珠三角河流飲用水源中皮質激素的污染與風險

林粲源,龔 劍*,熊小萍,周永順,吳翠琴

珠三角河流飲用水源中皮質激素的污染與風險

林粲源1,2,龔 劍1,2*,熊小萍1,2,周永順1,2,吳翠琴1,2

(1.廣州大學環境科學和工程學院,廣東省放射性核素污染控制與資源化重點實驗室,廣東 廣州 510006；2.廣州大學珠江三角洲水質安全與保護教育部重點實驗室,廣東 廣州 510006)

利用固相萃取聯合液相色譜-質譜法對珠三角河流飲用水源中的21種糖皮質激素(GCs)和3種鹽皮質激素(MCs)進行了研究.結果發現,24種目標物在水源水中均有檢出,檢出率在8%(可的松)~75%(地夫可特)之間,總濃度(∑CSs)(平均值/中值)為0.29~8.7ng/L(2.6ng/L/1.6ng/L),污染以布地奈德、丙酸氯倍他索、醛固酮為主.東江東莞段和流溪河下游水源水中腎上腺皮質激素(CSs)濃度水平總體高于西江和北江,各水源地的CSs組成與濃度存在一定的季節性差異.冗余分析發現,水源水中大部分CSs與水溫、電導率、pH值以及溶解氧呈負相關關系,表明這些環境因子是影響CSs含量分布的重要因素.CSs在珠三角河流水源地的危害指數(HI)(平均值/中值)在<0.1~0.65(0.25/0.29)之間,總體處于中低風險水平.

皮質激素；飲用水源；內分泌干擾物；珠江三角洲

環境內分泌干擾物(EEDCs),是一種外源性干擾內分泌系統的化學物質,通過攝入、積累等各種途徑,通過干擾生物或人體內保持自身平衡和調解發育過程天然激素的合成、分泌、運輸、結合、反應和代謝等過程對生物體或人類的生殖、神經和免疫系統等功能產生影響[1-3].

近幾十年,關于水環境中典型內分泌干擾物研究主要集中在類固醇性激素和烷基酚類上[4-5],而同樣參與人體重要代謝功能的另一類類固醇:腎上腺皮質激素(CSs)的相關研究相對較少[6-8].這類類固醇激素主要產生于脊椎動物的腎上腺皮質,分為糖皮質激素(GCs)和鹽皮質激素(MCs).它們主要參與的生理過程包括應激反應、免疫反應等[9].目前,皮質激素藥物被廣泛應用于人和動物的炎癥性疾病治療[10],它們可以通過污水處理廠以及城市地表徑流進入到環境水體中[11-15].近年來的研究發現,CSs對環境中的低等脊椎動物例如魚類的行為、免疫功能、繁殖和發育產生影響或造成損害[15-17].例如,即使暴露于環境濃度(ng/L至μg/L)水平的皮質醇、潑尼松龍、醋酸氟氫可的松等常見CSs條件下,魚類的血糖濃度、白細胞數量、基因轉錄等生理指標和功能均會受到不利影響[18-20].盡管CSs的生態環境效應和潛在危害性開始引起了廣泛關注,但國內外針對這類“新興”污染物在環境中存在狀態和污染狀況等相關研究最近幾年才剛剛起步[13,21-22].除生活污水直排外,現代水處理工藝亦不能完全去除污水、廢水中的CSs[13],導致有大量未被處理的CSs隨污水處理廠以及納污河流出水排入到自然水體中[23],進而對水生態安全和人體健康形成威脅.

珠江水系是珠江三角洲主要的飲用水源,其污染水平直接關系到居民的飲用水的安全[24].針對珠江三角洲河流EEDCs的研究已逐步深入,尤其是環境雌激素(EEs)已在地表水中廣泛檢出,其中在珠江三角洲河流的污染水平處于中高值區,濃度在數ng/L到數千ng/L之間,以酚類雌激素壬基酚(NP)、雙酚A (BPA)、類固醇雌激素雌酮(E1)、雌二醇(E2)的污染為主[25-33].不僅如此,風險評估發現,環境雌激素(EEs)已對當地水生生態環境構成潛在威脅,其中珠江廣州河段以及東江東莞河段已成為中高風險區[33-36].可見,EEDCs產生的環境效應不容忽視,甚至可能已威脅到人們的飲水安全[37].然而,專門針對EEDCs在珠三角水源地的研究仍相對較少[38-39],對CSs這類“新興”EEDC在珠三角流域的污染現狀及其潛在風險更是知之甚少,幾乎未見報道.

本文以珠江水系中的西江、北江、流溪河以及東江東莞段的集中式飲用水源地作為研究區域,以24種常見、常用的CSs(包括21種GCs和3種MCs)為目標物,研究了它們的污染現狀、時空分布特征及其影響因素,并對其潛在的生態風險進行了初步評價,以期為珠三角飲用水源的生態安全及健康風險評估提供科學依據.

1 材料與方法

1.1 實驗材料

實驗用甲醇、乙酸乙酯、乙腈均為色譜純級,購自Merck(德國,Darmstadt);溶液的配制、淋洗等所有實驗用水均為超純水,電阻率為18.25MΩ·cm.24種CSs標準品(表1)購自Sigma-Aldrich(美國,St. Louis, Missouri)和Dr. Ehrenstorfer GmbH(德國, Augsburg),純度均大于98%.5種同位素內標(表1)均購自Toronto Research Chemicals公司,純度均大于95%.玻璃纖維膜(GF/F,0.7μm)和Oasis HLB固相萃取柱(500mg,6m L)分別購自Whatman和Waters.所有玻璃器皿,玻璃纖維濾膜和無水硫酸鈉在使用前均在450℃下烘烤5h.

1.2 樣品采集

根據廣東省飲用水水源保護區劃分,分別于2018年1月和7月從西江思賢窖(X1)、金本村(X2),北江寶鴨洲(B1)、順德水道(B2~B3),流溪河下游石門(S1)以及東江東莞段北干流(D1~D4)、南支流(D5~D6)水源地進行樣品采集,同時對水體理化指標進行監測.利用便攜式采樣泵采集各水源地表層水樣4L,收集到干凈的棕色玻璃采樣瓶中.加入0.4g疊氮化鈉抑制微生物的降解.樣品低溫保存下于當日運回實驗室置于4℃冰柜避光保存,并在24h內完成富集萃取工作.

圖1 采樣點分布

1.3 樣品前處理

利用蠕動泵將水樣通過玻璃纖維濾膜去除顆粒物后,取1L濾液,加入10ng 的同位素內標,混和均勻;使用全自動固相萃取儀(Auto Trace,Thermo公司)對濾液中的目標化合物進行富集;HLB固相萃取柱預先用6mL乙酸乙酯、6mL乙腈和12mL超純水活化;儀器設定流速為10mL/min;待樣品全部通過固相萃取柱后,使用10mL10%(體積分數)乙腈水溶液進行淋洗、凈化,去除干擾基質;柱子經高純氮氣干燥后,用6mL乙酸乙酯:乙腈(1:1,/)和6mL乙酸乙酯進行洗脫.洗脫液合并后經高純氮氣吹至剛干,用甲醇定容至0.5mL,過0.2μm微孔濾膜,待測.

1.4 水樣理化參數的測定

采用CDT48M多參數儀(SST,德國)在野外現場測定各采樣點的水溫(T)、電導率(COND)、溶解氧(DO)、葉綠素a (Chl a)、pH值等環境參數.

1.5 儀器分析

利用高效液相色譜-串聯質譜(HPLC-MS/MS, 1260Infinity-6460QQQ, Agilent)對24種目標化合物進行定量分析.色譜柱選擇Agilent ZORBAX Eclipse Plus C8柱(100mm×3.0mm,1.8μm).色譜條件:柱溫為30℃;進樣量為3μL;流動相A為0.1%(/)乙酸,流動相B為乙腈;流速0.3mL/min;液相梯度洗脫程序為0min 28% B;8.0min 28% B;8.1min 40% B;12.0min 40% B;12.1min 60% B;16.0min 70% B;16.5min 100% B; 19.5min 100% B.質譜條件:離子源為ESI±模式,霧化器壓力為276kPa(40psi);干燥氣溫度為300℃,干燥氣流速為11L/min;毛細管電壓為4000V,采用動態多反應監測(DMRM)模式對目標物的特征離子對掃描[40].使用內標法進行定量,分別定義信噪比S/N=10和S/N=3所對應的濃度作為被測化合的方法定量限和方法檢測限(如表1所示).

表1 目標化合物信息及其在水源水中的檢出限和定量限(ng/L)

續表1

注:LOD:方法檢出限;LOQ:方法定量限;GCs:糖皮質激素;MCs:鹽皮質激素;RSD:相對標準偏差;* 定量離子.

1.6 質量控制與質量保證

本研究設置7組標準溶液,質量濃度分別為0.5, 1, 2, 5, 10, 20, 50μg/L,其線性方程的2>0.99.為確保數據的準確性和精密度,每批實驗均設有方法空白,加標水樣和樣品平行,對實驗過程進行監控.儀器分析中,每6個樣品添加一個溶劑空白和質控標準樣,對儀器狀態進行監控.實驗結果顯示,所有空白樣品均呈陰性,所有目標化合物的平均回收率在75%~107%,相對標準偏差(RSD)均低于10%,方法檢出限范圍在0.2~0.68ng/L(如表1所示).

1.7 風險評價方法

根據歐盟技術指導文件(ECTGD)[41]和Hernando等[42]中關于風險評價的方法,本研究采用風險商(RQ)法對水源地的CSs污染進行初步的生態風險評價.該評價標準分為3個風險等級,分別為低風險(RQ<0.1);中等風險(0.1￡RQ<1);以及高風險(RQ31).因受限于當前有限的CSs毒理數據,本文采用地塞米松當量(DEQ)表征CSs對水生生物的風險水平,計算式如下 :

DEQ=REP×MEC (1)

RQ=DEQ/PNEC(DEX)(2)

式中:REP為地塞米松當量因子;MEC為測定的環境暴露濃度,ng/L;PNEC(DEX)為DEX的PNEC值,取值為78.4ng/L[43].選取已有REP值報道的15種CSs進行風險評價,如表2所示.

表2 CSs的REP值匯總

注: EC50為半數效應濃度;REP為地塞米松當量因子.

多種CSs同時存在時,則以混合風險商即危害指數(HI)來表征它們的綜合風險水平,如式(3):

HI=ΣRQ(3)

2 結果與討論

2.1 飲用水源中CSs的組成與濃度水平

西江、北江、流溪河以及東江東莞段水源地中CSs的檢出濃度如表3所示.3種MCs和21種GCs在水樣中均有檢出,檢出率在8%(COR)~75%(DC),其中GCs的濃度范圍為<0.38(PNL)~4.7ng/L (BDN), MCs的平均濃度在<0.2(FLCact)~2.24ng/L (ADS)之間,表明CSs廣泛存在于珠三角水源水中.水樣中CSs的總濃度(ΣCSs)在0.29~8.7ng/L之間,平均值和中值分別為2.6和1.6ng/L.

有7種GCs和1種MCs在冬夏兩季均被檢出,平均濃度在0.23ng/L(DC)~3.8ng/L(BDN)之間. ΣCSs的濃度水平和組成存在一定季節性差異,夏季的污染水平普遍高于冬季.冬季水樣中有1~8種的CSs被檢出,ΣCSs濃度平均值和中位值(范圍)分別為0.57和0.34ng/L(未檢出(ND)~2.2ng/L),其中CLOprop和CRL的檢出率較高,均達到50%;夏季各水源地中均有1~7種CSs被檢出,ΣCSs濃度平均值和中位值(范圍)分別為0.90和0.37ng/L (ND~4.7ng/L),其中DC和BDN的檢出率分別高達75%和50%.此外,冬夏兩季的目標物的組成也存在顯著差異.冬季水源地污染以CLOprop、BDN和ADS為主,分別占當季CSs總量的29%、13%和11%,而夏季的污染則主要來自BDN,其貢獻高達56%.

表3 珠三角水源水中CSs的濃度水平(ng/L)

續表3

注: LOQ為定量限.

2.2 水源地CSs的時空分布

如圖2所示,西江和北江冬夏兩季ΣCSs濃度平均值均在1ng/L左右,無顯著差異.流溪河石門的水樣中測得較高濃度的CSs,可能與該點位于流溪河下游,距離廣州市區較近,受居民生活污水排放影響有關.冬季石門水源水中ΣCSs濃度高達8.8ng/L,約高出夏季1倍(4.5ng/L),這主要因為夏季(豐水季)降雨量(占全年總量的85%以上)[44]、徑流量(約為枯水季的10倍)[45]大,對污染物的稀釋作用較為明顯.東江水源地的情況則不相同,其冬季ΣCSs濃度平均值為1.2ng/L,明顯低于夏季的平均水平(5.2ng/L).該季節性差異可能與周邊的工農業生產生活的季節性排放有關,具體的原因有待進一步的調查.

空間分布上,4條河流水源地CSs的總體污染水平(ΣCSs濃度平均值)為:東江東莞段(1.2ng/L)>流溪河石門(0.95ng/L)>北江(0.55ng/L)>西江(0.40ng/L).東江東莞段水源地中, BDN和CLOprop為主要污染物,分別占改水源地總污染物濃度水平的60%和13%.而在流溪河中,檢出的CSs類較多,污染以ADS、BC、FN、BDN以及CLOprop為主,它們的濃度之和占珠江水源總污染物濃度水平的58%.值得注意的是,人工合成GCs中BDN和CLOprop在東江東莞段和流溪河石門水源地均是主要的污染物,這可能與它們的廣泛使用有關.作為常見、常用的2種CSs類藥物,它們廣泛應用于皮膚病和鼻炎的治療.加之東莞、廣州兩地人口稠密、藥物使用量較大,這些化合物可隨生活污水大量地排入附近流域,進而影響水源地的水質.另外,冬季珠江三角洲河流水源地中CSs的分布總體呈現下游高于上游的特征.例如,北江ΣCSs從上游的0.32ng/L(B1)到下游的2.18 (B2)和0.72ng/L(B3),西江ΣCSs從上游的0.29ng/L(X1)到下游的1.84ng/L(X2),東江東莞段ΣCSs從上游的0.79ng/L(D2)到下游的2.49ng/L(D3).這可能因為西江、北江和東江上游人口稀疏,人類活動較少,而下游接近城市及工業園區,因此有相當數量的污染物隨廢水進入到環境中,并在下游聚集.而在夏季,雨、水豐沛,受稀釋作用影響,上述流域中的CSs并無明顯的空間分布特征.

圖2 珠江三角洲河流水源地中CSs的時空分布

2.3 CSs與環境參數的相關性

對所有檢出的CSs進行了去趨勢對應分析,發現排序中第一軸的長度為1.4(<3),因此可以采用冗余分析(RDA)來評估CSs濃度與環境參數之間的相關性[46].結果如圖3所示.前兩主軸的特征值分別為85.7%和10.8%,共解釋了總變量關系的96.5%.圖中箭頭的長度反映了兩者之間的關系強度而箭頭間交點的夾角則表示相關程度.相關性分析發現, CSs的濃度與DO、水溫均呈負相關關系,這一結果與之前一些典型EEDCs以及PPCPs的研究結果相似[34,47-48].這可能因為在水溫較高、溶解氧充足的條件下,水中微生物及浮游生物的活性較大,它們對水相中CSs的降解、吸附作用也隨之增強,以致其濃度降低[49-50].部分CSs與COND呈負相關關系的這一發現與之前EEs的研究結果類似[51].由于鹽析效應的影響, CSs更易于與顆粒物等非水相介質結合,以致CSs的水溶性降低.pH值與CSs濃度呈負相關關系,可能與CSs的酸離解常數(pKa)有關.在不同的pH值條件下,顆粒物對CSs吸附作用會受到去質子化程度的影響[52].本研究水樣的pH值在6.4~8.0之間,高于大部分CSs的pKa值(0~13.81)[53],它們大多以非離子形態存在,易于被顆粒物吸附.環境中pH值越高越不利于大部分CSs離解成離子狀態賦存于水相.

圖3 水源水中CSs與水環境因子的冗余分析

2.4 風險評價

就化合物而言,所有水樣中TRI、ADS、PNL、CRL、PNS、COR、MPNL、DEX、FMS、FN、TRIact、FCNact、FML、FLCact、AM、FLUprop的RQ值均低于0.1,表明它們的風險水平較低;BDN(<0.1~ 0.42)和CLOprop(<0.1~0.94)的RQ值則相對較高,處于中低風險水平.

水源地的總RQ(ΣRQs)即HI的時空分布如圖4所示.從季節上看,冬季CSs的HI值范圍(中值):< 0.1~0.97(0.30)處于中低風險水平,其中CLOprop是主要貢獻者,其RQ范圍在<0.1~0.94之間.夏季水源地HI范圍(中值)在<0.1~0.42之間(0.29),主要貢獻來自BDN(RQ:0.30~0.42).冬季西江、北江、流溪河以及東江東莞段的HI范圍(中值)分別為<0.1~0.15 (0.12),<0.1~0.25(0.10),0.69,<0.1~0.97(0.49),表明各個流域水源地均處于中低風險水平,主要貢獻來自FLUprop、CLOprop、BDN等人工合成的CSs.夏季西江和北江各取樣點的HI值均<0.1,處于低風險水平;流溪河石門和東江東莞段水源水的HI值分別為0.3、0.30~0.42(0.34),處于中等風險水平,風險的主要來源與冬季情況相似.

圖4 珠江三角洲河流水源地中CSs的總風險商(危害指數)

空間上,西江、北江、流溪河石門和東江東莞段水源地兩季HI平均值范圍分別為<0.1~0.15,<0.1~ 0.25,0.63,0.19~0.65,總體處于中低風險水平.其中,西江和北江水源中CSs風險的主要貢獻來自FLUprop,貢獻率分別為74%和29%,而流溪河和東江東莞段水源地的風險則主要來自CLOprop和BDN,貢獻率分別為47%、26%(流溪河石門)以及53%、44%(東江東莞段).

綜上所述,珠江三角洲河流水源地在冬季的潛在生態風險大于夏季,西江、北江處于低風險水平,而流溪河和東江東莞段處于中等風險.

3 結論

3.1 珠江三角洲河流飲用水源中,ΣCSs濃度(平均值/中值)在0.29~8.7ng/L(/1.6ng/L)之間,污染主要以CLOprop、BDN、ADS等人工合成GCs為主.東江東莞段和流溪河水源水中CSs濃度水平總體高于西江和北江.不同流域水源地的CSs組成與濃度存在一定的季節性差異

3.2 RDA分析結果顯示,水源水中大部分CSs與T、COND、pH值以及DO呈負相關關系,表明上述環境因子在控制水源水中CSs的發生和分布方面發揮著重要作用.

3.3 初步的風險評價發現,珠三角河流水源地CSs的HI(平均值/中值)在<0.1~0.65(0.25/0.29ng/L)之間,其中西江、北江水源處于低風險水平,而流溪河和東江東莞段水源則處于中等風險水平.結果表明,珠三角部分飲用水源地CSs的污染可能已對水生態及飲用水安全形成威脅,其環境效應不容忽視.

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Occurrence and risks of typical corticosteroids in drinking water sources of the rivers from the Pearl River Delta.

LIN Can-yuan1,2, GONG Jian1,2*, XIONG Xiao-ping1,2, ZHOU Yong-shun1,2, WU Cui-qin1,2

(1.Guangdong Provincial Key Laboratory of Radionuclides Pollution Control and Resources, School of Environmental Science and Engineering, Guangzhou University, Guangzhou 510006, China；2.Key Laboratory for Water Quality and Conservation of the Pearl River Delta, Ministry of Education, Guangzhou University, Guangzhou 510006, China)., 2019,39(11)：4752~4761

The occurrence and eco-risks of typical corticosteroids (CSs) including 21 glucocorticoids and 3 mineralocorticoids were studied in the drinking water sources of the rivers from the Pearl River Delta. The solid phase extraction and liquid chromatography-mass spectrometry were employed. The 24 target compounds were all detected in the source water samples. Their detection frequencies ranged from 8% (cortisone) to 75% (deflazacort), and the total concentrations (∑CSs) were in a range (mean/median) of 0.29~8.7ng/L (2.6ng/L/1.6ng/L). Budesonide, clobetasol propionate and aldosterone were the major pollutants. The concentrations of CSs in the source water from the Dongjiang River and lower reach of the Liuxi River were generally higher than those of the Xijiang River and Beijiang River. Besides the CS compositions and concentrations varied seasonally from river to river. Redundancy analysis showed that most of CSs in the source water were negatively correlated with water temperature, conductivity, pH, and dissolved oxygen, suggesting that the occurrence and distribution of CSs in the source water can be influenced by these environmental factors. Moreover, the hazard index (HI) of CSs in the water sources of the Pearl River Delta ranged from <0.1to 0.65 (mean/median: 0.25/0.29), indicating that low and medium risks were present in these waters.

corticosteroids；drinking water source；endocrine disrupting chemicals；Pearl River Delta

X522

A

1000-6923(2019)11-4752-10

林粲源(1994-),男,廣東廣州人,廣州大學碩士研究生,主要從事內分泌干擾物的水陸環境行為、風險研究.發表論文3篇.

2019-04-18

國家自然科學基金資助面上項目(41673110);廣州市科技計劃項目(201607010217)

* 責任作者, 副研究員, gong_jian@mails.ucas.ac.cn