Fate of cancerostatic platinum compounds in biological wastewater treatment of hospital effluents

The present work focuses on the fate of two cancerostatic platinum compounds (CPC), cisplatin and carboplatin, as well as of two inorganic platinum compounds, [PtCl₄]²⁻ and [PtCl₆]²⁻ in biological wastewater treatment. Laboratory experiments modelling adsorption of these compounds onto activated sludge showed promising specific adsorption coefficients K_D and K_OC and Freundlich adsorption isotherms. However, the adsorption properties of the investigated substances were differing significantly. Adsorption decreased following the order cisplatin > [PtCl₆]²⁻ > [PtCl₄]²⁻ > carboplatin. Log K_D-values were ranging from 2.5 to 4.3 , log K_OC from 3.0 to 4.7.

A pilot membrane bioreactor system (MBR) was installed in a hospital in Vienna and fed with wastewater from the oncologic in-patient treatment ward to investigate CPC-adsorption in a sewage treatment plant. During three monitoring periods Pt-concentrations were measured in the influent (3–250 μg l⁻¹ Pt) and the effluent (2–150 μg l⁻¹ Pt) of the treatment plant using ICP-MS. The monitoring periods (duration 30 d) revealed elimination efficiencies between 51% and 63% based on averaged weekly input–output budgets. The derived log K_D-values and log K_OC-values ranged from 2.4 to 4.8 and from 2.8 to 5.3, respectively. Species analysis using HPLC-ICP-MS proofed that mainly carboplatin was present as intact drug in the influent and – due to low log K_D – in the effluent of the MBR.     

Mobility of pharmaceuticals carbamazepine, diclofenac, ibuprofen, and propyphenazone in miscible-displacement experiments

Many pharmaceuticals pass the unsaturated zone before reaching an aquifer. Therefore, laboratory sand column transport experiments were conducted to study the transport behavior of carbamazepine, diclofenac, ibuprofen, and propyphenazone under unsaturated conditions. The test water was artificial sewage effluent to simulate the infiltration of reused wastewater. The test water was spiked with the pharmaceutically active compounds and the tracer LiCl. Afterwards it was passed through laboratory sand columns, one experiment for each pharmaceutical. The physical and chemical parameters were recorded and general ions measured. Pharmaceuticals were measured using solid phase extraction, derivatization, and detection with GC-MS. The column experiments indicate a significant elimination of ibuprofen (54%), propyphenazone (55%), and diclofenac (35%), whereas carbamazepine was not eliminated. Retardation factors varied between 1.84 for carbamazepine, 2.51 for propyphenazone, 3.00 for ibuprofen, and 4.80 for diclofenac. These results show that mobility and elimination of diclofenac, ibuprofen, and propyphenazone is about in the same range as for experiments under saturated conditions whereas carbamazepine had a significantly lower sorption and elimination under unsaturated conditions.     

Effects of 3-chlorobiphenyl on photosynthetic oxygen production, glutathione content and detoxication enzymes in the aquatic macrophyte Ceratophyllum demersum

Organic contaminants of environmental concern such as polychlorinated biphenyls have dispersed widely throughout the ecosystems and accumulate in living organisms, and a variety of adverse biological effects have been reported. In this study, we investigated the effects of 3-chlorobiphenyl in the aquatic macrophyte Ceratophyllum demersum and the capacity of its detoxication system. After 24 h of exposure to various concentrations of 3-chlorobiphenyl, the total glutathione content (tGSH) was determined and the dose-response curves for glutathione reductase (GR) and microsomal/cytosolic glutathione S-transferases (m- and c-GSTs, respectively) were established. C. demersum showed a decrease of photosynthesis after exposure to 3-chlorobiphenyl, although only significantly at 5 microgl(-1). At 0.005 and 0.05 microgl(-1) the GR, m-GST and c-GST activities were significantly increased and concomitantly a non-significant effect on total GSH was observed. At 0.5 microgl(-1), GR as well as c-GST were still significantly induced, while at 5 microgl(-1) none of the enzymes were activated. These results show that detoxication through glutathione conjugation takes place at low concentrations of 3-chlorobiphenyl, while concentrations in the order of parts per billion cause the inactivation of the enzymatic systems evaluated, enough to place C. demersum in an important physiological stress condition.     

Tetracycline as a selector for resistant bacteria in activated sludge

Tetracycline, one of the most widely used antibiotics, is excreted into wastewater after consumption by humans and animals. The focus of this research was to evaluate the fate of tetracycline resistant bacteria in the activated sludge process as a function of tetracycline loading. The studies were conducted with aerobic biological sequencing batch reactors (SBRs). When comparing 250 microgl(-1) tetracycline fed SBRs with parallel SBRs having a background influent wastewater tetracycline concentration of approximately 1 microgl(-1), tetracycline fed reactors were found to have increased concentrations and production rates of tetracycline resistant bacteria, higher net growth rates of resistant bacteria, and higher percentages of tetracycline resistant bacteria, which were amplified by increase in organic loading and growth rates.     

A case study of molinate application in a Portuguese rice field: herbicide dissipation and proposal of a clean-up methodology

This study was designed to monitor molinate losses in surface and underground waters during Ordram application in a rice field situated in central Portugal. Water samples were collected from different sites, before, during and about one month and a half after Ordram application. Molinate quantification was based on a solid-phase microextraction (SPME) method followed by gas chromatography with flame photometric detector (GC-FPD) analysis, and led to the conclusion that the herbicide was dissipated in the environment, reaching levels as high as 3.9 microgl(-1) in underground water and 15.8 microgl(-1) in the river receiving tail waters. The feasibility of the application of treatment methodologies based on adsorption or biodegradation as processes to remove molinate from real-world waters was assessed. These methods seem suitable to reduce molinate concentrations to values in the range of the legally recommended limits (<0.5 microgl(-1)).     

麦秆黄原酸酯对水中Cu(II)的吸附

采用农业废弃物麦秆为原料制备黄原酸酯,通过傅立叶变换红外光谱FT-IR、扫描电子显微镜SEM等技术对麦秆黄原酸酯物理化学性质进行表征,并对水中Cu2+进行吸附特性研究,考察了不同条件对Cu2+吸附效果的影响,并将其应用于跌水式吸附法对含重金属沼液进行处理,为麦秆黄原酸酯应用于实际污水处理提供理论参考。结果表明,麦秆黄原酸酯对Cu2+的吸附行为符合伪二级动力学吸附模型与Langmuir等温吸附方程,298 K时,Cu2+的饱和吸附量为28.33 mg/g,溶出率为4.97%,对Cu2+的固持能力较强;黄原酸酯跌水吸附法对于含量为50 mg/L以下的Cu2+废水去除率达到80%以上,对实际沼液中Pb、Zn、Cd、Cu的去除率为44.42%~90.16%,去除顺序为Cd>Pb>Cu>Zn。     

Leaching of the organophosphorus nematicide fosthiazate

Fosthiazate is an organophosphorus nematicide which was recently included in Annex I of the Directive 91/414/EEC under the clause that it should be used with special care in soils vulnerable to leaching. Thus, the leaching of fosthiazate was investigated in columns packed with three different soils which represented situations of high (site 2), intermediate (site 1) and low (site 3) leaching potential. The recommended dose of fosthiazate was applied at the surface of the soil columns and fosthiazate fate and transport was investigated for the next two months. Fosthiazate concentrations in the leachate collected from the bottom of the columns packed with soil from site 2 exceeded 0.1 microgl(-1) in most cases. This soil was characterized as acidic, indicating longer fosthiazate persistence, with low organic matter content, indicating weak adsorption, thus representing a situation vulnerable to leaching. In contrast, the lowest concentrations of fosthiazate in the leachate were evident in the columns packed with soil from site 3. This soil was characterized as alkaline, indicating faster degradation, with higher organic matter content, indicating stronger adsorption, thus representing a situation not favoring leaching of fosthiazate. The highest concentration of fosthiazate in the leachate from the columns packed with soil from site 2 was 3.44 microgl(-1) compared to 1.17 and 0.16 microgl(-1), which were the corresponding maximum values measured in columns packed with soil from sites 1 and 3, respectively. The results of the current study further suggest that fosthiazate is mobile in soil and can leach under conducive soil conditions like acidic soils with low organic matter content.     

Treatment of dilute methylene blue-containing wastewater by coupling sawdust adsorption and electrochemical regeneration

In the present work, the coupling of adsorption and electrochemical oxidation on a boron-doped diamond (BDD) electrode to treat solutions containing dyes is studied. This coupling may be convenient for the treatment of diluted pollutant that is limited by the low rate of electrooxidation due to mass-transfer limitation. A pre-concentration step by adsorption could minimize the design of the electrochemical reactor. The adsorbent chosen was mixed with softwood sawdust, and methylene blue was chosen as the model dye molecule. Isotherms of adsorption and kinetics were investigated as well as the effects of current density and regeneration time. The BDD electrochemical oxidation of methylene blue adsorbed onto sawdust led simultaneously to its degradation and sawdust regeneration for the next adsorption. It was observed that multiple adsorption and electrochemical regeneration cycles led to an enhancement of adsorption capacity of the sawdust. This study demonstrated that adsorption–electrochemical degradation coupling offers a promising approach for the efficient elimination of organic dyes from wastewater.     

Bioconcentration, biomagnification and metabolism of 14C-terbutryn and 14C-benzo[a]pyrene in Gammarus fossarum and Asellus aquaticus

The contribution of bioconcentration and biomagnification of 14C-terbutryn and 14C-benzo[a]pyrene via food and water to the bioaccumulation in Gammarus fossarum and Asellus aquaticus was investigated in single species-tests. In this investigation the uptake of 14C-terbutryn and 14C-benzo[a]pyrene via food and water by G. fossarum (L.) and A. aquaticus (L.) was examined. Bioconcentration factors (BCFs) and biomagnification factors (BMFs) were determined. Calculated BCFs were clearly higher than BMFs, indicating that water is the primary route of uptake. The uptake of terbutryn and benzo[a]pyren via water in G. fossarum and A. aquaticus is faster than uptake via food. The elimination and metabolism of the two chemicals by G. fossarum and A. aquaticus were studied. Terbutryn was eliminated almost completely in both species. In general, the elimination of terbutryn from G. fossarum and A. aquaticus was fast with half-life of 5 h. The elimination of terbutryn by G. fossarum after biomagnification is slower than after bioconcentration. No difference was found in elimination of terbutryn by A. aquaticus after biomagnification and after bioconcentration. Metabolites of terbutryn in G. fossarum and A. aquaticus were analyzed by HPLC. After the bioconcentration experiment a higher percentage of metabolites was found in G. fossarum than in A. aquaticus. This was confirmed for the experiment with uptake via food. The spectrum of metabolites was similar in both species, with hydroxyterbutryn being the major metabolism product in water. 14C-B[a]P could nearly completely be eliminated by G. fossarum (rest of activity 2%) after uptake via water. 14C-B[a]P could not be eliminated by G. fossarum and A. aquaticus after uptake via food. The metabolite could not be identified.     

Development of a simple, accurate SPME-based method for assay of VOCs in column breakthrough experiments

Solid-phase microextraction (SPME) with gas chromatography is to be used for assay of effluent liquid samples from soil column experiments associated with VOC fate/transport studies. One goal of the fate/transport studies is to develop accurate, highly reproducible column breakthrough curves for 1,2-cis-dichloroethylene (cis-DCE) and trichloroethylene (TCE) to better understand interactions with selected natural solid phases. For SPME, the influences of the sample equilibration time, extraction temperature and the ratio of volume of sample bottle to that of the liquid sample (V(T)/V(w)) are the critical factors that could influence accuracy and precision of the measured results. Equilibrium between the gas phase and liquid phase was attained after 200 min of equilibration time. The temperature must be carefully controlled due to variation of both the Henry's constant (K(h)) and the fibre/gas phase distribution coefficient (K(fg)). K(h) decreases with decreasing temperature while K(fg) increases. Low V(T)/V(w) yields better sensitivity but results in analyte losses and negative bias of the resultant assay. High V(T)/V(w) ratio yields reduced sensitivity but analyte losses were found to be minimal, leading to better accuracy and reproducibility. A fast SPME method was achieved, 5 min for SPME extraction and 3.10 min for GC analysis. A linear calibration function in the gas phase was developed to analyse the breakthrough curve data, linear between a range of 0.9-236 microgl(-1), and a detection limit lower than 5 microgl(-1).     

Endocrine disruptors compounds, pharmaceuticals and personal care products in urban wastewater: implications for agricultural reuse and their removal by adsorption process

In the last years, a lot of emerging contaminants, such as, endocrine disruptors compounds (EDCs), pharmaceuticals, and personal care products (PPCPs) have been detected in wastewater. Because of their toxicity and possible adverse effects on the environment and humans, their release from urban wastewater treatment plants (UWWTPs) effluents should be minimized, particularly when a wastewater reuse for crops irrigation is expected. Many processes have been investigated for advanced treatment of UWWTP effluents as well as for emerging contaminant degradation; among these, adsorption process was successfully used to remove EDCs and PPCPs from wastewater. This article shortly reviews EDCs and PPCPs removal from UWWTP effluents by adsorption process using conventional and non-conventional adsorbents. The fate of EDCs and PPCPs in UWWTPs and the implications for agricultural wastewater reuse has been addressed too. In spite of the adsorption process looking to be a valuable alternative to other advanced technologies for the removal of emerging contaminants from wastewater, some gaps still remain to evaluate the actual feasibility at full scale. However, according to a few studies available in scientific literature on the use of both powdered activated carbon and granular activated carbon at full scale, adsorption process by activated carbon is a promising, potentially effective, and economically feasible solution for producing safe wastewater for agricultural reuse.     

吸附氧化/纳滤/吸附组合工艺处理丙烯腈工业废水

针对高浓度丙烯腈工业废水,采用絮凝、吸附氧化、纳滤以及吸附的组合工艺进行处理,考察了不同工艺过程处理高浓度丙烯腈工业废水的效果和费用。结果表明,废水经过絮凝-纳滤-吸附氧化处理工艺,使废水的COD降低到1 000 mg/L以下,氨氮含量低于25 mg/L,CN-含量降低至5 mg/L以下,满足丙烯腈工业废水处理出水指标要求,且操作费用适中,为实现丙烯腈生产工业废水的循环利用奠定了坚实的技术基础。     

海绵铁还原耦合活性炭吸附-微波再生技术降解甲基橙

采用海绵铁(s-Fe0)还原耦合活性炭(GAC)吸附-微波(MW)再生技术降解甲基橙(MO)溶液,重点考察了s-Fe0投加量、粒径、微波功率等因素对MO去除效果的影响。结果表明,s-Fe0投加剂量为15.0 g/L、粒径为3～5 mm、超声波功率为200 W,反应1 h,MO的去除率为94.2%。其次,采用GAC吸附-MW再生技术(800 W,照射1 min)循环处理上述脱色后的MO废水。结果表明,GAC吸附可有效降低废水的生物毒性及残留的染料、TOC和总铁离子浓度,且MW辐射可有效再生吸附饱和的GAC颗粒。因此,s-Fe0还原耦合GAC吸附-MW再生技术可以有效降解MO染料,具有处理效果好、实现资源循环利用等优点。     

Occurrence, fate and antibiotic resistance of fluoroquinolone antibacterials in hospital wastewaters in Hanoi, Vietnam

Occurrence and behavior of fluoroquinolone antibacterial agents (FQs) were investigated in hospital wastewaters in Hanoi, Vietnam. Hospital wastewater in Hanoi is usually not treated and this untreated wastewater is directly discharged into one of the wastewater channels of the city and eventually reaches the ambient aquatic environment. The concentrations of the FQs, ciprofloxacin (CIP) and norfloxacin (NOR) in six hospital wastewaters ranged from 1.1 to 44 and from 0.9 to 17 micrgl(-1), respectively. Total FQ loads to the city sewage system varied from 0.3 to 14 g d(-1). Additionally, the mass flows of CIP and NOR were investigated in the aqueous compartment in a small wastewater treatment facility of one hospital. The results showed that the FQ removal from the wastewater stream was between 80 and 85%, probably due to sorption on sewage sludge. Simultaneously, the numbers of Escherichia coli (E. coli) were measured and their resistance against CIP and NOR was evaluated by determining the minimum inhibitory concentration. Biological treatment lead to a 100-fold reduction in the number of E. coli but still more than a thousand E. coli colonies per 100ml of wastewater effluent reached the receiving water. The highest resistance was found in E. coli strains of raw wastewater and the lowest in isolates of treated wastewater effluent. Thus, wastewater treatment is an efficient barrier to decrease the residual FQ levels and the number of resistant bacteria entering ambient waters. Due to the lack of municipal wastewater treatment plants, the onsite treatment of hospital wastewater before discharging into municipal sewers should be considered as a viable option and consequently implemented.     

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.     

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.     

Adsorption isotherms of 17beta-estradiol on granular activated carbon (GAC).

The adsorption characteristics of three types of activated carbon for 17beta-estradiol were studied by long term experiments to assess the time which is necessary to reach equilibrium between the solid and the liquid phase. The adsorption kinetics were measured by liquid scintillation counting using radio-labelled 17beta-estradiol at various concentrations of 17beta-estradiol in the ppt range. 17beta-estradiol is quickly adsorbed and conditions close to equilibrium were reached after 50-180 min. The equilibrium concentrations were calculated to be at 49-81% of the initial concentration in the concentration range between I and 100 ng/l, with 0.51 ng/l for a 1 ng/l and between 5.9 and 14.6 ng/l for 100 ng/l initial concentration.     

Ti/Cu交联累托石光催化氧化处理硝基苯废水研究

以钛酸丁酯为钛源,掺杂铜(CuCl2)制备交联剂.制得柱状Ti/Cu交联累托石,结合其吸附特性并通过其在光催化氧化条件下处理含硝基苯有机废水.在pH=9,交联累托石用量为30 g/L,一根20 W紫外灯光辐照2 h的处理条件下,硝基苯由73.81 mg/L降至3.17 mg/L,去除率达到95.71%,优于GB-8978-1996三级标准,用其处理含硝基苯工业废水,COD去除率为83.73%,由4800 mg/L降至530.4 mg/L,硝基苯去除率达92.3l%,由10.32 mg/L降至0.79 mg/L,小于GB-8978-1996-级标准.     

污泥基活性炭吸附Cu2+的应用研究

以城市污水处理厂剩余污泥为原料,以ZnCl₂为活化剂制取污泥基活性炭。以此污泥基活性炭为吸附剂,对含Cu²⁺的废水进行了吸附实验研究。考察了溶液pH值、Cu²⁺的起始浓度对Cu²⁺离子吸附量的影响;利用等温吸附实验作出吸附等温线,并考察了污泥基活性炭吸附剂吸附Cu²⁺的动力学方程。实验结果表明,污泥基活性炭对Cu²⁺具有良好的吸附性能。吸附的最佳pH值为5;吸附符合Langmuir和Freundlich吸附等温方程,吸附为优惠吸附,吸附量随着吸附质溶液浓度的增加而增大;吸附平衡时间为4 h,吸附动力学符合二级动力学方程。