郭 建,羅孝俊,管克蘭,呂銀知,曾艷紅,麥碧嫻

石化工業(yè)園員工PAHs的皮膚暴露及健康風(fēng)險(xiǎn)

郭 建1,2,羅孝俊1*,管克蘭1,2,呂銀知1,2,曾艷紅1,麥碧嫻1

(1.中國(guó)科學(xué)院廣州地球化學(xué)研究所,有機(jī)地球化學(xué)國(guó)家重點(diǎn)實(shí)驗(yàn)室與廣東省資源環(huán)境利用與保護(hù)重點(diǎn)實(shí)驗(yàn)室,廣東 廣州 510640；2.中國(guó)科學(xué)院大學(xué),北京 100049)

本文選取典型石化城市茂名市某石化工業(yè)園30名員工(男女各15名)進(jìn)行裸露(額頭、手掌)和遮蔽皮膚部位(前臂、小腿)的擦拭采樣,通過(guò)氣相色譜-質(zhì)譜聯(lián)用儀(GC-MS)測(cè)定了擦拭樣品中15種多環(huán)芳烴的濃度(∑15PAHs)并計(jì)算了經(jīng)皮膚暴露和手-口接觸的人體暴露劑量.結(jié)果表明,皮膚樣品中∑15PAHs的濃度范圍為21～1.9×104ng/m2,不同部位間PAHs濃度存在顯著性差異(<0.01),表現(xiàn)為額頭>手掌>前臂>小腿.PAHs以3～4環(huán)PAHs組成為主.男女性別間PAHs組成無(wú)顯著差異,∑15PAHs女性高于男性,但無(wú)統(tǒng)計(jì)差異性.經(jīng)皮膚吸收的PAHs日暴露劑量(DADderm)女性[41ng/(kg×d)]顯著高于男性[28ng/(kg×d)].手-口接觸暴露劑量[0.34ng/(kg×d)]相比于皮膚暴露劑量[34ng/(kg×d)]可忽略不計(jì).皮膚暴露劑量主要來(lái)自裸露部位皮膚的貢獻(xiàn)(88%).風(fēng)險(xiǎn)評(píng)價(jià)結(jié)果表明,PAHs的皮膚暴露和手-口接觸暴露不存在明顯的非致癌風(fēng)險(xiǎn);但約7%員工的皮膚致癌風(fēng)險(xiǎn)高于可接受的水平(10-4),表明存在一定的PAH致癌風(fēng)險(xiǎn).

多環(huán)芳烴；石化員工；皮膚暴露；健康風(fēng)險(xiǎn)

進(jìn)入環(huán)境中的多環(huán)芳烴(PAHs)可通過(guò)消化道、呼吸道和皮膚等各種途徑進(jìn)入人體,并對(duì)人體健康產(chǎn)生潛在的負(fù)面效應(yīng),從而對(duì)人體的呼吸系統(tǒng)、循環(huán)系統(tǒng)、神經(jīng)系統(tǒng)、肝臟、腎臟等造成損傷[1-4].目前有16種PAHs被美國(guó)環(huán)境保護(hù)署(USEPA)列為優(yōu)先控制的有機(jī)污染物.

當(dāng)前,呼吸系統(tǒng)暴露和飲食暴露是人體污染物暴露研究的重點(diǎn).研究表明,成人對(duì)于PM2.5中PAHs的呼吸暴露風(fēng)險(xiǎn)高于兒童,人們?cè)诙镜腜AHs呼吸暴露風(fēng)險(xiǎn)高于其他季節(jié)[5-6];燃煤或燃柴的家庭居民,因PAHs呼吸暴露可能存在較高的致癌風(fēng)險(xiǎn)[7].許多流行病學(xué)研究表明,人類(lèi)的部分癌癥與飲食相關(guān),包括通過(guò)飲食攝入PAHs[8-10].食物中的PAHs水平取決于其所處環(huán)境的PAHs水平以及食物自身的特性[11].皮膚暴露也是人體污染物暴露的一個(gè)重要途徑[12-14].皮膚吸附有機(jī)污染物的途徑包括接觸含污染物的介質(zhì)(如附著于皮膚表面的顆粒物)、直接從空氣中以及衣物中吸收等.通過(guò)對(duì)戶(hù)外燒烤人群的PAHs暴露研究發(fā)現(xiàn)[15],皮膚對(duì)于低分子PAHs的攝入大于呼吸攝入,通過(guò)皮膚暴露排出的羥基PAHs與通過(guò)皮膚和呼吸聯(lián)合暴露排出的劑量相當(dāng).對(duì)于有機(jī)污染物的皮膚暴露劑量更多是通過(guò)環(huán)境中污染物濃度的測(cè)定,然后應(yīng)用模型對(duì)皮膚暴露的劑量進(jìn)行估算[16-17].當(dāng)前,關(guān)于人體皮膚擦拭樣品及皮膚模擬吸收的研究逐漸增加[18].然而,與飲食暴露和呼吸系統(tǒng)暴露的研究相比,直接利用人體皮膚擦拭樣品研究PAHs皮膚暴露的研究仍較少.精細(xì)化不同皮膚部位的暴露貢獻(xiàn)研究仍不多見(jiàn),皮膚暴露與手-口接觸暴露的相對(duì)重要性仍存有爭(zhēng)議[19].

本研究以中國(guó)南方重要的石油化工基地茂名市一個(gè)典型的石化工業(yè)園區(qū)為研究區(qū)域,以該園區(qū)的員工為研究對(duì)象,通過(guò)對(duì)員工不同部位皮膚擦拭樣品的分析,以期了解人體皮膚不同部位PAHs的暴露情況,計(jì)算皮膚吸收與手-口接觸的人體PAHs暴露劑量,并評(píng)價(jià)其健康風(fēng)險(xiǎn),為全面評(píng)價(jià)人體PAHs暴露及風(fēng)險(xiǎn)提供參考.

1 材料與方法

1.1 樣品采集

于2020年12月下旬,在茂名市某石化工業(yè)園區(qū)對(duì)30名從業(yè)時(shí)間1a以上的員工(男女各15名)進(jìn)行采樣.采樣前,使用索氏抽提法(二氯甲烷)對(duì)采樣紗布?jí)K(7.5cm×7.5cm)凈化72h,紗布經(jīng)真空干燥后,用錫箔紙包裹緊密并密封于樣品袋中,置于零下20℃保存?zhèn)溆?采樣人員配戴一次性手套,用異丙醇將已凈化的紗布浸泡至濕潤(rùn)狀態(tài),每個(gè)采樣部位使用1塊紗布,用紗布正反面分別擦拭采樣部位的表皮膚3次,再迅速將紗布?jí)K用錫箔紙包裹緊密并密封于樣品袋內(nèi),置于零下20℃保存.同時(shí)采集場(chǎng)地空白對(duì)照樣品(將紗布置于空氣中約20s替代擦拭操作).使用軟尺測(cè)量采樣對(duì)象的額頭、手臂、小腿采樣部位的表面積數(shù)據(jù);使用坐標(biāo)紙計(jì)算手掌采樣部位表面積;測(cè)量采樣對(duì)象的身高和體重.要求被采樣者采樣前2h內(nèi)不能水洗取樣部位.

1.2 樣品前處理

1.3 樣品分析

使用氣相色譜-質(zhì)譜聯(lián)用儀(SHIMADZU GC- MS-QP2020NX),在電子轟擊離子源(EI)及離子檢測(cè)(SIM)模式下進(jìn)行樣品分析.載氣為高純氦氣,流速為1mL/min.進(jìn)樣口溫度為290℃,離子源溫度為230℃,傳輸線(xiàn)溫度為280℃.在高壓不分流模式下自動(dòng)進(jìn)樣器進(jìn)樣量為1μL.目標(biāo)化合物使用色譜柱Rtx-5MS(30m×0.25mmID×0.25um,SHIMADZU)進(jìn)行分離.色譜柱升溫程序如下:初始溫度80℃,保留5min,以4℃/min升溫至310℃,保留15min.16種目標(biāo)PAHs與分子標(biāo)志物的儀器檢出限為0.08～6.6ng.因萘具有較強(qiáng)的揮發(fā)性導(dǎo)致較低的回收率,萘不納入后續(xù)數(shù)據(jù)處理分析,本研究目標(biāo)化合物為15種 PAHs(見(jiàn)表1),均屬于US EPA公布優(yōu)先控制的PAHs污染物.

1.4 質(zhì)量保證與控制

1.5 PAHs的皮膚及手-口接觸暴露劑量

石化員工體表皮膚PAHs的每日平均攝入量(DADderm) 采用滲透系數(shù)模型進(jìn)行計(jì)算,具體見(jiàn)式(1).PAHs的手-口接觸每日平均攝入量(DADoral)按照式(2)進(jìn)行計(jì)算[12,16,20-22].

式中:face、hand、arm和others分別為頭頸部、雙手、雙上臂及雙前臂、小腿和其他部位皮膚表面的PAHs濃度,ng/m2;face、hand、armothers分別為頭頸部、雙手、雙上臂及雙前臂、小腿和其他部位的皮膚表面積,m2;p-l指皮膚表面脂質(zhì)層PAHs的滲透系數(shù),μm/h,其為化合物分子量與辛醇-水分配系數(shù)的函數(shù),具體計(jì)算過(guò)程參見(jiàn)文獻(xiàn)[16];ED指暴露時(shí)間,h/d,按員工的實(shí)際工作時(shí)間取值8h/d;m指皮膚表面脂層厚度,μm,取值1.3μm[21];TE指轉(zhuǎn)換率,取值50%[23];SAC指接觸手掌表面積的比例,取值10%[24];EF指暴露頻率,contacts/d,相關(guān)文獻(xiàn)取值24contacts/d[23],本文按員工實(shí)際暴露時(shí)間取值8contacts/d;BW指體重,kg.

人體體表總面積參照文獻(xiàn)[25],使用身高及體重?cái)?shù)據(jù)進(jìn)行計(jì)算,見(jiàn)式(3)和式(4).

(4)

式中:w-male和w-female分別為男性和女性人體總表面積,m2;指身高,cm.其他部位表面積根據(jù)《人體損傷致殘程度分級(jí)》的“體表面積的九分估算法”進(jìn)行計(jì)算[26].其中頭頸部占人體體表總表面積的9%,濃度采用額頭的PAHs濃度;雙上臂及雙前臂占人體體表總表面積的13%,濃度采用前臂的PAHs濃度;雙手占人體體表總表面積的5%,濃度采用手掌的PAHs濃度;其他部位(前軀、后軀、雙大腿、雙小腿、雙足、臀部、會(huì)陰等)占人體體表總表面積的73%,濃度采用小腿的PAHs濃度.

1.6 健康風(fēng)險(xiǎn)評(píng)價(jià)方法

1.6.1 非致癌風(fēng)險(xiǎn) 通過(guò)非致癌風(fēng)險(xiǎn)的風(fēng)險(xiǎn)商值(HQs)和風(fēng)險(xiǎn)指數(shù)(HI)評(píng)價(jià)石化員工PAHs的皮膚和手-口接觸暴露健康風(fēng)險(xiǎn),見(jiàn)式(5)和式(6)[27].

式中:RfDderm-i和RfDoral-i分別代表PAHs單體的皮膚和手-口接觸暴露的參考劑量,ng/(kg·d);EF指每年暴露的天數(shù),根據(jù)員工實(shí)際工作天數(shù)取值,312d; AT指每年的總天數(shù),取值365d;HI為不同PAHs單體風(fēng)險(xiǎn)商值之和,當(dāng)HI值<1時(shí),表明石化員工不存在明顯的非致癌風(fēng)險(xiǎn);當(dāng)HI值>1時(shí),表明石化員工可能存在潛在的非致癌影響.因缺乏部分PAHs的RfDderm和RfDoral數(shù)據(jù),本研究只選用苊、芴、蒽、熒蒽、芘和苯并[a]芘6種PAHs進(jìn)行石化員工的非致癌健康風(fēng)險(xiǎn)評(píng)價(jià).

1.6.2 致癌風(fēng)險(xiǎn) 采用苯并[a]芘毒性當(dāng)量因子計(jì)算PAHs各單體的等效致癌毒性濃度(TEC),評(píng)估 PAHs 的皮膚暴露致癌風(fēng)險(xiǎn),見(jiàn)式(7)[27]:

TEC=C′TEF(7)

PAHs 的皮膚暴露致癌風(fēng)險(xiǎn)(CSR)和手-口接觸暴露致癌風(fēng)險(xiǎn)(COR)見(jiàn)式(8)和式(9):

式中:CSF代表基于苯并[a]芘的皮膚攝入致癌斜率因子,取值37.47×10-6[ng/(kgBW×d)][29],EF取值312d,AT取值365d;DADderm-BaP、DADoral-BaP分別代表DADderm、DADoral的苯并[a]芘當(dāng)量總濃度. USEPA 將致癌風(fēng)險(xiǎn)劃分為:可接受致癌風(fēng)險(xiǎn)水平(Risk<10-4),不可接受致癌風(fēng)險(xiǎn)水平(Risk310-4)[30].

2 結(jié)果和討論

2.1 皮膚擦拭樣PAHs的含量及組成特征

由表1可見(jiàn),除DahA及BghiP在樣品中未檢出外,其他13種PAHs均有不同程度的檢出.3～4環(huán)PAHs的檢出率和濃度均高于5～6環(huán)PAHs,這與李大雁等對(duì)某大型石化企業(yè)鄰近工業(yè)區(qū)大氣沉降中的PAHs研究結(jié)果一致[31].皮膚擦拭樣品∑15PAHs的濃度范圍為21～1.9×104ng/m2,無(wú)論男女,不同部位之間的∑15PAHs濃度均存在顯著性差異(單因素因子分析,<0.01),表現(xiàn)為額頭>手掌>前臂>小腿(圖1),其濃度范圍分別為3.6×103～1.9×104,170～ 1.7×103,49～1.6×103,21～490ng/m2,相應(yīng)的幾何平均濃度為6.7×103,630,200,91ng/m2.石化員工裸露皮膚部位的S15PAHs濃度顯著高于衣物遮蔽部位,S15PAHs濃度最高部位(額頭)與濃度最低部位(小腿)之間的幾何平均濃度相差約74倍.由此可見(jiàn),直接裸露的皮膚更容易吸附PAHs,衣物可有效阻隔和減少皮膚對(duì)PAHs的吸附.有研究表明,潔凈的衣物可有效減少氣相半揮發(fā)性有機(jī)污染物(SVOCs)的暴露,相反,受污染的衣物可放大氣相SVOCs的暴露[32]. Gong等[33]對(duì)人體皮膚擦拭樣品中鄰苯二甲酸酯濃度進(jìn)行研究,結(jié)果表現(xiàn)為手掌>手背>前臂3額頭.Cao等[12]對(duì)多氯聯(lián)苯、多溴聯(lián)苯醚的皮膚擦拭樣品的研究也發(fā)現(xiàn)手掌的濃度要高于額頭,這與本研究正相反.鄰苯二甲酸酯、多溴聯(lián)苯醚及多氯聯(lián)苯都是人為制造的工業(yè)品,添加于很多工業(yè)品或者商用品中.手與物品接觸是該類(lèi)化合物重要的暴露途徑.而PAHs不添加于任何工業(yè)品中,缺乏這一暴露途徑,這可能是其手掌濃度相對(duì)較低的原因.國(guó)外學(xué)者對(duì)鋪路工人手掌部位PAHs濃度的檢測(cè)結(jié)果為7.8×104ng/m2(16種PAHs)[34]、2.2×104ng/m2(9種PAHs)[35],比石化員工手掌部位的PAHs濃度高約2個(gè)數(shù)量級(jí).

表1 15種PAHs的檢出率及濃度范圍

注: MDL為方法檢出限(method detection limit).

男女性∑15PAHs濃度范圍分別為33～1.3×104, 21～1.9×104ng/m2,相應(yīng)的幾何平均濃度為490, 570ng/m2.同一部位樣品的∑15PAHs濃度都表現(xiàn)為女性>男性(圖1),但不存在統(tǒng)計(jì)學(xué)意義上的顯著性(額頭:= 0.19,手掌:= 0.52,前臂:= 0.20,小腿:= 0.48).

圖1 不同采樣部位及不同性別間的PAHs濃度

箱圖方框的下端和上端分別是數(shù)據(jù)的第25位和第75位百分位數(shù);方框中的橫線(xiàn)為中位數(shù);圓圈代表極端值

如圖2,對(duì)不同環(huán)數(shù)PAHs占總PAHs的比例分析可知,男性和女性,不同部位之間PAHs的組成變異性均較大,總體表現(xiàn)為3環(huán)>4環(huán)>5～6環(huán),比例分別為15%～83%,4%～73%和

2.2 PAHs的皮膚及手-口接觸暴露劑量

30名員工15種PAHs的體表皮膚每日平均攝入量(DADderm)及經(jīng)手-口接觸每日平均攝入量(DADoral)范圍分別為17～69,0.10～0.92ng/(kg·d),幾何平均值分別為34,0.34ng/(kg·d),兩者相差約100倍,由此可見(jiàn),相對(duì)PAHs的皮膚暴露途徑而言,經(jīng)手-口接觸暴露的劑量可忽略不計(jì).

進(jìn)一步對(duì)員工裸露皮膚部位(頭頸部、手掌)和衣物遮蔽皮膚部位的DADderm分析可知,裸露部位和遮蔽部位的DADderm范圍分別為16～65,0.86～ 14ng/(kg·d),幾何平均值分別為29,3.6ng/(kg·d),裸露部位的DADderm顯著高于遮蔽部位(<0.01),兩者的貢獻(xiàn)率分別為88%和12%.由此可見(jiàn),雖然人體遮蔽部位的表面積比例(86%)大于裸露部位(14%),裸露部位仍是人體皮膚攝入PAHs的主要部位.這與多氯聯(lián)苯(PCBs)、多溴聯(lián)苯醚(PBDEs)污染物的暴露部位貢獻(xiàn)明顯不同,PCBs和PBDEs在遮蔽部位的貢獻(xiàn)大于裸露部位[12].額頭PAH濃度高于其他部位PAH濃度幾個(gè)數(shù)量級(jí)是造成這種差異的主要原因.因此、臉部清潔應(yīng)是有效降低人體皮膚PAH攝入的有效方式.

對(duì)30名員工不同性別之間的DADderm及DADoral分析可知(圖3),DADderm及DADoral均表現(xiàn)為女性>男性.其中,男女性DADderm的范圍分別為17～53,27～69ng/(kg·d),幾何平均值分別為28,41ng/ (kg·d),兩者間存在顯著性差異(<0.01);男女性DADoral的范圍分別為0.10～0.92,0.10～0.87ng/(kg·d),幾何平均值分別為0.32,0.36ng/(kg·d),兩者間不存在顯著性差異(= 0.44).

2.3 PAHs的健康風(fēng)險(xiǎn)評(píng)價(jià)

2.3.1 非致癌風(fēng)險(xiǎn)評(píng)價(jià) 30名石化員工6種PAHs的HI范圍為9.5×10-5～1.2×10-2,說(shuō)明石化員工的皮膚和手-口接觸暴露不存在明顯的非致癌風(fēng)險(xiǎn),這與國(guó)外學(xué)者對(duì)于石化工業(yè)排放的揮發(fā)性有機(jī)化合物(VOCs)導(dǎo)致的非致癌風(fēng)險(xiǎn)研究結(jié)果一致(HI< 1)[36-37].進(jìn)一步對(duì)30名石化員工不同類(lèi)別HI值總和的貢獻(xiàn)率分析可知,皮膚暴露的HI值總和(HIderm)和手-口接觸暴露的HI值總和(HIoral)對(duì)HItotal的貢獻(xiàn)率分別為97.2%和2.8%(表2);裸露皮膚部位的HI值總和(HIbare)和衣物遮蔽皮膚部位的HI值總和(HIcover)對(duì)HIderm的貢獻(xiàn)率分別為94.7%和5.3%,兩者之間存在顯著性差異(<0.01);男性皮膚HI值總和(HIderm-male)和女性皮膚HI值總和(HIderm-female)對(duì)HIderm的貢獻(xiàn)率分別為51.9%和48.1%,兩者之間不存在顯著性差異(=0.89);男性手-口接觸暴露的HI值總和(HIoral-male)和女性手-口接觸暴露的HI值總和(HIoral-female)對(duì)HIoral的貢獻(xiàn)率分別為46.0%和54.0%,兩者之間不存在顯著性差異(= 0.74).

2.3.2 致癌風(fēng)險(xiǎn)評(píng)價(jià) 30名石化員工15種PAHs的TEC范圍為1.1～510ng/m2,幾何平均值為30ng/m2.人體裸露和遮蔽皮膚部位的TEC范圍分別為6.7～3.6×103和0.038～22ng/m2,幾何平均值分別為160和2.5ng/m2,兩者之間存在顯著性差異(<0.01);男性和女性樣品的TEC范圍分別為1.1～410和3.9～510ng/m2,幾何平均值均為30ng/m2,兩者之間不存在顯著性差異(=0.94).30名石化員工3～6環(huán)PAHs的TEC值總和貢獻(xiàn)率分別為0.5%、0.5%、98.5%和0.5%(圖4).濃度貢獻(xiàn)率只有20.9%的5環(huán)PAHs貢獻(xiàn)了98.5%的致癌風(fēng)險(xiǎn),其中濃度貢獻(xiàn)率只有9.3%的單體BaP貢獻(xiàn)了90.8%的致癌風(fēng)險(xiǎn),這與珠江三角洲城市大氣中PAHs的致癌風(fēng)險(xiǎn)相似,濃度貢獻(xiàn)率約20%的5環(huán)PAHs貢獻(xiàn)了超過(guò)70%的致癌風(fēng)險(xiǎn)[38].

表2 不同暴露途徑、暴露部位及性別的HI值貢獻(xiàn)率

30名石化員工15種PAHs的CSR范圍為9.0×10-7～1.3×10-4,CSR的平均值為2.3×10-5,其中處于可接受致癌風(fēng)險(xiǎn)水平范圍的員工比例為93%,處于不可接受致癌風(fēng)險(xiǎn)水平范圍的員工比例為7%.男性和女性的CSR范圍分別為9.0×10-7～1.1×10-4和2.0×10-6～1.3×10-4,兩者之間不存在顯著性差異(= 0.94).30名石化員工15種PAHs的COR范圍為4.0× 10-9～4.7×10-6,COR的平均值為7.5×10-7,均處于可接受的致癌風(fēng)險(xiǎn)水平范圍.

國(guó)內(nèi)外的研究結(jié)果表明,石化園區(qū)比非石化園區(qū)的PAH暴露與致癌風(fēng)險(xiǎn)水平普遍較高.如中國(guó)南方某石化工業(yè)園區(qū)周邊0.5km內(nèi)居民的PAHs呼吸暴露致癌風(fēng)險(xiǎn)為1.2×10-4[39],馬來(lái)西亞某石化工業(yè)園區(qū)5km內(nèi)的3所小學(xué)兒童吸入PAHs的致癌風(fēng)險(xiǎn)為2.2×10-6[40],中國(guó)長(zhǎng)江三角洲[41],中國(guó)臺(tái)灣[42],西班牙加泰羅尼亞[43],韓國(guó)大邱[44]等地區(qū)石化工業(yè)排放的VOCs致癌風(fēng)險(xiǎn)分別為1.1×10-5,9.3×10–5～1.7×10–4, 2.2×10?5～4.4×10?4,2.6×10?4.而非石化園區(qū),如中國(guó)南方農(nóng)村居民冬季家庭污染氣體中PAHs的致癌風(fēng)險(xiǎn)為8.1×10-6[45],中國(guó)寶雞市冬季PM2.5中成年人PAHs暴露的致癌風(fēng)險(xiǎn)為3.8×10-6[46],馬來(lái)西亞某石化工業(yè)園區(qū)20km外的3所小學(xué)兒童吸入PAHs的致癌風(fēng)險(xiǎn)為3.0×10-9[40];美國(guó)洛杉磯城市通勤者在路途中PAHs暴露的致癌風(fēng)險(xiǎn)為1.2×10-9[47].因此,石化工業(yè)排放的PAHs污染問(wèn)題應(yīng)當(dāng)引起重視,受其影響的人群應(yīng)注意做好個(gè)人防護(hù)措施,如盡量減少裸露的皮膚面積,注意個(gè)人衛(wèi)生,勤洗手洗臉洗澡,及時(shí)更換臟衣物等.

圖4 石化員工各環(huán)PAHs的濃度貢獻(xiàn)率與TEC貢獻(xiàn)率

3 結(jié)論

3.1 皮膚擦拭樣品中∑15PAHs濃度表現(xiàn)為額頭(6.7×103ng/m2)>手掌(630ng/m2)>前臂(200ng/m2)>小腿(91ng/m2);裸露皮膚部位的∑15PAHs濃度顯著高于衣物遮蔽皮膚部位,說(shuō)明直接暴露的皮膚更容易吸附PAHs,衣物可有效阻隔和降低皮膚對(duì)PAHs的吸附;不同性別樣品的S15PAHs濃度表現(xiàn)為女性[41ng/(kg×d)]>男性[28ng/(kg×d)],但不存在顯著性.

3.2 石化員工15種PAHs的DADderm比DADoral高約100倍,相對(duì)PAHs的皮膚暴露途徑而言,手-口接觸暴露的劑量可忽略不計(jì).兩性間的DADderm及DADoral均表現(xiàn)為女性>男性,但只有兩性間的DADderm存在顯著性差異(<0.01).

3.3 皮膚暴露對(duì)員工不存在明顯的非致癌風(fēng)險(xiǎn),但約有7%的員工皮膚暴露導(dǎo)致皮膚癌的風(fēng)險(xiǎn)超過(guò)可接受水平,表明存在致癌風(fēng)險(xiǎn),而手-口接觸暴露途徑的致癌風(fēng)險(xiǎn)均在可接受水平.

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A study on employees’ skin exposure to polycyclic aromatic hydrocarbons and health risk in a petrochemical industrial park.

GUO Jian1,2, LUO Xiao-jun1*, GUAN Ke-lan1,2, LV Yin-zhi1,2, ZENG Yan-hong1, MAI Bi-xian1

(1.State Key Laboratory of Organic Geochemistry and Guangdong Key Laboratory of Environmental Resources Utilization and Protection, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640, China；2.University of Chinese Academy of Sciences, Beijing 100049, China)., 2022,42(11)：5427～5435

In the study, skin wipe samples were collected from four typical skin parts (forehead, palm, forearm and shank) of 30 volunteers (15 men and 15 women), who work in a Petrochemical Industrial Park in Maoming City (a typical petrochemical city). The concentrations of 15 polycyclic aromatic hydrocarbons (∑15PAHs) in wiping samples were determined by gas chromatography-mass spectrometry (GC-MS), and the human exposure doses through skin exposure and hand-mouth contact were calculated. The concentration of Σ15PAHs in skin samples ranged from 21 to 1.9×104ng/m2. The PAH concentrations exhibited significant differences among different skin parts (<0.01) with the order of forehead > palm > forearm > shank. PAHs are mainly composed of 3～4rings. Although no statistical difference was observed in ∑15PAHs between female and male, the daily dermal absorption doses of PAH (DADderm) was significantly higher in female [41ng/(kg×d)] than male [28ng/(kg×d)]. The hand-mouth exposure dose [0.34ng/(kg×d)] was negligible to compare with the dermal absorption dose [34ng/(kg×d)]. The bared skins contribute to 88% of dermal absorption dose. There was no obvious non-carcinogenic risk but risks of skin cancer were higher than the acceptable level (1×10-4) for 7% staff, indicating potential skin cancer risk.

polycyclic aromatic hydrocarbons；petrochemical employees；skin exposure；health risk

X511

A

1000-6923(2022)11-5427-09

郭 建(1984-),男,廣東茂名人,中國(guó)科學(xué)院廣州地球化學(xué)研究所(中國(guó)科學(xué)院大學(xué))博士研究生,主要研究方向?yàn)橛袡C(jī)污染物的暴露評(píng)估及健康風(fēng)險(xiǎn)評(píng)價(jià).發(fā)表論文6篇.

2022-04-26

國(guó)家自然科學(xué)基金資助項(xiàng)目(41877386,41931290);廣東省科技項(xiàng)目(2020B1212060053,2019B121205006)

* 責(zé)任作者, 研究員, luoxiaoj@gig.ac.cn