封 麗, 程艷茹, 封 雷, 張 晟*, 劉異齊
1.重慶市環(huán)境科學(xué)研究院, 重慶市生態(tài)環(huán)境遙感監(jiān)測(cè)大數(shù)據(jù)應(yīng)用協(xié)同創(chuàng)新中心, 重慶 401147 2.重慶大學(xué)材料科學(xué)與工程學(xué)院, 重慶 400044 3.中國(guó)科學(xué)院重慶綠色智能技術(shù)研究院大數(shù)據(jù)挖掘與應(yīng)用中心(兼三峽工程生態(tài)環(huán)境在線監(jiān)測(cè)中心), 重慶 400714
三峽庫(kù)區(qū)主要水域典型抗生素分布及生態(tài)風(fēng)險(xiǎn)評(píng)估
封 麗1,2, 程艷茹1, 封 雷3, 張 晟1*, 劉異齊1
1.重慶市環(huán)境科學(xué)研究院, 重慶市生態(tài)環(huán)境遙感監(jiān)測(cè)大數(shù)據(jù)應(yīng)用協(xié)同創(chuàng)新中心, 重慶 401147 2.重慶大學(xué)材料科學(xué)與工程學(xué)院, 重慶 400044 3.中國(guó)科學(xué)院重慶綠色智能技術(shù)研究院大數(shù)據(jù)挖掘與應(yīng)用中心(兼三峽工程生態(tài)環(huán)境在線監(jiān)測(cè)中心), 重慶 400714
抗生素; 地表水; 污染特征; 生態(tài)風(fēng)險(xiǎn)評(píng)估; 三峽庫(kù)區(qū)
Abstract: The mass concentrations of 28 kinds of antibiotics (6 types) from the stem streams and 6 tributaries of the Yangtze River in the Three Gorges Reservoir area were investigated by solid phase extraction, high performance liquid chromatography and triple quadrupole mass spectrometry (SPE-HPLC-MS/MS). The ecological risks were assessed by the rating method proposed by Hernando and according to the EU environmental risk assessment method to calculate the risk quotient value (RQS) and joint risk quotient value (RQsum). The results indicated that 10 antibiotics were detected from drugs for livestock and poultry with a mass concentration range of 0.6-218 ng/L, except ofloxacin (OFX) and chloramphenicol (CAP). The detected antibiotics included sulfadiazine (SDI), sulfamethoxazole(SMX), sulfamethazine(SMZ), erythromycin (ERM), roxithromycin (ROM), tylosin (TYL), florfenicol (FF) and lincomycin (LIN). Among them, FF and LIN are ranked in the top five livestock and poultry drugs used in China. Moreover, the RQsumexhibited an interesting finding: Laixi River > Qiongjiang River > Qijiang River > Bixi River > Jialing River > Yangtze River > Wujiang River. RQsumvalue in Laixi River reached up to 5.5, indicating higher risk of toxicity to aquatic organisms from three kinds of antibiotics SMX, ERM and OFX. In contrast, RQsumin Qiongjiang River, Qijiang River, Bixi River and Jialing River were in the range of 1 to 2 with relatively high risk, but the individual RQSin each of the four rivers was less than 1, implying low risk. In addition, RQsumvalue of the Yangtze River was 0.605; the risk status of antibiotics TYL, ERM and ROM were in the middle level, and the risk status of other antibiotics risk were at a low level. Interestingly, RQsumof Wujiang River was 0.013, and the detected antibiotics were at low risk, indicating that the water body had minimum interference by human activities. Although the contents of antibiotics in major water basins around the Three Gorges Reservoir were slightly lower than those in other rivers, the antibiotics are used in great doses in the livestock and poultry breeding industry. Therefore, regulations should be strengthened and more studies should be conducted on limiting the amount of livestock and poultry feces that is returned to the fields.
Keywords: antibiotics; surface water; pollution characteristics; ecological risk assessment; Three Gorges Reservoir
三峽水庫(kù)是我國(guó)特大型水庫(kù),具有防洪、發(fā)電、供水、養(yǎng)殖等功能,綜合效益顯著,同時(shí)亦關(guān)系著長(zhǎng)江中下游沿線幾億人的生產(chǎn)生活用水,因此其生態(tài)功能極其關(guān)鍵[1]. 目前,針對(duì)庫(kù)區(qū)水環(huán)境的研究多集中于常規(guī)污染物的分布、累積及環(huán)境影響[2],水環(huán)境中新型污染物抗生素的調(diào)查研究還屬起步階段,鮮有針對(duì)庫(kù)區(qū)大范圍水域中抗生素污染的研究,缺乏調(diào)查評(píng)價(jià)的基礎(chǔ)數(shù)據(jù). 抗生素是用于治療各種細(xì)菌感染或抑制致病微生物感染的藥物,按照化學(xué)結(jié)構(gòu)主要分為β-內(nèi)酰胺類、磺胺類、大環(huán)內(nèi)酯類、四環(huán)素類、氟喹諾酮類等[3]. 抗生素在人類和動(dòng)物體內(nèi)不能被充分吸收,大多會(huì)以原形或活性代謝產(chǎn)物的形式隨排泄物進(jìn)入污水處理廠或直接進(jìn)入環(huán)境[4-5]. 雖然大部分抗生素的半衰期較短,但由于其頻繁使用并進(jìn)入環(huán)境,導(dǎo)致形成“假持續(xù)”現(xiàn)象,對(duì)生態(tài)環(huán)境構(gòu)成潛在風(fēng)險(xiǎn)[6-8]. 抗生素對(duì)水生生物可能存在一定的急性或慢性毒性,其在抑制或殺滅病原體的同時(shí)也可能抑制環(huán)境中有益微生物的活性,干擾甚至破壞生態(tài)系統(tǒng)循環(huán)[9-10]. 抗生素在生物體內(nèi)殘留對(duì)人體健康具有潛在危害,一般不表現(xiàn)為急性毒性作用,但長(zhǎng)期攝入含低劑量抗生素類藥物的食品,可能由于累積對(duì)器官產(chǎn)生影響[11-12]. 2013年,我國(guó)36種主要抗生素使用總量約為 92 700 t,人類和畜禽以原藥或代謝產(chǎn)物等形式排出體外的抗生素約 54 000 t,最終通過(guò)生活污水排放、養(yǎng)殖廢水排放、農(nóng)業(yè)糞肥灌溉徑流等不同途徑被環(huán)境接收的抗生素約為 53 800 t[13]. 我國(guó)抗生素過(guò)量使用情況嚴(yán)重[14],由此所導(dǎo)致的環(huán)境污染和生態(tài)毒性已逐漸演變成重大環(huán)境問(wèn)題之一[15].
抗生素在水環(huán)境中的檢出受各地區(qū)用藥習(xí)慣影響顯著,參考我國(guó)36種主要抗生素使用特征,根據(jù)庫(kù)區(qū)衛(wèi)計(jì)委、藥監(jiān)局等部門提供的抗生素相關(guān)資料,結(jié)合問(wèn)卷調(diào)查和現(xiàn)場(chǎng)調(diào)查的結(jié)果,選取6類28種抗生素作為分析對(duì)象,研究其在庫(kù)區(qū)長(zhǎng)江干流及重要支流(嘉陵江、烏江、瀨溪河、碧溪河、綦江河、瓊江)水環(huán)境中的分布特征,并初步評(píng)估其污染水平和生態(tài)風(fēng)險(xiǎn),以期為庫(kù)區(qū)水環(huán)境保護(hù)和特殊污染物研究提供數(shù)據(jù)基礎(chǔ)和技術(shù)參考.
1.1 樣品采集
2016年5—6月(非洪水期),在三峽庫(kù)區(qū)長(zhǎng)江、嘉陵江、烏江、瀨溪河、碧溪河、綦江河、瓊江等7條河流按照水體流向分別設(shè)置4~6個(gè)采樣斷面,累計(jì)布設(shè)斷面31個(gè),每個(gè)斷面設(shè)置左、中、右3個(gè)水平采樣點(diǎn),共采集樣品93個(gè),分別進(jìn)行分析. 具體布點(diǎn)見(jiàn)圖1.
水樣的采集和保存按GB/T 12999—1999《水質(zhì)采樣 樣品保存和管理技術(shù)規(guī)定》中的一般性規(guī)定執(zhí)行. 每次取表層水面以下0.5 m處水樣,pH調(diào)節(jié)為3,密閉保存于棕色玻璃采樣瓶中帶回實(shí)驗(yàn)室并盡快進(jìn)行固相萃取富集濃縮.
1.2 儀器與試劑
儀器:液相色譜-質(zhì)譜/質(zhì)譜聯(lián)用儀(LC-MC/MS,Shimadzu LC-20A+AB API 4000);全自動(dòng)固相萃取儀(Reeko FOTECTOR-06C);HLB固相萃取柱(6 mL,1 000 mg,waters Oasis HLB);WXH微型漩渦混合器;超聲波清洗器;DC-12氮?dú)獯蹈蓛x;0.7 μm玻璃纖維濾膜;0.22 μm針頭式過(guò)濾器.
圖1 三峽庫(kù)區(qū)主要水域采樣斷面分布Fig.1 Sampling sites in main waters of the Three Gorges Reservoir area
試劑:28種抗生素標(biāo)品,購(gòu)自Dr. Ehrenstorfer GmbH公司;乙腈、甲醇為色譜純,購(gòu)自Thermo Fisher公司;鹽酸、乙二胺四乙酸二鈉、磷酸氫二鉀為分析純,購(gòu)自國(guó)藥集團(tuán)化學(xué)試劑有限公司;實(shí)驗(yàn)室用水按照GB/T 6682—2008《分析實(shí)驗(yàn)室用水規(guī)格和試驗(yàn)方法》一級(jí)水要求制備.
1.3 分析方法
樣品預(yù)處理:將1 L水樣經(jīng)0.7 μm孔徑的玻璃纖維濾膜過(guò)濾,加入0.5 g乙二胺四乙酸二鈉和8.7 g磷酸氫二鉀,攪拌并超聲溶解. HLB固相萃取柱使用前依次以10 mL甲醇、10 mL超純水活化. 水樣以3~5 mL/min的流速通過(guò)HLB固相萃取柱,水樣萃取完后,萃取柱在真空下抽干30 min,再以10 mL水淋洗,最后依次以5 mL純甲醇、10 mL 5%(體積比)氨水甲醇洗脫. 收集的洗脫液在40 ℃水浴條件下用氮?dú)饩従彺抵两?,? mL 20%(體積比)乙腈水溶液溶解殘?jiān)?,?jīng)0.22 μm濾膜過(guò)濾,供LC-MS/MS測(cè)定.
液相條件:Shimadzu VP-ODS C18色譜柱(4.6 mm×150 mm,5 μm);進(jìn)樣量10 μL;流動(dòng)相流速:0.3 mL/min;柱溫40 ℃;流動(dòng)相A(0.1%甲酸的乙腈),流動(dòng)相B(2 mmol/L乙酸銨,含0.1%甲酸). 測(cè)定時(shí)采用的流動(dòng)相梯度:0~7 min,10%~40% A;7~9 min,40%~60% A;9~10 min,60%~10% A;10~12 mim,10%A. 目標(biāo)抗生素質(zhì)譜參數(shù)根據(jù)抗生素種類不同進(jìn)行調(diào)整.
以甲醇為溶劑配制28種抗生素的儲(chǔ)備液(1.000 g/L),然后分別取28種儲(chǔ)備液用甲醇配制成 1 000 μg/L的混合標(biāo)準(zhǔn)液,最后以水為溶劑逐級(jí)稀釋混合標(biāo)準(zhǔn)液制備0.8、4、10、20、100、200 μg/L 6個(gè)質(zhì)量濃度的系列標(biāo)準(zhǔn)溶液,經(jīng)分析獲得工作曲線,28種目標(biāo)成分的相關(guān)系數(shù)范圍為 0.997 5~0.999 6. 在1 L水源水中加入10、50和200 ng抗生素混標(biāo),同時(shí)測(cè)定空白組分的抗生素含量,并分種類計(jì)算回收率,每組設(shè)3個(gè)平行樣. 抗生素回收率在89.2%~105.8%,方法相對(duì)標(biāo)準(zhǔn)偏差小于5%.
2.1 抗生素質(zhì)量濃度
由表2可見(jiàn),在檢出的10種抗生素中,F(xiàn)F、LIN的檢出率最高,達(dá)80.65%;ERM、ROM和CAP的檢出率均在60%以上;SDI的檢出率最低,不到10%. LIN、FF、ERM、ROM和CAP的檢出率均在60%以上,是庫(kù)區(qū)水域中主要?dú)埩舻目股?
環(huán)境中抗生素主要來(lái)源于醫(yī)藥使用、畜禽養(yǎng)殖、水產(chǎn)養(yǎng)殖和醫(yī)藥工業(yè)廢水排放等[18]. 2015年,研究區(qū)域內(nèi)的畜禽養(yǎng)殖場(chǎng)接近1.2×104個(gè),其中豬場(chǎng)有 7 448 個(gè),集約化以上的養(yǎng)殖場(chǎng)(小區(qū))達(dá)54%;牛(肉牛、奶牛)場(chǎng)有890個(gè),集約化以上的養(yǎng)殖場(chǎng)(小區(qū))達(dá)57%;雞(肉雞、蛋雞)場(chǎng)有 2 271 個(gè),集約化以上的養(yǎng)殖場(chǎng)(小區(qū))達(dá)38%. 上述3類養(yǎng)殖規(guī)?;竞w了養(yǎng)殖總量的90%以上,所產(chǎn)生的糞尿量也涵蓋了總畜禽糞尿量的90%以上(以常年存欄量估算). 抗生素在動(dòng)物體內(nèi)不能完全代謝降解,隨動(dòng)物尿糞排出體外,直接進(jìn)入水體,或者通過(guò)污水灌溉和糞便施肥等資源化利用途徑進(jìn)入土壤,隨地表徑流等方式進(jìn)入水環(huán)境[19-20]. 在檢出的10種抗生素中,有8種為主要的畜禽藥品,即SDI、SMX、SMZ、ERM、ROM、TYL、FF和LIN. LIN、FF在我國(guó)抗生素藥品中使用量排名居前五位,研究水域LIN和FF較高水平的質(zhì)量濃度和檢出率應(yīng)引起注意,并且LIN對(duì)厭氧菌和革蘭氏陽(yáng)性菌均有較強(qiáng)的抗菌能力和抑制作用[21],常規(guī)污水處理工藝很難降解;磺胺類藥物是應(yīng)用最早的人工合成抗菌藥物,磺胺類(SDI、SMX、SMZ)雖然檢出率不高,但其質(zhì)量濃度均較高,其中ρ(SDI)(90.7 ng/L)最高,豬糞上清液中磺胺類抗生素是其優(yōu)勢(shì)組分[22];大環(huán)內(nèi)酯類易水解或吸附在土壤中,對(duì)土壤的硝化作用、植物對(duì)營(yíng)養(yǎng)物質(zhì)的攝入等產(chǎn)生影響,破壞土壤生態(tài)平衡[23],雖然ERM(5.8 ng/L)、ROM(16.4 ng/L)、TYL(9.2 ng/L)檢出的最高質(zhì)量濃度均不高,但檢出率均在40%及以上.
表1 三峽庫(kù)區(qū)主要水域抗生素質(zhì)量濃度
注:ND表示低于檢出限(下同).
表2 三峽庫(kù)區(qū)主要水域抗生素的統(tǒng)計(jì)特征
2.2 抗生素分布特征
從圖2可見(jiàn),三峽庫(kù)區(qū)主要水域中抗生素平均質(zhì)量濃度由高到低依次為瀨溪河>碧溪河>瓊江>綦江河>長(zhǎng)江>嘉陵江>烏江,支流水體中抗生素質(zhì)量濃度(105.8~352.7 ng/L)明顯高于長(zhǎng)江、嘉陵江和烏江(6.4~83.8 ng/L),由于支流水體自凈能力遠(yuǎn)低于干流,水體中抗生素的殘留濃度受水文條件影響較顯著.
圖2 三峽庫(kù)區(qū)主要水域抗生素分布特征Fig.2 Distribution of the contamination of antibiotics in the main waters of the Three Gorges Reservoir area
按照河流分析,瀨溪河殘留抗生素質(zhì)量濃度(352.7 ng/L)明顯高于其他河流. 瀨溪河發(fā)源于重慶市大足區(qū),重慶境內(nèi)流經(jīng)大足區(qū)、榮昌區(qū),多年平均流量20.6 m3/s,流域涵蓋29個(gè)鎮(zhèn)街,服務(wù)人口131.56×104人,流域范圍內(nèi)規(guī)?;笄蒺B(yǎng)殖場(chǎng)498家,以豬、牛、雞養(yǎng)殖為主,2013年年末生豬出欄83×104頭,家禽584×104只,大牲畜8 496頭. 瀨溪河流域檢出的8種抗生素中,除OFX外均為畜禽用藥,ρ(LIN) 高達(dá)218 ng/L,水體受流域內(nèi)畜禽養(yǎng)殖影響顯著,應(yīng)引起重視. 按照檢出抗生素種類分析,瀨溪河最多,共檢出8種;其次為長(zhǎng)江、碧溪河、瓊江,均檢出7種;嘉陵江、綦江河檢出6種;烏江檢出最少,僅3種.
研究區(qū)域檢出抗生素存在較明顯的地域差異,SDI(ρmax=90.7 ng/L)僅在碧溪河檢出,SMZ(ρmax=38.1 ng/L)僅出現(xiàn)在長(zhǎng)江;OFX(ρmax=16.4 ng/L)僅在瀨溪河檢出;CAP、FF、LIN在7條河流均檢出,CAP(ρmax=3.4 ng/L)最大值出現(xiàn)在長(zhǎng)江,F(xiàn)F(ρmax=39.5 ng/L)最大值出現(xiàn)在碧溪河,LIN最大值出現(xiàn)在瀨溪河;ERM、ROM在除烏江外的其余6條河流均被檢出,其最大值(ERM:ρmax=21.4 ng/L. ROM:ρmax=39.7 ng/L)均出現(xiàn)在瀨溪河;TYL在長(zhǎng)江、嘉陵江、瀨溪河和瓊江均被檢出,TYL(ρmax=19.5 ng/L)出現(xiàn)在嘉陵江. 抗生素在水環(huán)境中的殘留受人類生產(chǎn)生活干擾顯著,瀨溪河(7號(hào)采樣點(diǎn))、碧溪河(11號(hào)采樣點(diǎn))、綦江河(16號(hào)采樣點(diǎn))、瓊江(29號(hào)采樣點(diǎn))等點(diǎn)位屬于源頭區(qū)域,人類活動(dòng)跡象不明顯,水體中均未有抗生素檢出[24].
2.3 不同區(qū)域地表水抗生素分布水平
目前,在水環(huán)境中已發(fā)現(xiàn)超過(guò)30種抗生素存在,抗生素在水環(huán)境中檢出質(zhì)量濃度的不同反映了不同區(qū)域抗生素使用的差異. 由表3可見(jiàn),三峽庫(kù)區(qū)檢出抗生素質(zhì)量濃度比其他水域略低,僅ρ(SDI)、ρ(ROM)、ρ(OFX)略高于長(zhǎng)江入江口[25-26]和黃浦江[27-28],低于黃河[29]、珠江[30-33]和深圳河[33]及其他國(guó)家檢出水體;ρ(SMX)、ρ(SMZ)、ρ(ERM)、ρ(FF)、ρ(CAP) 均不同程度地低于已有研究數(shù)據(jù)[34-39];ρ(LIN) 與意大利波河[36]相當(dāng). 總體來(lái)看,我國(guó)水環(huán)境中抗生素質(zhì)量濃度與國(guó)外相當(dāng),檢出質(zhì)量濃度多在幾到幾百ng/L;沿海水域檢出抗生素質(zhì)量濃度偏高,珠江中的ρ(SMZ)、ρ(ERM)、ρ(ROM)及深圳河中的ρ(ERM)均超過(guò)1 000 ng/L. 從抗生素檢出種類分析,三峽庫(kù)區(qū)水域中檢出抗生素以磺胺類和LIN為主,其次是氟喹諾酮類和大環(huán)內(nèi)酯類;長(zhǎng)江入江口除TYL、LIN未查到文獻(xiàn)檢出外,其余與三峽庫(kù)區(qū)水域中檢出抗生素保持一致,濃度水平相當(dāng);黃浦江檢出ρ(SMZ)偏高,最大值為623.3 g/L;珠江和深圳河抗生素污染較嚴(yán)重,檢出抗生素均保持較高質(zhì)量濃度. 國(guó)外其他水域中,越南湄公河ρ(SMZ)最高(19 153 g/L),其他檢出種類和最大濃度均低于我國(guó). 因此,抗生素在我國(guó)水環(huán)境中的殘留應(yīng)引起重視.
2.4 抗生素生態(tài)風(fēng)險(xiǎn)評(píng)價(jià)
環(huán)境中痕量污染物質(zhì)可以根據(jù)歐盟環(huán)境風(fēng)險(xiǎn)評(píng)價(jià)方法[31],以RQS(風(fēng)險(xiǎn)商值)評(píng)估其生態(tài)風(fēng)險(xiǎn):
RQS=PEC/PNEC
或
RQS=MEC/PNEC
式中:PEC為污染物環(huán)境預(yù)測(cè)質(zhì)量濃度,ng/L;MEC為污染物實(shí)際監(jiān)測(cè)質(zhì)量濃度,ng/L;PNEC為預(yù)測(cè)無(wú)效應(yīng)濃度,ng/L,通過(guò)從文獻(xiàn)中收集抗生素對(duì)一些物種的急性和慢性毒理數(shù)據(jù)求得,即用最敏感生物的毒性數(shù)據(jù)除以適當(dāng)?shù)脑u(píng)價(jià)因子即得到PNEC,有一項(xiàng)短期實(shí)驗(yàn)數(shù)據(jù)的(EC50)評(píng)價(jià)因子選 1 000,一項(xiàng)長(zhǎng)期實(shí)驗(yàn)數(shù)據(jù)的(NOEC)評(píng)價(jià)因子選100[42],見(jiàn)表4.
表3 不同區(qū)域水體中抗生素質(zhì)量濃度比較
注:—表示未檢測(cè).
表4 抗生素對(duì)應(yīng)最敏感物種的毒理數(shù)據(jù)
注:EC50為半最大效應(yīng)濃度;NOEC 為最大無(wú)效應(yīng)濃度.
基于影響最大考慮,RQS的計(jì)算采用篩選出最敏感物種的PNEC,并且以抗生素質(zhì)量濃度的最大值進(jìn)行計(jì)算[43].
按照Hernando等[45]提出的RQS分類方法表征生態(tài)風(fēng)險(xiǎn)的不同程度:RQS<0.1為低風(fēng)險(xiǎn);0.1≤RQS<1為中風(fēng)險(xiǎn);RQS≥1為高風(fēng)險(xiǎn). 目前調(diào)查及相關(guān)研究表明,多種藥品在水環(huán)境中會(huì)因共存而毒害作用加強(qiáng),根據(jù)國(guó)外參考文獻(xiàn),利用簡(jiǎn)單疊加模型[11]計(jì)算聯(lián)合毒性風(fēng)險(xiǎn)商(RQsum):
式中,RQi為化合物i的RQ值,n為目標(biāo)化合物的種類數(shù).
按河流分析,由表5和圖3可見(jiàn),7條河流抗生素表現(xiàn)出的RQsum由高到低依次為瀨溪河>瓊江>綦江>碧溪河>嘉陵江>長(zhǎng)江>烏江. 其中瀨溪河RQsum高達(dá)5.532,SMX、ERM和OFX這3種抗生素均為高風(fēng)險(xiǎn),說(shuō)明其對(duì)瀨溪河水體中相應(yīng)的水生生物表現(xiàn)出較高的毒性風(fēng)險(xiǎn);瓊江、綦江、碧溪河和嘉陵江的RQsum均處于1~2之間,表現(xiàn)出較高生態(tài)風(fēng)險(xiǎn),但4條河流檢出抗生素的單個(gè)RQS均小于1,部分處于低風(fēng)險(xiǎn);長(zhǎng)江的RQsum為0.605,檢出抗生素中TYL、ERM和ROM處于中風(fēng)險(xiǎn),其余為低風(fēng)險(xiǎn);烏江的RQsum為0.013,檢出抗生素均處于低風(fēng)險(xiǎn),說(shuō)明水體受人類活動(dòng)干擾最小.
表5 三峽庫(kù)區(qū)主要水域抗生素風(fēng)險(xiǎn)評(píng)估商值
圖3 三峽庫(kù)區(qū)主要水域抗生素聯(lián)合生態(tài)風(fēng)險(xiǎn)Fig.3 RQsum for the antibiotics in the main waters of the Three Gorges Reservoir area
按檢出抗生素種類分析,由圖4可見(jiàn),F(xiàn)F、CAP和磺胺類SMZ的RQS均小于0.1,但FF、CAP在7條河流中均有檢出,說(shuō)明這2種抗生素在三峽庫(kù)區(qū)使用廣泛,但其表現(xiàn)出的生態(tài)風(fēng)險(xiǎn)還不顯著;SDI、TYL、ERM、ROM和LIN表現(xiàn)為中等風(fēng)險(xiǎn)水平,并且ERM和ROM在除烏江外的水體中均有檢出,ERM的RQS最大值處于高風(fēng)險(xiǎn)水平,這5種抗生素對(duì)生態(tài)的潛在影響應(yīng)引起重視;SMX和OFX表現(xiàn)出較高的急性和慢性毒性風(fēng)險(xiǎn),應(yīng)進(jìn)一步加強(qiáng)監(jiān)管,規(guī)范瀨溪河、瓊江、綦江、碧溪河等流域內(nèi)畜禽養(yǎng)殖抗生素的使用,研究經(jīng)處理后的畜禽糞便、堆肥以及以畜禽糞便為主要原料制成的各種肥料在農(nóng)田中使用時(shí)抗生素所含限值,編制相關(guān)畜禽糞污中抗生素還田技術(shù)規(guī)范.
圖4 三峽庫(kù)區(qū)主要水域抗生素風(fēng)險(xiǎn)商值Fig.4 RQS for the antibiotics in the main waters of the Three Gorges Reservoir area
a) 分析三峽庫(kù)區(qū)長(zhǎng)江干流和主要支流表層水體中6類28種抗生素的質(zhì)量濃度特征,共檢出4類10種,包括磺胺類的SDI、SMX、SMZ;大環(huán)內(nèi)酯類的ERM、ROM、TYL;氟喹諾酮類的OFX;其他類的CAP、FF、LIN. 其中,除OFX和CAP外,其余8種均為畜禽藥品,并且FF、LIN在我國(guó)畜禽藥品中使用量排名前五位.
b) 三峽庫(kù)區(qū)主要水域中抗生素平均質(zhì)量濃度由高到低依次為瀨溪河>碧溪河>瓊江>綦江河>長(zhǎng)江>嘉陵江>烏江,支流水體中抗生素質(zhì)量濃度(105.8~352.7 ng/L)高于長(zhǎng)江、嘉陵江和烏江(6.4~83.8 ng/L).
c) 三峽庫(kù)區(qū)檢出抗生素質(zhì)量濃度比其他水域略低,ρ(SDI)、ρ(ROM)、ρ(OFX)略高于長(zhǎng)江入江口和黃浦江,低于黃河、珠江和深圳河及其他國(guó)家檢出水域;ρ(SMX)、ρ(SMZ)、ρ(ERM)、ρ(FF)、ρ(CAP)均不同程度低于其他有檢出數(shù)據(jù)的水域;ρ(LIN)與意大利波河相當(dāng).
d) 7條河流抗生素表現(xiàn)出的RQsum由高到低依次為瀨溪河>瓊江>綦江>碧溪河>嘉陵江>長(zhǎng)江>烏江,SMX和OFX在瀨溪河、瓊江、綦江、碧溪河均表現(xiàn)出較高的急性或慢性毒性風(fēng)險(xiǎn). 三峽庫(kù)區(qū)應(yīng)進(jìn)一步加強(qiáng)抗生素的使用監(jiān)管,特別是畜禽養(yǎng)殖行業(yè),應(yīng)開(kāi)展畜禽糞污還田技術(shù)規(guī)范中抗生素含量限制的相關(guān)研究.
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Distribution of Typical Antibiotics and Ecological Risk Assessment in Main Waters of Three Gorges Reservoir Area
FENG Li1,2, CHENG Yanru1, FENG Lei3, ZHANG Sheng1*, LIU Yiqi1
1.Chongqing Environmental Sciences Research Institute, Chongqing Collaborative Innovation Center of Big Data Application in Eco-Environmental Remote Sensing, Chongqing 401147, China 2.College of Materials Science and Engineering, Chongqing University, Chongqing 400044, China 3.Chongqing Institute of Green and Intelligent Technology, Chinese Academy of Sciences, Online Monitoring Center of Ecological and Environmental of the Three Gorges Project, Chongqing 400714, China
2016-11-23
2017-03-16
重慶市基礎(chǔ)科研項(xiàng)目(2015cstc-jbky-01607)
封麗(1983-),女,重慶涪陵人,高級(jí)工程師,碩士,主要從事區(qū)域水體污染防治研究,17495028@qq.com.
*責(zé)任作者,張晟(1971-),男,重慶江津人,研究員,博士,主要從事污染生態(tài)學(xué)研究,shengzsts@126.com
X524
1001- 6929(2017)07- 1031- 10
A
10.13198/j.issn.1001- 6929.2017.02.33
封麗,程艷茹,封雷,等.三峽庫(kù)區(qū)主要水域典型抗生素分布及生態(tài)風(fēng)險(xiǎn)評(píng)估[J].環(huán)境科學(xué)研究,2017,30(7):1031- 1040.
FENG Li,CHENG Yanru,FENG Lei,etal.Distribution of typical antibiotics and ecological risk assessment in main waters of Three Gorges Reservoir area[J].Research of Environmental Sciences,2017,30(7):1031- 1040.