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.     

Removal of estrogenicity in Swedish municipal sewage treatment plants

The human estrogen receptor alpha-test, hosted in a yeast strain, was used to quantify estrogenicity in three-week composite samples of untreated and treated effluents from 20 Swedish municipal sewage treatment plants. The treatment plants were selected to represent different treatment processes regarding chemical precipitation and microbial procedures. The discharge from Swedish domestic sewage treatment plants contained estrogenic compounds corresponding to <0.1-15 ng estradiol equivalents/L. Low levels of estrogenic activity were also found in a river receiving municipal effluents, 3.5-35 km downstream the outlet from a sewage treatment works. The range of estrogenicity in untreated, raw sewage effluents was found to be 1-30 ng estradiol equivalents/L. Generally, wastewater treatment reduced the estrogenicity and extended biological treatment was most effective in its removal. Activated sludge treatment tended to be more effective than trickling filters, whereas chemical precipitation using iron or aluminium salts without biological treatment showed little effectivity. The study showed that treatment methods in current use are able to eliminate or largely reduce estrogenicity in domestic wastewater.     

Simultaneous determination of biogenic amines and estrogens in foodstuff by an improved HPLC method combining with fluorescence labeling

Biogenic amines (BA) and estrogens (ES) have attracted increasing attentions due to their significance on food safety and food quality. In this study, a novel HPLC-FLD method using ethyl-acridine-sulfonyl chloride (EAC) as fluorescence labeling reagent has been developed for simultaneous determination of BA and ES in food samples. The labeling conditions including labeling time, pH of borate buffers and amount of EAC were optimized. The simultaneous labeling of BA and ES can be finished in as little as 6 min. This method without complex pre-treatment offered the low LOD of 0.27–0.69 ng/mL. It was applied to analyze several food samples (beer, cheese, fish, sausage and shrimp), and showed excellent applicability.     

Occurrence and removal of estrogens and beta blockers by various processes in wastewater treatment plants

This study aims at evaluating occurrence and treatment efficiency of five estrogenic hormones and ten beta blockers in wastewater treatment plants (WWTP). The use of consistent sampling procedures, analytical techniques and data processing enabled to achieve an accurate comparison of the performances of the different treatment processes. First, the occurrence of molecules was evaluated in fourteen rural and urban WWTP located in France. Free and total estrogens were analyzed showing that more than 84% of estrogens in the dissolved phase of influent samples are in the free form. In effluent samples, comparable mean values but higher variation are underlined (RSD from 13 to 54% depending on the estrogen, compared to 11-21% for influents). Most of the target molecules are quantified in 30 influent and 31 effluent samples. Similar occurrence frequencies are obtained for influents from rural (6 WWTP) and urban areas (8 WWTP), except for betaxolol which is only quantified in urban wastewaters. Removal efficiencies of 8 biological treatments were studied: suspended growth biomass (activated sludge) and attached growth systems (biofilter, rotating biological contactor, reed-bed filter, trickling filter). Biological treatments are efficient to remove estrogens from the dissolved phase, with removal rate around 90%. For beta blockers, acebutolol and nadolol are efficiently removed (mean removal rate of 80%), whereas sotalol and propranolol are hardly impacted by biological treatments (removal rate below 20%). Finally, 9 tertiary treatment processes were evaluated. Ozonation, reverse osmosis and activated carbon filtration prove a high removal efficiency for beta blockers (above 80%). On the contrary, high speed chemical settler, sand filtration, silex filtration, microfiltration and UV present generally removal rates below 30% for all beta blockers. The polishing pond studied presents variable removal performances depending on the molecules (up to 75% for propranolol). The role of the hydraulic retention time on the removal efficiencies is confirmed.     

Nylon 6 electrospun nanofibers mat as effective sorbent for the removal of estrogens: kinetic and thermodynamic studies

Nylon 6 electrospun nanofibers mat was prepared via electrospinning for the removal of three estrogens, namely, diethylstilbestrol (DES), dienestrol (DS), and hexestrol (HEX) from aqueous solution. Static adsorption as well as the dynamic adsorption was evaluated by means of batch and dynamic disk flow mode, respectively. The kinetic study indicated that the adsorption of the target compounds could be well fitted by the pseudo-second-order equation, suggesting the intra-particle/membrane diffusion process as the rate-limiting step of the adsorption process. The adsorption equilibrium data were all fitted well to the Freundlich isotherm models, with a maximum adsorption capacity values in the range of 97.71 to 208.95 mg/g, which can be compared to or moderately higher than other sorbents published in the literatures. The dynamic disk mode studies indicated that the mean removal yields of three model estrogens were over 95% with a notable smaller amount of adsorbent (4 mg). Thermodynamic study revealed that the adsorption process was exothermic and spontaneous in nature. Desorption results showed that the adsorption capacity can remain up to 80% after seven times usage. It was suggested that Nylon 6 electrospun nanofibers mat has great potential as a novel effective sorbent material for estrogens removal.     

Solid phase extraction coupled to liquid chromatography-tandem mass spectrometry analysis of sulfonamides, tetracyclines, analgesics and hormones in surface water and wastewater in Luxembourg

In the early 1990s different studies highlighted the relationship between pharmaceuticals, human health and the environment. Among the emerging contaminants, antibiotics are obviously of high concern, because of their potential for inducing antibiotic resistance. In addition, natural and synthetic hormones are relevant because of their potential endocrine-disrupting effects on wildlife. This investigation focuses on the analysis of four classes of veterinary and human pharmaceuticals (sulfonamides, tetracyclines, analgesics and hormones) in surface water and wastewater in Luxembourg. The selected eleven pharmaceuticals include four sulfonamides (sulfathiazole, sulfamethoxazole, sulfadimethoxine and sulfamethazine), two tetracyclines (tetracycline and oxytetracycline), two analgesics (ibuprofen and diclofenac), and three hormones (2 naturals, estrone and β-estradiol, and a synthetic one, 17-α-ethinyl estradiol). The most innovative parts of this study are the simultaneous extraction of the above-mentioned pharmaceuticals as well as tracking their behaviour during flood events in a small river catchment. The method includes pre-concentration by solid phase extraction using Oasis® HLB (Hydrophilic Lipophilic Balance) which gave superior results compared to Chromabond® C-18EC, Chromabond® EASY and Bond Elut® PLEXA cartridges, also evaluated in this investigation. The analysis of the investigated pharmaceutical compounds is carried out by high performance liquid chromatography coupled to a triple quadrupole mass spectrometer. The limits of quantification were 1 ng L^− 1, except for β-estradiol (2 ng L^− 1) and 17-α-ethinyl estradiol (6 ng L^− 1). Recovery rates range from 70 to 94%, with relative standard deviations between 4 and 19%. Application of this method to river concentration and flood events revealed high concentrations of ibuprofen (10-4000 ng L^− 1), with highest levels during flood events, while concentrations of estrogens (1-240 ng L^− 1) and sulfonamides (1-20 ng L^− 1) were comparatively low.     

天然及人工合成雌激素的环境学研究

环境中由粪源产生的雌激素,由于其活性高、产生量大而对人类的生存和健康产生严重威胁。本文就国内外有关天然和人工合成雌激素的性质、环境行为、危害以及雌激素的活性检测方法等进行综述,并得出了一些有益的结论,以期为下一步工作提供一定的依据。     

SEs在水体及水处理工艺中污染状况的研究与展望

综述了甾体雌激素(SEs)对不同国家和地区的水环境所造成的污染及其在水处理工艺中的分布。结果表明,世界各地水环境中都检出了SEs污染物,其浓度一般达到pg/L～ng/L水平,而水处理工艺对其处理效果不佳。水环境中SEs主要来源于人和动物的排泄物等,在水环境中会发生进一步转化。目前亟需建立针对性的水质安全评价方法,进行SEs去除条件下的毒性削减技术研究。     

Photochemical induced changes of in vitro estrogenic activity of steroid hormones

Steroid estrogens are endocrine disrupting contaminants frequently detected in natural waters. Because these estrogens can elicit significant biological responses in aquatic organisms, it is important to study their rates and pathways of degradation in natural waters and to identify whether the transformation products retain biological activity. Photochemical kinetics experiments were conducted under simulated solar light for the hormones 17β-estradiol (E2), 17α-ethinylestradiol (EE2), estrone (E1), equilin (EQ), and equilenin (EQN) under direct and indirect photolysis conditions. All of these hormones were susceptible to direct photodegradation, with half-lives ranging from 40 min for E1 to about 8 h for E2 and EE2. Indirect photolysis experiments with added Suwannee River fulvic acid (SRFA) lead to faster degradation rates for E2, EE2, and EQ. Added SRFA caused slower photodegradation rates for E1 and EQN, indicating that it acts primarily as an inner filter for these analytes. The well-established yeast estrogen screen (YES) was used to measure the estrogenicity of the analytes and their photoproducts. Results of YES assay experiments show that only the direct photolysis of E1 gave estrogenic products. Lumiestrone, the major E1 direct photolysis product, was isolated and characterized. It formed in 53% yield and exhibited moderate estrogenic activity. When photolysed in the presence of perinaphthenone, a potent synthetic sensitizer, E1 degraded via an indirect photolysis pathway and did not produce lumiestrone or any other active products. These results suggest that under typical natural water conditions photochemical reactions of E2, EE2, EQ, and EQN are expected to produce inactive products while E1 will give the estrogenic product lumiestrone in moderate yield.     

High estrogen concentrations in receiving river discharge from a concentrated livestock feedlot

Environmental estrogenic chemicals interrupt endocrine systems and generate reproductive abnormalities in wildlife, especially natural and synthetic estrogenic steroid hormones such as 17β-estradiol (E2), estrone (E1), estriol (E3), 17α-ethynylestradiol (EE2), and diethylstilbestrol (DES). Concentrated animal feedlot operations (CAFOs) are of particular concern since large amounts of naturally excreted estrogens are discharged into aquatic environments. This study investigated E2, E1, E3, EE2, and DES with high performance liquid chromatography/tandem mass (HPLC-MS/MS) analyses along Wulo Creek in southern Taiwan, near a concentrated livestock feedlot containing 1,030,000 broiler chickens, 934,000 laying hens, 85,000 pigs, and 1500 cattle. Sampling was performed from December 2008 to May 2009, in which 54 samples were collected. Experimental results indicate that concentrations of EE2 were lower than the limit of detection (LOD), and concentrations of DES were only detected twice. Concentrations ranged from 7.4 to 1267 ng/L for E1, from not detected (ND) to 313.6 ng/L for E2, and from ND to 210 ng/L for E3. E1 had the highest average mass fraction (72.2 ± 3.6%), which was significantly higher than E3 (16.2 ± 1.7%) and E2 (11.5 ± 2.6%). Additionally, the mean E2 equivalent quotient (EEQ) ranged from 17.3 to 137.9 ng-E2/L. Despite having a markedly lower concentration than E1, E2 more significantly contributed (52.4 ± 6.0%) EEQ than E1 (19.7 ± 3.5%). Moreover, the concentrations of E2, E1, and E3 upstream were significantly higher than concentrations downstream, suggesting a high attenuation effect and fast degradation in the study water. Most concentrations in winter season were higher than those of spring season due to the low dilution effect and low microbial activity in the winter season. Based on the results of this study, we recommend further treatment of the wastewater discharge from the feedlot.