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.     

Occurrence of several acidic drugs in sewage treatment plants in Switzerland and risk assessment

The occurrence and fate of five acidic drugs (Mefenamic acid, Ibuprofen, Ketoprofen, Diclofenac and Clofibric acid) were analysed in three sewage treatment plants (STP) over 4-7 consecutive days. The results point out that the five substances were persistent in wastewater effluents after municipal wastewater treatment. At the most, half of Mefenamic acid was eliminated. Ibuprofen was well removed (80%) by one sewage treatment plant. The removal of Ibuprofen is dependent on the residence time of wastewater in the STPs. A long raining period induce an important decrease of removal of Ibuprofen and Ketoprofen. Removal rates showed a great variability according to sewage treatment plants and types of treatments (e.g. biological, physico-chemical). The concentrations of Ibuprofen, Mefenamic acid and Diclofenac were relatively high in the effluents (150-2000 ng/l), showing a potential contamination of surface water. An environmental risk assessment is presented. Mefenamic acid seems to present a risk for the aquatic environment, with a ratio PEC/PNEC higher than one.     

Behavior of pharmaceuticals, cosmetics and hormones in a sewage treatment plant

Two cosmetic ingredients (galaxolide, tonalide), eight pharmaceuticals (carbamazepine, diazepam, diclofenac, ibuprofen, naproxen, roxithromycin, sulfamethoxazole and iopromide) and three hormones (estrone, 17beta-estradiol and 17alpha-ethinylestradiol) have been surveyed along the different units of a municipal Sewage Treatment Plant (STP) in Galicia, NW Spain. Among all the substances considered, significant concentrations in the influent were only found for the two musks (galaxolide and tonalide), two anti-inflammatories (ibuprofen and naproxen), two natural estrogens (estrone, 17beta-estradiol), one antibiotic (sulfamethoxazole) and the X-ray contrast medium (iopromide), where the other compounds studied were below the limit of quantification. In the primary treatment, only the fragrances (30-50%) and 17beta-estradiol (20%) were partially removed. On the other hand, the aerobic treatment (activated sludges) caused an important reduction in all compounds detected, between 35% and 75%, with the exception of iopromide, which remained in the aqueous phase. The overall removal efficiencies within the STP ranged between 70-90% for the fragrances, 40-65% for the anti-inflammatories, around 65% for 17beta-estradiol and 60% for sulfamethoxazole. However, the concentration of estrone increased along the treatment due to the partial oxidation of 17beta-estradiol in the aeration tank.     

Occurrence and removal of pharmaceuticals in a municipal sewage treatment system in the south of Sweden

The occurrence and removal rate of seven pharmaceuticals (ibuprofen, naproxen, diclofenac, fluoxetine, ofloxacin, norfloxacin, ciprofloxacin), two metabolites (norfluoxetine, clofibric acid), one degradation product (4-isobutylacetophenone) and 3 estrogens (17α-ethinylestradiol, 17β-estradiol, estrone) were studied in the inlet and outlet of a tertiary sewage treatment plant (STP) in Sweden as well as between different treatment steps in the STP which includes a conventional activated sludge step. Pharmaceuticals in raw household and raw hospital sewage streams leading to the STP were as well investigated. Hydraulic retention times (HRT) of each treatment step was considered for sampling and for the calculation of the removal rates. These rates were above 90%, except for diclofenac, clofibric acid, estrone and ofloxacin. However, only diclofenac and naproxen showed significant effluent loads (> 145 mg/d/1000 inh). Diclofenac was not eliminated during the treatment and in fact even higher concentrations were found at the effluent than in the inlet of the STP. 17α-Ethinylestradiol was not detected in any of the samples. Results indicate that a STP such as the one in Kristianstad, Sweden, with a tertiary treatment is sufficient to remove significantly most of the investigated pharmaceuticals. The chemical treatment improved the removal of several pharmaceuticals especially the antibiotics, which showed step removal rates between 55 and 70%. The expected concentration levels of the pharmaceuticals in the surface water (dilution 1 to 10) close to the outlet of the STP are below the no-observed effect-concentration (NOEC). However, despite that this would imply no important effects in the aquatic environment one cannot rule out negative consequences nearby the STP because most of the NOEC values are derived from acute toxicity data. This may underestimate the real impact of pharmaceuticals in the aquatic ecosystem.     

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.     

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 and risk assessment of acidic pharmaceuticals in the Yellow River, Hai River and Liao River of north China

Pharmaceuticals in the aquatic environment have received great attentions from the general and scientific community due to their potential impacts on ecological and human health. We investigated the occurrence of twelve acidic pharmaceuticals and herbicides (salicylic acid, clofibric acid, ibuprofen, gemfibrozil, fenoprofen, naproxen, ketoprofen, mefenamic acid, tolfenamic acid, diclofenac, meclofenamic acid and indomethacin) in surface waters of the Yellow River, Hai River and Liao River in north China during the wet and dry seasons and assessed the potential risks to aquatic organisms posed by these acidic compounds. Seven acidic compounds were detected in the rivers, including five non-steroidal anti-inflammatory drugs (salicylic acid, ibuprofen, diclofenac, mefenamic acid and naproxen), and two blood lipid regulators (clofibric acid and gemfibrozil). The concentrations for acidic pharmaceuticals in the Yellow River and Liao River were in most cases higher in the dry season than in the wet season, but the concentrations of acidic compounds in the Hai River were generally higher in July than in November. High concentrations of these detected compounds in the Yellow River, Hai River and Liao River were found more frequently at those sites located in metropolitan areas, lower reaches or river confluences. Only diclofenac and ibuprofen were found to have medium to high risks in the three rivers based on the calculated risk quotients.     

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.     

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.     

Elimination of pharmaceuticals in sewage treatment plants in Finland

The occurrence of eight pharmaceuticals (beta-blockers: acebutolol, atenolol, metoprolol and sotalol; antiepileptic: carbamazepine; fluoroquinolone antibiotics: ciprofloxacin, norfloxacin, ofloxacin) were assessed in the raw and treated sewage of 12 sewage treatment plants (STPs) in Finland. The average concentrations in the raw and treated sewage ranged from 100 to 1060 ng L(-1) and from <24 to 755 ng L(-1), respectively. The average daily loads ranged from 36 to 405 mg/1000 inh and from 2 to 302 mg/1000 inh, respectively. In the treatment plants, fluoroquinolones were eliminated by >80%. Carbamazepine was not eliminated during the treatment and in fact even higher concentrations were frequently found in the treated than in the raw sewages. The increase in concentration was shown to be most likely due to enzymatic cleavage of the glucuronic conjugate of carbamazepine and release of the parent compound in the treatment plant. The beta-blockers were eliminated in average by less than 65% and the elimination varied greatly between the treatment plants. Especially the dilution of raw sewage by rainwater and a consequent decrease in the hydraulic retention time of a treatment plant was found to deteriorate the elimination of the beta-blockers. The work shows that especially carbamazepine and the beta-blockers may reach the recipient waters and there is a need to enhance their elimination in the sewage treatment plants. In this attempt, a denitrifying biofilter as a tertiary treatment could be of minor importance since in this study it did not result in further elimination of the target compounds.     

Removal of cosmetic ingredients and pharmaceuticals in sewage primary treatment

Two physico-chemical processes, coagulation-flocculation and flotation, have been assessed for enhancing the removal of some selected pharmaceutical and personal care products (PPCPs) present in sewage. Eight compounds, representative of three main groups of PPCPs according to their physico-chemical properties, have been selected: lipophilic compounds (the synthetic musks Galaxolide and Tonalide), neutral compounds (the tranquillizer Diazepam and the antiepileptic Carbamazepine) and acidic compounds (the anti-inflammatories Ibuprofen, Naproxen and Diclofenac). During the coagulation-flocculation assays, the main parameters considered were the selection of the additives, their doses and the temperature of operation (12 or 25 degrees C). Musks-which are highly lipophilic and Diclofenac-with significant sorption affinity-were removed around 50-70% at both temperatures independently of the dose and type of coagulant used. However, the rest of the compounds, which are more hydrophilic, were affected to a lesser degree (with maximum reductions below 25%). The exceptions to this behavior were Carbamazepine and Ibuprofen, which were not removed under any condition tested. During the flotation assays, the parameters studied were the initial content of fat in wastewaters and temperature. Again, musks were removed to a greater degree (35-60%), followed by Diazepam (40-50%) and Diclofenac (20-45%) and, to a lesser extent, Carbamazepine (20-35%), Ibuprofen (10-25%) and Naproxen (10-30%). The best results were always obtained at 25 degrees C, although in some cases the operation at 12 degrees C gave similar results. The removal of musks and neutral compounds was higher in wastewaters with a high fat content (around 150 mgl(-1)).     

A field study on 8 pharmaceuticals and 1 pesticide in Belgium: Removal rates in waste water treatment plants and occurrence in surface water

Only recently, attention has been drawn towards the occurrence of pharmaceuticals in the environment. In recent years many reports have been made on the occurrence of the large, differentiated group of pharmaceuticals in waste water, surface water, ground water and in soil. In this study, we demonstrate the applicability of a previously developed LC-MS/MS method by evaluating in waste water and surface water samples from Belgium the occurrence of 8 pharmaceuticals and 1 pesticide (flubendazole, pipamperone, rabeprazole, domperidone, ketoconazole, itraconazole, cinnarizine, miconazole and propiconazole). Removal rates in five public waste water treatment plants were assessed. Introduction of several compounds into the aquatic environment by discharge of effluent could be demonstrated. For several compounds, the highest concentrations (up to 35.6 μg/l for pipamperone) were observed in the effluent of a WWTP receiving water from chemo-pharmaceutical and other industrial companies. The occurrence of these compounds in the aquatic environment was assessed by analyzing 16 surface water samples, taken from various locations. Four pharmaceuticals (flubendazole, pipamperone, domperidone and cinnarizine) could be detected in at least one sample at low concentrations (up to 26.4 ng/l). The pesticide propiconazole was found in comparable concentrations (up to 85.9 ng/l) as in effluent, suggesting potential introduction by direct seepage of water from rural grounds. The highest concentrations of flubendazole, pipamperone, domperidone, propiconazole and cinnarizine (up to 961.3 ng/l) were observed in a sample, taken near the discharge of a WWTP receiving water from chemo-pharmaceutical and other industries. An initial environmental risk assessment was done based on these results.     

Pharmaceutical chemicals and endocrine disrupters in municipal wastewater in Tokyo and their removal during activated sludge treatment

We measured six acidic analgesics or anti-inflammatories (aspirin, ibuprofen, naproxen, ketoprofen, fenoprofen, mefenamic acid), two phenolic antiseptics (thymol, triclosan), four amide pharmaceuticals (propyphenazone, crotamiton, carbamazepine, diethyltoluamide), three phenolic endocrine disrupting chemicals (nonylphenol, octylphenol, bisphenol A), and three natural estrogens (17beta-estradiol, estrone, estriol) in 24-h composite samples of influents and secondary effluents collected seasonally from five municipal sewage treatment plants in Tokyo. Aspirin was most abundant in the influent, with an average concentration of 7300 ng/L (n = 16), followed by crotamiton (921 ng/L), ibuprofen (669 ng/L), triclosan (511 ng/L), and diethyltoluamide (503 ng/L). These concentrations were 1 order of magnitude lower than those reported in the USA and Europe. This can be ascribed to lower consumption of the pharmaceuticals in Japan. Aspirin, ibuprofen, and thymol were removed efficiently during primary + secondary treatment (> 90% efficiency). On the other hand, amide-type pharmaceuticals, ketoprofen, and naproxen showed poor removal (< 50% efficiency), which is probably due to their lower hydrophobicity (logKow < 3). Because of the persistence of crotamiton during secondary treatment, crotamiton was most abundant among the target pharmaceuticals in the effluent. This is the first paper to report ubiquitous occurrence of crotamiton, a scabicide, in sewage. Because crotamiton is used worldwide and it is persistent during secondary treatment, it is a promising molecular marker of sewage and secondary effluent.     

Pathways and metabolites of microbial degradation of selected acidic pharmaceutical and their occurrence in municipal wastewater treated by a membrane bioreactor

Laboratory degradation tests with five acidic pharmaceuticals using activated sludge as inocculum under aerobic conditions were performed and microbial metabolites were analysed by liquid chromatography-mass spectrometry (LC-MS). Ketoprofen was partly mineralized as a sole source of carbon and energy and the metabolites determined by LC-MS suggest microbial ketoprofen degradation to proceed along the pathway known for biphenyls and related compounds. Bezafibrate, naproxen and ibuprofen were degraded only cometabolically whereas no transformation was obtained for diclofenac. Some biodegradation intermediates in these batch tests could be tentatively identified by means of LC-MS. The first step in microbial bezafibrate degradation appears to be the hydrolytic cleavage of the amide bond, generating well degradable 4-chlorobenzoic acid as one of the hydrolysis products. As previously found for mammals, ether cleavage and formation of desmethylnaproxen was the initial step in microbial degradation of naproxen. Two isomers of hydroxy-ibuprofen were detected as intermediates in the mineralization of ibuprofen. Laboratory studies suggest that naproxen and ibuprofen can be fully mineralized whereas more stable metabolites occur in microbial ketoprofen and bezafibrate transformation, that may deserve further attention. A LC-MS method for the trace analysis of these metabolites in water was developed and applied to municipal wastewater. Municipal wastewater treatment by a membrane bioreactor may gradually improve the removal of these pharmaceuticals.     

Occurrence and fate of quinolone and fluoroquinolone antibiotics in a municipal sewage treatment plant

This study developed a method for analysis of nineteen quinolone and fluoroquinolone antibiotics (FQs) in sludge samples, and investigated the occurrence and fate of the FQs in a municipal sewage treatment plant (STP) with anaerobic, anoxic, and aerobic treatment processes. Eleven compounds, including pipemidic acid, fleroxacin, ofloxacin, norfloxacin, ciprofloxacin, enrofloxacin, lomefloxacin, sparfloxacin, gatifloxacin, moxifloxacin, and sarafloxacin (only in sludge), were detected in the STP. The predominance of ofloxacin and norfloxacin, followed by lomefloxacin, ciprofloxacin, gatifloxacin, and moxifloxacin, were found in wastewater, suspended solids, and sludge. The total concentrations of FQs were 2573 ± 241 ng/L, 1013 ± 218 ng/L, and 18.4 ± 0.9 mg/kg in raw sewage, secondary effluent, and sludge, respectively. Extremely low mass change percentages were observed for FQs in anaerobic, anoxic, and aerobic treatment units, suggesting biodegradation to be of minor importance in the removal of FQs in STPs. 50-87% of the initial FQs loadings (except for pipemidic acid (36%)) were ultimately found in the dewatered sludge. Mean removal efficiencies of FQs in the STP were 56-75%, except for new generation drugs such as moxifloxacin (40 ± 5%) and gatifloxacin (43 ± 13%). A significant positive correlation was found between removal efficiencies and K_d of FQs. The major factor in the removal of FQs in the STP was sorption to sludge, which was not governed by hydrophobic interactions. The long-term cycling and persistence of FQs in the STP has made activated sludge as a huge reservoir of FQ antibiotics.     

Environmental risk assessment of antibiotics in the Swedish environment with emphasis on sewage treatment plants

The potential risks associated with antibiotics present in the Swedish environment were assessed using concentrations found in hospital effluent, and sewage treatment waters and sludge, in combination with data on their environmental effects obtained from the literature. For the aqueous environment, measured environmental concentrations and effect/no observed effect concentration ratios were much lower than one in most cases. The only exceptions, where concentrations of the investigated substances were high enough to pose potential risks, were the concentrations of the two fluoroquinolones, ofloxacin and ciprofloxacin, in the hospital effluent. Treating digested dewatered sludge by heat did not fully eliminate norfloxacin or ciprofloxacin, thus pellets may still contain high amounts of these substances (sub to low mgkg(-1)dw). In leaching tests less than 1% of the amounts of these fluoroquinolones in the sludge or pellets reached the aqueous phase, indicating that their mobility is limited if sludge is used to fertilize soil.     

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 and suitability of sucralose as an indicator compound of wastewater loading to surface waters in urbanized regions

Urban watersheds are susceptible to numerous pollutant sources and the identification of source-specific indicators can provide a beneficial tool in the identification and control of input loads, often times needed for a water body to achieve designated beneficial uses. Differentiation of wastewater flows from other urban wet weather flows is needed in order to more adequately address such environmental concerns as water body nutrient impairment and potable source water contamination. Anthropogenic compounds previously suggested as potential wastewater indicators include caffeine, carbamazepine, N,N-diethyl-meta-toluamide (DEET), gemfibrozil, primidone, sulfamethoxazole, and TCEP. This paper compares the suitability of a variety of anthropogenic compounds to sucralose, an artificial sweetener, as wastewater indicators by examining occurrence data for 85 trace organic compounds in samples of wastewater effluents, source waters with known wastewater point source inputs, and sources without known wastewater point source inputs. The findings statistically demonstrate the superior performance of sucralose as a potential indicator of domestic wastewater input in the U.S. While several compounds were detected in all of the wastewater effluent samples, only sucralose was consistently detected in the source waters with known wastewater discharges, absent in the sources without wastewater influence, and consistently present in septic samples. All of the other compounds were prone to either false negatives or false positives in the environment.     

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.     

Octanol-water partitioning of chemical constituents in river water and treated sewage effluent

A shake-flask approach has been employed to determine the n-octanol-water partitioning of chemical constituents in various river waters and in treated sewage effluent. The bulk inorganic composition of the water samples (conductivity, pH and the concentrations of major solutes: Ca, K, Mg, Na) was unaffected by the presence of solvent. Boron, however, exhibited increasing partition with decreasing sample pH, because its dominant form in freshwaters, B(OH)₃, is neutral, covalent and acidic. Constituents having significant association with dissolved organic matter (DOM), including components of DOM itself (C, S) and trace metals that form complexes with organic ligands (Al, Cu, Fe, Pb, Zn), exhibited measurable partition into the solvent in most cases, with conditional partition coefficients, D_ow, in the region 0.03-2.5. Significant differences in the partitioning among these constituents and among the environments studied did not appear to be related to bulk sample characteristics or the degree of association of the constituent with DOM. These observations suggest that partition is sensitive to the nature of the organic matter (C, S) and the availability of specific binding ligands (trace metals). Thus, although D_ow is critical for defining the biogeochemical behaviour and potential impacts of chemical constituents in the environment, it appears to be a difficult parameter to model or predict.