Carbamazepine and diclofenac: removal in wastewater treatment plants and occurrence in water bodies

In the aquatic environment, pharmaceuticals have been widely found. Among them, carbamazepine and diclofenac were detected at the highest frequency. To evaluate the worldwide environmental impacts of both drugs, their global consumption volumes are estimated, based on the dose per capita. The metabolites of these pharmaceuticals are also of environmental concerns, especially trans-10,11-dihydro-10,11- dihydroxycarbamazepine (CBZ-diol) which probably has a similar concentration in water bodies to that of its parent drug. The removal efficiencies and mechanisms of both drugs in the wastewater treatment plants (WWTPs) are discussed with the actual state of knowledge. The occurrences of both drugs are examined in various water bodies including WWTP effluents, surface waters, groundwater and drinking water. Their chemical, physical and pharmacological properties are also addressed in context, which can largely influence their environmental behaviors. The ecotoxicological studies of both drugs imply that they do not easily cause acute toxic effects at their environmental concentrations. However their chronic effects need cautious attention.     

Behavior of sartans (antihypertensive drugs) in wastewater treatment plants,their occurrence and risk for the aquatic environment

Pharmaceuticals and other anthropogenic trace contaminants reach wastewaters and are often not satisfactorily eliminated in sewage treatment plants. These contaminants and/or their degradation products may reach surface waters, thus influencing aquatic life. In this study, the behavior of five different antihypertonic pharmaceuticals from the sartan group (candesartan, eprosartan, irbesartan, olmesartan and valsartan) is investigated in lab-scale sewage plants. The elimination of the substances with related structures varied broadly from 17 % for olmesartan up to 96 % for valsartan. Monitoring data for these drugs in wastewater effluents of six different sewage treatment plants (STPs) in Bavaria, and at eight rivers, showed median concentrations for, e.g. valsartan of 1.1 and 0.13 μg L^?1, respectively. Predicted environmental concentrations (PEC) were calculated and are mostly consistent with the measured environmental concentrations (MEC). The selected sartans and the mixture of the five sartans showed no ecotoxic effects on aquatic organisms in relevant concentrations. Nevertheless, the occurrence of pharmaceuticals in the environment should be reduced to minimize the risk of their distribution in surface waters, ground waters and bank filtrates used for drinking water.     

Drugs in the environment: emission of drugs, diagnostic aids and disinfectants into wastewater by hospitals in relation to other sources--a review.

After administration, pharmaceuticals are excreted by the patients into wastewater. Unused medications are sometimes disposed of in drains. The drugs enter the aquatic environment and eventually reach drinking water if they are not biodegraded or eliminated during sewage treatment. Additionally, antibiotics and disinfectants are supposed to disturb the wastewater treatment process and the microbial ecology in surface waters. Furthermore, resistant bacteria may be selected in the aeration tanks of STPs by the antibiotic substances present. Recently, pharmaceuticals have been detected in surface water, ground water and drinking water. However, only little is known about the significance of emissions from households and hospitals. A brief summary of input by different sources, occurrence, and elimination of different pharmaceutical groups such as antibiotics, anti-tumour drugs, anaesthetics and contrast media as well as AOX resulting from hospital effluent input into sewage water and surface water will be presented.     

Perfluorooctane surfactants in waste waters, the major source of river pollution

Perfluorooctanoate (PFOA) and perfluorooctane sulfonate (PFOS) are persistent and widely distributed in the environment. Recently, the discharge of municipal waste water has been shown to be an important route of such perfluoroalkyl surfactants into the aquatic environment. The aim of this study was to assess the mass flow of PFOA and PFOS from typical waste water treatment plants (WWTPs) into surface waters. Samples were collected at different stages of treatment of four WWTPs in Northern Bavaria, Germany, and from the rivers receiving the treated waste waters (WW). The outflow of PFOA from the WWTPs to the rivers was 20-fold higher than the inflow to the plants; about a tenth was removed with the sludge. For PFOS, the increase from inlet to outlet was about 3-fold; almost half of it was retained in the sludge. Both surfactants were released into river water from the WWTP of a medium-sized city with domestic, industrial and commercial waste waters; in domestic waste waters the surfactants were found at much lower levels.     

A risk assessment of selected phthalate esters in North American and Western European surface waters

Potential risks to aquatic organisms by four commercial phthalate esters, dimethyl (DMP), diethyl (DEP), di-n-butyl (DBP), and butylbenzyl (BBP), were assessed using measured and calculated concentrations in North American and Western European surface waters. Predicted no effect concentrations (PNECs) were calculated using statistical extrapolation procedures and the large aquatic toxicity database. Surface water concentrations of DMP, DEP, DBP, and BBP were calculated using reported emissions to US surface waters from the toxics release inventory (TRI). Monitoring data obtained from the US EPA STORET database and literature surveys from North America and Western Europe show that DMP, DEP, DBP, and BBP are infrequently detected in surface water. Calculated and measured concentrations of DMP, DEP, DBP, and BBP are typically several orders of magnitude below their respective PNECs, indicating that these phthalate esters do not pose a ubiquitous threat to aquatic organisms in North American and Western European surface waters.     

Aquatic arsenic: phytoremediation using floating macrophytes

Phytoremediation, a plant based green technology, has received increasing attention after the discovery of hyperaccumulating plants which are able to accumulate, translocate, and concentrate high amount of certain toxic elements in their above-ground/harvestable parts. Phytoremediation includes several processes namely, phytoextraction, phytodegradation, rhizofiltration, phytostabilization and phytovolatilization. Both terrestrial and aquatic plants have been tested to remediate contaminated soils and waters, respectively. A number of aquatic plant species have been investigated for the remediation of toxic contaminants such as As, Zn, Cd, Cu, Pb, Cr, Hg, etc. Arsenic, one of the deadly toxic elements, is widely distributed in the aquatic systems as a result of mineral dissolution from volcanic or sedimentary rocks as well as from the dilution of geothermal waters. In addition, the agricultural and industrial effluent discharges are also considered for arsenic contamination in natural waters. Some aquatic plants have been reported to accumulate high level of arsenic from contaminated water. Water hyacinth (Eichhornia crassipes), duckweeds (Lemna gibba, Lemna minor, Spirodela polyrhiza), water spinach (Ipomoea aquatica), water ferns (Azolla caroliniana, Azolla filiculoides, and Azolla pinnata), water cabbage (Pistia stratiotes), hydrilla (Hydrilla verticillata) and watercress (Lepidium sativum) have been studied to investigate their arsenic uptake ability and mechanisms, and to evaluate their potential in phytoremediation technology. It has been suggested that the aquatic macrophytes would be potential for arsenic phytoremediation, and this paper reviews up to date knowledge on arsenic phytoremediation by common aquatic macrophytes.     

Investigation of the behaviour of haloketones in water samples

The behaviour of the haloketones (HKs) 1,1-Dichloropropanone (1,1-DCP), 1,1,1-Trichloropropanone (1,1,1-TCP) and 1,3-Dichloropropanone (1,3-DCP) in ultrapure water solutions and in fortified drinking water samples was investigated. Their concentrations were determined at regular time intervals by the use of a gas chromatography-electron capture detector (GC-ECD) method. Two different temperatures were studied. The results have shown that HKs decompose both in ultrapure water solutions and in drinking water samples. The decomposition rates are higher in the drinking water samples, especially at higher temperature. 1,1,1-TCP is the compound which decomposes fastest followed by 1,3-DCP and 1,1-DCP. Chloroform was formed both in the ultrapure water solutions and in the drinking water samples, probably due to the decomposition of 1,1,1-TCP. In the drinking water samples, formation of chloral hydrate was also observed.     

Occurrences and potential risks of 16 fragrances in five German sewage treatment plants and their receiving waters

Fragrances are used in a wide array of everyday products and enter the aquatic environment via wastewater. While several musk compounds have been studied in detail, little is known about the occurrence and fate of other fragrances. We selected 16 fragrance compounds and scrutinized their presence in Bavarian sewage treatment plants (STP) influents and effluents and discussed their ecological risks for the receiving surface waters. Moreover, we followed their concentrations along the path in one STP by corresponding time-related water sampling and derived the respective elimination rates in the purification process. Six fragrance substances (OTNE, HHCB, lilial, acetyl cedrene, menthol, and, in some grab samples, also methyl-dihydrojasmonate) could be detected in the effluents of the investigated sewage treatment plants. The other fragrances under scrutiny were only found in the inflow and were eliminated in the purification process. Only OTNE and HHCB were found in the receiving surface waters of the STP in congruent concentrations, which exceeded the preliminary derived environmental thresholds by a factor of 1.15 and 1.12, respectively, indicating potential risks. OTNE was also detected in similar concentration ranges as HHCB in muscles and livers of fish from surface waters and from ponds that are supplied with purified wastewater. The findings show that some fragrance compounds undergo high elimination rates, whereas others—not only musks—are present in receiving surface water and biota and may present a risk to local aquatic biota. Hence, our results suggest that the fate and potential effects of fragrance compounds in the aquatic environment deserve more attention.     

Perfluorinated Surfactants in Surface and Drinking Waters (9 pp)

Background, Aim and Scope In this paper recent results are provided of an investigation on the discovery of 12 perfluorinated surfactants (PS) in different surface and drinking waters (Skutlarek et al. 2006 a, Skutlarek et al. 2006 b). In the last years, many studies have reported ubiquitous distribution of this group of perfluorinated chemicals, especially perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) in the environment, particularly in wildlife animal and human samples (Giesy and Kannan 2001, Houde et al. 2006, Prevedouros et al. 2006). Perfluorinated surfactants (e.g. PFOS and PFOA) have shown different potentials for reproductory interference and carcinogenity in animal experiments as well as partly long half-lives in humans (Guruge et al. 2006, FSA UK 2006a, FSA UK 2006b, 3M 2005, OECD 2002, Yao and Zhong 2005). They possess compound-dependent extreme recalcitrance against microbiological and chemical degradation and, in addition, they show variable potentials for bioaccumulation in animals and humans (Houde et al. 2006). Materials and Methods: Surface and drinking water samples were collected from different sampling sites: - Surface waters: samples taken from the rivers Rhine, Ruhr, Moehne and some of their tributaries. Further samples were taken from the Rhine-Herne-Canal and the Wesel-Datteln-Canal. - Drinking waters: samples taken in public buildings of the Rhine-Ruhr area. After sample clean-up and concentration by solid-phase extraction, the perfluorinated surfactants were determined using HPLC-MS/MS. Results: All measured concentrations (sum of seven mainly detected components) in the Rhine river and its main tributaries (mouths) were determined below 100 ng/L. The Ruhr river (tributary of the Rhine) showed the highest concentration (94 ng/L), but with a completely different pattern of components (PFOA as major component), as compared with the other tributaries and the Rhine river. Further investigations along the Ruhr river showed remarkably high concentrations of PS in the upper reaches of the Ruhr river and the Moehne river (tributary of the Ruhr) (Ruhr: up to 446 ng/L, Moehne: up to 4385 ng/L). The maximum concentration of all drinking water samples taken in the Rhine-Ruhr area was determined at 598 ng/L with the major component PFOA (519 ng/L). Discussion: The surface water contaminations most likely stem from contaminated inorganic and organic waste materials (so-called 'Abfallgemisch'). This waste material was legally applied to several agricultural areas on the upper reaches of the Moehne. Perfluorinated surfactants could be detected in some suchlike soil samples. They contaminated the river and the reservoir belonging to it, likely by superficial run-off over several months or probably years. Downstream, dilution effects are held responsible for decreasing concentrations of PS in surface waters of the Moehne and the Ruhr river. In analogy to the surface water samples, PS (major component PFOA) can be determined in many drinking water samples of the Rhine-Ruhr area where the water supplies are mainly based on bank filtration and artificial recharge. Conclusions: The concentrations found in drinking waters decreased with the concentrations of the corresponding raw water samples along the flow direction of the Ruhr river (from east to west) and were not significantly different from surface water concentrations. This indicates that perfluorinated surfactants are at present not successfully removed by water treatment steps. Recommendations and Perspectives: Because of their different problematic properties (persistence, mobility, toxicity, bioaccumulation), the concentrations of specific perfluorinated surfactants and their precursors in drinking waters and food have to be minimised. Therefore, it is of utmost importance to take the initiative to establish suitable legal regulations (limitations/ban) concerning the production and use of these surfactants and their precursors. Furthermore, it is indispensable to protect water resources from these compounds. A discussion on appropriate limit values in drinking water and foodstuffs is urgently needed. Concerning the assumed soil contamination, the corresponding regulation (Bioabfall-Verordnung 1998 – Regulation on Organic Waste 1998) should be extended to allow the control of relevant organic pollutants.     

Human pharmaceuticals, antioxidants, and plasticizers in wastewater treatment plant and water reclamation plant effluents.

The primary objective of this study was to determine the presence of unregulated organic chemicals in reclaimed water using complementary targeted and broad spectrum approaches. Eleven of 12 targeted human pharmaceuticals, antioxidants, and plasticizers, and 27 tentatively identified non-target organic chemicals, were present in secondary effluent entering tertiary treatment trains at a wastewater treatment plant and two water reclamation facilities. The removal of these compounds by three different tertiary treatment trains was investigated: coagulant-assisted granular media filtration (California Title-22 water, 22 CCR 60301-60357; Barclay [2006]), lime clarification/reverse osmosis (lime/ RO), and microfiltration-reverse osmosis (MF/RO). Carbamazepine, clofibric acid, gemfibrozil, ibuprofen, p-toluenesulfonamide, caffeine, butylated hydroxyanisole (BHA), butylated hydroxytoluene (BHT), and N-butyl benzenesulfonamide (N-BBSA) were present at low to high nanogram-per-liter levels in Title 22 water. The lime/RO product waters contained lower concentrations of clofibric acid, ibuprofen, caffeine, BHA, and N-BBSA (<10 to 71 ng/L) than their Title 22 counterparts. The MF/RO treatment reduced concentrations to levels below their detection limits, although BHT was present in MF/RO product water from one facility. The presence of the target analytes in two surface waters used as raw drinking water sources and a recharged groundwater was also examined. Surface waters used as raw drinking water sources contained caffeine, BHA, BHT, and N-BBSA, while recharged groundwater contained BHT, BHA, and N-BBSA. Nontarget compounds in recharged groundwater appeared to be attenuated with increased residence time in the aquifer.     

The health effects and ecological significance of chlorine residuals in water

During the past several years, chlorine residuals and chlorinated organic compounds in drinking waters and aquatic environments have become a significant topic of study for scientists concerned about the quality of life in aquatic ecosystems as well as general public health. The effects of direct toxicity and/or carcinogenicity to human and aquatic life are the focal points for this concern.The effects of chloramines and chlorinated organic compounds present in the water distribution system after chlorination treatments are reviewed. Also discussed are the effects of chlorinated discharges from municipal secondary treatment plants and power plants on human health and aquatic life. The toxic significance of environmental chemicals are described.     

Endocrine disrupters in the aquatic environment

Possible mechanisms to explain endocrine effects on reproduction and sex differentiation are presented for selected pharmaceuticals, agrochemicals, industrial chemicals and plant sterols which are known to be present in the aquatic environment. Disruptions of the hormonal coordination can be induced by xenobiotics on various levels of the hierachically organised endocrine system of vertebrates. Phthalate plasticisers, for example, may disrupt the pituitary control of gonadal functions; prenatal/larval exposure to synthetic estrogen impairs sex differentiation and neuroendocrine sexual determination of the central nervous system; phenylurea herbicides block the androgen receptor; the biotransformation of weakly estrogenic plant sterol components of paper mill wastewater (e.g. βsitosterol) may lead to androgenic compounds. The effect of hypolipidemic drugs on lipid homeostasis (peroxysom proliferation) is transmitted via a receptor protein that seems to be closely related to the endocrine system both functionally as well as phylogenetically; possible interferences with the neuroendocrine control of sex differentiation are also discussed. In invertebrates, tributyltin is known to effect the biosynthesis of steroidal sexual hormones. PCBs are suspected to be competitive inhibitors of the steroid catabolism. In order to identify potential risks caused by chemicals to the reproductive capacities of aquatic animals and to the quality of drinking water, methods should be established to detect endocrine disrupters at the various levels of the endocrine system.     

Determination of pharmaceuticals, personal care products, and pesticides in surface and treated waters: method development and survey

Water is fundamental to the existence of life since it is essential to a series of activities, such as agriculture, power generation, and public and industrial supplies. The residual water generated by these activities is released into the environment, reaches the water systems, and becomes a potential risk to nontarget organisms. This paper reports the development and validation of a quantitative method, based on solid-phase extraction and liquid chromatography tandem mass spectrometry, for the simultaneous analysis of 18 pharmaceuticals and personal care products (PPCPs) and 33 pesticides in surface and drinking waters. The accuracy of the method was determined by calculating the recoveries, which ranged from 70 to 120 % for most pesticides and PPCPs, whereas limits of quantification ranged from 0.8 to 40 ng/L. After the validation step, the method was applied to drinking and surface waters. Pesticides and PPCPs were found in concentrations lower than 135.5 ng/L. The evaluation of different water sources with regard to contamination by pesticides and PPCPs has been quite poor in southern Brazil.     

Investigation of pharmaceutical metabolites in environmental waters by LC-MS/MS

Pharmaceuticals, once ingested, are commonly metabolized in the body into more polar and soluble forms. These compounds might not be completely removed in the wastewater treatment plants and consequently being discharged into the aquatic ecosystem. In this work, a multi-class sensitive method for the analysis of 21 compounds, including 7 widely consumed pharmaceuticals and 14 relevant metabolites, has been developed based on the use of UHPLC-MS/MS in selected reaction monitoring (SRM) mode. The method was validated in six surface waters (SW) and six effluent wastewaters (EWW) at realistic concentration levels that can be found in waters. The optimized method was applied to the analysis of different types of water samples (rivers, lakes and effluent wastewater), detecting nearly all the parent compounds and metabolites investigated in this work. This fact illustrates that not only pharmaceuticals but also their metabolites are commonly present in these types of waters. Analytical research and monitoring programs should be directed not only towards parent pharmaceuticals but also towards relevant metabolites to have a realistic overview of the impact of pharmaceuticals in the aquatic environment.     

Trace organic chemicals contamination in ground water recharge

Population growth and unpredictable climate changes will pose high demands on water resources in the future. Even at present, surface water is certainly not enough to cope with the water requirement for agricultural, industrial, recreational and drinking purposes. In this context, the usage of ground water has become essential, therefore, their quality and quantity has to be carefully managed. Regarding quantity, artificial recharge can guarantee a sustainable level of ground water, whilst the strict quality control of the waters intended for recharge will minimize contamination of both the ground water and aquifer area. However, all water resources in the planet are threatened by multiple sources of contamination coming from the extended use of chemicals worldwide. In this respect, the environmental occurrence of organic micropollutants such as pesticides, pharmaceuticals, industrial chemicals and their metabolites has experienced fast growing interest. In this paper an overview of the priority and emerging organic micropollutants in the different source waters used for artificial aquifer recharge purposes and in the recovered water is presented. Besides, some considerations regarding fate and removal of such compounds are also addressed.     

Occurrence and fate of the human pharmaceutical metabolite ritalinic acid in the aquatic system

To investigate the occurrence and fate of ritalinic acid - the main human metabolite of the psychostimulant drug methylphenidate - in the aquatic environment, a HPLC-electrospray-MS/MS method for the quantification of ritalinic acid in wastewater, surface water and bank filtrate was developed. Carbamazepine known as very stable in the aquatic environment was analyzed as anthropogenic marker in parallel. Furthermore, the removal of ritalinic acid was studied in a sewage treatment plant using an activated sludge system during a field study and in lab-scale plants. In good agreement between lab-scale and field studies a low removal rate of 13% and 23%, respectively, was determined. As a consequence, the concentration of ritalinic acid in the wastewater effluents were in the range of <50-170 ngL(-1) which corresponds to a mean specific load per capita of 17.7 μgd(-1). Ritalinic acid has further been detected in German rivers at concentrations of 4-23 ngL(-1) and in bank filtrate samples in 100-850 m distance from the river up to 5 ngL(-1) demonstrating the widespread occurrence of this stable metabolite in the aquatic environment. A comparison to available sales data shows that a significant amount of methylphenidate applied can be found in waters as ritalinic acid.     

Biodegradation of haloacetic acids by bacterial enrichment cultures

Haloacetic acids (HAAs) are toxic organic chemicals that are frequently detected in surface waters and in drinking water distribution systems. The aerobic biodegradation of HAAs was investigated in serum bottles containing a single HAA and inoculated with washed microorganisms obtained from enrichment cultures maintained on either monochloroacetic acid (MCAA) or trichloroacetic acid (TCAA) as the sole carbon and energy source. Biodegradation was observed for each of the HAAs tested at concentrations similar to those found in surface waters and in drinking water distribution systems. The MCAA culture was able to degrade both MCAA and monobromoacetic acid (MBAA) with pseudo-first order rate constants of 1.06 x 10(-2) and 1.13 x 10(-2) l(mg protein)(-1) d(-1), respectively, for concentrations ranging from 10(-5) to 2 mM. The pseudo-first order rate constant for TCAA degradation by the TCAA culture was 6.52 x 10(-3) l(mg protein)(-1) d(-1) for concentrations ranging from 5.33 x 10(-5) to 0.72 mM. The TCAA culture was also able to degrade MCAA with the rate accelerating as incubation time increased. Experiments with radiolabeled HAAs indicated that the 14C was primarily converted to 14CO2 with minor incorporation into cell biomass. The community structure of the enrichment cultures was analyzed by both cultivation-dependent and cultivation-independent approaches. Denaturing gradient gel electrophoresis (DGGE) of the PCR-amplified 16S rRNA gene fragments showed that each of the two enrichment cultures had multiple bacterial populations, none of which corresponded to HAA-degrading bacteria cultivated on HAA-supplemented agar plates. This research indicates that biodegradation is a potential loss mechanism for HAAs in surface waters and in drinking water distribution systems.     

Occurrence of phthalates in aquatic environment and their removal during wastewater treatment processes: a review

Phthalates are plasticizers and are concerned environmental endocrine-disrupting compounds. Due to their extensive usage in plastic manufacturing and personal care products as well as the potential to leach out from these products, phthalates have been detected in various aquatic environments including drinking water, groundwater, surface water, and wastewater. The primary source of their environmental occurrence is the discharge of phthalate-laden wastewater and sludge. This review focuses on recent knowledge on the occurrence of phthalate in different aquatic environments and their fate in conventional and advanced wastewater treatment processes. This review also summarizes recent advances in biological removal and degradation mechanisms of phthalates, identifies knowledge gaps, and suggests future research directions.     

Assessment of the environmental fate and effects of the PPARgamma receptor agonist, pioglitazone

The environmental fate and effects of pioglitazone prescribed for the treatment of type 2 diabetes were evaluated in an environmental risk assessment following the European Medicines Agency (EMA) "Guideline on the Environmental Risk Assessment of Medicinal Products for Human Use"; EMEA/CHMP/SWP/4447/00. A predicted environment concentration (PEC) for surface water was estimated at 0.023μgL(-1), (action limit of 0.01μgL(-1)) triggering a comprehensive battery of laboratory evaluations. Pioglitazone and its major metabolites were determined not to significantly adsorb to sewage solids, were not persistent in the aquatic environment, did not bioaccumulate and were non-toxic to aquatic organisms. Pioglitazone does not pose an unacceptable risk to groundwater supplies, with concentrations not anticipated to be a risk to aquatic organisms or human drinking water supplies. Pioglitazone does not pose a risk of secondary poisoning.