Occurrence and removal of pharmaceuticals and personal care products (PPCPs) in an advanced wastewater reclamation plant

The occurrence of nineteen pharmaceutically active compounds and personal care products was followed monthly for 12 months after various stages of treatment in an advanced wastewater reclamation plant in Gwinnett County, GA, U.S.A. Twenty-four hour composite samples were collected after primary clarification, activated sludge biological treatment, membrane filtration, granular media filtration, granular activated carbon (GAC) adsorption, and ozonation in the wastewater reclamation plant. Compounds were identified and quantified using high performance liquid chromatography/tandem mass spectrometry (LC-MS/MS) and gas chromatography/mass spectrometry (GC-MS) after solid-phase extraction. Standard addition methods were employed to compensate for matrix effects. Sixteen of the targeted compounds were detected in the primary effluent; sulfadimethoxine, doxycycline, and iopromide were not found. Caffeine and acetaminophen were found at the highest concentrations (∼10⁵ ng/L), followed by ibuprofen (∼10⁴ ng/L), sulfamethoxazole and DEET (∼10³ ng/L). Most of the other compounds were found at concentrations on the order of hundreds of ng/L. After activated sludge treatment and membrane filtration, the concentrations of caffeine, acetaminophen, ibuprofen, DEET, tetracycline, and 17α-ethynylestradiol (EE2) had decreased by more than 90%. Erythromycin and carbamazepine, which were resistant to biological treatment, were eliminated by 74 and 88%, on average, by GAC. Primidone, DEET, and caffeine were not amenable to adsorption by GAC. Ozonation oxidized most of the remaining compounds by >60%, except for primidone and DEET. Of the initial 16 compounds identified in the primary effluent, only sulfamethoxazole, primidone, caffeine and DEET were frequently detected in the final effluent, but at concentrations on the order of 10-100 ng/L. Removal of the different agents by the various treatment processes was related to the physical-chemical properties of the compounds.     

Occurrence of emerging pollutants in urban wastewater and their removal through biological treatment followed by ozonation

This work reports a systematic survey of over seventy individual pollutants in a Sewage Treatment Plant (STP) receiving urban wastewater. The compounds include mainly pharmaceuticals and personal care products, as well as some metabolites. The quantification in the ng/L range was performed by Liquid Chromatography-QTRAP-Mass Spectrometry and Gas Chromatography coupled to Mass Spectrometry. The results showed that paraxanthine, caffeine and acetaminophen were the main individual pollutants usually found in concentrations over 20 ppb. N-formyl-4-amino-antipiryne and galaxolide were also detected in the ppb level. A group of compounds including the beta-blockers atenolol, metoprolol and propanolol; the lipid regulators bezafibrate and fenofibric acid; the antibiotics erythromycin, sulfamethoxazole and trimethoprim, the antiinflammatories diclofenac, indomethacin, ketoprofen and mefenamic acid, the antiepileptic carbamazepine and the antiacid omeprazole exhibited removal efficiencies below 20% in the STP treatment. Ozonation with doses lower than 90 μM allowed the removal of many individual pollutants including some of those more refractory to biological treatment. A kinetic model allowed the determination of second order kinetic constants for the ozonation of bezafibrate, cotinine, diuron and metronidazole. The results show that the hydroxyl radical reaction was the major pathway for the oxidative transformation of these compounds.     

Fate of pharmaceuticals in contaminated urban wastewater effluent under ultrasonic irradiation

The application of sonolysis (US) for remediation of wastewater is an area of increasing interest. The aim of this study was to evaluate the ultrasonic (US) process on the degradation of pharmaceuticals (diclofenac (DCF), amoxicillin (AMX), carbamazepine (CBZ)) in single solutions and also in three mixtures spiked in urban wastewater effluent. Several operating conditions, such as power density (25-100 W L⁻¹), initial substrate concentrations (2.5-10 mg L⁻¹), initial solution pH (3-11), and air sparging were varied for the evaluation and understanding of the process. The degradation (as assessed by measuring UV absorbance), the generation of hydroxyl radicals (as assessed measuring H₂O₂ concentration), the mineralization (in terms of TOC and COD removal), and the aerobic biodegradability (as assessed by the BOD₅/COD ratio) were monitored during sonication. Ecotoxicity to Daphnia magna, Pseudokirchneriella subcapitata and Lepidium sativum before and after treatment was also evaluated. It was found that the pharmaceuticals conversion is enhanced at increased applied power densities, acidic conditions and in the presence of dissolved air. The reaction rate increases with increasing initial concentration of single pharmaceuticals but it remains constant in the mixtures, indicating different kinetic regimes (i.e. first and zero order respectively). Mineralization is a slow process as reaction by-products are more stable than pharmaceuticals to total oxidation; nonetheless, they are also more readily biodegradable. The toxicity of the wastewater samples before and after contamination with pharmaceuticals both in mixtures and in single substance-containing solutions was observed more severely on P. subcapitata; a fact that raises concerns in regards to the discharge of such effluents. D. magna displayed less sensitivity compared to P. subcapitata because it belongs in a lower taxonomic species than D. magna. The germination index of L. sativum in the presence of the drugs' mixture was stimulated instead of inducing any toxicity effect and this might be attributed to the fact the sample, laden with very low drug concentrations was able to act as a provider of additional nutrient elements.     

Screening of 47 organic microcontaminants in agricultural irrigation waters and their soil loading

Reclaimed water usage for crop irrigation is viewed both as an excellent sustainable water source and as a potential entrance for emerging organics into the food chain. This concern is backed by the already documented pollutant crop uptake potential. In the present study, irrigation waters used in agricultural fields (Torroella de Montgri, NE Spain) were screened for 47 analytes in a two year study (2007-2008). A total of 26 contaminants belonging to different chemical classes namely, pesticides, pharmaceuticals, personal care products, phenolic estrogens, antioxidants and disinfection by-products, were detected. Marked differences in concentration trends for the different chemical classes were evidenced from 2007 to 2008, and attributed to a persistent drought endured by the region in 2008. Also, loading mass rates of chemical classes were estimated based on crop irrigation regimes and they ranged from 0.8 to 121.3 g ha⁻¹ per crop cycle. These values were contrasted with those obtained for other water sources from countries where crop irrigation is commonly practiced. Finally, crops grown under these irrigation regimes, namely alfalfa and apple, were analyzed and 5 anthropogenic compounds were identified and quantitated, whose concentrations ranged from 13.9 to 532 ng g⁻¹ (fresh weight).     

Occurrence and removal of antibiotics, hormones and several other pharmaceuticals in wastewater treatment plants of the largest industrial city of Korea

Occurrence and removal efficiencies of 20 pharmaceuticals and personal care products (PPCPs) including antibiotics, hormones, and several other miscellaneous pharmaceuticals (analgesics, antiepileptics, antilipidemics, antihypertensives, antiseptics, and stimulants) were investigated in five wastewater treatment plants (WWTPs) of Ulsan, the largest industrial city of Korea. The compounds were extracted from wastewater samples by solid-phase extraction (SPE) and analyzed by High-performance liquid chromatography coupled with tandem mass spectrometry (HPLC-MS/MS). The results showed that acetaminophen, atenolol and lincomycin were the main individual pollutants usually found in concentrations over 10 μg/L in the sewage influent. In the WWTPs, the concentrations of analgesic acetaminophen, stimulant caffeine, hormones estriol and estradiol decreased by over 99%. On the contrary, the antibiotic sulfamethazine, the antihypertensive metoprolol, and the antiepileptic carbamazepine exhibited removal efficiencies below 30%. Particularly, removal of antibiotics was observed to vary between − 11.2 and 69%. In the primary treatment (physico-chemical processes), the removal of pharmaceuticals was insignificant (up to 28%) and removal of majority of the pharmaceuticals occurred during the secondary treatment (biological processes). The compounds lincomycin, carbamazepine, atenolol, metoprolol, and triclosan showed better removal in WWTPs employing modified activated sludge process with co-existence of anoxic-oxic condition. Further investigation into the design and operational aspects of the biological processes is warranted for the efficient removal of PPCPs, particularly antibiotics, to secure healthy water resource in the receiving downstream, thereby ensuring a sustainable water cycle management.     

Runoff of pharmaceuticals and personal care products following application of dewatered municipal biosolids to an agricultural field

Municipal biosolids are a useful source of nutrients for crop production, and commonly used in agriculture. In this field study, we applied dewatered municipal biosolids at a commercial rate using broadcast application followed by incorporation. Precipitation was simulated at 1, 3, 7, 21 and 34 days following the application on 2 m² microplots to evaluate surface runoff of various pharmaceuticals and personal care products (PPCPs), namely atenolol, carbamazepine, cotinine, caffeine, gemfibrozil, naproxen, ibuprofen, acetaminophen, sulfamethoxazole, triclosan and triclocarban. There was little temporal coherence in the detection of PPCPs in runoff, various compounds being detected maximally on days 1, 3, 7 or 36. Maximum concentrations in runoff ranged from below detection limit (gemfibrozil) to 109.7 ng L^− 1 (triclosan). Expressing the total mass exported as a percentage of that applied, some analytes revealed little transport potential (< 1% exported; triclocarban, triclosan, sulfamethoxazole, ibuprofen, naproxen and gemfibrozil) whereas others were readily exported (> 1% exported; acetaminophen, carbamazepine, caffeine, cotinine, atenolol). Those compounds with little transport potential had log K_ow values of 3.18 or greater, whereas those that were readily mobilized had K_ow values of 2.45 or less. Maximal concentrations of all analytes were below toxic concentrations using a variety of endpoints available in the literature. In summary, this study has quantified the transport potential in surface runoff of PPCPs from land receiving biosolids, identified that log K_ow may be a determinant of runoff transport potential of these analytes, and found maximal concentrations of all chemicals tested to be below toxic concentrations using a variety of endpoints.     

Laccase-catalyzed oxidation of oxybenzone in municipal wastewater primary effluent

Pharmaceuticals and personal care products (PPCPs) are now routinely detected in raw and treated municipal wastewater. Since conventional wastewater treatment processes are not particularly effective for PPCP removal, treated wastewater discharges are the main entry points for PPCPs into the environment, and eventually into our drinking water. This study investigates the use of laccase-catalyzed oxidation for removing low concentrations of PPCPs from municipal wastewater primary effluent. Oxybenzone was selected as a representative PPCP. Like many other PPCPs, it is not recognized directly by the laccase enzyme. Therefore, mediators were used to expand the oxidative range of laccase, and the efficacy of this laccase-mediator system in primary effluent was evaluated. Eight potential mediators were investigated, and 2,2′-Azino-bis(3-ethylbenzthiazoline-6sulphonic acid) diammonium salt (ABTS), a synthetic mediator, and acetosyringone (ACE), a natural mediator, provided the greatest oxybenzone removal efficiencies. An environmentally relevant concentration of oxybenzone (43.8 nM, 10 μg/L) in primary effluent was completely removed (below the detection limit) after two hours of treatment with ABTS, and 95% was removed after two hours of treatment with ACE. Several mediator/oxybenzone molar ratios were investigated at two different initial oxybenzone concentrations. Higher mediator/oxybenzone molar ratios were required at the lower (environmentally relevant) oxybenzone concentration, and ACE required higher molar ratios than ABTS to achieve comparable oxybenzone removal. Oxybenzone oxidation byproducts generated by the laccase-mediator system were characterized and compared to those generated during ozonation. Enzymatic treatment generated byproducts with higher mass to charge (m/z) ratios, likely due to oxidative coupling reactions. The results of this study suggest that, with further development, the laccase-mediator system has the potential to extend the treatment range of laccase to PPCPs not directly recognized by the enzyme, even in a primary effluent matrix.     

Occurrence, partition and removal of pharmaceuticals in sewage water and sludge during wastewater treatment

During 8 sampling campaigns carried out over a period of two years, 72 samples, including influent and effluent wastewater, and sludge samples from three conventional wastewater treatment plants (WWTPs), were analyzed to assess the occurrence and fate of 43 pharmaceutical compounds. The selected pharmaceuticals belong to different therapeutic classes, i.e. non-steroidal anti-inflammatory drugs, lipid modifying agents (fibrates and statins), psychiatric drugs (benzodiazepine derivative drugs and antiepileptics), histamine H2-receptor antagonists, antibacterials for systemic use, beta blocking agents, beta-agonists, diuretics, angiotensin converting enzyme (ACE) inhibitors and anti-diabetics. The obtained results showed the presence of 32 target compounds in wastewater influent and 29 in effluent, in concentrations ranging from low ng/L to a few μg/L (e.g. NSAIDs). The analysis of sludge samples showed that 21 pharmaceuticals accumulated in sewage sludge from all three WWTPs in concentrations up to 100 ng/g. This indicates that even good removal rates obtained in aqueous phase (i.e. comparison of influent and effluent wastewater concentrations) do not imply degradation to the same extent. For this reason, the overall removal was estimated as a sum of all the losses of a parent compound produces by different mechanisms of chemical and physical transformation, biodegradation and sorption to solid matter. The target compounds showed very different removal rates and no logical pattern in behaviour even if they belong to the same therapeutic groups. What is clear is that the elimination of most of the substances is incomplete and improvements of the wastewater treatment and subsequent treatments of the produced sludge are required to prevent the introduction of these micro-pollutants in the environment.     

Reconnaissance of selected PPCP compounds in Costa Rican surface waters

Eighty-six water samples were collected in early 2009 from Costa Rican surface water and coastal locations for the analysis of 34 pharmaceutical and personal care product compounds (PPCPs). Sampling sites included areas receiving treated and untreated wastewaters, and urban and rural runoff. PPCPs were analyzed using a combination of solid phase extraction and liquid chromatography tandem mass spectrometry. The five most frequently detected compounds were doxycycline (77%), sulfadimethoxine (43%), salicylic acid (41%), triclosan (34%) and caffeine (29%). Caffeine had the maximum concentration of 1.1 mg L⁻¹, possibly due to coffee bean production facilities upstream. Other compounds found in high concentrations include: doxycycline (74 μg L⁻¹), ibuprofen (37 μg L⁻¹), gemfibrozil (17 μg L⁻¹), acetominophen (13 μg L⁻¹) and ketoprofen (10 μg L⁻¹). The wastewater effluent collected from an oxidation pond had similar detection and concentrations of compounds compared to other studies reported in the literature. Waters receiving runoff from a nearby hospital showed higher concentrations than other areas for many PPCPs. Both caffeine and carbamazepine were found in low frequency compared to other studies, likely due to enhanced degradation and low usage, respectively. Overall concentrations of PPCPs in surface waters of Costa Rica are inline with currently reported occurrence data from around the world, with the exception of doxycycline.     

EU-wide monitoring survey on emerging polar organic contaminants in wastewater treatment plant effluents

In the year 2010, effluents from 90 European wastewater treatment plants (WWTPs) were analyzed for 156 polar organic chemical contaminants. The analyses were complemented by effect-based monitoring approaches aiming at estrogenicity and dioxin-like toxicity analyzed by in vitro reporter gene bioassays, and yeast and diatom culture acute toxicity optical bioassays. Analyses of organic substances were performed by solid-phase extraction (SPE) or liquid–liquid extraction (LLE) followed by liquid chromatography tandem mass spectrometry (LC-MS-MS) or gas chromatography high-resolution mass spectrometry (GC-HRMS). Target microcontaminants were pharmaceuticals and personal care products (PPCPs), veterinary (antibiotic) drugs, perfluoroalkyl substances (PFASs), organophosphate ester flame retardants, pesticides (and some metabolites), industrial chemicals such as benzotriazoles (corrosion inhibitors), iodinated x-ray contrast agents, and gadolinium magnetic resonance imaging agents; in addition biological endpoints were measured. The obtained results show the presence of 125 substances (80% of the target compounds) in European wastewater effluents, in concentrations ranging from low nanograms to milligrams per liter. These results allow for an estimation to be made of a European median level for the chemicals investigated in WWTP effluents. The most relevant compounds in the effluent waters with the highest median concentration levels were the artificial sweeteners acesulfame and sucralose, benzotriazoles (corrosion inhibitors), several organophosphate ester flame retardants and plasticizers (e.g. tris(2-chloroisopropyl)phosphate; TCPP), pharmaceutical compounds such as carbamazepine, tramadol, telmisartan, venlafaxine, irbesartan, fluconazole, oxazepam, fexofenadine, diclofenac, citalopram, codeine, bisoprolol, eprosartan, the antibiotics trimethoprim, ciprofloxacine, sulfamethoxazole, and clindamycine, the insect repellent N,N′-diethyltoluamide (DEET), the pesticides MCPA and mecoprop, perfluoroalkyl substances (such as PFOS and PFOA), caffeine, and gadolinium.     

Effects of biologically-active chemical mixtures on fish in a wastewater-impacted urban stream

Stream flow in urban aquatic ecosystems often is maintained by water-reclamation plant (WRP) effluents that contain mixtures of natural and anthropogenic chemicals that persist through the treatment processes. In effluent-impacted streams, aquatic organisms such as fish are continuously exposed to biologically-active chemicals throughout their life cycles. The North Shore Channel of the Chicago River (Chicago, Illinois) is part of an urban ecosystem in which > 80% of the annual flow consists of effluent from the North Side WRP. In this study, multiple samplings of the effluent and stream water were conducted and fish (largemouth bass and carp) were collected on 2 occasions from the North Shore Channel. Fish also were collected once from the Outer Chicago Harbor in Lake Michigan, a reference site not impacted by WRP discharges. Over 100 organic chemicals with differing behaviors and biological effects were measured, and 23 compounds were detected in all of the water samples analyzed. The most frequently detected and highest concentration (> 100 μg/L) compounds were ethylenediaminetetraacetic acid and 4-nonylphenolmono-to-tetraethoxycarboxylic acids. Other biologically-active chemicals including bisphenol A, 4-nonylphenol, 4-nonylphenolmono-to-tetraethoxylates, 4-tert-octylphenol, and 4-tert-octylphenolmono-to-tetraethoxylates were detected at lower concentrations (< 5 μg/L). The biogenic steroidal hormones 17β-estradiol, estrone, testosterone, 4-androstene-3,17-dione, and cis-androsterone were detected at even lower concentrations (< 0.005 μg/L). There were slight differences in concentrations between the North Side WRP effluent and the North Shore Channel, indicating minimal in-stream attenuation. Fish populations are continuously exposed to mixtures of biologically-active chemicals because of the relative persistency of the chemicals with respect to stream hydraulic residence time, and the lack of a fresh water source for dilution. The majority of male fish exhibited vitellogenin induction, a physiological response consistent with exposure to estrogenic compounds. Tissue-level signs of reproductive disruption, such as ovatestis, were not observed.     

Removal of selected endocrine disrupting chemicals (EDCs) and pharmaceuticals and personal care products (PPCPs) during ferrate(VI) treatment of secondary wastewater effluents

We investigated the removal efficiencies of 68 selected endocrine disrupting chemicals (EDCs) and pharmaceuticals and personal care products (PPCPs) spiked in a wastewater matrix by ferrate (Fe(VI)) and further evaluated the degradation of these micropollutants present in secondary effluents of two wastewater treatment plants (WWTPs) by applying Fe(VI) treatment technology. Fe(VI)treatment resulted in selective oxidation of electron-rich organic moieties of these target compounds, such as phenol, olefin, amine and aniline moieties. But Fe(VI) failed to react with triclocarban, 3 androgens, 7 acidic pharmaceuticals, 2 neutral pharmaceuticals and erythromycin-H₂O.Thirty-one target EDCs and PPCPs were detected in the effluents of the two WWTPs with concentrations ranging from 0.2 ± 0.1 ng L⁻¹ to 1156 ± 182 ng L⁻¹.Fe(VI) treatment resulted in further elimination of the detected EDCs and PPCPs during Fe(VI) treatment of the secondary wastewater effluents. The results from this study clearly demonstrated the effectiveness of Fe(VI) treatment as a tertiary treatment technology for a broad spectrum of micropollutants in wastewater.     

The removal of pharmaceuticals, personal care products, endocrine disruptors and illicit drugs during wastewater treatment and its impact on the quality of receiving waters

A 5-month monitoring program was undertaken in South Wales in the UK to determine the fate of 55 pharmaceuticals, personal care products, endocrine disruptors and illicit drugs (PPCPs) in two contrasting wastewater plants utilising two different wastewater treatment technologies: activated sludge and trickling filter beds. The impact of treated wastewater effluent on the quality of receiving waters was also assessed.PPCPs were found to be present at high loads reaching 10 kg day⁻¹ in the raw sewage. Concentrations of PPCPs in raw sewage were found to correlate with their usage/consumption patterns in Wales and their metabolism. The efficiency of the removal of PPCPs was found to be strongly dependent on the technology implemented in the wastewater treatment plant (WWTP). In general, the WWTP utilising trickling filter beds resulted in, on average, less than 70% removal of all 55 PPCPs studied, while the WWTP utilising activated sludge treatment gave a much higher removal efficiency of over 85%. The monitoring programme revealed that treated wastewater effluents were the main contributors to PPCPs concentrations (up to 3 kg of PPCPs day⁻¹) in the rivers studied. Bearing in mind that in the cases examined here the WWTP effluents were also major contributors to rivers' flows (dilution factor for the studied rivers did not exceed 23 times) the effect of WWTP effluent on the quality of river water is significant and cannot be underestimated.     

Occurrence of androgens and progestogens in wastewater treatment plants and receiving river waters: Comparison to estrogens

Research has shown that exposure to androgens and progestogens can cause undesirable biological responses in the environment. To date, however, no detailed or direct study of their presence in wastewater treatment plants has been conducted. In this study, nine androgens, nine progestogens, and five estrogens were analyzed in influent and final effluent wastewaters in seven wastewater treatment plants (WWTPs) of Beijing, China. Over a period of three weeks, the average total hormone concentrations in influent wastewaters were 3562 (Wujiacun WWTP)-5400 ng/L (Fangzhuang WWTP). Androgens contributed 96% of the total hormone concentrations in all WWTP influents, with natural androgen (androsterone: 2977 ± 739 ng/L; epiandrosterone: 640 ± 263 ng/L; and androstenedione: 270 ± 132 ng/L) being the predominant compounds. The concentrations of synthetic progestogens (megestrol acetate: 41 ± 25 ng/L; norethindrone: 6.5 ± 3.3 ng/L; and medroxyprogesterone acetate: 6.0 ± 3.2 ng/L) were comparable to natural ones (progesterone: 66 ± 36 ng/L; 17α,20β-dihydroxy-4-progegnen-3-one: 4.9 ± 1.2 ng/L; 21α-hydroxyprogesterone: 8.5 ± 3.0 ng/L; and 17α-hydroxyprogesterone: 1.5 ± 0.95 ng/L), probably due to the wide and relatively large usage of synthetic progestogens in medical therapy. In WWTP effluents, androgens were still the dominant class accounting for 60% of total hormone concentrations, followed by progestogens (24%), and estrogens (16%). Androstenedione and testosterone were the main androgens detected in all effluents. High removal efficiency (91-100%) was found for androgens and progestogens compared with estrogens (67-80%), with biodegradation the major removal route in WWTPs. Different profiles of progestogens in the receiving rivers and WWTP effluents were observed, which could be explained by the discharge of a mixture of treated and untreated wastewater into the receiving rivers.     

Occurrence of endocrine disrupting compounds, pharmaceuticals, and personal care products in the Han River (Seoul, South Korea)

The occurrence of 31 selected endocrine disrupting compounds (EDCs) and pharmaceuticals and personal care products (PPCPs) in Korean surface waters was investigated. The area was selected since there is a lack of information in the Seoul area on the suspected contamination of rivers by micropollutants, although over 99% of drinking water is produced from surface waters in this area that has a population of approximately 15 million inhabitants. Samples were collected from upstream/downstream and effluent-dominated creeks along the Han River, Seoul (South Korea) and analyzed by liquid chromatography with tandem mass spectrometry (LC-MS/MS) with electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI). Most target compounds were detected in both the Han River samples (63%) and the effluent-dominated creek samples (79%). Iopromide, atenolol, TCPP, TECP, musk ketone, naproxen, DEET, carbamazepine, caffeine, and benzophenone were frequently detected in both river and creek samples, although the mean concentrations in effluent-dominated creek samples (102 ng/L-3745 ng/L) were significantly higher than those in river samples (56 ng/L-1013 ng/L). However, the steroid hormones 17β-estradiol, 17α-ethynylestradiol, progesterone, and testosterone, were not detected (< 1 ng/L) in both the river and creek samples. Numerous target compounds (15) were found to be positively correlated (over 0.8) to the conventional water quality parameters (chemical oxygen demand, biochemical oxygen demand, dissolved organic carbon, and ultraviolet absorbance). Results of this study provide increasing evidence that certain EDCs and PPCPs commonly occur in the Han River as the result of wastewater outfalls.     

Occurrence and fate of emerging wastewater contaminants in Western Balkan Region

This paper reports on a comprehensive reconnaissance of over seventy individual wastewater contaminants in the region of Western Balkan (WB; Bosnia and Herzegovina, Croatia and Serbia), including some prominent classes of emerging contaminants such as pharmaceuticals and personal care products, surfactants and their degradation products, plasticizers, pesticides, insect repellents, and flame retardants. All determinations were carried out using a multiresidue analytical approach, based on the application of gas chromatographic and liquid chromatographic techniques coupled to mass spectrometric detection. The results confirmed a widespread occurrence of the emerging contaminants in municipal wastewaters of the region. The most prominent contaminant classes, determined in municipal wastewaters, were those derived from aromatic surfactants, including linear alkylbenzene sulphonates (LAS) and alkylphenol polyethoxylates (APEO), with the concentrations in raw wastewater reaching into the mg/l range. All other contaminants were present in much lower concentrations, rarely exceeding few microg/l. The most abundant individual compounds belonged to several classes of pharmaceuticals (antimicrobials, analgesics and antiinflammatories, beta-blockers and lipid regulators) and personal care products (fragrances). Due to the rather poor wastewater management practices in WB countries, with less than 5% of all wastewaters being biologically treated, most of the contaminants present in wastewaters reach ambient waters and may represent a significant environmental concern.     

Occurrence and removal of pharmaceuticals, caffeine and DEET in wastewater treatment plants of Beijing, China

The occurrence and removal of 13 pharmaceuticals and 2 consumer products, including antibiotic, antilipidemic, anti-inflammatory, anti-hypertensive, anticonvulsant, stimulant, insect repellent and antipsychotic, were investigated in four wastewater treatment plants (WWTPs) of Beijing, China. The compounds were extracted from wastewater samples by solid-phase extraction (SPE) and analyzed by ultra-performance liquid chromatography coupled with tandem mass spectrometry (UPLC-MS/MS). Most of the target compounds were detected, with the concentrations of 4.4 ng L⁻¹-6.6 μg L⁻¹ and 2.2-320 ng L⁻¹ in the influents and secondary effluents, respectively. These concentrations were consistent with their consumptions in China, and much lower than those reported in the USA and Europe. Most compounds were hardly removed in the primary treatment, while their removal rates ranging from −12% to 100% were achieved during the secondary treatment. In the tertiary treatment, different processes showed discrepant performances. The target compounds could not be eliminated by sand filtration, but the ozonation and microfiltration/reverse osmosis (MF/RO) processes employed in two WWTPs were very effective to remove them, showing their main contributions to the removal of such micro-pollutants in wastewater treatment.     

A simple method for the measurement of organic iodine in wastewater and surface water

Total adsorbable organic iodine (TAOI) has been used as a surrogate parameter for X-ray contrast media in municipal wastewater. Available methods require specialized equipment for pyrolyzing these compounds to convert the covalently bound iodine into iodide, which is then measured by ion chromatography. In this study we describe a simple method for liberating iodide from these compounds with Cu(II) and hydrogen peroxide. Concentrations of TAOI were measured in wastewater effluent, surface waters that were expected to be impacted by wastewater, and unimpacted surface waters. TAOI concentrations ranged between 1.9 and 16.3 microg/L I in wastewater with a median of 6.5 microg/L I. The lowest TAOI concentrations consistently were detected in a wastewater treatment plant that apparently had few hospitals within its collection area. In comparison, TAOI concentrations in surface water that was unimpacted by sewage were between 0.3 and 3.5 microg/L I. TAOI concentrations in surface waters that were impacted by sewage were consistent with the expected conservative behavior of TAOI.     

Occurrence of pharmaceuticals in Taiwan's surface waters: Impact of waste streams from hospitals and pharmaceutical production facilities

We investigated the occurrence and distribution of pharmaceuticals (including antibiotics, estrogens, non-steroidal anti-inflammatory drugs (NSAIDs), beta-blockers, and lipid regulators) in three rivers and in the waste streams of six hospitals and four pharmaceutical production facilities in Taiwan. The most frequently detected pharmaceuticals were acetaminophen, erythromycin-H₂O, sulfamethoxazole, and gemfibrozil. NSAIDs were the next most-often detected compounds, with a detection frequency > 60%. The other analytes were not detected or were seen in only a few samples at trace concentrations. The present study demonstrates a significant discharge of human medications from hospital and drug production facilities into surface waters in the Taipei district. The high concentrations of pharmaceuticals found in the Sindian and Dahan rivers demonstrate the alarming degree to which they have been impacted by urban drainage (waste effluents from hospitals, households, and pharmaceutical production facilities). The ubiquitous occurrence at extremely high concentrations of acetaminophen and erythromycin-H₂O in both rivers (up to 15.7 and 75.5 µg/L) and in wastewater from hospitals and pharmaceutical production facilities (up to 417.5 and 7.84 µg/L) was unique. This finding, in combination with acetaminophen's status as the drug most often prescribed by Taiwan's dominant clinical institute, suggests the potential use of acetaminophen as a molecular indicator of contamination of Taiwan's aqueous environments with untreated urban drainage.     

Occurrence of acidic pharmaceuticals in raw and treated sewages and in receiving waters

The occurrence of five acidic pharmaceuticals, ibuprofen, naproxen, ketoprofen, diclofenac and bezafibrate, in seven different sewage treatment plants (STP) and three receiving waters were determined. The analytical procedure included solid phase extraction, liquid chromatographic separation and detection by a triple-quadrupole mass spectrometer. The studied pharmaceuticals were found in all the STPs. The pattern of the occurrence of individual compounds was the same in every STP and matched the consumption figures reported in the literature. Ibuprofen is the most used pharmaceutical in Finland and was accordingly found to be the most abundant compound in the raw sewage. In the treatment processes, the highest removal rate was observed for ibuprofen and the lowest for diclofenac, 92%+/-8% and 26%+/-17%, respectively. Due to the incomplete removal in the STPs, the pharmaceuticals were found in rivers at the discharge points of the STP effluents. Downstream from the discharge points, the concentrations decreased significantly mainly due to dilution in the river water. The risk to the aquatic environment was estimated by a ratio of measured environmental concentration (MEC) and predicted no-effect concentration (PNEC). At the concentrations the compounds were found in the surface waters, they should not pose risk for the aquatic environment. However, at dry seasons and/or during malfunctions of STPs, ibuprofen could be associated with a risk in small river systems.