Environmental Levels and Degradation Behavior of Pharmaceuticals and Personal Care Products (PPCPs) in the Water Environment
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摘要:
药物和个人护理品（PPCPs）是一种存在于各种介质中的新污染物，具有生物富集、致癌致畸性，近年来在水环境中被广泛检出，其种类和浓度也有逐渐增多和加重的趋势，加之与人类生活密切相关，可以通过家庭垃圾、医院废水、垃圾填埋场、污水处理厂等方式直接污染地表水，并进一步污染孔隙水、地下水等，致使生态环境和人体健康存在风险。因此，广泛了解PPCPs在各种环境介质中的浓度水平对于防范生态健康风险具有重要意义。近年来，对PPCPs浓度的调查研究取得了较大进展，自1976年美国堪萨斯城首次报道药物以来，各国陆续报道了不同介质中PPCPs的存在，弥补了各研究区污染物及浓度的空白，有利于开展综合治理工作。PPCPs在水环境中常见的降解方式有水解、光解及生物降解，同时在降解过程还会受到pH、温度、共存离子等影响，而且在各种降解过程中生成的产物也有所不同。污水处理厂因为去除工艺的限制，使得地表水中许多PPCPs虽然经过了废水的生物降解环境，但是光降解仍然可能比暴露在阳光下的生物降解更强。其中，抗生素在水环境中主要发生光降解；布洛芬、碘普罗胺、咖啡因等更易发生生物降解；而自然界中PPCPs发生水解的概率较低，酯类和酰胺类是其中最常见的易水解的官能团，除此之外，四环素类等因为吸附到沉积物中，也会发生水解反应。目前，对于PPCPs浓度水平的研究很多集中在单一水体，而海水、雨水等介质缺乏监测和分析，同时对于降解行为的研究大都没有关注到降解过程和降解产物，使得一些降解产物的高毒性被低估。因此，全面了解各种水环境介质中PPCPs浓度可以较为准确、系统地获知各地区PPCPs的污染情况，对于PPCPs治理与削减工作具有重要的现实意义；而探究PPCPs在水环境中的降解行为，有利于了解其在环境中的残留和代谢情况，厘清中间产物和最终产物的性质，以便针对性地对PPCPs的环境生态效应进行评估分析，降低风险。
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关键词:
- 水环境 /
- 药物和个人护理品（PPCPs） /
- 浓度水平 /
- 降解行为 /
- 影响因素
Abstract:Pharmaceuticals and personal care products (PPCPs) are a class of chemicals used by humans for daily life. PPCPs are closely related to people’s production and life, and are even used every day worldwide. PPCP-like compounds were first detected in treated wastewater in Kansas City, USA in 1976 (concentrations of 0.8-2μg/L[6]), and subsequently detected in various countries. The mass production and use of PPCPs have led to increasing concentrations in the environment. PPCPs can induce microorganisms to produce resistance genes because of their persistence and bioaccumulation, thus changing the structure and community of microorganisms in the ecosystem. At the same time, they are accumulated at the top of the food chain or food web[17-21], destroying the balance of the ecosystem. In addition, PPCPs also have chronic toxicity, teratogenicity and carcinogenicity. For example, sulfonamides will damage tissues and organs and cause drug resistance of pathogenic bacteria[9]. Synthetic musk interferes with the secretion of hormones and can also lead to asthma, allergies, migraines and other diseases[20]. Long-term use will lead to liver and kidney damage and induce cancer[21], causing irreversible damage to human health.
PPCPs are mainly accumulated in the environment through hospitals, landfills, farms, factory wastewater and domestic sewage, and enter the water environment through various pathways. After the production of PPCPs, some are used by humans, some are directly generated in the production of waste, and some are used by animals in livestock farms. The solid or liquid waste generated in the above three ways will enter the sewage treatment plant or landfill. Then through sewage, landfill leachate directly into the surface water, through further infiltration into the sediment, pore water, groundwater, ocean and other environments, in addition to the surface water through evaporation and precipitation can also return to the water environment. The above environmental behaviors will cause harm to the ecological environment, ecosystem, and humans.
PPCPs exist in surface water, groundwater, sediment, and other environmental media, but the pollution degree varies in different countries. In recent years, a large concentration of PPCPs has been detected in various water environmental media, and sulfonamides, antibiotics, ibuprofen, carbamazepine and DEET are widely distributed in the environment, among which sulfamethoxazole has the highest detection frequency and the highest concentration can reach 1080ng/L[8]. China is the world's largest consumer of drugs, with more than 20000t PPCPs used annually, which have been widely detected in surface water, groundwater, soil and sediments, among which antibiotics transmitted through water bodies are used more[7] than others. In addition, PPCPs are also detected in water environmental media in the United States[50], Europe[57], and Africa[9], and the study found that the concentration of PPCPs is positively correlated with the degree of economic development. In China, the highest concentration of sulfamethoxazole is detected in the sediments of the Qingpu District of Shanghai, with a concentration of 688.59ng/L[44], while the highest concentration of sulfamethoxazole in other countries is detected in groundwater of the United States, with a concentration of 1110ng/L[50]. The concentration of PPCPs in pore water and seawater is relatively low, and caffeine is the most widely detected PPCP in seawater. Some compounds have been detected in rainwater because of their volatility. Atrazine has been reported in Mississippi and at the mouth of the Yangtze River[60-61]. The presence of ofloxacin and ciprofloxacin has also been detected in Minnesota, USA[38]. PPCPs in groundwater are mainly produced through the infiltration of domestic sewage, hospital and aquaculture wastewater, and compounds with greater polarity are more likely to penetrate into groundwater[59]. Antibiotics such as lincomycin and erythromycin have been detected in groundwater in North America, Jianghan Plain of China[53,50] and Harbin[52]. Carbamazepine is one of the most commonly detected drugs in sediments, and it has been reported in the Haihe River and Baiyang Lake[55], with the highest concentration of 14.7ng/g, and also in the sediments of the Taihu Lake Basin[54], the concentrations of ciprofloxacin and ofloxacin are relatively high, 15.33ng/g and 18.27ng/g respectively. The ocean is considered by many to be an important sink of pollutants. Studies have found that more than 20 kinds of antibiotics with concentrations as high as μg/L have been detected in seawater[62]. Among them, caffeine has been widely detected in the Aegean and Baltic Sea. Besides caffeine, sulfamethoxazole and clarithromycin also have a high detection frequency[57]. PPCPs were also detected in pore water and rainwater. The pore water samples of Baiyangdian Lake[55] mainly contain erythromycin and caffeine, but their concentrations are much lower than those of surface water in the same area. In Taihu Lake[56], the concentrations of oxytetracycline and ofloxacin are found, but the concentrations of surface water are lower than those of pore water. Therefore, the different physical and chemical conditions of environmental substrates in different study areas are considered to be the cause. There are relatively few reports of PPCPs in rainwater, and the content of PPCPS is less than 10ng/L.
PPCPs will degrade after entering water, and different degradation processes have their own degradation mechanisms. The degradation behavior of PPCPs in water mainly includes hydrolysis, photodegradation and biodegradation. Hydrolysis is an important way to eliminate or reduce the concentration of PPCPs in a water environment. Its essence is nucleophilic substitution reaction, that is, the nucleophilic group (hydroxide ion or water molecule) attacks the electrophilic group in the compound (RX), and replaces the associated strong electron-withdrawing group (X) with a negative electric tendency. For example, the hydrolysis of penicillin G and amoxicillin is the intramolecular nucleophilic attack of the side chain on the β-lactam carbonyl group, and the C-N bond is broken causing degradation. Degradation can be divided into direct photolysis and indirect photolysis processes. PPCPs with light-absorbing groups can be directly degraded by absorbing light energy. PPCPs without light-absorbing groups need to absorb photons through other substances to obtain energy, so that indirect photodegradation occurs. For example, atenolol is a degradation process that directly absorbs light energy, while acyclovir is an indirect photodegradation process by adding a catalyst. Biodegradation means that microorganisms change the chemical structure of PPCPs through a series of biochemical reactions under aerobic or anoxic conditions, and finally achieve the purpose of removal. At present, studies on the biodegradation of PPCPs mainly focus on three aspects: sewage treatment system, natural surface water and laboratory simulation system[79]. For sewage treatment plants, PPCPs are mainly removed through biodegradation of secondary treatment[80].
The degradation of PPCPs is affected by various factors, among which pH and temperature are the main influencing factors. The study on hydrolysis of PPCPs mainly considers the influence of pH on PPCPs. Different pH and target compounds will have different reactions, which have certain effects on the hydrolysis rate and hydrolysis products. In addition, temperature will also affect hydrolysis. In general, the higher the temperature, the faster the hydrolysis of a compound[61], because the hydrolysis process of a compound is a thermal reaction, and the activation energy mainly comes from the collision between molecules. The mechanism of photodegradation of PPCPs in water mainly lies in the molecular absorption of light energy into an excited state, which triggers various reactions[71]. There are many factors affecting the photodegradation of PPCPs in a water environment, mainly including pH of water and co-existing ions. It is generally believed that the higher pH in a water environment, the faster the photodegradation rate. Because many PPCP molecules contain acid-base dissociative groups, they are easily ionized in aqueous solution to produce a variety of dissociative forms, and the reason for affecting the ionization of PPCPs is the change of solution pH[74]. The presence of co-existing ions can either promote or inhibit the photodegradation of pollutants. The pH and temperature of the environment will affect the absorption, growth and metabolism of nutrients by microorganisms, thus changing the growth and living state of microorganisms, and then affecting biodegradation[82]. In addition, different compounds have different sensitivity to pH and temperature in the process of biodegradation. Also, the types of degraded strains have a certain impact on degradation. In general, photodegradation and biodegradation are more common than hydrolysis. In surface water, many PPCPs have avoided the strict biodegradation environment of wastewater treatment, and photochemistry may have a greater effect than the biodegradation under sunlight, in which antibiotics are mainly photodegraded in the water environment; ibuprofen, iopromide and caffeine are more prone to biodegradation; esters and amides are the most common functional groups that are easily hydrolyzed in PPCPs[63], and tetracycline can undergo hydrolysis reactions due to adsorption into sediments. The factors affecting the degradation of PPCPs include pH, temperature, co-existing ions and dissolved organic matter, among which pH and temperature are the main factors affecting the degradation. Exploring the fate of PPCPs in the environment is the key to studying their distribution and environmental level, so it is necessary to analyze the degradation mode of PPCPs in a water environment to help further understand the degradation principle and behavior of PPCPs.
Future research on PPCPs should be more in-depth and detailed. More emphasis will be placed on the water environment such as rain and sea water, which has been studied less before, to make the system more complete. The current research mainly focuses on the migration, transformation and toxic effects of PPCPs, and the toxic effects of degradation products need to be studied further. It is necessary to study the behavior, migration, transformation and toxic effects of PPCPs metabolites in the water environment, so as to provide basis for water environment pollution removal. In addition, the content of PPCPs in the water environment is very low, and the testing technology and instrument requirements are relatively strict. The existing analysis technology and instrument conditions need to be continuously improved to establish a more comprehensive and systematic testing system.
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Keywords:
- water environment /
- pharmaceuticals and personal care products (PPCPs) /
- concentration level /
- degradation behavior /
- influencing factors
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铊属于稀散元素，常分散赋存于岩石中；在地球化学上既有亲石性，又有亲硫性。亲石性表现为以类质同象的形式与钾、钠等元素在云母和钾长石等富钾矿物共生；而在低温高硫环境中，则表现为亲硫性，以类质同象的形式进入各种铅锌铜铁等硫化物矿物中。20世纪70年代，为了寻找放射性同位素205Pb曾经存在的证据和探究核素合成的机理，科研人员开始了对铊同位素的研究［1］。在早期的研究中，由于测试用的热电离质谱仪(TIMS)的质量分馏不稳定，且难以激发高电离能的元素，导致铊同位素分析结果的精密度较差，不能满足大部分研究的需要。近些年，随着具备高电离能力的多接收器电感耦合等离子体质谱仪(MC-ICP-MS)的出现，同时得益于铅对分析过程中铊同位素分馏的校正，使分析结果的精密度有了大幅提高(优于0.05‰)［2-5］。
由于铊兼有亲石和亲硫性，其同位素组成对吸附、共沉淀、氧化还原等过程较为敏感，因此可以被应用于天体演化［6］、古环境变化［7］、矿床成因［8］及污染物迁移［9-11］等过程的示踪。但因为自然界样品中铊的含量低(地壳中铊的平均含量仅为0.75mg/kg)，且同位素组成的变化范围和自然分馏效应很小［12］，导致很难获得高精度和高准确度的铊同位素数据。因此，除高精度的仪器测量外，样品的消解、分离和纯化等化学前处理流程对铊同位素分析结果的准确与否也至关重要。对于铊含量的分析，分解试样时如果不知道矿石中铊的赋存状态，一般选用含有氢氟酸的混合酸或强碱性熔剂分解［13-16］。而对于富含有机质的样品，由于亚铊的氧化物、氯化物等具有挥发性，应避免使用直接灼烧法除去有机质，而是采用湿法氧化分解［14，16］。目前国内外地质样品中铊同位素测定的消解方法主要为电热板加热法。这种方法便于在洁净的化学实验室完成，但清洗容器和样品消解过程的用时较长，耗时往往超过一周［4］。根据地质样品岩性的不同，消解所用的混合酸体系也不相同，尚无统一的标准。铊的分离和纯化一般利用Tl+和Tl3+在盐酸介质中与Cl−络合能力的不同。需要注意的是，在纯化后的铊馏分中应尽可能减小铅量，否则由于残留的铅同位素组成是未知的(校正时添加标液的铅同位素是已知的)，会影响铊的同位素分馏校正；此外，天然样品204Pb的自然丰度虽然仅有铅总量的1.4%，但204Pb1H多原子离子干扰对于铊同位素的高精度测量仍不可忽视。目前，使用阴离子交换树脂(如AG1-X8或AG-MP-1M树脂)二次过柱是普遍采用的铊提纯方法。该方法由Rehkämper等［2］首次提出，后经Nielsen等［3］、Baker等［6］、Owens等［17］研究团队发展和完善。该方法两次过柱均采用同一种阴离子交换树脂，第一次分离时采用装有1.5mL树脂的石英柱，依次用硝酸-氢溴酸-饱和溴水淋洗液洗脱基体元素、盐酸-饱和溴水淋洗液洗脱干扰元素铅，最后用盐酸-二氧化硫淋洗液收集铊。收集到的铊馏分经硝酸蒸干后，加入氢溴酸-饱和溴水提取液进行二次过柱，以保证完全消除干扰组分的影响。第二次过柱时，除所用体积与第一次不同之外，淋洗液的类型和浓度均与第一次相同。此外，Wang等［5］开发了磷酸三丁酯(TBP)树脂和AG50W-X12阳离子交换树脂的两级串联分离纯化方案，以NIST 997为参考物质测定BHVO-2、BCR-2、AGV-2、GSP-2、COQ-1、NOD-P-1、NOD-A-1、GBW07406、SCO-1共9种地质标准样品的同位素组成，获得了理想的结果。
微波消解是一种利用微波的穿透性和激活反应能力加热密闭容器内的试剂和样品的技术，具有省时、省酸、安全、空白值低、易实现自动监控、污染小以及损失少等优点，已广泛应用于食物［18-19］、环境［20］、生物［21］、植物［22］以及矿物［23-26］等样品中重金属元素的分析。本文为提高铊同位素分析中化学前处理流程的效率，研究了利用微波消解技术分解地质样品进行铊同位素分析的可行性，比较了硝酸-氢氟酸-盐酸-过氧化氢和硝酸-氢氟酸-高氯酸混合酸体系对样品的消解情况。消解后的样品经AG1-X8阴离子交换树脂分离纯化后，采用MC-ICP-MS结合铅标准溶液(NIST SRM981)质量分馏校正法进行同位素分析。使用优化后的实验方案分析了4个地质标准物质的铊同位素组成，获得较为满意的结果。
1. 实验部分
1.1 仪器和主要装置
铊同位素组成的测试运用Neptune plus多接收器电感耦合等离子体质谱仪(MC-ICP-MS，美国ThermoFisher公司)完成，进样系统包括双路气旋式雾化室、Jet样品锥和X截取锥，检测器包括9个法拉第杯和1个离子计数器。
淋洗曲线标定及回收率测试应用7500cx电感耦合等离子体质谱仪(ICP-MS，美国Agilent公司)完成，内标溶液为10ng/mL铑(2%硝酸介质)。MC-ICP-MS和ICP-MS质谱仪的主要工作参数见表1。
表 1 MC-ICP-MS和ICP-MS仪器主要工作参数Table 1. Main operation conditions of MC-ICP-MS and ICP-MS instruments工作参数 设定值 MC-ICP-MS ICP-MS 冷却气(Ar)流速(L/min) 16.00 14.95 辅助气(Ar)流速(L/min) 0.86 0.28 雾化气(Ar)流速(L/min) 0.05 0.92 射频功率(W) 1152 1470 积分时间(s) 4.194 / 每组测量次数 30 / 测量组数 1 / 实验用水由超纯水系统(美国Millipore公司)制备，电阻率18.2MΩ·cm。
高纯酸由NJ-SCH-I酸纯化器(南京滨正红仪器有限公司)纯化。
样品消解由Ethos1微波消解仪(意大利Milestone公司)完成。
PFA微型离子交换柱：北京博明远科技有限公司，下部为0.65cm(内径)×10.0cm(高)，上部为1.5cm(内径)×5cm(高)，总容量约15mL，底部为孔径20μm的亲水性筛板。
1.2 标准物质和主要试剂
铅同位素标准溶液NIST SRM981、铊标准溶液GSB 04-1758-2004和地质标准物质(NOD-P-1、NOD-A-1、GBW07406、GSP-2)详细信息见表2。
表 2 地质标准物质和同位素标准溶液的详细信息Table 2. Details of geological reference materials and isotope reference solutions标准物质编号 样品类型 研制单位 推荐值 铊 铅 NIST SRM 981 铅同位素标准溶液 美国标准与技术研究院(NIST) / 10μg/mL GSB 04-1758-2004 铊标准溶液 中国有色金属及电子材料分析测试中心 1000μg/mL / NOD-P-1 铁锰结核 美国地质调查局(USGS) 210±2μg/g 560±6μg/g NOD-A-1 铁锰结核 美国地质调查局(USGS) 120±1.0μg/g 846±8.2μg/g GBW07406 土壤 中国地质科学院地球物理地球化学勘查研究所 2.2±0.6μg/g 314±25μg/g GSP-2 花岗岩 美国地质调查局(USGS) 1.1±0.1μg/g 43±3μg/g 阴离子交换树脂(AG1-X8，100～200目)：购自美国Bio-Rad公司。
优级纯的盐酸、硝酸和氢氟酸(上海国药集团化学试剂有限公司)：经二次亚沸蒸馏纯化后使用；高氯酸(优级纯，上海国药集团化学试剂有限公司)；过氧化氢、饱和溴水(分析纯，广州西陇化工股份有限公司)；二氧化硫标准气体(99.9%，广东英德市西洲气体有限公司)。
0.1mol/L盐酸-6%二氧化硫溶液的配制：将二氧化硫标准气体通入0.1mol/L盐酸中，使其质量增加6%，现用现配。
1.3 样品消解
根据铊在样品中的含量，称取50～300mg粉末状样品(200目，105℃烘干2h)于干净的PFA(可溶性聚四氟乙烯)消解罐中，用少量水润湿，加入2mL氢氟酸、2mL硝酸和0.5mL高氯酸；充分混匀，放置反应1h后，加盖拧紧；按表3的升温程序进行微波消解。冷却后，缓慢泄压放气，打开消解罐，将样品转移至15mL 聚四氟乙烯杯中180℃加热至白烟冒尽，加入2mL 6mol/L盐酸溶解，120℃蒸干，重复一次(除尽氢氟酸、硝酸和高氯酸)。最后加入2mL 2mol/L硝酸-1%饱和溴水，加盖密闭后80℃加热12h，待溶液冷却，离心后进行色谱分离。
表 3 样品处理微波消解程序Table 3. Microwave digestion procedure for sample pretreatment步骤 消解温度
(℃)消解功率
(W)加热时间
(min)保持时间
(min)1 120 400 5 5 2 150 800 5 5 3 190 1200 5 20 需要特别注意的是：①所有的敞口操作必须在超净工作台进行，以防外部环境中铅及其他元素的污染；②为避免酸的损失和安全伤害，消解罐必须完全冷却后才能泄压开盖［22］。
1.4 铊的纯化
铊的纯化流程在Nielsen等［3，27］的研究基础上作了部分优化，优化内容主要包括：①将双柱淋洗修改为单柱淋洗；②控制淋洗液的总体积在28mL。详细步骤如下(流程见表4)：采用湿法填充树脂柱，将约2mL AG1-X8树脂置于微型离子交换柱中，依次用1mL 0.1mol/L盐酸-6%二氧化硫和1mL超纯水清洗两遍，再用2mL 2mol/L硝酸-1%溴水平衡树脂2次；然后将离心后的样品溶液加载于树脂柱上，用2mL 2mol/L硝酸-1%溴水淋洗6次和2mL超纯水淋洗1次，以除去基体元素；随后用2mL 0.1mol/L盐酸-6%二氧化硫淋洗5次，收集铊。最后将收集到的0.1mol/L盐酸-6%二氧化硫溶液置于电热板120℃蒸干，然后用0.5mL 0.1%硫酸-2%硝酸溶解，准备进行质谱测试。
表 4 铊同位素的离子交换流程(2mL AG1-X8树脂，100～200目)Table 4. Chemical purification procedure for Tl isotopes (2mL AG1-X8 resin, 100-200 mesh)步骤 淋洗液 淋洗液体积
(mL)淋洗
次数实验目的 1 0.1mol/L盐酸-6%二氧化硫 1 2 清洗树脂 2 超纯水 1 2 清洗树脂 3 2mol/L硝酸-1%溴水 2 2 清洗/平衡树脂 4 2mol/L硝酸-1%溴水 2 / 装载样品 5 2mol/L硝酸-1%溴水 2 6 洗脱基质 6 超纯水 2 1 洗脱NO3−和BrO− 7 0.1mol/L盐酸-6%二氧化硫 2 5 收集铊 1.5 铊同位素分析
铊同位素的分析测定在桂林理工大学广西隐伏金属矿产勘查重点实验室进行。由于自然界样品的铊同位素组成的变化范围很小，用传统的千分偏差“δ”往往不能有效地反映其同位素组成的差异，所以国际上铊同位素测试结果普遍以万分偏差“ε”来表示［1］。另外，由于未购买到国际上普遍认可的铊同位素标准物质NIST 997，本文选择以中国有色金属及电子材料分析测试中心研制的铊同位素物质GSB 04-1758-2004为参照，即用ε205TlGSB Tl表示：
$$ \varepsilon^{205}\mathrm{T}\mathrm{l}_{\mathrm{G}\mathrm{S}\mathrm{B}\ \mathrm{T}\mathrm{l}}=\left[\frac{(^{205}\mathrm{T}\mathrm{l}/^{203}\mathrm{T}\mathrm{l})_{\mathrm{s}\mathrm{a}\mathrm{m}\mathrm{p}\mathrm{l}\mathrm{e}}}{(^{205}\mathrm{T}\mathrm{l}/^{203}\mathrm{T}\mathrm{l})_{\mathrm{G}\mathrm{S}\mathrm{B}\mathrm{ }\ \mathrm{T}\mathrm{l}}}-1\right]\times10000 $$ 测试时MC-ICP-MS仪器的法拉第杯结构为：L3(202Hg)、L2(203Tl)、L1(204Pb)、C(205Tl)、H1(206Pb)、H2(207Pb)、H3(208Pb)，其他主要工作参数见表1。样品引入时的介质均采用2%的硝酸，2ng/mL GSB 04-1758-2004标准溶液对应205Tl电压信号约为1.2V。测试过程产生的质量歧视通过加入已知铅同位素组成的溶液(NIST SRM981)进行校正，计算方法参考文献[5]。在这项研究中，铅标准溶液的质量按照mPb/mTl=10/1加入。在每次测量开始之前，都需要仔细调整仪器参数，以确保铊和铅的信号强度最大化；同时，进行重复的质量扫描，以检查法拉第杯位置是否合适并监测峰形，确保同位素比值测量的仪器条件。此外，为了校正样品的铊同位素组成，在每次分析前后均测量一次标准物质GSB 04-1758-2004。
2. 结果与讨论
2.1 消解条件的优化
2.1.1 无机酸组成及用量的影响
针对土壤和沉积物样品中的金属总量分析，中国环境保护标准《土壤和沉积物 金属元素总量的消解-微波消解法》(HJ 832—2017)推荐使用11mL硝酸-氢氟酸-盐酸的混合酸组合对样品进行消解。然而，若地质样品中的有机质或难溶矿物含量较高时，样品难以被完全分解，需使用硝酸-氢氟酸-高氯酸进行二次消解［28］。高氯酸和过氧化氢可以提高消解体系的分解能力，因此，本文试验了硝酸-氢氟酸-盐酸-过氧化氢和硝酸-氢氟酸-高氯酸两种混合酸体系对样品的消解情况。此外，为了控制干扰元素(特别是铅)的引入，实验中对酸的用量也进行了优化。
选择土壤标样GBW07406，称样量0.2g，加入不同的混合酸组合，按表3中程序进行微波消解，测定结果见表5。在硝酸-氢氟酸-盐酸-过氧化氢混合酸体系中，当用酸量总体积为4mL(组号1-1)时，消解液中有少量不溶的白色沉淀，此时铊回收率仅有84.7%，说明酸用量太少，不足以将0.2g样品消解完全。将酸用量进一步提升(组号1-2和1-3)，所得消解液为清亮透彻的黄色溶液，铊回收率均接近100%，说明硝酸-氢氟酸-盐酸-过氧化氢体系中，7mL酸用量(组号1-2)就可以将0.2g样品消解完全。在硝酸-氢氟酸-高氯酸混合酸体系中，消解样品所用的酸量要少，仅4.5mL(组号2-2)就可将0.2g样品消解完全，此时得到的消解液为清澈透亮的黄色溶液，铊回收率为98.2%。鉴于同位素分析中尽可能低本底的需求，本实验选择2mL硝酸-2mL氢氟酸-0.5mL高氯酸(组号2-2)的混合酸体系对样品进行消解。
表 5 不同无机酸种类及用量的消解效果对比(n=3)Table 5. Comparison of digestion effects of different types and volumes of inorganic acids (n=3)混合酸体系 实验组号 混合酸体系各酸用量
(mL)样品消解效果观察 铊回收率
(%)硝酸-氢氟酸-
盐酸-过氧化氢1-1 1+1+1+1 有少量不溶白色沉淀 84.7 1-2 2+2+2+1 黄色消解液清澈透亮 98.4 1-3 5+3+3+1 黄色消解液清澈透亮 98.6 硝酸-氢氟酸-
高氯酸2-1 1+1+0.5 有少量不溶白色沉淀 81.9 2-2 2+2+0.5 黄色消解液清澈透亮 98.2 2-3 5+3+0.5 黄色消解液清澈透亮 99.0 需要特别指出的是，高氯酸与有机质在密闭系统中反应剧烈，易发生爆炸，使用时不仅要严格控制其用量，还要在微波消解之前放置反应一段时间(本文建议时长为1h)。
2.1.2 微波消解程序的选择
为了考察微波消解程序中的最高温度和保持时间对消解效果影响，本文选择土壤标样GBW07406为试验样品，保持其他条件不变；以表3中步骤3的消解温度和保持时间为因素，进行正交试验，分析结果如表6所示。结果表明，当消解温度设定在190℃，保持时间为20min时，铊的回收率大于98%。继续升高消解温度和增加保持时间并不能使铊的回收率显著提高，且高温高压易造成微波消解内管变形，影响其密闭性。因此，190℃保持20min为本文推荐使用的微波消解条件，此时总的微波消解时间为45min。
表 6 消解温度和保持时间的正交试验结果(n=3)Table 6. Orthogonal test results of digestion temperature and holding time (n=3)编号 因素水平 铊回收率
(%)消解温度(℃) 时间(min) 1 180 15 86.6 2 180 20 93.1 3 190 15 94.0 4 190 20 98.2 5 200 15 97.8 6 200 20 99.1 2.2 铊在阴离子交换树脂上的淋洗曲线
203Tl和205Tl的干扰主要来自163Dy40Ar、165Ho40Ar、187Re16O、189Os16O、202Hg1H、204Hg1H和204Pb1H等多原子离子团，因此在进行铊的纯化时需特别关注共存元素镝、钬、铼、锇、汞和铅的分离情况。
选择0.2g消解后的标准物质GBW07406为试验样品，按表4中铊同位素的离子交换流程，以1mL为单位接取馏分；利用ICP-MS测定各馏分中相应元素的含量并绘制淋洗曲线，结果如图1所示。从淋洗曲线中可以看出，绝大多数基质元素及干扰元素(包括镝、钬、铼、锇、汞和铅)被最开始的6mL 2mol/L硝酸-1%溴水洗脱。为了尽可能地减少铅的残留，本课题组继续使用了6mL 2mol/L硝酸-1%溴水淋洗；接下来，用2mL超纯水将树脂中的氧化性离子(NO3−和BrO−)洗脱。随后以10mL 0.1mol/L盐酸-6%二氧化硫淋洗并收集馏分中的铊。通过对该馏分的组分分析发现，铊的回收率约为98.5%，镝、钬、铼、锇和汞几乎无残留，铅的残留量不足铊量的1/10，钡有一定的残留，约为总钡量的4%。其中，接取液中钡和极少量铅的残留对铊的同位素测试没有影响，当地质样品中的铅/铊比值大于1000时，铅的残留可能会导致铊同位素组成测定结果偏高［5］，此时建议进行二次过柱。
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图 1 铊的淋洗曲线(AG1-X8树脂，100～200目)，其中2mol/L硝酸-1%溴水洗脱基体元素，超纯水洗脱残留NO3−和BrO−，0.1mol/L盐酸-6%二氧化硫收集铊Figure 1. Elution curves of Tl (AG1-X8 resin, 100-200 mesh), 2mol/L HNO3-1% Br2 for eluting matrix elments, ultrapure water for eluting NO3− and BrO−, 0.1mol/L HCl-6% SO2 for collecting Tl.2.3 基质中铁钙铝对铊测量的影响
铊在地质样品中的含量通常低于0.1μg/g，往往需要加大称样量来提高测试精度。大多数样品以硅质或碳质为主，经消解后，硅和碳都挥发除去，所留下的盐分很少，而富含赤铁矿(铁高)、灰岩(钙高)和高岭土(铝高)等类型的地质样品，消解后的溶液中金属离子的浓度很高，而树脂的总离子交换容量一般在3～6mmol/g(干基)或1～2mmol/g(湿基)。因此，为考察这三种阳离子对淋洗流程的干扰，本文采用标准加入法考察了三氧化二铁、氧化钙和三氧化二铝对上述淋洗曲线中铊回收率的影响。操作步骤为：取三组1mL 1μg/mL铊标准溶液(GSB 04-1758-2004)，分别加入0.1～0.5g的Fe2O3、CaO和Al2O3，按第1.3、1.4、1.5节进行前处理和样品测试。三种元素的加入量与铊回收率之间的关系如图2所示。
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图 2 三氧化二铁、氧化钙和三氧化二铝对铊回收率的影响(n=3)Figure 2. Influences of the load of Fe2O3, CaO and Al2O3 on the recovery of Tl (n=3)从图2可以看出，CaO的加入对铊回收率的影响很小，可以忽略。Fe2O3的影响最大，当其加入量为0.4g(约2.56mmol)时，铊的回收率开始下降，约为90%；当加入量为0.5g时，铊的回收率下降到只有75%左右。这可能是因为随着样品中Fe3+的增多，用盐酸淋洗时容易形成络合物FeCl4−，占据离子交换反应位点，使树脂的交换容量达到饱和，从而降低了铊的回收率。而对于Al2O3，当其加入量为0.5g(约4.90mmol)时，铊的回收率略有下降，约为93%，从观察到的实验现象判断，原因应是Al2O3有部分结晶，夹杂着少量铊进入固相析出而导致的。因此，对于基质中含铁、铝矿物较高的样品应控制其称样量，以防树脂的交换容量饱和而导致铊回收率偏低。
2.4 流程空白
通过三份空白试验使用第1.3、1.4、1.5节步骤中的流程进行铊同位素分析，最终确定整个实验流程中铊的空白值低于10pg，远低于普通地质样品中铊含量的1‰，对测试结果的影响可以忽略［23］。
2.5 地质标准物质中铊同位素组成的测定结果
为了确保MC-ICP-MS测定铊同位素的长期可重复性，对铊标准溶液GSB 04-1758-2004进行40次测量，结果如图3所示。图中的205Tl/203Tl值是以铅标准溶液NIST SRM981为外标校正后的结果(相对于208Pb/206Pb=2.1076)。本实验室的测量结果为205Tl/203Tl=2.38775，标准偏差(2σ)为0.00011，说明仪器的稳定性较好。
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图 3 铊标准溶液GSB 04-1758-2004测量结果的稳定性(n=40)Figure 3. The reproducibility of analytical results for Tl standard solution GSB 04-1758-2004 (n=40)按照优化后的化学流程，处理4个地质标准物质，并进行铊同位素组成的测定。从表7中的测定结果可以发现，4个标准物质的2SD均优于0.3(n=6)，说明本方法具有较高的精密度。由于与文献选用的同位素标准物质不同，方法的准确度可以用两者间差值变化情况来考察。通过与文献的结果对比发现，标准物质NOD-P-1、GBW07406和GSP-2的ε205Tl差值(ε205TlNIST 997−ε205TlGSB Tl)均为0.8，NOD-A-1的ε205Tl差值为0.7，说明方法具有较好的准确性；此外，可以估算标准物质GSB 04-1758-2004相对于NIST 997的ε205Tl值应约等于0.8。
表 7 地质标准物质中铊同位素组成的测定结果及文献对比Table 7. Comparison of analytical results of Tl isotope composition in geological reference materials determined by this method and those in the literatures3. 结论
通过对铊同位素分析中的消解方法、淋洗曲线和流程空白的分析讨论可知，采用微波消解法，在2mL硝酸-2mL氢氟酸-0.5mL高氯酸的混合酸体系中选用适当的消解程序，可以将0.2g土壤标准物质GBW07406彻底消解；利用AG1-X8阴离子交换树脂，依次以2mL 2mol/L硝酸-1%饱和溴水淋洗6次、2mL超纯水淋洗1次和2mL 0.1mol/L盐酸-6%二氧化硫淋洗5次，并收集0.1mol/L盐酸-6%二氧化硫的馏分，可有效地纯化地质样品中的铊。该淋洗流程所允许上样溶液中含有三价铁和三价铝离子的量分别不应超过2.56mmol和4.90mmol，否则引起树脂的离子交换容量饱和而导致铊回收率降低。与前人相比，该流程缩短了消解时间，采用AG1-X8树脂单柱法进行铊同位素的纯化，将淋洗液的总体积优化至24mL。本工作提高了铊同位素分析中化学前处理流程的效率，将此方法应用于4个不同地质标准物质的铊同位素比值的测定，结果证明具有较好的精密度和准确性。
需要指出的是，由于外界因素的制约，国际上普遍认可的NIST 997标准物质在中国已很难购买，影响了国内铊同位素地球化学研究工作的开展，所以中国亟需研制出国际上认可的铊同位素标准物质。
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图 1 水环境中PPCPs的来源与迁移归趋
Figure 1. Source and migration fate of PPCPs in water environment.
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表 1 抗生素、激素、消炎止痛药、降压药类等常见PPCPs的物理化学特征
Table 1 Physical and chemical characteristics of common PPCPs such as antibiotics, hormones, anti-inflammatory painkillers and antihypertensive drugs.
PPCPs
的常见类别中文名称 英文名称 缩写 分子式 医学应用 CAS号 抗生素 磺胺甲噁唑 Sulfamethoxazole SMX C10H11N3O3S 抗菌 723-46-6 诺氟沙星 Norfloxacin NOR C16H18FN3O3 治疗肠炎痢疾 70458 -96-7四环素 Tetracycline TC C22H24N2O8 杀菌 60-54-8 土霉素 Oxytetracycline OTC C22H28N2O11 治疗犬、猫的呼吸道、尿道感染 79-57-2 红霉素 Erythromycin ERY C37H67NO13 治疗呼吸道感染 114-07-8 激素 地塞米松 Dexamethasone DEX C22H29FO5 抗炎、免疫抑制 50-02-2 雌酮 Estrone E1 C18H22O2 维持雌性个体的第二生理特征 53-16-7 乙烯雌酚 Diethylstilbestrol DES C18H20O2 治疗雌激素低下症及激素平衡失调引起的功能性出血 56-53-1 消炎止痛药 萘普生 Naproxen NAP C14H14O3 止痛解热 22204 -53-1双氯芬酸 Diclofenac Acid DIC CHClNO 治疗风湿性关节炎等 15307 -86-5布洛芬 Ibuprofen IBU C13H18O2 镇痛、抗炎 15687 -27-1降压药 科素亚 Losartan - C22H22ClKN6O 降血压 124750 -99-8缬沙坦 Valsartan ARB C24H29N5O3 降血压 137862 -53-4降血脂药 吉非罗齐 Gemfibrozil GEM C15H22O3 调血脂 25812 -30-0苯扎贝特 Bezafibrate BZF CHClNO 调血脂 41859 -67-0β-受体阻断药 阿替洛尔 Atenolol - C14H22N2O3 降压、调整心率 29122 -68-7美托洛尔 Metoprolol MPL C15H25NO3 降压、调整心率 51384 -51-1抗精神病药 卡马西平 Carbamazepine CBZ CHN2O 治疗癫痫、神经性疾病 298-46-4 可铁宁 Cotinine - C10H12N2O 促进神经系统兴奋 486-56-6 驱虫剂 避蚊胺 Diethyltoluamide DEET C12H17NO 防止蚊虫叮咬 134-62-3 合成麝香 佳乐麝香 Galaxolide HHCB C18H26O 用于化妆品、调制香料 1222 -05-5吐纳麝香 Tonalide AHTN C18H26O 用于化妆品、调制香料 1506 -02-1消毒杀菌剂 三氯生 Triclosan TCS C12H7Cl3O2 抗菌除臭 3380 -34-5三氯卡班 Triclocarban TCC C13H9Cl3N2O 杀菌除臭 101-20-2 除草剂 阿特拉津 Atrazine ATZ C8H14ClN5 除草 1912-24-9 
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表 2 水环境中抗生素类PPCPs在地表水、地下水、沉积物、孔隙水、海水、雨水中的检出情况
Table 2 Detection of antibiotic PPCPs in surface water, groundwater, sediment, pore water, seawater and rainwater.
水环境
介质PPCPs化合物 PPCPs检出含量
（ng/L）水环境 数据来源 地表水 磺胺甲恶唑 ND~57.76 中国上海市青浦区 [44] 28.34 中国上海黄浦江 [45] ＜MDL~934 斯里兰卡 [46] 0.7~16 意大利米兰 [47] 77.7（最大浓度） 密西西比河国家河和娱乐河 [13] 氧氟沙星 114 中国黄河 [42] 0 中国黄浦江 [45] 诺氟沙星 152 中国黄河 [42] 0 中国黄浦江 [45] 红霉素 34 中国黄河 [42] 0~722.04 中国天津 [48] 罗红霉素 53 中国黄河 [42] 3.63 中国黄浦江 [45] 四环素 113.89 中国黄浦江 [45] 0~9.74 天津 [48] 地下水 醋磺胺甲恶唑 ND~91 中国北运河 [49] 磺胺二甲基嘧啶 ND~969.7 中国北运河 [49] 磺胺甲恶唑 ND~14.2 中国北运河 [49] 1110 美国 [50] 23.40 西班牙 [51] 磺胺嘧啶 11.62 西班牙 [51] 29.9 哈尔滨 [52] 环丙沙星 4~9.68 中国江汉平原 [53] 0.82 哈尔滨 [52] 四环素 2.26~9.51 中国江汉平原 [53] 罗红霉素 1.47~13.8 中国江汉平原 [53] 诺氟沙星 4.74~52.6 中国江汉平原 [53] 土霉素 1.1~7.24 中国江汉平原 [53] 林可霉素 0.32 美国 [50] 沉积物 磺胺甲恶唑 1. 27~688.59 中国上海市青浦区 [44] 0~11.3 中国太湖 [54] 磺胺嘧啶 0~0.41 中国太湖 [54] 土霉素 0~8.73 中国太湖 [54] 环丙沙星 0~15.33 中国太湖 [54] 氧氟沙星 0.9~18.27 中国太湖 [54] 罗红霉素 0.15~3.96 中国太湖 [54] 孔隙水 红霉素 29.9 中国白洋淀 [55] 林可霉素 20.2 中国白洋淀 [55] 土霉素 47.8 中国太湖 [56] 氧氟沙星 33.6 中国太湖 [56] 雨水 环丙沙星 10.3 美国明尼苏达州 [38] 恩诺沙星 2.97 美国明尼苏达州 [38] 海水 磺胺甲恶唑 42 波罗的海 [57] 11 希腊爱琴海 [57] 7.2 意大利威尼斯 [57] 克拉霉素 14 波罗的海 [57] 16 希腊爱琴海 [57] 8.5 意大利威尼斯 [57]
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表 3 水环境中PPCPs常见化合物的降解类型、影响和因素及降解产物
Table 3 Types, effects, factors, and degradation products of common PPCPs in the water environment.
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