白洋淀喹諾酮類抗生素在底棲動物中的生物富集特征

付 雨,劇澤佳,陳 慧,趙鑫宇,宋圓夢,王廣志,張璐璐,2*,崔建升,2

白洋淀喹諾酮類抗生素在底棲動物中的生物富集特征

付 雨1,劇澤佳1,陳 慧1,趙鑫宇1,宋圓夢1,王廣志1,張璐璐1,2*,崔建升1,2

(1.河北科技大學(xué)環(huán)境科學(xué)與工程學(xué)院,河北 石家莊 050000；2.河北省污染防治生物技術(shù)實驗室,河北 石家莊 050000)

利用超高效液相色譜串聯(lián)質(zhì)譜法(HPLC-MS)對白洋淀水體、沉積物以及7種底棲動物中喹諾酮類抗生素(QNs)進(jìn)行檢測,并探究QNs在底棲動物中的生物富集特征及其與環(huán)境因子的相關(guān)性.結(jié)果表明:在白洋淀水體中,ΣQNs濃度為0.7380～2004ng/L,其中氟甲喹(FLU)平均濃度最高(168.0ng/L),而在底棲動物中,氧氟沙星(OFL)和諾氟沙星(NOR)的檢出率最高(Freq=100%),其次為FLU和恩諾沙星(ENR)(Freq350%),其余QNs檢出率小于40%(Freq￡40%),底棲動物中ΣQNs濃度為23.70～289.4ng/g,其中FLU(29.43ng/g)和環(huán)丙沙星CIP(40.38ng/g)平均濃度最高;QNs在底棲動物中的生物富集系數(shù)(BCF)為219.6(BCFMAR)～1754L/kg(BCFENR),這表明QNs在底棲動物中的生物富集能力較高;檢出率較高的OFL、恩諾沙星(ENR)和NOR的營養(yǎng)放大因子(TMF)為0.1299(TMFFLU)～6.426(TMFENR),其中NOR、ENR呈營養(yǎng)放大,而FLU、OFL呈營養(yǎng)稀釋;相關(guān)性分析結(jié)果表明ENR、CIP、FLU和ORB的BCF與水深(WD)、溫度()、透明度(SD)、溶解氧(DO)和沉積物總有機(jī)碳(TOCs)呈顯著正相關(guān),而與化學(xué)需氧量(COD)、總磷(TP)、總氮(TN)、NO3--N、PO43-、沉積物總碳(TCs)、沉積物總氮(TNs)和NH3-Ns呈顯著負(fù)相關(guān);TMFOFL與WD、、SD、DO和TOCs呈顯著負(fù)相關(guān),與COD、TP、TN、NO3--N、PO43-、TCs、TNs和NH3-Ns呈顯著正相關(guān).這表明生活污水和養(yǎng)殖廢水對QNs的貢獻(xiàn)最大.

白洋淀；喹諾酮類抗生素(QNs)；優(yōu)勢底棲動物；生物富集；空間分異；環(huán)境因子

中國是世界上最大的抗生素生產(chǎn)和使用國[1].據(jù)估計,我國抗生素年使用量超過1.6×105t[2],抗生素因其分子較大,不能被機(jī)體完全吸收,約90%以母體化合物或代謝產(chǎn)物的形式隨糞便或尿液排出體外[3-4],最終進(jìn)入水環(huán)境[5].常見的抗生素包括β類酰胺類、喹酮類、大環(huán)內(nèi)酯類、四環(huán)素類和磺胺類等.其中,喹諾酮類(QNs)藥物[6-7]屬于廣譜抗生素,可有效預(yù)防和治療多種傳染病,在水產(chǎn)養(yǎng)殖領(lǐng)域中被廣泛應(yīng)用,在湖泊中含量更高.它可破壞水生環(huán)境中的微生物群落,引起抗菌基因的產(chǎn)生,同時干擾水體生態(tài)系統(tǒng)的物質(zhì)循環(huán)與能量流動,打破原有生態(tài)系統(tǒng)的平衡[8-10],被水生生物吸收的抗生素還可發(fā)生生物富集和營養(yǎng)放大[11-12],進(jìn)而對人類和動物健康以及生態(tài)環(huán)境造成極大的威脅.

QNs的生物降解率較低,在地表水[12-15]、地下水[16-17]、飲用水[18-19]和海洋[20]中廣泛檢出.有研究表明,QNs易富集于水生生物中[21-23],黃河[24]周邊海域中QNs在蝦和蟹體內(nèi)具有生物累積作用,累積系數(shù)為46～766L/kg和35～2261L/kg.Bai等[25]的研究結(jié)果表明,恩諾沙星和環(huán)丙沙星在遼河海域亞洲海岸蟹中的生物富集系數(shù)分別為11192和150L/kg.北部灣水生生物體內(nèi)依諾沙星、諾氟沙星、氧氟沙星和恩諾沙星的生物富集系數(shù)為83.18,57.54,66.07和67.61L/kg.海陵島[27]周邊海域環(huán)丙沙星和恩諾沙星在蝦體內(nèi)的生物富集系數(shù)為23,650L/kg[26].不同水環(huán)境中抗生素污染情況不同,不同底棲動物對抗生素的生物富集和傳遞作用也存在顯著差異.然而此前的研究多集中于抗生素在生物體內(nèi)的生物富集和營養(yǎng)傳遞行為,對抗生素生物富集和營養(yǎng)傳遞行為與環(huán)境因子的相關(guān)性研究較為缺乏.

白洋淀是華北平原最大的淺水草型湖泊,底棲動物群落是水生食物鏈的重要組成部分,對于維持水生態(tài)系統(tǒng)的健康具有重要意義.然而,白洋淀長期遭受保定市城市污水、養(yǎng)殖廢水以及周邊居民生活污水排放的影響,與其它湖泊相比,白洋淀抗生素污染水平相對較高[22,28-29].如:白洋淀水體和沉積物中QNs濃度分別為0.7400～2004ng/L和0.5100～ 1540ng/g,且QNs在水生生物體內(nèi)也被檢出[22,28,30-31].研究表明,白洋淀環(huán)境因子和QNs呈顯著空間差異性[28,32],且生物體內(nèi)抗生素的濃度與環(huán)境因子密切相關(guān)[33].因此,為了明晰典型抗生素在底棲動物中的生物累積和營養(yǎng)傳遞行為及其主要環(huán)境影響因子,本文以白洋淀為研究區(qū),選取QNs為典型抗生素,分析優(yōu)勢底棲動物中QNs濃度,探討QNs在優(yōu)勢底棲動物中的生物富集特征和營養(yǎng)傳遞行為,建立優(yōu)勢底棲動物中QNs與環(huán)境因子的相關(guān)性,以期為白洋淀生態(tài)修復(fù)和風(fēng)險管控提供理論參考和數(shù)據(jù)支撐.

1 材料與方法

1.1 樣品采集

2018年4月和8月,在白洋淀8個研究區(qū)25個采樣點(圖1)采集了水體、沉積物和底棲動物樣品.依據(jù)白洋淀水體理化特征,采樣點共分為3個生境,生境1(I、II)主要受上游保定市城市污水影響,生境2(V、VIII)主要受當(dāng)?shù)厮a(chǎn)養(yǎng)殖廢水和生活污水影響,生境3(III、VI、VII)受人類活動干擾較小.每個采樣點采集4L表層水,做好標(biāo)記,保存于冷藏箱中,運回實驗室于-20℃冰柜內(nèi)儲存待用[29];在各個采樣點使用干凈的不銹鋼鏟采集足量的沉積物樣品,并裝袋標(biāo)記,24h內(nèi)運送至實驗室,在-20℃的黑暗中冷凍保存,待實驗[33];共采集10種優(yōu)勢底棲動物,包括中國圓田螺()、梨形環(huán)棱螺()、中華圓田螺()、扁蛭()、中華米蝦()、日本沼蝦()、蘿卜螺()、克氏螯蝦()、中華絨毛蟹()、馬大頭();每種底棲動物樣品不少于8只,共采集80只,兩批次樣品混合后進(jìn)行測定分析;水樣進(jìn)行理化分析(水深(WD)、水溫()、pH值、溶解氧(DO)、透明度(SD)、化學(xué)需氧量(COD)、總磷(TP)、總氮(TN)、氨氮(NH4+-N)、硝氮(NO3--N)和PO43-等).

圖1 白洋淀采樣點示意

1.2 QNs測定

1.2.1 底棲動物樣品前處理 底棲動物樣品采樣時間分別為2018年4月(春季)、2018年8月(夏季).底棲動物取樣采用1/16m2彼得森采泥器,在各采樣點采集底泥2份,均勻混合,取其中一半當(dāng)場用60目尼龍篩清洗后倒入樣品瓶,瓶中加入質(zhì)量分?jǐn)?shù)為10%的甲醛溶液后密封保存,泥樣帶回實驗室后用60目尼龍篩再次清洗,剩余物倒入解剖盤中,用鑷子將動物活體逐一撿出,放入盛有質(zhì)量分?jǐn)?shù)為80%無水乙醇的離心管中,離心速率為1500r/min,時間為5min,隨后在顯微鏡中進(jìn)行鑒定、計數(shù),并用濾紙擦拭干凈后在萬分之一的天平上稱重,最終結(jié)果換算單位面積的生物量(g/m2)[34].

1.2.2 質(zhì)量控制采用外標(biāo)法定量QNs.以甲醇水(:=1:1)逐級稀釋儲備液(1μg/mL)制備0.1,0.5,1.0, 5.0,10.0,100.0ng/mL6個系列標(biāo)準(zhǔn)溶液,經(jīng)HPLC- MS分析獲得質(zhì)量濃度與峰面積的標(biāo)準(zhǔn)曲線,相關(guān)系數(shù)均大于或等于0.99,各樣品中QNs抗生素的回收率為72.8%～105.6%.

1.3 QNs在底棲動物中的富集與傳遞

底棲動物對QNs的累積效應(yīng)用生物富集系數(shù)(BCF)表征[35],計算公式見式(1).

式中:底棲為底棲動物體內(nèi)QNs含量,ng/g;水為水體中QNs的質(zhì)量濃度,ng/L.

QNs在底棲動物中的營養(yǎng)傳遞水平用營養(yǎng)放大因子(TMF)表征,計算公式如下:

式中:TL為底棲動物的營養(yǎng)級;為軸的截距;為斜率.

底棲動物的營養(yǎng)級由文獻(xiàn)[36]計算:

式中:15N底棲為底棲動物的同位素值;15N基準(zhǔn)為基準(zhǔn)生物(中國圓田螺)的平均同位素值,其值選擇之前研究[37]中的數(shù)值(10.36‰(生境1)、9.43‰(生境2)和8.74‰(生境3))計算;2.98是每個營養(yǎng)級水平的預(yù)期15N值[38];2是基線生物(中國圓田螺)的理論營養(yǎng)級水平[39-40].白洋淀底棲動物同位素15N分析和結(jié)果詳見文獻(xiàn)[37].

1.4 數(shù)據(jù)統(tǒng)計與分析

采用Origin 2018軟件進(jìn)行理化參數(shù)、抗生素濃度分布以及底棲動物生物量分布制圖;BCF和TMF與環(huán)境因子和生物量間的相關(guān)性采用SPSS 24.0軟件和Canoco 5進(jìn)行相關(guān)分析;各采樣點分布利用ArcGIS 10.6軟件進(jìn)行繪圖;利用Gephy繪制網(wǎng)絡(luò)相關(guān)分析圖.

2 結(jié)果與分析

2.1 白洋淀優(yōu)勢底棲動物空間分異特征

底棲動物最大生物量出現(xiàn)在生境3(1237g/m2),最小值出現(xiàn)在生境1 (337.4g/m2)(圖2).中國圓田螺的生物量較高(250.5g/m2),而馬大頭的生物量較低(3.400g/m2);中國圓田螺的生物量在生境3較高(394.2g/m2),在生境1較低(28.00g/m2).中國圓田螺、梨形環(huán)棱螺、中華圓田螺、克氏螯蝦和中華米蝦在3個生境均有檢出,中華絨毛蟹、扁蛭、日本沼蝦和蘿卜螺的檢出為66.70%.而馬大頭的檢出率最低(33.30%)最低.生境3底棲動物出現(xiàn)頻率較高(100%),在生境3,中國圓田螺的生物量占比最高(33.20%);結(jié)果表明,白洋淀底棲動物的生物量和分布呈現(xiàn)顯著的空間差異.

圖2 白洋淀優(yōu)勢底棲動物的時空分異特征

2.2 白洋淀優(yōu)勢底棲動物的QNs濃度

選取白洋淀底棲動物中抗生素含量較高的5種,共檢出10種QNs,包括環(huán)丙沙星(CIP),依諾沙星(ENO),恩諾沙星(ENR),氟羅沙星(FLE),氟甲喹(FLU),馬波沙星(MAR),諾氟沙星(NOR),氧氟沙星(OFL),奧比沙星(ORB),吡哌酸(PIP),其中NOR和OFL檢出率最高(100%),其次為FLU和ENR(350%), QNs平均濃度為2.990 (ENO)～40.38(CIP)ng/g(圖3).底棲動物中ΣQNs濃度為23.70～289.4ng/g.其中,中國圓田螺在生境1中ΣQNs平均濃度最高(34.34ng/g),扁蛭在生境3中ΣQNs平均濃度最低(4.450ng/g).CIP(40.38ng/g)和FLU(29.43ng/g)在底棲動物體內(nèi)的平均濃度高于其它QNs(<25.00ng/g);除CIP、ENO和ENR外,其余QNs均呈現(xiàn)生境1>生境2>生境3,與水體中QNs濃度空間分布一致.

圖3 底棲動物中QNs含量特征

空白部分表示未檢出

如圖4所示,背角無齒蚌和扁蛭中QNs檢出種類較多(>6種),其中背角無齒蚌檢出種類為10種.底棲動物中FLU平均相對豐度最高(36%),其最高豐度(49%)在生境3的梨形環(huán)棱螺中,最低豐度(18%)在生境1的背角無齒蚌中;其次為OFL(31.20%),其最高豐度(72%)在生境2的中華圓田螺中,最低豐度(7%)在生境3的背角無齒蚌中;PIP的相對豐度最小.結(jié)果表明,白洋淀底棲動物中QNs豐度呈現(xiàn)顯著空間差異,與水體中QNs質(zhì)量濃度基本一致,表明底棲動物中與其生活的水環(huán)境中QNs濃度特征具有一定相似性.

2.3 白洋淀QNs在優(yōu)勢底棲動物中的BCF和TMF

如圖5所示,背角無齒蚌的BCF平均值最高(325.2L/kg),中華圓田螺的BCF平均值最低(81.90L/ kg);除了梨形環(huán)棱螺和扁蛭外,其余底棲動物體內(nèi)QNs的BCF在生境3值最大,梨形環(huán)棱螺和扁蛭體內(nèi)QNs的BCF在生境2值最大.

由表1可知,BCFENR平均值最高(1639L/kg), BCFMAR的平均值最低(240.7L/kg);BCF在生境1的范圍為228.3L/kg(BCFMAR)～1569L/kg(BCFENR),生境2為219.6L/kg(BCFMAR)～1593L/kg(BCFENR),生境3為274.3L/kg(BCFMAR)～1754L/kg(BCFENR).結(jié)果表明,白洋淀優(yōu)勢底棲動物中QNs的BCF呈現(xiàn)顯著的空間差異.

圖5 優(yōu)勢底棲動物QNs的BCF

表1 白洋淀3個生境中優(yōu)勢底棲動物中QNs的BCF(L/kg)

方差分析結(jié)果表明,水生植物15N穩(wěn)定同位素在不同生境存在差異性(表2),生境1(10.36‰(中國圓田螺)～11.45‰(扁蛭))和生境2(9.430‰(中國圓田螺)～10.93‰(扁蛭))的15N高于生境3(8.740‰(中國圓田螺)～10.14‰(扁蛭)).就底棲動物種類而言,中國圓田螺的15N值最低(8.740‰),扁蛭的最高(11.45‰).3個生境中各底棲動物營養(yǎng)級(TL)為2.000～2.500;扁蛭的營養(yǎng)級最高(2.500),為2.370(生境1)～2.500(生境2);中國圓田螺的營養(yǎng)級最低(2.000);底棲動物營養(yǎng)級的空間分布特征為:生境3(2.000～2.470)>生境2(2.000～2.500)>生境1(2.000～ 2.370).結(jié)果表明,白洋淀同種底棲動物的營養(yǎng)級存在顯著的空間差異.

在本研究中,優(yōu)勢底棲動物中QNs的濃度和檢出率均呈現(xiàn)較大差異.因此,為了計算TMF數(shù)據(jù)的準(zhǔn)確性,選擇檢出率>50%的QNs(ENR、NOR、FLU和OFL)來計算優(yōu)勢底棲動物的TMF值(圖6),3個生境中QNs的TMF為0.1299(TMFFLU,生境3)～6.4261 (TMFENR,生境1).OFL和ENR的TMF值都是在生境1最大,其值分別為0.7648、6.4261;而TMFOFL呈現(xiàn)生境1>生境2>生境3的趨勢,其值分別為0.7648、0.7470和0.1326;而TMFFLU和TMFNOR呈現(xiàn)生境2>生境1>生境3的趨勢;就QNs種類而言,TMF呈現(xiàn)出TMFENR>TMFNOR> TMFOFL>TMFFLU的趨勢,其中TMFENR為1.3290～ 6.4261,TMFNOR為0.8028～1.0576,TMFOFL為0.1326～ 0.7648,TMFFLU為0.1299～0.1704.

表2 白洋淀底棲動物δ15N穩(wěn)定同位素和營養(yǎng)級(TL)空間差異

圖6 3個生境中底棲動物中QNs含量對數(shù)與TL的關(guān)系

1、2和3分別為生境1、生境2和生境3中對應(yīng)的公式(2)中的值;TMF1、TMF2和TMF3分別為生境1、生境2和生境3中魚類的TMF

2.4 白洋淀QNs的BCF和TMF與環(huán)境因子的相關(guān)性

圖7 環(huán)境因子與抗生素BCF和TMF相關(guān)性網(wǎng)絡(luò)

節(jié)點根據(jù)相關(guān)性進(jìn)行著色,連接表示顯著(<0.05)和極顯著(<0.01)相關(guān),根據(jù)連接數(shù)加權(quán)節(jié)點大小

由圖7和表3可知,部分QNs的BCF(如CIP、ENR、FLU和ORB)與WD、、SD、DO和TOCs在<0.01水平呈顯著正相關(guān),相關(guān)性系數(shù)為1.000**,其中,BCFORB和BCFPIP與其他因子相關(guān)性最高;而與COD、TP、TN、NO3--N、PO43-、沉積物總碳(TCs)、沉積物總氮(TNs)和NH3-Ns在<0.01水平呈顯著負(fù)相關(guān),相關(guān)性系數(shù)為1.000**;BCFFLE和BCFPIP與WD、、SD、DO、TOCs在<0.01水平呈顯著負(fù)相關(guān),相關(guān)性系數(shù)為1.000**;而與COD、TP、TN、NO3--N、PO43-、TNs、NH3-Ns在<0.01水平呈顯著正相關(guān),相關(guān)性系數(shù)為1.000** (表3);主成分分析結(jié)果顯示(圖8),和SD是底棲動物中QNs生物富集因子的主要影響因子,結(jié)果表明城市廢水以及生活污水和養(yǎng)殖廢水是底棲動物中QNs的主要來源,因此未來需要對白洋淀區(qū)域中城市廢水以及生活污水和養(yǎng)殖廢水的抗生素排放加強管理.TMFOFL與其他因子相關(guān)性最強(圖7),TMFOFL與WD、、SD、DO和TOCs在<0.01水平呈顯著負(fù)相關(guān),相關(guān)性系數(shù)為1.000**;而與COD、TP、TN、NO3--N、PO43-、TCs、TNs和NH3-Ns在<0.01水平呈顯著正相關(guān),相關(guān)性系數(shù)為1.000**;TMFENR與pH值在<0.01水平呈顯著正相關(guān),相關(guān)性系數(shù)為1.000**;TMFFLU關(guān)與NO3--Ns在<0.01水平呈顯著正相關(guān),相關(guān)性系數(shù)為1.000**.

表3 環(huán)境因子與QNs的BCF/TMF的Spearman相關(guān)性

注:*表示<0.05水平顯著相關(guān);**表示<0.01水平顯著相關(guān).

圖8 環(huán)境因子與QNs的BCF和TMF間的PCA分析

2.5 白洋淀QNs的BCF和TMF與底棲動物生物量的相關(guān)性

圖9 底棲動物生物量與抗生素BCF和TMF相關(guān)性網(wǎng)絡(luò)

節(jié)點根據(jù)相關(guān)性進(jìn)行著色,連接表示顯著(<0.05)和極顯著(<0.01)相關(guān),根據(jù)連接數(shù)加權(quán)節(jié)點大小

由圖9和表4可知,BCF和TMF與底棲動物生物量存在相關(guān)性(相關(guān)性為-1.000**～1.000**).結(jié)果表明,底棲動物生物量與TMF呈顯著相關(guān), TMFOFL與其他物質(zhì)相關(guān)性最高,其中中國圓田螺和中華圓田螺的生物量與TMFOFL在<0.01水平呈顯著負(fù)相關(guān),相關(guān)性系數(shù)為1.000**;克氏螯蝦和中華絨毛蟹的生物量與TMFOFL在<0.01水平呈顯著正相關(guān),相關(guān)性系數(shù)為1.000**;梨形環(huán)棱螺的生物量與TMFNOR在<0.01水平呈顯著負(fù)相關(guān),相關(guān)性系數(shù)為1.000**;對于生物富集系數(shù)而言, BCFPIP與其他物質(zhì)相關(guān)性最強,中國圓田螺和中華圓田螺的生物量與BCFCIP、BCFENR、BCFFLU、BCFORB在<0.01水平呈顯著正相關(guān),相關(guān)性系數(shù)為1.000**,與BCFPIP和BCFFLE在<0.01水平呈顯著負(fù)相關(guān),相關(guān)性系數(shù)為1.000**;克氏螯蝦和中華絨毛蟹的生物量BCFCIP、BCFENR、BCFFLU、BCFORB在<0.01水平呈顯著負(fù)相關(guān),相關(guān)性系數(shù)為1.000**,與BCFPIP和BCFFLE在<0.01水平呈顯著正相關(guān),相關(guān)性系數(shù)為1.000**;中華米蝦的生物量與BCFENO、BCFMAR在<0.01水平呈顯著負(fù)相關(guān),相關(guān)性系數(shù)為1.000**.這可能與高濃度抗生素對底棲動物脅迫有關(guān)[40].

表4 底棲動物生物量與QNs的BCF/TMF的Spearman相關(guān)性

注:*表示<0.05水平顯著相關(guān);**表示<0.01水平顯著相關(guān).

3 討論

3.1 白洋淀與國內(nèi)其它湖泊沉積物以及底棲動物中QNs含量比較

將氧氟沙星、環(huán)丙沙星、以及恩諾沙星與典型河流沉積物中含量進(jìn)行對比.結(jié)果發(fā)現(xiàn),白洋淀沉積物中氧氟沙星(10.91ng/g)的平均含量高于黃浦江(4.100ng/g)[41]、中國渤海(1.500ng/g)[42]和膠州灣(2.700ng/g)[43],稍高于中國太湖(9.900ng/g)[44];但是其最高含量可達(dá)92.83ng/g,遠(yuǎn)高于黃浦江(12.40ng/g)和太湖(28.40ng/g)沉積物中氧氟沙星含量;環(huán)丙沙星(6.870ng/g)平均含量高于中國渤海(4.400ng/g)和膠州灣(1.410ng/g),遠(yuǎn)高于大亞灣(0.1500ng/g)和海陵島(0.4500ng/g)[45],稍低于太湖(9.800ng/g),但遠(yuǎn)低于北意大利波湖(26.15ng/g)[46];恩諾沙星(4.260ng/g)平均含量遠(yuǎn)高于膠州灣(0.1800ng/g),稍高于渤海(2.000ng/g)和黃浦江(3.200ng/g),最高含量(5.530ng/ g)稍低于渤海(5.700ng/g)和黃浦江(8.900ng/g),高于膠州灣(1.970ng/g)和長江口(4.800ng/g).比較發(fā)現(xiàn)白洋淀沉積物中喹諾酮類抗生素污染處于較高水平,應(yīng)引起重視,加強白洋淀入淀水質(zhì)、生活污水集中處理以及對畜禽養(yǎng)殖業(yè)的管控.

底棲動物中FLU濃度為11.50～51.10ng/g、OFL濃度為3.700～46.60ng/g和NOR濃度為2.460～ 10.50ng/g.與之前白洋淀的研究相比,本研究中底棲動物的QNs濃度低于Li等[22]的研究結(jié)果(17.80～ 167.0ng/g),也低于遼河流域[25]底棲動物中QNs的研究結(jié)果(770.1ng/g).這可能一方面是因為白洋淀水環(huán)境中抗生素濃度降低,進(jìn)而底棲動物吸收到體內(nèi)的濃度降低[25-26,28];另一方面可能是由于近幾年白洋淀水環(huán)境質(zhì)量好轉(zhuǎn),底棲動物生物量顯著增加[47-49],進(jìn)而產(chǎn)生了生物量稀釋效應(yīng).

3.2 QNs的生物累積特征及其與環(huán)境因子的相關(guān)性

白洋淀3個生境中底棲動物中10種QNs的BCF為219.6L/kg(BCFMAR,生境2)～1754L/kg (BCFENR,生境3),表明QNs在底棲動物的生物富集相對較高[38].BCFENR、BCFNOR、BCFOFL、BCFCIP、BCFENO、BCFFLU、BCFORB、BCFFLE、BCFPIP、BCFMAR的平均值分別為1639,1193,1111,838.5,622.0,523.3, 508.8,467.6,395.3和240.8L/kg,低于白洋淀之前底棲動物QNs的研究(219.0～1990L/kg(BCFCIP)、1720～ 3120L/kg(BCFENR)、246.0～2000L/kg(BCFFLE)、267.0～1400L/kg(BCFOFL))[22];明顯低于之前底棲動物體內(nèi)QNs的研究(4.200～462.4L/kg(BCFNOR)、0.5800～394.0L/kg(BCFCIP)、52.10～2542L/kg (BCFENR)、67.30～3040L/kg(BCFOFL)和4.560～ 587.0L/kg(BCFENO));本研究中的TMFOFL(0.1326～ 0.7648)高于之前的白洋淀[22](0.3800～0.5200)和太湖[23]研究中的值(0.4500～0.5200);環(huán)境因子對抗生素的歸趨和殘留起著重要的作用[50-51],這種現(xiàn)象可能是環(huán)境因子在不同地區(qū)的時空差異所導(dǎo)致[23,52].

TMFs/BCFs與理化因子的相關(guān)性網(wǎng)絡(luò)和spearman秩相關(guān)分析結(jié)果顯示,大多數(shù)理化因子都與TMFs/BCFs顯著相關(guān),主要影響因子為和SD;白洋淀之前的研究結(jié)果顯示,TOC、和SD是影響底棲動物的春季主要影響因子,水體溫度是底棲生物生長發(fā)育的重要因素,適宜的溫度對于底棲動物的生存發(fā)展具有促進(jìn)作用[53-54],而溫度及pH值的變化也會改變抗生素在沉積物中的吸附條件,從而解吸到水體中被底棲動物吸收[55-57];也有研究表明,抗生素在水體中存在狀態(tài)也受環(huán)境因子的影響(pH值、、鹽度、SD),環(huán)境因子的改變會使抗生素降解為離子態(tài)存在于水體中[53,58-60],降低水體中抗生素的濃度以及水生生物吸收到體內(nèi)的抗生素,進(jìn)而影響抗生素在水生生物體內(nèi)的生物富集與營養(yǎng)傳遞.

4 結(jié)論

4.1 白洋淀優(yōu)勢底棲動物中QNs存在空間差異,且不同底棲動物中QNs的濃度也存在差異.

4.2 底棲動物對QNs的生物富集系數(shù)在生境3最高,其次為生境2和生境1;其中,ENR和NOR呈營養(yǎng)放大,FLU和OFL呈營養(yǎng)稀釋.

4.3 多數(shù)水體和沉積物理化參數(shù)與QNs在底棲動物中的生物富集和傳遞行為顯著相關(guān),尤其是SD和.

4.4 白洋淀底棲動物生物量與QNs的BCF和TMF呈顯著負(fù)相關(guān),會產(chǎn)生生物量稀釋效應(yīng).

[1] Zhang Q Q, Ying G G, Pan C G, et al. Comprehensive evaluation of antibiotics emission and fate in the river basins of China: Source analysis, multimedia modeling, and linkage to bacterial resistance [J]. Environmental Science & Technology, 2015,49(11):6772-6782.

[2] Zhou L J, Ying G G, Zhao J L, et al. Trends in the occurrence of human and veterinary antibiotics in the sediments of the Yellow River, Hai River and Liao River in northern China [J]. Environmental Pollution, 2011,159(7):1877-1885.

[3] Carvalho I T, Santos L. Antibiotics in the aquatic environments: A review of the European scenario [J]. Environment International, 2016,94:736-757.

[4] Yang S F, Lin C F, Lin Y C, et al. Sorption and biodegradation of sulfonamide antibiotics by activated sludge: Experimental assessment using batch data obtained under aerobic conditions [J]. Water Research, 2011,45(11):3389-3397.

[5] Zhang L L, Qin S, Shen L N, et al. Bioaccumulation, trophic transfer, and human health risk of quinolones antibiotics in the benthic food web from a macrophyte-dominated shallow lake, North China [J]. Science of the Total Environment, 2020,712:136557.

[6] 劉家尊.氟喹諾酮類藥物的臨床用藥及不良反應(yīng)分析[J]. 中國實用醫(yī)藥, 2019,14(7):125-126.

Liu J Z. Analysis of clinical medication and adverse reactions of fluoroquinolones[J]. Chinese Practical Medicine, 2019,14(7):125-126.

[7] Rossi R, Saluti G, Moretti S, et al. Multiclass methods for the analysis of antibiotic residues in milk by liquid chromatography coupled to mass spectrometry: A review [J]. Food Additives & Contaminants Part A, 2017,35(2):241-257.

[8] Shen L N, Zhang L L, Qin S, et al. The correlation between quinolone antibiotics and microbial community structure and diversity in Baiyangdian Lake [J]. Acta Scientiae Circumstantiae, 2020,40(2):574- 584.

[9] 申立娜,張璐璐,秦 珊,等.白洋淀喹諾酮類抗生素與微生物群落結(jié)構(gòu)和多樣性相關(guān)性研究[J]. 環(huán)境科學(xué)學(xué)報, 2020,40(2):574-584.

Shen L N, Zhang L L, Qin S, et al. The correlation between quinolone antibiotics and microbial community structure and diversity in Baiyangdian Lake [J]. Journal of Environmental Science, 2020,40(2): 574-584.

[10] Wang Z, Han M, Li E, et al. Distribution of antibiotic resistance genes in an agriculturally disturbed lake in China: Their links with microbial communities, antibiotics, and water quality [J]. Journal of Hazardous Materials, 2020,393:122426.

[11] Zhou L J, Wang W X, Lv Y J, et al. Tissue concentrations, trophic transfer and human risks of antibiotics in freshwater food web in Lake Taihu, China [J]. Ecotoxicology and Environmental Safety, 2020,197: 110626.

[12] Cheng D M, Liu X H, Zhao S N, et al. Influence of the natural colloids on the multi-phase distributions of antibiotics in the surface water from the largest lake in North China [J]. Science of the Total Environment, 2017,578:649-659.

[13] 孫秋根,王智源,董建瑋,等.太湖流域河網(wǎng)4種典型抗生素的時空分布和風(fēng)險評價[J]. 環(huán)境科學(xué)學(xué)報, 2018,38(11):4400-4410.

Sun Q G, Wang Z Y, Dong J W, et al. Spatial-temporal distribution and risk evaluation of four typical antibiotics in river networks of Taihu Lake Basin [J]. Journal of Environmental Science, 2018,38(11):4400- 4410.

[14] 張國棟.南四湖流域典型抗生素時空分布及遷移規(guī)律研究[D]. 濟(jì)南:山東師范大學(xué), 2019:21-26.

Zhang G D. Spatial and temporal distribution and migration of typical antibiotics in nansihu lake basin [D]. JiNan: Shandong Normal University, 2019:21-26.

[15] 劉 昔,王 智,王學(xué)雷,等.我國典型區(qū)域地表水環(huán)境中抗生素污染現(xiàn)狀及其生態(tài)風(fēng)險評價[J]. 環(huán)境科學(xué), 2019,40(5):2094-2100.

Liu X, Wang Z, Wang X L, et al. Status of antibiotic contamination and ecological risks assessment of several typical Chinese surface- water environments [J]. Environmental Science, 2019,40(5):2094- 2100.

[16] Yao L L, Wang Y X, Tong L, et al. Occurrence and risk assessment of antibiotics in surface water and groundwater from different depths of aquifers: A case study at Jianghan Plain, central China [J]. Ecotoxicology and Environmental Safety, 2017,135:236-242.

[17] 陳衛(wèi)平,彭程偉,楊 陽,等.北京市地下水中典型抗生素分布特征與潛在風(fēng)險[J]. 環(huán)境科學(xué), 2017,38(12):5074-5080.

Chen W P, Peng C W, Yang Y, et al. Distribution characteristics and risk analysis of antibiotic in the groundwater in Beijing [J]. Environmental Science, 2017,38(12):5074-5080.

[18] Zhang R J, Zhang G, Tang J H, et al. Levels, spatial distribution and sources of selected antibiotics in the East River (Dongjiang), South China [J]. Aquatic Ecosystem Health & Management, 2012,15(2): 210-218.

[19] 廖 杰,魏曉琴,肖燕琴,等.蓮花水庫水體中抗生素污染特征及生態(tài)風(fēng)險評價[J]. 環(huán)境科學(xué), 2020,41(9):205-211.

Liao J, Wei X Q, Xiao Y Q, et al. Pollution characteristics and risk assessment of antibiotics in Lianhua Reservoir [J]. Environmental Science, 2020,41(9):205-211.

[20] Liu K, Yin X F, Zhang D L, et al. Distribution, sources, and ecological risk assessment of quinotone antibiotics in the surface sediments from Jiaozhou Bay wetland, China [J]. Marine Pollution Bulletin, 2018, 129(2):859-865.

[21] Liu S S, Zhao H X, Lehmler H J, et al. Antibiotic pollution in marine food webs in Laizhou Bay, North China: Tropho dynamics and human exposure implication [J]. Environmental Science & Technology, 2017, 51(4):2392-2400.

[22] Li W H, Shi Y L, Gao L H, et al. Occurrence of antibiotics in water, sediments, aquatic plants, and animals from Baiyangdian Lake in North China [J]. Chemosphere, 2012,89:1307-1315.

[23] Xie Z X, Lu G H, Yan Z H, et al. Bioaccumulation and trophic transfer of pharmaceuticals in food webs from a large freshwater lake [J]. Environmental Pollution, 2017,222:356-366.

[24] Han Q F, Zhao S, Zhang X R, et al. Distribution, combined pollution and risk assessment of antibiotics in typical marine aquaculture farms surrounding the Yellow Sea, North China [J]. Environment International, 2020,138:105551.

[25] Bai Y , Meng W , Xu J , et al. Occurrence, distribution and bioaccumulation of antibiotics in the Liao River Basin in China [J]. Environmental Science Processes & Impacts, 2014,16(3):586-593.

[26] Qi W, Cgpab C, Yhwab C, et al. Antibiotics in a subtropical food web from the Beibu Gulf, South China: Occurrence, bioaccumulation and trophic transfer [J]. Science of The Total Environment, 2020,751: 141718.

[27] Chen H, Shan L, Xu X R, et al. Antibiotics in typical marine aquaculture farms surrounding Hailing Island, South China: Occurrence, bioaccumulation and human dietary exposure [J]. Marine Pollution Bulletin, 2015,90(1/2):181-187.

[28] Cheng D M, Liu X H, Wang L, et al. Seasonal variation and sediment-water exchange of antibiotics in a shallower large lake in North China [J]. Science of the Total Environment, 2014,476-477: 266-275.

[29] 申立娜,張璐璐,秦 珊,等.白洋淀喹諾酮類抗生素污染特征及其與環(huán)境因子相關(guān)性研究[J]. 環(huán)境科學(xué)學(xué)報, 2019,39(11):3888-3897.

Shen L N, Zhang L L, Qin S, et al. The occurrence and distribution of quinolones (QNs) and correlation analysis between QNs and physical-chemical parameters in Baiyangdian Lake, North China [J]. Journal of Environmental Science, 2019,39(11):3888-3897.

[30] Cheng D M, Liu X H, Zhao S N, et al. Influence of the natural colloids on the multi-phase distributions of antibiotics in the surface water from the largest lake in North China [J]. Science of the Total Environment, 2017,578:649-659.

[31] Zhang L L, Shen L N, Qin S, et al. Quinolones antibiotics in the Baiyangdian Lake, China: Occurrence, distribution, predicted no-effect concentrations (PNECs) and ecological risks by three methods [J]. Environmental Pollution, 2020,256:113458.

[32] Zhang L L, Qin S, Shen L N, et al. Bioaccumulation, trophic transfer, and human health risk of quinolones antibiotics in the benthic food web from a macrophyte-dominated shallow lake, North China [J]. Science of the Total Environment, 2020,712:136557.

[33] 劉 珂.膠州灣典型海岸帶沉積物中喹諾酮抗生素時空分布特征及風(fēng)險評價[D]. 青島:青島大學(xué), 2018.

Liu K. Spatial, temporal distribution and risk assessment of quinotine antibiotics in the surface sediments of coastal zone, Jiaozhou Bay [D]. Qingdao: Qingdao University, 2018.

[34] 郭寧寧,李 希,周訓(xùn)軍,等.亞熱帶丘陵區(qū)人工濕地底棲動物群落特征研究[J]. 中國環(huán)境科學(xué), 2021,41(2):930-940.

Guo N N, Li X, Zhou X J, et al. Characteristics of zoobenthos community in constructed wetlands in subtropical hilly area [J]. China Environmental Science, 2021,41(2):930-940.

[35] Arnot J A, Gobas F A. A review of bioconcentration factor (BCF) and bioaccumulation factor (BAF) assessments for organic chemicals in aquatic organisms [J]. Environmental Reviews, 2006,14(4):257-297.

[36] Post, D M. Using stable isotopes to estimate trophic position: models, methods, and assumptions [J]. Ecology, 2002,83(3):703-718.

[37] Gujarathi N P, Han B, Linden J C, et al. Phytoremediation of Oxytetracycline from Wastewater [C]. The 2005Annual Meeting, 2005.

[38] Iglesias C, Meerhoff M, Johansson L S, et al. Stable isotope analysis confirms substantial differences between subtropical and temperate shallow lake food webs [J]. Hydrobiologia, 2017,784(1):111-123.

[39] Ponsard V S. Sources of Variation in Consumer-Diet15N Enrichment: A Meta-Analysis [J]. Oecologia, 2003,136(2):169-182.

[40] 周品成,劉希強,康興生,等.4種水生植物對獸用抗生素去除效果比較[J]. 華南農(nóng)業(yè)大學(xué)學(xué)報, 2019,40(6):67-73.

Zhou P C, Liu X Q, Kang X S, et al. Removal effects of four aquatic plants on veterinary antibiotics [J]. Journal of South China Agricultural University, 2019,40(6):67-73.

[41] 申立娜,張璐璐,秦 珊,等.白洋淀喹諾酮類抗生素污染特征及其與環(huán)境因子相關(guān)性研究[J]. 環(huán)境科學(xué)學(xué)報, 2019,39(11):3888-3897.

Shen L N, Zhang L L, Qin S, et al. The occurrence and distribution of quinolones (QNs) and correlation analysis between QNs and physical-chemical parameters in Baiyangdian Lake, North China [J]. Acta Scientiae Circumstantiae, 2019,39(11):3888-3897.

[42] Chen K, Zhou J L. Occurrence and behavior of antibiotics in water and sediments from the Huangpu River, Shanghai, China [J]. Chemosphere, 2013,95:604- 612.

[43] Liu X H, Zhang H B, Li L Z, et al. Levels, distributions and sources of veterinary antibiotics in the sediments of the Bohai Sea in China and surrounding estuaries [J]. Marine Pollution Bulletin, 2016,109(1): 597-602.

[44] 劉 珂,張道來,劉 娜,等.膠州灣海岸帶表層沉積物中典型喹諾酮類抗生素污染特征研究[J]. 海洋環(huán)境科學(xué), 2017,36(5):655-661.

Liu K, Zhang D L, Liu N, et al. Investigation on the typical quinolone antibiotics in the surface sediments of Jiaozhou bay, China [J]. Marine Environmental Science, 2017,36(5):655-661.

[45] Xu J, Zhang Y, Zhou C B, et al. Distribution, sources and composition of antibiotics in sediment, overlying water and pore water from Taihu Lake, China [J]. Science of the Total Environment, 2014,497-498: 267-273.

[46] He X T, Wang Z H, Nie X P, et al. Residues of fluoroquinolones in marine aquaculture environment of the Pearl River Delta, South China [J]. Environmental Geochemistry and Health, 2012,34(3):323-335.

[47] Calamarid D, Zuccato E, Castiglioni S, et al. Strategic survey of therapeutic drugs in the rivers Po and Lambro in North-ern Italy [J]. Environmental Science & Technology, 2003,37(7):1241-1248.

[48] Cai Y J, Gong Z J, Qin B Q. Benthic macroinvertebrate community structure in Lake Taihu, China: Effects of trophic status, wind-induced disturbance and habitat complexity [J]. Journal of Great Lakes Research, 2012,38(1):39-48.

[49] Cai Y J, Gong Z J, Xie P. Community structure and spatiotemporal patterns of macrozoobenthos in Lake Chaohu (China) [J]. Aquatic Biology, 2012,17(1):35-46.

[50] 佟霽坤.近十年白洋淀水質(zhì)特征及營養(yǎng)狀態(tài)分析[D]. 保定:河北大學(xué), 2020.

Dong J K. Analysis of water quality characteristics and nutrient status in Baiyang Lake in recent ten years [D]. Baoding :Hebei University, 2020.

[51] Wenk J, Von Gunten U, Canonica S. Effect of dissolved organic matter on the transformation of contaminants induced by excited triplet states and the hydroxyl radical [J]. Environmental Science & Technology, 2011,45(4):7945.

[52] Petrie B, Barden R, Barbara K H. A review on emerging contaminants in wastewaters and the environment: Current knowledge, understudied areas and recommendations for future monitoring [J]. Water Research, 2015,72:3-27.

[53] Du B, Haddad S P, Luek A, et al. Bioaccumulation of human pharmaceuticals in fish across habitats of a tidally influenced urban bayou [J]. Environmental Toxicology and Chemistry, 2016,35(4):966- 974.

[54] 陳澤豪,楊 文,王 穎,等.白洋淀大型底棲動物群落結(jié)構(gòu)及其與環(huán)境因子關(guān)系[J]. 生態(tài)學(xué)雜志, 2021,40(7):2175-2185.

Chen Z H, Yang W, Wang Y, et al. Community structure of macrozoobenthos and its relationship with environmental factors in Baiyangdian Lake [J]. Journal of Ecology, 2021,40(7):2175-2185.

[55] 李光錦.贛江干流底棲動物群落結(jié)構(gòu)及其與環(huán)境因子的關(guān)系[D]. 南昌:南昌工程學(xué)院, 2019.

Li G J. The characteristics of zoobenthos community and their relationships to environment factors in Mainstem of Gnjiang River [D]. Nanchang :Nanchang Institute of Technology, 2019.

[56] 李 娟,王沛芳,紀(jì)靚靚,等.抗生素在沉積物中的吸附機(jī)制及其影響因素[J]. 四川環(huán)境, 2013,32(2):87-88,94-95,93.

Li J, Wang P F, Ji L L, et al. Mechanisms and Influencing Factors for Sorption of Antibiotics in Sediments [J]. Sichuan Environment. 2013,32(2):87-88,94-95,93.

[57] 孔慧敏,楊四福,遲寶明,等.喹諾酮類抗生素在水環(huán)境中降解和吸附影響因素[J]. 科學(xué)技術(shù)與工程, 2021,21(3):1196-1201.

Kong H M, Yang S F, Chi B M, et al. Factors influencing the degradation and absorption of Quinolone antibiotics in aqueous environment [J]. Science Technology and Engineering, 2021,21(3): 1196-1201.

[58] Dorival G N, Zafra G A, Navalon A, et al. Removal and degradation characteristics of quinolone antibiotics in laboratory- scale activated sludge reactors under aerobic, nitrifying and anoxic conditions [J]. Journal of Environmental Management, 2013,120:75-83.

[59] Peng K, Qin B Q, Cai Y J, et al. Water column nutrient concentrations are related to excretion by benthic invertebrates in Lake Taihu, China [J]. Environmental Pollution, 2020,261:114161.

[60] Yang Y F, Yi Y J, Zhou Y, et al. Spatio-temporal variations of benthic macroinvertebrates and the driving environmental variables in a shallow lake-Science direct [J]. Ecological Indicators, 2019,110: 105948.

The bioaccumulation characteristics of quinolones (QNs) in macrobenthos-A case study of Baiyangdian Lake.

FU Yu1, JU Ze-jia1, CHEN Hui1, ZHAO Xin-yu1, SONG Yuan-meng1, WANG Guang-zhi1, ZHANG Lu-lu1,2*, CUI Jian-sheng1,2

(1.Academy of Environmental Science, Hebei University of Science and Technology, Shijiazhuang 050000, China；2.Biotechnology laboratory for pollution control in Hebei Province, Shijiazhuang 050000, China)., 2022,42(2)：878～888

The concentrations of quinolones (QNs) in water and macrobenthos samples were detected by high performance liquid chromatography tandem mass spectrometry (HPLC-MS). Correlation analysis was conducted between the characteristics of bioaccumulation for QNs in macrobenthos and environmental parameters in Baiyangdian Lake. The results showed that: The concentrations of ΣQNs in water varied from 0.7380 to 2004ng/L, the average concentrations of FLU (168.0ng/L) were the highest and the detection frequency of ofloxacin (OFL) and norfloxcin (NOR) in macrobenthos was the highest (Freq=100%), followed by flumequine (FLU) and enrofloxa (ENR) (Freq350%), while the detection rate of other QNs was less than 40% (Freq￡40%), While in the macrobenthos, the concentrations of ΣQNs varied from 23.70ng/g to 289.4ng/g, thereinto, the average concentrations of FLU(29.43ng/g) and CIP(40.38ng/g) were the highest; The bioaccumulation factors (BCF) of QNs in macrobenthos were in the range of 219.6 (BCFMAR)～1754 (BCFENR) L/kg, which indicated that the bioaccumulation of QNs was high in macrobenthos; The trophic magnification factors (TMF) of OFL, ENR, and NOR varied from 0.1299 (TMFFLU) to 6.426 (TMFENR), indicating NOR and ENR appeared trophic magnification, while FLU and OFL appeared trophic dilution; Through correlation analysis, the results showed that the BCF of ENR、CIP、FLU and ORB were significant positively correlated with water depth (WD), temperature (), secchi depth (SD), dissolved oxygen (DO), and total organic carbon (TOCs), while significant negatively correlated with chemical oxygen demand (COD), total phosphorus (TP), total nitrogen (TN), nitrate nitrogen (NO3--N), PO43-, total carbon (TCs), total phosphorus (TNs), and NH3-Ns; TMFOFLwas significantly positive correlation to COD, TP, TN, NO3-N, PO43-, TCs, TNs and NH3-Ns, while significant negatively correlated with WD,, SD, DO and TOCs, indicating that domestic sewage and aquaculture wastewater contributed the most to QNS.

Baiyangdian Lake；quinolones；dominant macrobenthos；bioaccumulation；spatial distribution；environmental parameters

X171.5

A

1000-6923(2022)02-0878-11

付 雨(1995-),女,河北唐山人,河北科技大學(xué)碩士研究生,主要從事湖泊生態(tài)學(xué)相關(guān)研究.發(fā)表論文1篇.

2021-06-28

河北省自然科學(xué)基金資助項目(D2019208152);河北省高等學(xué)?？茖W(xué)技術(shù)研究重點項目(ZD2021046)

* 責(zé)任作者, 副教授, zhanglulu19850703@163.com