典型PPCPs的生态毒理效应与强化处理技术

人类长期且大量的使用药品及个人护理用品（PPCPs），使其持续不断地输入环境，导致它们在环境中的残留浓度日益增加，并对人类和其他生物产生了不良的生态毒理效应。本文以四种典型PPCPs（对乙酰氨基酚、土霉素、三氯生、佳乐麝香）为研究对象，采用常规的毒理学实验方法，研究了它们对小麦种子发芽、根伸长的急性毒性，以及低浓度长期暴露对小麦幼苗叶绿素（CHL）、可溶性蛋白（SP）、过氧化物酶（POD）和超氧化物歧化酶（SOD）等生理生化特性的影响。由于PPCPs具有生态风险性，而传统的水处理工艺却不能有效的将这些物质去除。因此，开发更多的新技术以强化处理PPCPs，使它们在环境中残留的浓度尽可能降低是一项很重要的工作。本研究以零价铁处理有机物的原理为依据，自制铁铜双金属复合物，研究了其对PPCPs溶液的处理效果及影响因素，并对整个过程中的反应机理进行了初探。实验结果表明： 实验浓度下，四种PPCPs与小麦根长及芽长抑制率之间具有良好的剂量-效应关系。根据线性回归方程计算的EC50可知，不同种类的PPCPs对小麦种子发芽的毒性大小不同，而且小麦的芽及根部对不同PPCPs胁迫的敏感部位不同。对乙酰氨基酚、土霉素、三氯生对小麦根长的抑制较芽长显著，它们的EC50分别为668.8 mg/L、34.7 mg/L和147.8mg/L；而佳乐麝香对小麦芽长的抑制更为显著，EC50为143.4 mg/L。实验浓度范围内，四种PPCPs对小麦种子的发芽率均没有显著的抑制作用。四种PPCPs暴露21天后，2.8～22.4 mg/L对乙酰氨基酚、0.15～2.4 mg/L土霉素以及0.2～3.0 mg/L三氯生和佳乐麝香显著抑制小麦叶片/根部中的CHL和SP，而且使POD和SOD酶活性降低或上升，从而打破抗氧化系统的动态平衡；暴露21天内对CHL、SP、POD和SOD等含量在不同PPCPs胁迫下的变化趋势具有各自的特点。 以零价铁降解有机物的原理为依据，自制了铁铜双金属复合体系，以强化处理PPCPs溶液。电子扫描显微镜（SEM）及X-衍射（XRD）分析得出铁铜复合物（FeCu/Cu2O）由Fe、Cu及Cu2O组成。与零价铁相比，FeCu/Cu2O显著提高了对PPCPs的去除效果，主要是由于Cu的存在扩大了反应的电极电位差，即增加了Fe-Cu之间的外加阳极电流，从而加速Fe的阳极溶解，产生更多的高活性物质以更好的去除PPCPs。溶解氧是影响FeCu/Cu2O对PPCPs处理效果的重要因素，它们可以在FeCu/Cu2O表面获得电子后生成O2-，形成类Fenton体系。此外，由于Cu2O的光化学活性，光照也可以强化FeCu/Cu2O对PPCPs的处理效果。不同的反应条件下体系内的pH值及自由基的产生量不同。根据实验现象及相关的经典理论，本文对FeCu/Cu2O处理PPCPs的作用机理进行了初探，认为整个反应过程包括Fe的还原反应、Cu2O的光催化反应、Fe-Cu微电解反应以及絮凝过程等。

Estudio y propuestas de tratamiento de PPCP’s en aguas residuales

La reutilización de las aguas residuales es una parte esencial del uso sostenible del agua. Sin embargo, las actuales plantas de tratamiento no están preparadas para tratar determinados compuestos como los llamados “contaminantes emergentes”. Los hábitos de consumo actuales estan generando una serie de residuos o microcontaminantes que hace tan solo unos años no existian. Entre esas nuevas sustancias aparecen los PPCP’s (Pharmaceuticals & Personal Care Products) que son un amplio grupo de compuestos químicos utilizados en veterinaria, prácticas agrícolas, salut humana y cosmetología. El mayor problema que presentan estas substancias en la actualidad es el parcial desconocimiento sobre sus efectos, la ausencia de reglamentaciones que determinen las concentraciones máximas admisibles en los cauces de vertido, la reducción en procesos de depuración convencionales, así como los tratamientos específicos aplicables a su eliminación. Los objetivos del presente proyecto són: estudiar las tipologías de PPCP’s y sus influencias para la salud humana y el medio ambiente, estudiar los diferentes sistemas de tratamiento de aguas existentes en plantas depuradoras y evaluar su eficiencia en la depuración de PPCP

Brief for GSDR - Emerging Contaminants in urban stormwater: Challenges and perspectives for sustainable water use

Emerging contaminants (ECs) are chemical compounds commonly present in water. It is only recently that this family of compounds is being recognized as significant water pollutants (. ECs include a wide variety of chemicals such as pharmaceutical and personal care products (PPCPs), pesticides, hydrocarbons and hormones, among others, that once released into the environment exert adverse impacts on the human and wildlife endocrine system. Natural attenuation and conventional treatment processes are not capable of removing these micro-pollutants detected in wastewater influent and effluent and surface and drinking water. The main challenges related with presence of ECs in stormwater in the context of reuse are: a) Development of suitable laboratory test methodologies and protocols for ECs identification and quantification b) Identification of the sources of ECs in the urban environment; c) Understanding their impacts on human and/or ecosystem health; and d). Development of cost-effective removal technologies which are appropriate for large as well as small-scale application.

人工合成麝香的环境污染、生态行为与毒理效应研究进展

人工合成麝香作为一种替代型香料被广泛应用于日用化工行业,由于其持续不断地输入环境,其中的一些典型化合物如加乐麝香和吐纳麝香等在水、土壤和大气环境中的浓度日益升高,并且在动物体和人体组织中产生了蓄积作用,其效应相当于持久性有机污染物.因此,人工合成麝香作为一种新型污染物,已成为药物和个人护理品污染物(PPCPs)的重要组成部分.首先对人工合成麝香的种类与应用情况、环境来源和污染水平进行了简要介绍.在此基础上,从人工合成麝香的生物蓄积行为、环境降解行为和生物转化行为等3个方面,对人工合成麝香所具有的持久性有机污染物的行为特征进行了分析;概述了人工合成麝香的环境激素毒性、遗传毒性效应、生理生态毒性、对酶活性的影响以及对微生物毒性效应的研究进展,展示了人工合成麝香所可能产生的不良生态效应.最后,根据目前对人工合成麝香的研究进展,提出了今后有关重点研究内容的建议,为合理评价和降低人工合成麝香的生态风险提供理论基础.

天然溶解有机质和环境污染物的相互作用--以铜、汞离子和卡马西平为例

天然溶解有机质（natural dissolved organic matter，DOM）是由动植物残体经过复杂的物理、化学和生物过程形成的高分子有机混合物，它广泛分布于水体、土壤和沉积物中。DOM的结构十分复杂，分子量从几百到几十万不等，元素组成和化学结构随时空和来源不同而变化。腐殖物质是DOM的主要组成部分，以溶解有机碳计约占DOM总量的50%~80%。腐殖物质可以分为：富里酸（fulvic acid， FA任何pH值条件下都溶于水），腐殖酸（humic acid，HA在pH 1时不溶于水）和胡敏素（humin，任何pH条件下都不溶于水）。 DOM能影响许多生物地球化学过程。例如DOM是一个重要的碳汇，它能影响微生物的食物链和全球碳循环；DOM和营养元素含量、食物链结构等一起决定水生生态系统的属性和发展动态；它还能吸收自然光，从而影响紫外线在水中的穿透能力和浮游植物的光合作用；DOM含有多种弱酸和弱碱官能团，是天然水体pH的调节剂和控制因素；DOM和痕量金属离子或有机污染物发生作用，从而影响它们的形态、毒性、迁移转化和生物有效性；在饮用水消毒过程中，DOM能生成致癌物三卤甲烷和其它消毒副产物。 天然水体中的痕量金属离子（如Cu2+和Hg2+）主要以DOM络合态存在。在海水中DOM控制铜的主要存在形态；在淡水中 90%以上的铜离子与DOM发生配位。通过配位作用DOM能抑制浮游生物对Hg的吸收，增加鱼类对Hg的蓄积。目前，人们对金属离子在环境中的迁移转化机理的理解还不够深入，尤其是对有机质参与下的有毒重金属循环还缺乏必要地认识。条件稳定常数是描述重金属离子与DOM配位能力的基本参数。前人运用多种手段对DOM与金属离子的结合能力进行了研究，主要包括：离子选择性电极法、溶出伏安法、超滤及荧光淬灭滴定法等。紫外吸收滴定法可用于研究单一有机化合物和金属离子的相互作用，在这一领域的应用尚未报道。本文首次将紫外吸收滴定法应用于测定DOM与Cu2+和Hg2+的条件稳定常数。实验表明紫外吸收滴定法迅速、简便、可望成为研究DOM和痕量金属离子相互作用的有力工具。 药品和个人护理品（pharmaceuticals and personal care products，PPCPs）在环境中普遍存在。有证据表明，环境中的有些PPCPs能对生物体产生影响，如改变生物体的性别比例，影响植物生长，动物幼虫的孵化，甚至具有明显的致畸效应。卡马西平（Carbamazepine，CBZ）是一种常用的抗癫痫、止痛药物和抗抑郁药。毒理学实验表明，环境中的CBZ能严重影响鱼、蚌等水生生物的免疫和循环系统。CBZ使用量大，在环境中含量高，在地下水渗透过程和常规污水处理中保持稳定，因此CBZ成为衡量人类活动和污水处理工艺效率的标志物。但是目前人们对CBZ的环境地球化学循环知之甚少。DOM能与许多有机污染物发生相互作用，从而影响它们的生物环境地球化学行为，但DOM对CBZ的影响尚未见报道。本论文利用三维荧光光谱技术和同步荧光光谱技术，研究了DOM与CBZ的结合强度、结合类型、影响因素，并且初步总结了DOM对CBZ环境地球化学循环的影响。为理解其它PPCPs的生物地球化学循环，预测它们的迁移转化、归宿和环境毒性提供参考。 本文运用紫外吸收滴定法和荧光淬灭滴定法研究了不同来源的DOM和金属离子（Cu2+和Hg2+）的相互作用，运用三维荧光光谱法和同步扫描荧光光谱法研究了DOM和卡马西平的相互作用。主要成果简述如下： 1、本文首次将紫外吸收滴定法应用于测定金属离子和DOM的条件稳定常数，结果表明紫外吸收滴定法操作更简便、测定迅速、仪器普及率高，可在DOM含量很低（约10-5 ~ 10-7 mol/L）的情况下也可以直接进行测定，不必进行复杂的预富集。可望成为DOM和痕量有毒重金属离子相互作用的有力工具。 2、重金属离子（Hg2+和Cu2+）与DOM的羧基和酚羟基等基团配位。配位后电子的离域性增加，导致紫外吸收增加。与此同时配位后分子极性的改变和铜离子顺磁性作用，引起DOM荧光淬灭。在Cu2+和Hg2+的滴定过程中，紫外吸光度和荧光强度之间呈极显著线性负相关关系（R2=0.99，P<0.001）。这说明荧光和紫外从不同侧面揭示了DOM和金属离子的配位作用。 3、紫外吸收滴定法和荧光淬灭滴定法测定其条件稳定常数（log K）一致，介于3.5 ~ 5.5之间。强配位作用是DOM影响有毒重金属离子环境地球化学行为的根源。研究还表明配位作用的强弱受DOM来源和体系pH的影响。 4、 CBZ和DOM能发生强烈的相互作用，结合常数（log K）介于3.41 ~ 5.04之间。DOM能明显减少游离态CBZ的浓度，提高CBZ溶解度和迁移转化能力。这对认识CBZ和其它PPCPs的环境地球化学循环及其影响因素具有指导意义。 5、荧光光谱研究表明CBZ对DOM发射的荧光具有明显的猝灭作用，其猝灭机理为静态猝灭。疏水作用是CBZ和DOM之间的主要作用力。DOM-CBZ受pH值的影响不大， Cu2+对CBZ和DOM的结合有一定的影响。

Potencial de plantas estuarinas na remediação de produtos farmacêuticos e de cuidado pessoal

Dissertação para obtenção do Grau de Mestre em Engenharia do Ambiente, Perfil de Engenharia de Sistemas Ambientais

Removal of organic contaminants from wastewater using the electrodialytic process

Pharmaceuticals and personal care products (PPCPs) are widely used on a daily basis. After their usage they reach the wastewater treatment plants (WWTPs). These compounds have different physico-chemical characteristics, which makes them difficult to completely remove in the WWTPs, througth conventional treatments. Currently, there is no legislation regarding PPCPs thresholds in effluent discharge. But, even at vestigial concentrations, these compounds enclose environmental risks due to, e.g., endocrine disruption potential. There is a need of alternative techniques for their removal in WWTPs. The main goal of this work was to assess the use of electrodialytic (ED) process to remove PPCPs from the effluent to be discharged. A two-compartment ED cell was used testing (i) the effluent position in the cell (anode and cathode compartment); (ii) the use of anion (AEM) and cation exchange membrane (CEM); (iii) the treatment period (6, 12 and 24 hours); (iv) effluent recirculation and current steps; (v) the feasibility of sequential treatments. Phosphorus (P) removal from effluent and energetic costs associated to the process were also evaluated. Five PPCPs were studied – caffeine (CAF), bisphenol A (BPA), 17 β-estradiol (E2), ethinyl estradiol (EE2) and oxybenzone (MBPh). The ED process showed to be effective in the removal when effluent is in the anode compartment. Oxidation is suggested to be the main removal process, which was between 88 and 96%, for all the compounds, in 6 hours. Nevertheless, the presence of intermediates and/or by-products was also observed in some cases. Effluent recirculation should have a retention time in the ED cell big enough to promote removal whereas the current steps (effluent in anode compartment) slightly increased removal efficiencies (higher than 80% for all PPCPs). The sequential set of ED treatment (effluent in anode compartment) showed to be effective during both periods with a removal percentage between 80 and 95% and 73 to 88% in the case of AEM and CEM, respectively. Again, the main removal process is strongly suggested to be oxidation in the anode compartment. However, there was an increase of BOD5 and COD, which might be explained by effluent spiking, these parameters limiting the effluent discharge. From these treatments, the use of AEM, enhanced the P removal from effluent to minimize risk of eutrophication. Energetic costs of the best set-up (6 hours) are approximately 0,8€/m3 of wastewater, a value considered low, attending to the prices of other treatment processes.

Desarrollo de metodologías de extracción y microextracción combinadas con sistemas cromatográficos para la determinación de fármacos y productos de cuidado personal en muestras ambientales

Programa de doctorado en oceanografía

Micropollutants affect the ability of phytoplankton communities to track environmental changes

Human activities strongly influence environmental processes, and while human domination increases, biodiversity progressively declines in ecosystems worldwide. High genetic and phenotypic variability ensures functionality and stability of ecosystem processes through time and increases the resilience and the adaptive capacity of populations and communities, while a reduction in functional diversity leads to a decrease in the ability to respond in a changing environment. Pollution is becoming one of the major threats in aquatic ecosystem, and pharmaceutical and personal care products (PPCPs) in particular are a relatively new group of environmental contaminants suspected to have adverse effects on aquatic organisms. There is still a lake of knowledge on the responses of communities to complex chemical mixtures in the environment. We used an individual-trait-based approach to assess the response of a phytoplankton community in a scenario of combined pollution and environmental change (steady increasing in temperature). We manipulated individual-level trait diversity directly (by filtering out size classes) and indirectly (through exposure to PPCPs mixture), and studied how reduction in trait-diversity affected community structure, production of biomass and the ability of the community to track a changing environment. We found that exposure to PPCPs slows down the ability of the community to respond to an increasing temperature. Our study also highlights how physiological responses (induced by PPCPs exposure) are important for ecosystem processes: although from an ecological point of view experimental communities converged to a similar structure, they were functionally different.

The Removal of Pharmaceuticals From Wastewater by Wet-Air Oxidation

The ubiquitous occurrence of pharmaceuticals and personal care products (PPCPs) in aquatic environments has raised concerns about potential adverse effects on aquatic ecology and human health. Certain pharmaceuticals have recently become a major focus of research to better understand the routes and persistence of these compounds once they enter into aquatic system. In this research, two model compounds were selected to represent pharmaceuticals that have been identified by recent research as being persistent; specifically, these compounds were trimethoprim (TMP, a basic antibiotic) and gemfibrozil (GEM, an acidic lipid regulator). Treatment of synthetic wastewater that contained these drugs was accomplished using wet-air oxidation (WAO). Pre- and post-treatment drug concentrations were determined by reversed-phase liquid chromatography. The influences of different operational conditions on removal efficiency of the drugs by WAO were evaluated, namely reaction time, initial drug concentration, oxygen concentration, and the amount and composition of additional organic matter used during WAO. The optimum removal efficiencies were found to be 91.9 % for TMP and 95.5 % for GEM.

Assessment of the occurrence and potential effects of pharmaceuticals and personal care products in South Florida waters and sediments

A LLE-GC-MS method was developed to detect PPCPs in surface water samples from Big Cypress National Park, Everglades National Park and Biscayne National Park in South Florida. The most frequently found PPCPs were caffeine, DEET and triclosan with detected maximum concentration of 169 ng/L, 27.9 ng/L and 10.9 ng/L, respectively. The detection frequencies of hormones were less than PPCPs. Detected maximal concentrations of estrone, 17β-estradiol, coprostan-3-ol, coprostane and coprostan-3-one were 5.98 ng/L, 3.34 ng/L, 16.5 ng/L, 13.5 ng/L and 6.79 ng/L, respectively. An ASE-SPE-GC-MS method was developed and applied to the analysis of the sediment and soil area where reclaimed water was used for irrigation. Most analytes were below detection limits, even though some of analytes were detected in the reclaimed water at relatively high concentrations corroborating the fact that PPCPs do not significantly partition to mineral phases. An online SPE-HPLC-APPI-MS/MS method and an online SPE-HPLC-HESI-MS/MS method were developed to analyze reclaimed water and drinking water samples. In the reclaimed water study, reclaimed water samples were collected from the sprinkler for a year-long period at Florida International University Biscayne Bay Campus, where reclaimed water was reused for irrigation. Analysis results showed that several analytes were continuously detected in all reclaimed water samples. Coprostanol, bisphenol A and DEET's maximum concentration exceeded 10 μg/L (ppb). The four most frequently detected compounds were diphenhydramine (100%), DEET (98%), atenolol (98%) and carbamazepine (96%). In the study of drinking water, 54 tap water samples were collected from the Miami-Dade area. The maximum concentrations of salicylic acid, ibuprofen and DEET were 521 ng/L, 301 ng/L and 290 ng/L, respectively. The three most frequently detected compounds were DEET (93%), carbamazepine (43%) and salicylic acid (37%), respectively. Because the source of drinking water in Miami-Dade County is the relatively pristine Biscayne aquifer, these findings suggest the presence of wastewater intrusions into the delivery system or the onset of direct influence of surface waters into the shallow aquifer.