Adsorption of two pesticides on a clay surface: a theoretical study

The contamination of water resources with many organic xenobiotic compounds poses a challenge to environmental sciences and technologies [1]. Although in many cases these contaminants are present only in small concentrations, the large variety of such compounds (some of which are classified as priority pollutants) is a matter of concern. Adsorption, alone or as part of a more complex water or wastewater treatment process, has been seen as playing a very important role in the removal of many of these pollutants [2]. In this regard, the choice of adsorbent materials is crucial, which requires an understanding of the details involved in the adsorption of more or less complex organic molecules by a variety of surfaces of different types. In addition to laboratory studies, computational studies may be valuable in this study [3]. MCPA (2-methyl-4-chlorophenoxyacetic acid, a herbicide) and Clofibric acid (2-(4-chlorophenoxy)-2-methylpropanoic, the metabolite of a pharmaceutical, clofibrate, and also a herbicide) are two phenoxy acids that differ only slightly in their structures. However, a quite distinct behavior in adsorption phenomena on clay materials has been observed in past studies [4]. By relating those differences with the molecules' structural features through atomistic computational studies, some insight may be gained into the respective adsorption processes of this type of compounds. In the present work quantum chemical calculations at density functional theory level have been performed to study the adsorption of MCPA and Clofibric acid by a clay surface model. Since hydration plays an important role for the adsorption process of these species, solvent effects were considered by inclusion of water molecules explicitly into the quantum chemical calculations. The deprotonated negatively charged species were found to strongly interact with the surface and the distinct behavior of both species upon adsorption was compared with experimental evidences

Removal of Pharmaceuticals in Conventional Wastewater Treatment Plants

Over the latest years, the occurrence of pharmaceutical residues in the environment has attracted great interest, in particular in regard to the possible harmful effects of many of these pollutants to living organisms. One of the main sources of pharmaceuticals in the environment is the discharge of effluents from wastewater treatment plants (WWTPs), where their removal is often incomplete. The widespread use of pharmaceuticals and their generally inefficient removal by most WWTPs are the main reasons for their frequent detection in many water quality monitoring studies. In fact, most WWTPs are inefficient for the removal of micropollutants in general (especially hardly biodegradable organic xenobiotics) as these conventional systems were mainly designed for removing bulk pollutants. It would therefore be valuable to determine if WWTPs could be cost-effectively modified/expanded to reduce pharmaceutical discharges. Recent research has been dedicated to evaluate the application of several advanced treatment technologies, such as advanced oxidation processes, adsorption processes and membrane processes, either for the removal of organic micropollutants in general or specifically for the removal of pharmaceutical residues. However, despite the sometimes high removal efficiencies attained, these technologies are in most cases too expensive to be considered as viable solutions on a large scale. Moreover, some of these treatments may originate some transformation products that are potentially more persistent or toxic than the parent compounds. Therefore, this field of research remains very active as the search for cost-effective treatment processes continues to be pursued. In this work we intend to present a review on the fate and the removal efficiencies of pharmaceuticals in conventional WWTPs, describe the main mechanisms involved in pharmaceuticals removal in WWTPs processes, as well as a discussion of the major factors influencing that removal. In addition, we present some of the research work that has been carried out over the latest years in attempting to improve the removals of these pollutants in WWTPs. Thereafter, we describe some of the main alternative processes that are suggested by that research that can be used to complement conventional WWTPs and attain more efficient treatment of wastewaters in regard to contamination with pharmaceuticals

Phytoremediation: An Option for Removal of Organic Xenobiotics from Water

Pollution by persistent organic pollutants (pesticides, pharmaceuticals, petroleum hydrocarbons, PAHs, PCBs, etc.) is an environmental problem that is recognized worldwide. In order to address this problem, cost effective technologies have been developed and evaluated for the decontamination of soil and water resources. Phytoremediation is a promising technology that uses plants and the associated rhizosphere microorganisms to remove, transform/detoxify, or accumulate organic and inorganic pollutants present in soils, sediments, surface or ground water, wastewater, and even the atmosphere. In fact, as a result of their sedentary nature, plants have evolved diverse abilities for dealing with toxic compounds in their environment. They, therefore, possess a variety of pollutant attenuation mechanisms that makes their use in remediating contaminated land and water more feasible than physical and chemical remediation. Currently, phytoremediation is used for treating many classes of organic xenobiotics including petroleum hydrocarbons, chlorinated solvents, polycyclic aromatic hydrocarbons, pesticides, explosives, pharmaceutical compounds and their metabolites, and it involves several decontamination mechanisms. There are several different types of phytotechnologies such as, for instance, treatment constructed wetlands. The aim of this work is to present a review on the application of phytoremediation technologies for water decontamination from persistent organic pollutants, with special emphasis focused on the removal of a class of emergent pollutants that has recently been receiving a lot of attention, the pharmaceutically active compounds. Within the realm of phytotechnologies, constructed wetlands for wastewater treatment are dedicated a special focus as these systems have been used with success for the removal of several different types of organic xenobiotics

Removal Processes of Pharmaceuticals in Constructed Wetlands

Over the latest years the occurrence of pharmaceutical residues in the environment has been motivating an increasing concern over the possible harmful effects of many of these pollutants to living organisms. In fact many reports are available in the literature about the detection of several of the most consumed pharmaceuticals, their metabolites and transformation products in wastewaters as well as surface and ground waters and even in drinking waters worldwide. This situation can be attributed to the general inadequacy of the conventional treatment processes used in wastewater treatment plants (WWTPs) in dealing with trace pollutants. The reason for the low efficiencies of conventional WWTPs for removal of pharmaceuticals is the fact that these plants were designed to remove bulk constituents of wastewater such as suspended solids, dissolved biodegradable organic matter, pathogens and nutrients and not for also dealing with trace pollutants in general. Due to the highly variable physical and chemical properties of these organic compounds, the efficiencies by which they are removed may vary substantially. Despite the low concentration levels at which pharmaceuticals are generally present in the environment, there is a significant potential for synergistic effects between compounds with similar modes of action or related therapeutic targets, which is enough to be of serious concern. Therefore, there is an urgent need to find ways of retaining and removing these pollutants before they reach the receiving water bodies. Optimization of the WWTP processes has been tried by increasing hydraulic and solid retention times, for example. In addition, some advanced technologies have been evaluated to decrease their discharge into water bodies. However, despite the sometimes high removal efficiencies attained, these processes are generally not cost-effective on a large scale. In fact, it remains a crucial necessity to find applicable technologies for removing pharmaceuticals from wastewater with higher efficiencies at reasonable cost of operation and maintenance. Constructed wetlands systems (CWS) are being increasingly used as an option to remove micropollutants, in particular organic xenobiotic compounds, from wastewaters. There is a vast range of studies highlighting the high efficiencies of these systems in removing a wide variety of compound types, including some pharmaceuticals. For this reason, this type of systems are being adopted as a tertiary treatment option in domestic wastewater treatment and, also, at least as part of the specialized wastewater treatment plants of some industries (such as chemical, dye, tannery, livestock, etc.). Often CWS have been studied under a “black box” approach where only influent and effluent pollutants concentrations were assessed and no further in-depth investigations were pursued. However, in order to use CWS as a more efficient response to new challenges such as those presented by the more recalcitrant micropollutants, a thorough characterization of the processes involved in pollutants removal in CWS is direly needed, as well as some understanding of the ways the several CWS components (solid matrix, vegetation and microorganisms) may interact with each other synergistically. This, in fact, has been an effort which increasingly has been undertaken in the most recent years as a new trend in CWS research, not only in field studies but also in numerous lab studies as well. As result of the increases knowledge of such processes and interactions, a better guidance in the selection and optimization of the CWS components for more specific applications becomes possible. In this work we intend to present a review of the main pharmaceutical removal and transformation processes in CWS, the roles played by the most important components of CWS in such processes and how the overall treatment system performance is affected by all these. Some attention will be given to the most recent studies published on this subject, especially those involving specific CWS application for the removal of pharmaceuticals and which focus on the characterization/optimization of processes or the selection of CWS components. Some of the questions remaining to be addressed about the removal mechanisms in CWS and the aspects of CWS operation that still require optimization will also be highlighted in this work

Removal of Antibiotics by “Green” Clay Sorbents

Contamination of water resources with pharmaceuticals has been one of the top concerns of environmental sciences in the latest years [1], the matter having received very significant media coverage recently [2]. Antibiotics in particular have been gathering considerable attention and are amongst the most serious worries due to the development of antibiotic resistant bacteria as result of prolonged exposure [1, 2]. Because most wastewater treatment plants were only designed for removing bulk pollutants, many other more specific pollutant types that are present in low concentrations in the wastewaters are often inefficiently treated and end up being released into receiving water bodies. Although in many cases these contaminants are detected only at small concentrations in environmental samples, the large variety of such compounds and the high potential for adverse interactions with living organisms (due to the nature of their action) is a matter of serious concern. Several advanced technologies have been evaluated as options to treat these contaminants, e.g. advanced oxidative processes or membrane filtration, but despite the sometimes high removal efficiencies attained, these technologies are too expensive to be considered as viable solutions on a large scale. Adsorption, alone or as part of a more complex water or wastewater treatment process, has been seen as playing a very important role in the removal of many organic xenobiotic pollutants [3]. In this regard, the choice of adsorbent materials is crucial. However, pollutants removal efficiency is not the sole selection criterion, as the cost of the materials may provide or preclude economic viability of the water/wastewater treatment system. Therefore, the quest for efficient adsorbents that are widely available, and do not require expensive processing in order to be used (thereby allowing lower production costs) is a very important aspect of research aimed to manage this environmental problem. In this work we present the study of sorption properties of clay materials (LECA and vermiculite) for the removal of some pharmaceuticals two antibiotics (sulfametoxanol and oxytetracycline) from water. The dependence of removal efficiencies on pollutants initial concentrations, contact time with the adsorbents and other system/environment conditions was assessed. The two clay materials were compared in terms of their more balanced performance towards the removal of the pharmaceuticals tested and the materials are suggested as a useful component of a water or wastewater treatment system designed for the removal of pharmaceutical contaminants

"Wetlands: Water Living Filters?",

Human societies have indirectly used natural wetlands as wastewater discharge sites for many centuries. Observations of the wastewater depuration capacity of natural wetlands have led to a greater understanding of the potential of these ecosystems for pollutant assimilation and have stimulated the development of artificial wetlands systems for treatment of wastewaters from a variety of sources. Constructed wetlands, in contrast to natural wetlands, are human-made systems that are designed, built and operated to emulate wetlands or functions of natural wetlands for human desires or needs. Constructed wetlands have recently received considerable attention as low cost, efficient means to clean-up not only municipal wastewaters but also point and non-point wastewaters, such as acid mine drainage, agricultural effluents, landfill leachates, petrochemicals, as well as industrial effluents. Currently, untreated wastewater discharge in the natural wetlands sites is becoming an increasingly abandoned practice whereas the use of constructed wetlands for treatment of wastewater is an emerging technology worldwide. However, natural wetlands still play an important role in the improvement of water quality as they act as buffer zones surrounding water bodies and as a polishing stage for the effluents from conventional wastewater treatment plants, before they reach the receiving water streams. In fact, one of the emerging issues in environmental science has been the inefficiency of wastewater treatment plants to remove several xenobiotic organic compounds such as pesticides and pharmaceutical residues and consequent contamination of the receiving water bodies. Recent studies have shown that wetlands systems were able to efficiently remove many of these compounds, thus reaffirming the importance of the role which can be played by wetlands in water quality preservation. The aim of this work is to present a review on the application of wetlands as “living” filters for water purification, with special emphasis focused in the removal of micropollutants, especially xenobiotic organic compounds such as pharmaceuticals and pesticides residues, which are not efficiently removed by conventional wastewater treatment plants. Furthermore, the role of wetlands as protection zones which contribute to the improvement of the aquatic ecosystems’ quality will be discussed

A DFT Study on the Adsorption of Benzodiazepines to Clay Surfaces

Benzodiazepines (BDZ) belong to the group of psychiatric substances which act on the central nervous system, having anxiolytic, sedative and hypnotic effects and is one of the most prescribed groups of pharmaceuticals throughout the world. These compounds are not exclusively used for human therapeutics, their prescription is also common in veterinary treatments for anxiolytic and appetite stimulation effects. Nowadays, there are several benzodiazepines under international control for therapeutic use. The widespread use of these compounds doesn’t come without a cost and trace levels of it can now be found disseminated on the environment, what is a matter of ecological concern. In fact, over the last decade, there has been a significant number of studies reporting the occurrence of BDZ in environmental matrices, namely in wastewater treatment plants influents and effluents, surface waters and drinking waters . Some of the more frequently detected BDZ include alprazolam, diazepam, lorazepam and oxazepam . The main reason for the ubiquitous presence of BDZ in the environment is associated not only with the large use but also the generally low efficiency of conventional biological wastewater treatment to remove these pharmaceutical residues. It has been suggested that this inefficiency is due to the halogenated structure of these compounds that significantly reduces their susceptibility to biodegradation . Adsorption processes are the most promising and cheap alternative for removal of these kind of organic xenobiotic from wastewaters. In recent years, inexpensive widely available materials have been investigated for the selection of efficient adsorbents that can make adsorption processes an attractive solution at reasonable costs. Among some of the adsorbents studied, clay-based materials have received some attention due to their interesting properties such as the high cation exchange capacity, swelling properties and high specific surface areas. In particular for the treatment of wastewaters, these materials can overcome the limitations of biological processes, as used in conventional wastewater treatment. A better understanding of the interactions of these organic molecules with clay minerals may thus allow a more judicious selection of materials for water/wastewater treatment filters that present significant enhancements in the removal of BDZ. In this work, electronic structure calculations based on the density functional theory (DFT) are presented on the interaction of two BDZ molecules (diazepam and alprazolam) with a periodic model surface of the vermiculite mineral. Geometry changes of the molecules upon adsorption were compared and the interaction energies with the surfaces were determined for a few different molecular orientations in order to understand the way these molecules interact with the clay surface and the essential factor governing the adsorption processes

Removal of Diclofenac by constructed wetlands planted with Phragmites australis and Typha spp.

In the modern society, an ever increasing number of pharmaceutical active compounds (PhACs) is used for the treatment and prevention of various diseases. Ingested drugs are only partially absorbed by the organisms and studies have shown that the excreted compounds are only partially removed in the sewage treatment plants (STPs) [1]. Diclofenac is a non-steroidal anti-inflammatory drug taken to reduce inflammation and as an analgesic reducing pain in certain conditions. In several studies, it was detected in surface water, thus indicating incomplete degradability of this substance in STPs. Despite the low concentrations detected (ng/L - μg/L), those studies have shown damaging effects of this and other pharmaceutical compounds on the aquatic ecosystems [2]. Subsurface flow constructed wetland systems (SSFs) are low cost wastewater treatment systems, usually used to provide a form of secondary or tertiary treatment for wastewaters. Depuration in SSFs is achieved by the concerted action between plant rhizomes, microorganisms and the support matrix components. SSFs’ efficiency can be significantly improved by optimization of the operation conditions which is achieved by careful selection of the support matrices, plants and microorganisms used. The aim of the present work was to evaluate the efficiency of SSF microcosms planted with Phragmites australis and Typha spp plants, to remove diclofenac from contaminated water. The wastewater samples were collected from a STP located in Évora-Portugal. In order to optimize the role played by the support matrix, light expanded aggregates (LECA) and cork, a very common material in Alentejo, were tested. Two different assays were performed, in winter and summer time, using doped wastewater, to evaluate the removal rates of diclofenac by the SSF systems. The quantification of diclofenac was achieved using HPLC-UV with a reversed phase column. [3]. The study results show that constructed wetlands can be an alternative system for removing diclofenac from contaminated water. REFERENCES [1] Fent, K., Weston, A. N., and Caminada, D., Aquatic Toxic. 76 (2006) 122. [2] Maurer, M., Escher, B.I., Richle, P., Schaffner, C., and Alder, A.C., Water Research 41 (2007) 1614. [3] Dordio A., Pinto J., Dias C., Pinto A.P., Carvalho A., Teixeira D.M., International Journal of Environmental Analytical Chemistry, 89 (2009) 835

Pilot-scale study on the removal of pharmaceuticals by LECA based SSF-constructed wetlands

In recent years, the occurrence and fate of pharmaceutically active compounds (PhACs) in the aquatic environment has been recognized as one of the emerging issues in environmental chemistry. Some compounds are just resistant to degradation in the sewage treatment plants (STPs) while others, although suffering partial degradation, still end up in receiving water bodies due to the large inputs received in STPs [1]. Clofibric acid (a metabolite from a series of widely used blood lipids lowering agents), ibuprofen (an anti-inflamatory non-prescription drug) and carbamazepine (an anticonvulsant and mood stabilizing drug) are some of the most frequently found PhACs in environmental monitoring studies [1]. Wastewater treatment by sub-surface flow constructed wetland systems (SSF-CWs) is a low-cost technology that has shown some capacity for removal of several organic xenobiotic pollutants, but fewer studies exist on pharmaceuticals behavior. The aim of the present work was to evaluate the efficiency of a pilot SSF-CW assembled with the plants cattail (Typha spp.) and a clay material (LECA 2/4) as support matrix, for the removal of three pharmaceuticals, namely ibuprofen (IB), carbamazepine (CB) and clofibric acid (CA), from contaminated wastewaters. Four beds were planted with pre-grown cattails (density of 80 plants/m2) and four were left unplanted to be used as controls. Experiments were conducted both in batch and in continuous mode with a flooding rate of 100%. Pharmaceutical concentrations were quantified by HPLC with UV detection at 210 nm (CB), 222 nm (IB) and 230 nm (CA). Solid phase extraction was used for sample pre-concentration whenever the measured pharmaceutical concentrations fell under the limit of quantification of the analytical method. The physico-chemical characterization of the support matrix material, LECA, involved the determination of properties such as pH, point of zero charge, electrical conductivity, apparent porosity, bulk density and hydraulic conductivity. In order to shed some light on the tolerance mechanisms developed by Typha spp. in the presence of these pharmaceuticals, biochemical and physiological parameters were evaluated. Typha spp. showed good tolerance to the presence of CA, CB and IB concentrations of 1 mg L-1, which is a value much higher than those usually reported in wastewaters. LECA alone was able to remove about 90% of the initial amounts of CB and IB in solution, and 50% of CA. IB was very susceptible to microbial degradation and up to 80% of the initial concentration could be removed by the microbial population present in the wastewater used. Overall, the CWS shows a higher removal performance for CA, CB and IB than any of its individual components (plants, support matrix, microorganisms) considered separately. CA proved to be the most resilient compound, which comes in agreement with other published data. However, this system enabled the removal of substantially higher amounts of CA than has previously been reported in other studies. The use of systems of this kind for the removal of pharmaceuticals from wastewaters seems like a promising alternative to the less efficient processes of conventional wastewater treatment

Applications of Clay Materials for the Removal of Organic Xenobiotics from Contaminated Waters

Clay minerals are one of the most common constituents of soils. Its ubiquity in nature makes this class of materials unsurprisingly one of the most extensively studied groups of adsorbents for organic pollutants (Dordio and Carvalho, 2013) . In fact, because of this high potential for ion exchange and surface interactions, in addition to the extensive sorption capacities resulting from their large surface areas (due to the sheet structure of these minerals) clays act as natural scavengers of pollutants (Akcay and Yurdakoc, 2000; Dordio et al., 2007; Dordio et al., 2009; Srivastava et al., 2009; Iglesias et al., 2010; Park et al., 2011; Dordio and Carvalho, 2013) . For such reasons, and adding to their wide availability and associated low cost, in recent years there has been an increasing interest in utilizing natural, processed or chemically-modified clays for the removal of contaminants from aqueous solutions. The aim of this work is to present a review on the extensive amount of studies on the adsorption of organic compounds to several materials of this type. The discussion is focused on the environmental applications, specifically for the decontamination of water and wastewater polluted with organic xenobiotics, and with the aim of providing resources for the screening of materials with potential to be used as efficient and economic water and wastewater treatment alternatives