗條件下的9.89和9.85倍.光照能夠加速塑料的老化過(guò)程,導(dǎo)致塑料內(nèi)部化學(xué)鍵斷裂,降低分子遷移的擴(kuò)散阻力,增加PAEs等塑化劑的溶出效應(yīng)[35].

2.2.2 細(xì)菌對(duì)浸出的影響 對(duì)比黑暗條件下殺菌對(duì)PVC溶出效應(yīng)的影響,發(fā)現(xiàn)殺菌條件下PVC浸出液中總塑化劑濃度略低于黑暗不殺菌,但主要浸出物DiBP的濃度略高,比不殺菌條件下增加了68%.從塑化劑組分來(lái)看,細(xì)菌存在導(dǎo)致PVC浸出液中塑化劑的成分構(gòu)成更加復(fù)雜.殺菌條件下CTR浸出液中總塑化劑濃度略高于不殺菌條件,但CTR主要浸出物DiBP和BPA的含量增加明顯,分別是不殺菌條件下的4.77和2.47倍.研究發(fā)現(xiàn),水中細(xì)菌可以通過(guò)氧化骨架重排、本位取代及酚環(huán)羥基化-間位裂解等3種途徑對(duì)BPA等雙酚類(lèi)物質(zhì)進(jìn)行降解,降低水中BPA的含量[36].對(duì)照有菌條件,細(xì)菌的存在會(huì)強(qiáng)化溶出物質(zhì)的遷移轉(zhuǎn)化過(guò)程,影響其水環(huán)境賦存特征.在無(wú)菌條件下,PVC和CTR浸出液中金屬物質(zhì)的濃度顯著高于有菌條件,黑暗殺菌條件下PVC和CTR浸出液中Ca和Zn含量增加尤為明顯,其中CTR中Zn的溶出量是黑暗不殺菌條件下的1.70倍.這可能是由于細(xì)菌的氧化作用改變了金屬物質(zhì)的存在形態(tài)[37].殺菌條件下,PVC和CTR溶出的Ca含量比不殺菌條件下高96.43, 91.24μg/g,這說(shuō)明細(xì)菌存在有效利用了塑料浸出液中的Ca,且對(duì)部分PAEs(如DiBP)和BPs(如BPA、BPF)起到一定的降解作用.Rastkari等[38]發(fā)現(xiàn),PAEs降解效果受溶液的pH值影響,在酸性光照條件下,DEP和DBP水解和光解率達(dá)到20%以上,而對(duì)DEHP無(wú)效.PVC和CTR浸出液中塑化劑、金屬的含量受光照、pH值、細(xì)菌、材質(zhì)等多種因素的共同作用,其生態(tài)危害與環(huán)境條件密切相關(guān).

圖2 不同環(huán)境條件下PVC和CTR浸出液中的塑化劑(A)和金屬(B)濃度

2.3 浸出液對(duì)大型溞生長(zhǎng)發(fā)育的影響

2.3.1 對(duì)大型溞的急性毒性 暴露期間對(duì)照組大型溞未發(fā)現(xiàn)死亡,PVC浸出液暴露組對(duì)大型溞的毒性較低,PVC暴露組死亡率均低于5%.在CTR浸出液暴露下大型溞死亡率隨著CTR浸出原液稀釋倍數(shù)的減小顯著升高,暴露于C1組(50%浸出液)大型溞在48h的死亡率就已經(jīng)達(dá)到100%,暴露72h后,除最大稀釋組C4(6.25%浸出液)外,其余組大型溞全部死亡.通過(guò)使用logistic函數(shù)進(jìn)行非線性回歸計(jì)算,CTR浸出液對(duì)大型溞的24h-LC50和48h-LC50分別為58.3%和19.1%.研究發(fā)現(xiàn),PVC微塑料懸浮液對(duì)大型溞96h-LC50為130.13mg/L,PVC浸出液毒性更小[39].CTR浸出液中DMEP、BPF和金屬Zn濃度較高,雖然BPF對(duì)大型溞的48h-LC50值(8.7mg/L)遠(yuǎn)高于CTR浸出液中BPF的濃度(0.052mg/L)[30],但是CTR浸出液中Zn的濃度(2.94mg/L)相對(duì)偏高.Zn可通過(guò)置換酶分子中心的金屬離子或者直接與酶功能基團(tuán)結(jié)合降低酶活性,引起大型溞死亡,在3.2mg/L時(shí)導(dǎo)致大型溞在24h之內(nèi)全部死亡[40].此外,DMEP為0.125～0.25mmol/L會(huì)顯著降低細(xì)胞線粒體DNA(mtDNA)拷貝數(shù),誘導(dǎo)細(xì)胞的線粒體損傷[41].這些結(jié)果表明,CTR浸出液中的Zn及主要塑化劑的毒害作用可能對(duì)大型溞的急性致死效應(yīng)有一定貢獻(xiàn).但先前研究表明Zn的存在能夠抑制鄰苯二甲酸酯類(lèi)污染物暴露導(dǎo)致的雄性生殖功能損傷,故本研究中對(duì)于浸出物復(fù)合污染下的毒性效應(yīng)尚不明確[42].

2.3.2 對(duì)大型溞的慢性毒性 整個(gè)暴露期間,清水對(duì)照組(W)、溶劑對(duì)照組(D0～D4)、PVC浸出液組(P0～P4)和CTR最大稀釋組(C4),大型溞死亡率低于10%,CTR浸出液組(C0～C3)中大型溞死亡率超過(guò)80%.由于清水對(duì)照組和溶劑對(duì)照組無(wú)明顯區(qū)別,本文將溶劑對(duì)照作為參照組,CTR浸出液組(C0～C3)大型溞死亡率較高,其慢性毒性數(shù)據(jù)不再呈現(xiàn).實(shí)驗(yàn)發(fā)現(xiàn),不同稀釋程度的PVC浸出液和最大稀釋程度的CTR浸出液(6.25%原液)對(duì)大型溞的心率、胸肢跳動(dòng)、游速等生態(tài)行為均產(chǎn)生顯著抑制效應(yīng)(圖3).

大型溞的呼吸代謝、攝食生長(zhǎng)和內(nèi)分泌調(diào)節(jié)等健康狀況與其體長(zhǎng)、胸肢跳動(dòng)、心率和運(yùn)動(dòng)活性密切相關(guān)[43].大型溞的心率和胸肢活動(dòng)是評(píng)價(jià)污染物對(duì)大型溞呼吸、代謝速率和攝食產(chǎn)生不利影響的重要指標(biāo)[44].與對(duì)照組相比,PVC浸出液能夠抑制大型溞的胸肢跳動(dòng)和心率,平均抑制率分別為15.86%和36.73%,最大抑制率達(dá)到17.39%和56.84%.最大稀釋程度的CTR浸出液對(duì)大型溞胸肢跳動(dòng)頻率和心率的抑制率達(dá)到16.18%和66.32%,心率抑制可能是CTR浸出液高濃度暴露組中大型溞死亡的主要原因.大型溞有著與哺乳動(dòng)物類(lèi)似的肌源性心臟,其心率的變化能夠反映出污染物對(duì)其能量代謝的影響以及污染物進(jìn)入血液循環(huán)系統(tǒng)的程度[45].研究表明,PEAs(如DEP、DMP)的暴露濃度超過(guò)8mg/L時(shí),大型溞的心率會(huì)明顯受到抑制[46],并且溶液中浸出的BPF也對(duì)大型溞的心率產(chǎn)生抑制作用,當(dāng)其濃度為10～100μg/L會(huì)顯著抑制大型溞的心率,并且呈現(xiàn)濃度依賴關(guān)系[47].心率受到抑制導(dǎo)致供給胸肢跳動(dòng)的能量減少,使胸肢跳動(dòng)頻率下降.同時(shí),研究發(fā)現(xiàn)PVC浸出液中所含有的PAEs能夠?qū)Υ笮蜏械纳窠?jīng)系統(tǒng)產(chǎn)生毒害作用,降低其機(jī)體協(xié)同能力[48].大型溞的心率和胸肢跳動(dòng)降低會(huì)造成血液流動(dòng)減緩、攝食不足,營(yíng)養(yǎng)物質(zhì)供給和氣體交換能力減弱,對(duì)其生長(zhǎng)發(fā)育構(gòu)成威脅[49].

圖3 PVC和CTR浸出液對(duì)大型溞心率(A)、胸肢跳動(dòng)(B)、體長(zhǎng)(C)、游泳活性(D)的影響

*表示差異顯著(<0.05)

大型溞體長(zhǎng)是指示生物健康程度的重要指標(biāo),體長(zhǎng)的改變雖小,但其變化會(huì)影響物種的種群穩(wěn)定性[50].PVC浸出液原液(P0組)顯著增加了大型溞的體長(zhǎng),其他暴露組無(wú)明顯改變.研究發(fā)現(xiàn),1mol/L的DBP和DEHP能夠增加大型溞體內(nèi)的脂質(zhì)積累[51],且BPA等雙酚類(lèi)物質(zhì)能夠在脂肪中積累[52],導(dǎo)致脂肪細(xì)胞代謝功能障礙,增加肥胖的風(fēng)險(xiǎn)[53].PVC浸出液原液中高濃度的PAEs和BPs作用可能是導(dǎo)致大型溞體長(zhǎng)變大的主要原因.大型溞游泳行為受到生理、感知、神經(jīng)和肌肉等系統(tǒng)多方面的影響,游泳能力強(qiáng)弱與其捕食、逃避天敵等行為直接相關(guān)[43].與對(duì)照組相比,不同濃度PVC浸出液均對(duì)大型溞的游泳速率產(chǎn)生顯著抑制效應(yīng),最大抑制率達(dá)到67.26% (6.25%原溶液),最大稀釋程度的CTR浸出液(C4)對(duì)大型溞游泳活性抑制率也達(dá)到63.02%.陳勝等[54]將大型溞置于11.4μg/L的BPA溶液中暴露21d,大型溞游泳速率抑制率達(dá)32.65%,BPAF對(duì)大型溞游泳速率有類(lèi)似的抑制作用.乙酰膽堿酯酶(AChE)是水生生物中常用的神經(jīng)毒性標(biāo)志物,它的活性與生物的游泳活性呈顯著正相關(guān)[55],AChE酶活性受到抑制會(huì)導(dǎo)致神經(jīng)刺激延長(zhǎng),引起心率、游泳活性降低[56].研究發(fā)現(xiàn),PVC浸出液能夠下調(diào)貽貝AChE酶活性[19],浸出液中的金屬Zn也是生物AChE酶活性的重要抑制劑,在6.5mg/L濃度下抑制率達(dá)到30%[57].且長(zhǎng)期暴露于Zn溶液中,能夠引起大型溞氧化損傷,抑制大型溞抗氧化酶的活性[58].

3 結(jié)論

3.1 經(jīng)過(guò)42d的浸泡處理后,PVC浸出液的主要目標(biāo)塑化劑是DiBP和BPA(最高浸出量分別為2.71, 0.89μg/g),主要金屬物質(zhì)是Ca和Zn(最高浸出量分別為953.79, 4.54μg/g); CTR浸出液中的主要塑化劑是DMEP和BPF(13.22, 3.51μg/g),主要金屬是Ca和Zn(898.77, 102.79μg/g).CTR浸出液中塑化劑和金屬物質(zhì)總量均最高,分別達(dá)到17.68, 1127.89μg/g,是PVC的8.81倍和1.20倍.光照條件能夠有力促進(jìn)PVC中塑化劑和金屬物質(zhì)的環(huán)境釋放,細(xì)菌對(duì)浸出液中DiBP、BPA等物質(zhì)的降解或轉(zhuǎn)化有一定的促進(jìn)作用,對(duì)Ca的利用率接近100%.

3.2 急性毒性(48h)試驗(yàn)表明,PVC浸出液對(duì)大型溞無(wú)明顯致死效應(yīng);CTR浸出液對(duì)大型溞的致死效應(yīng)明顯,隨CTR浸出原液稀釋倍數(shù)的減小而升高.通過(guò)計(jì)算得到CTR浸出液24h-LC50為浸出原液的58.3%,48h-LC50為浸出原液的19.1%,CTR的致死效應(yīng)可能與浸出物質(zhì)對(duì)大型溞心率抑制作用有關(guān).

3.3 慢性毒性(7d)試驗(yàn)結(jié)果表明,PVC浸出液能導(dǎo)致大型溞肥胖,顯著抑制大型溞的胸肢跳動(dòng)、心率和游速活性;CTR浸出液最大稀釋程度仍對(duì)大型溞生長(zhǎng)發(fā)育產(chǎn)生顯著抑制作用,PVC和CTR顆粒中化學(xué)物質(zhì)的溶出對(duì)水生生物產(chǎn)生不利影響,且CTR的生態(tài)危害性更加嚴(yán)重和復(fù)雜.

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Leaching behavior and ecotoxicity of chemical composition in polyvinyl chloride and rubber.

LIU Jian-chao*, HU Yong-rong,

(Key Laboratory for Integrated Regulation and Resources Development on Shallow Lakes, Ministry of Education, College of Environment, Hohai University, Nanjing 210098, China)., 2022,42(11)：5408～5417

To investigate the leaching behavior and ecotoxicity of chemical composition in plastics, polyvinyl chloride (PVC) and rubber (CTR) widely existed in the environment were selected as the subjects of the study. Leaching potential of 25 organic plasticizers and 15 metals as the target substances were analyzed for PVC and CTR materials. The acute lethal effects and chronic sublethal effects (heart rate, thoracic limb activity and swimming activity) ofwere used to characterize the ecotoxicological effects of PVC and CTR leachates. The results showed that 21 chemical compositions were detected in PVC and CTR leachates, with higher leaching concentrations of diisobutyl phthalate (DiBP), di (2-methoxy) ethyl phthalate (DMEP), bisphenol A (BPA), bisphenol F (BPF), Ca and Zn. The total concentrations of plasticizers and metals leached from CTR were 8.8 times and 1.2 times higher than those from PVC, respectively. The concentration of the new plasticizer BPF leached from CTR reached 3.51μg/g, which was significantly higher than that of BPA. Comparing the concentration of substances leached under different conditions, it was found that light can accelerate the release of DiBP, Zn and Ca from PVC and CTR, and their occurrence characteristics were affected by bacteria. Acute toxicity of CTR leachate tois obvious, with the 48h-LC50of 19.1% of the leaching solution. For chronic toxicity, the PVC leachate significantly inhibited the heart rate, thoracic limb activity and swimming activity of, and caused body hypertrophy of. The biological toxic effects caused by the continuous discharge of PVC and CTR in the aquatic environment should not be ignored.

PVC；rubber；leaching solution；；ecotoxicity

X503

A

1000-6923(2022)11-5408-10

劉建超(1985-),河南商丘人,副教授,博士,主要從事新污染物環(huán)境行為、水環(huán)境保護(hù)與修復(fù)等方面的研究工作.發(fā)表論文90余篇.

2022-04-12

國(guó)家自然科學(xué)基金面上項(xiàng)目項(xiàng)目(521709063)

* 責(zé)任作者, 副教授, jianchao-liu@hhu.edu.cn