Pollution characteristics and risk assessment of sulfonamide antibiotics during shallow groundwater recharge in the Shijiazhuang section of the Hutuo River
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摘要:
为识别地下水回补过程中磺胺类抗生素（SAs）的污染特征及风险水平，于2020—2021年分2期采集滹沱河补水沿线16口浅层监测井的地下水样品，采用固相萃取-超高效液相色谱串联质谱法，测定分析地下水中20种SAs的浓度水平及分布特征，并利用风险熵值法进行生态及人体健康风险评价。结果表明，地下水中SAs总体污染程度较低，回补初期地下水中共检出7种SAs，按检出率大小依次为磺胺甲恶唑（93.75%）、磺胺嘧啶（37.50%）、磺胺氯哒嗪（18.75%）、磺胺吡啶（18.75%）、磺胺甲氧嘧啶（6.25%)、磺胺脒（6.25%）、磺胺醋酰（6.25%）,平均检出浓度最高的为磺胺嘧啶（29 ng/L）和磺胺甲恶唑（9.2 ng/L）。在优质南水北调水回补的混合稀释作用下，地下水中SAs检出率和检出浓度呈明显下降趋势。历史污水处理厂排放及农业畜禽养殖污染是造成局部区域下水中SAs污染的主要原因。地下水中磺胺甲恶唑和磺胺嘧啶在回补初期属于中等生态风险，且磺胺嘧啶对人体健康具有中等风险。回补后期各SAs评价均无明显生态风险和健康风险。
Abstract:In order to identify the pollution characteristics, ecological risk and health risk of sulfa antibiotics (SAs) in groundwater during the Hutuo River recharge process, sixteen shallow groundwater samples were collected twice along the Hutuo River bank from October 2020 to October 2021. The concentrations and distribution characteristics of 20 SAs were determined using solid-phase extraction-ultra high-performance liquid chromatography-tandem mass spectrometry. The results showed that the overall pollution level of SAs in groundwater was relatively low, and only 7 of the 20 SAs were detected in groundwater during the initial recharge period. The concentration of different SAs followed the order of characteristics: sulfametoxydiazine (93.75%), sulfadiazine (37.50%), sulfachlorpyridazine (18.75%), sulfapyridine (18.75%), sulfamonomethoxine (6.25%), sulfaguanidine (6.25%), sulfacetamide (6.25%). The highest average detection concentration SAs were sulfadiazine (29 ng/L) and sulfametoxydiazine (9.2 ng/L). Due to the mixed dilution effect of high-quality South-to-North Water Diversion water, the SAs detection frequency and average detection concentration declined gradually during the groundwater recharge. The historical pollution of sewage treatment plants and agricultural livestock and poultry in this area were the leading causes of SAs pollution in groundwater. The ecological and health risk assessment results indicated that the sulfametoxydiazine and sulfadiazine were medium ecological risks, and the sulfadiazine posed a moderate risk to human health. All SAs showed no obvious ecological risk and health risk in groundwater in the later period of the recharge process.
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图 1 滹沱河地下水回补采样点分布图
Figure 1. Distribution map of groundwater sampling points in the Hutuo River recharge area
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图 2 回补初期和后期地下水中SAs检出率及平均浓度
Figure 2. The detection rate and average concentration of groundwater SAs antibiotics during recharge process
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图 3 回补初期（a）和回补后期（b）地下水中SAs类抗生素分布特征
Figure 3. Distribution characteristics of SAs antibiotics in the initial (a) and later (b) recharge period
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图 4 回补初期（a）和后期（b）地下水中各类SAs浓度变化
Figure 4. Concentration changes of different SAs antibiotics in groundwater during the initial (a) and later (b) recharge period
表 1 研究区地下水回补过程中SAs检出浓度及检出率
Table 1 Concentrations and detection rate of SAs in groundwater during the recharge process
抗生素 回补初期（2020年10月） 回补后期（2021年10月） 范围/（ng·L−1） 平均值/（ng·L−1） 检出率/% 范围/（ng·L−1） 平均值/（ng·L−1） 检出率/% SMX ND~45.4 9.2 93.75 ND~9.5 3.5 60 STZ BLD BLD BLD BLD BLD BLD SMM ND~2.7 0.2 6.25 ND~3.5 0.4 13.33 SMR BLD BLD BLD BLD BLD BLD SCP ND~3.1 0.3 18.75 BLD BLD BLD MAF BLD BLD BLD BLD BLD BLD SGD ND~17.6 1.1 6.25 ND~2.6 0.6 26.67 SDZ ND~412.0 29 37.5 ND~9.0 1.2 20 SPZ BLD BLD BLD BLD BLD BLD SQX BLD BLD BLD BLD BLD BLD SMP BLD BLD BLD BLD BLD BLD SCT ND~17.1 1.1 6.25 ND~1.9 0.1 6.67 SPD ND~9.0 1.3 18.75 ND~5.2 0.6 20 SSZ BLD BLD BLD BLD BLD BLD SDX BLD BLD BLD BLD BLD BLD SM2 BLD BLD BLD BLD BLD BLD SFM BLD BLD BLD BLD BLD BLD SMZ BLD BLD BLD BLD BLD BLD SMTZ BLD BLD BLD BLD BLD BLD TMP BLD BLD BLD BLD BLD BLD ∑SAs ND~507.0 45.72 93.75 ND~94.6 10.5 62.5 注：BLD表示无数据， ND表示未检出或低于检出限值 
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表 2 地下水中SAs生态风险评价
Table 2 Ecological risk assessment of SAs in groundwater
SAs 对应最敏感
物种毒性 EC50 AF PNEC 回补初期（RQ） 回补后期（RQ） 参考文献 SMX S. leopoliesis 急性 0.27 1000 270 0.168 0.035 Benoǐt et al., 2004 SMM Lemna minor 急性 1.277 1000 1277 0.002 0.003 Turkdogan et al., 2009 SGD daphnia magna 急性 3.86 1000 3860 0.005 0.001 ECOSAR数据库 SDZ S.capricornutum 急性 2. 2 1000 2200 0.187 0.004 Eguchi et al.，2004 SPD Lemna minor 急性 0.46 1000 4600 0.002 0.001 Bialk-Bielinska et al.，2011
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表 3 地下水中典型SAs对人体的健康风险（RQH）
Table 3 RQH values of different populations for SAs antibiotics in groundwater
SAs 2020年 RQH 2021年 RQH 儿童男 儿童女 成人男 成人女 儿童男 儿童女 成人男 成人女 SMX 0.053 0.053 0.060 0.058 0.011 0.011 0.013 0.012 SDZ 0.244 0.238 0.271 0.264 0.005 0.005 0.006 0.006 SPD 0.011 0.010 0.012 0.012 0.006 0.006 0.007 0.007 注：其中BW(kg)取值：儿童男24，儿童女23，成人男66.1，成人女57.8；DWI(L/d)取值：儿童男0.81，儿童女0.76，成人男2.48，成人女2.12。ADI(μg/kg·d)取值：SDZ为20（王浩楠等, 2022）；SMX为10（李辉等, 2020）；SPD为10（Hanna et al., 2018）
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