Investigation of the behavior and metabolism of pharmaceutical residues during purification of contaminated ground water used for drinking water supply

Residues of phenazone-type pharmaceuticals originating from spills of a former pharmaceutical production plant have recently been detected in ground water in Berlin, Germany. The degradation pathways of phenazone, propyphenazone, and dimethylaminophenazone (DMAA) during water purification were enlightened in batch experiments with groundwater and filter material obtained from operating waterworks. For phenazone and propyphenazone a complete biological transformation into their respective metabolites 1,5-dimethyl-1,2-dehydro-3-pyrazolone (DP) and 4-(2-methylethyl)-1,5-dimethyl-1,2-dehydro-3-pyrazolone (PDP) was observed. Generally, removal of phenazone-type pharmaceutical residues during rapid sand filtration was almost exclusively caused by microorganisms only present in polluted raw water. DMAA applied to fresh filter materials was rapidly degraded into its metabolites 1-acetyl-1-methyl-2-phenylhydrazide (AMPH), acetoaminoantipyrine (AAA), formylaminoantipyrine (FAA), and 1-acetyl-1-methyl-2-dimethyloxamoyl-2-phenylhydrazide (AMDOPH). DMAA, AAA, and FAA were, however, only detected at low levels in a few samples of purified water from an operating water works. Whereas, the metabolites AMDOPH and DP were detected up to 1 μg l⁻¹. Propyphenazone was rapidly removed and AMPH, phenazone, and PDP were only measured with concentrations in the low ng l⁻¹ range. The concentrations of the metabolites DP and PDP are even higher in the purified water than in the raw water caused by their formation during degradation of phenazone and propyphenazone. Reduction of filtration velocity on an experimental filter from 5 m h⁻¹ down to 2 m h⁻¹ resulted in improved removal of phenazone, propyphenazone and their metabolites DP and PDP, respectively. AMDOPH, however, was highly persistent in all experiments independent from filtration velocities and contact times.     

Behaviour and redox sensitivity of pharmaceutical residues during bank filtration - Investigation of residues of phenazone-type analgesics

The behaviour of residues of phenazone-type pharmaceuticals during bank filtration was investigated at a field site in Berlin, Germany, where bank-filtered water is used for drinking water production. The concentrations of the pharmaceutical residues in the shallow, young bank filtrate (travel times相似文献   

Identification and significance of phenazone drugs and their metabolites in ground- and drinking water

Residues of three phenazone-type pharmaceuticals have been identified in routine analyses of groundwater samples from selected areas in the north-western districts of Berlin, Germany. Phenazone, propiphenazone, and dimethylaminophenazone have been detected in some wells at concentrations up to the low microg/l-level. Additionally, three phenazone-type metabolites namely 1-acetyl-1-methyl-2-dimethyl-oxamoyl-2-phenylhydrazide (AMDOPH), 1-acetyl-1-methyl-2-phenylhydrazide, and dimethyloxalamide acid-(N'-methyl-N-phenyl)-hydrazide have also been identified in these groundwater samples. The residues are suspected to originate from former production spills of a pharmaceutical plant located in a city north of Berlin. It was observed that with the exception of AMDOPH all other residues were efficiently removed during conventional drinking water treatment. The drug metabolite AMDOPH deriving from dimethylaminophenazone residues was found at concentrations of 0.9 microg/l in finished drinking water. However, a following study on the toxicological relevance of the AMDOPH residues has shown that there is no toxicological harm for humans at the low concentrations of AMDOPH observed in Berlin drinking water.     

Occurrence, fate and assessment of polar metamizole (dipyrone) residues in hospital and municipal wastewater

The occurrence and fate of residues from the therapeutic use of the non-steroidal anti-inflammatory drug metamizole have been studied in investigations of sewage effluents from a military hospital, municipal sewers and a sewage treatment plant (STP) in Berlin, Germany. The loads of the metabolites aminoantipyrin (AA), 4-acetylaminoantipyrin (AAA) and 4-formyl-aminoantipyrin (FAA), rapidly formed after the application of metamizole, were predicted from pharmacokinetic data and based on the evaluation of extensive data sets of on the administration in hospitals and private households. In parallel, the actual concentrations were measured within three field trials. For the military hospital, the estimated average annual discharges of AA/AAA and FAA were 10.5 and 3.2 kg, respectively. For the STP, annual loads of 333 and 133 kg were determined for AA/AAA and FAA, respectively. During sewage treatment, an average decrease of 26% of the loads was measured for AA/AAA whereas no changes were observed for FAA. Generally, the prediction of the loads resulted in an overestimation of the residue levels compared to those measured in the respective sewers. Thus, modeling of predicted loads or concentrations alone will not be sufficient for a realistic assessment. Concerns for human or other mammals' health are not expected from the occurrence of metamizole residues in the aquatic system measured at concentrations up to 7 microg l(-1) in STP effluents. However, a rest of uncertainty remains as it was not possible to derive a no observed effect level for the induction of rare but potentially fatal toxicological side effects reported for metamizole.     

Long-term comparison of trace organics removal performances between conventional and membrane activated sludge processes.

The removal of trace organic compounds through membrane bioreactors (MBR) compared with a conventional wastewater treatment plant (WWTP) in a long-term study was investigated. Two MBR pilot plants were operated in parallel to a full-scale WWTP fed with the same municipal raw wastewater. Polar compounds (phenazone-type pharmaceuticals, their metabolites, and carbamazepine) and less polar estrogenic steroids (estradiol, estrone, and ethinylestradiol) were quantified. The removal rate of phenazone, propyphenazone, and formylaminoantipyrine by the conventional WWTP was less than 15%. Significantly higher removal rates (60 to 70%) started to be clearly monitored in the pilot plants after approximately 5 months. Higher removal rates coincided with higher temperatures in the summer. The conventional WWTP removed, on average, more than 90% of the natural steroids estrone and estradiol and approximately 80% of the synthetic ethinylestradiol. Approximately 99% of estradiol and estrone and approximately 95% of ethinylestradiol was eliminated by the MBR processes.     

Determination of polar pharmaceuticals in sewage water of Greece by gas chromatography-mass spectrometry

Sewage influents and effluents of different urban areas of Greece, were analyzed for polar pharmaceutical residues, used in human medicine. Drugs investigated were the anti-inflammatory drugs diclofenac and ibuprofen, the metabolite of the drugs clofibrates used as blood lipid regulators, clofibric acid and the analgesics phenazone and propyphenazone. Analysis was carried out using capillary gas chromatography-mass spectrometry with selected ion monitoring. The method used was involved solid phase extraction (C(18)) and derivatization with pentafluorobenzyl bromide. Diclofenac was detected in every sewage effluent sample.     

Pharmaceuticals in the river Elbe and its tributaries

Medicinal drugs were found to be ubiquitous in the river Elbe, its tributary the river Saale and in other tributaries at their points of entry into the Elbe. The distribution of concentration peaks along the investigated river stretches provides an indication that they are mainly due to the emission of treated waste water from municipal sewage treatment works. This leads to the conclusion that medicinal substances can be regarded as faecal indicators for water pollution caused by human activity. The main substances found in the Elbe in 1998 were diclofenac, ibuprofen and carbamazepine as well as various antibiotics and lipid regulators in the concentration range of <20-140 ng/l. The more thorough investigations carried out in 1999 and 2000 show that in addition to the drugs (phenazone, isopropyl-phenazone and paracetamol) metabolite concentrations contributed significantly to the total concentration of pharmaceuticals in the Elbe. The metamizole metabolites N-acetyl-4-aminoantipyrine (AAA) and N-formyl-4-aminoantipyrine (FAA) were found in concentrations from <20 to 939 ng/l. A multivariate statistical analysis revealed a high correlation in respect of the distribution of persistent substances. The metoprolol distribution throughout the Saale demonstrated that the tributaries cause either an increase (Weisse Elster, Unstrut, Ilm) or a reduction (Wipper, Bode) in the concentration, depending on the respective load of waste water. Wide scale sampling in Saxony during 2002 showed the ubiquitous occurrence of carbamazepine in surface waters. The ecotoxicological effects of this contamination cannot be assessed at present. This is due to the fact that no legal framework in respect of these medicinal drugs for human consumption has been established and therefore little research and no risk assessment has been carried out. Therefore it is urgently necessary to include at least the quantitatively most significant substances in the new assessment concept of the EC White Paper.     

Behaviour and biodegradation of sulfonamides (p-TSA, o-TSA, BSA) during drinking water treatment

Three sulfonamides -para-toluenesulfonamide (p-TSA), ortho-toluenesulfonamide (o-TSA) and benzenesulfonamide (BSA) - have recently been detected in groundwater within a catchment area of one drinking water treatment plant (DWTP), which is located downstream of a former sewage farm. The degradation pathways of p-TSA, o-TSA and BSA were investigated during drinking water treatment with incubation experiments and an experimental filter. Incubation experiments showed that p-TSA is removed during the treatment by microbiological processes. Removal of p-TSA is performed by adapted microorganisms only present in polluted groundwater. The elimination in an experimental filter of 1.6m length applying filtration velocities from 2 to 6 m h(-1) was approximately 93% of p-TSA. The microbial degradation rates in the incubation experiment were approximately 0.029 microg l(-1) h(-1) (zero order reaction). In the experimental filter, the reaction rate constants were around 0.0063 s(-1) for all filtration velocities (1st order reaction). Drinking water treatment does not reduce the concentration of o-TSA and BSA under conditions encountered in Berlin. p-TSA, o-TSA and BSA were only measured in the low microg l(-1) concentrations range in the purified water.     

曝气生物活性炭滤池深度处理高浓度氨氮原水

实验研究曝气生物活性炭滤池对于高浓度氨氮原水的处理效果以及工艺运行稳定情况。以某自来水厂常规工艺沉淀池出水预加硫酸铵作为研究对象,原水氨氮平均浓度3.67 mg/L,实验条件:温度31.2℃,pH 7.13,滤速8~12 m/h,气水比0.5和1。采用3种不同工况条件进行实验,确定滤速10 m/h和气水比0.5的为最佳运行工况。在此工况下曝气生物活性炭滤池对于氨氮和COD Mn的平均去除率分别达到87.5%和19.2%,亚硝酸盐积累率为0.9%;出水氨氮浓度达到生活饮用水卫生标准GB5749-2006。同时炭滤池的出水浊度相比进水略微上升。     

炼油厂轻污染水回用试验研究

针对某炼油厂轻污染废水水质情况,选用了BAF(生物曝气滤池)工艺+SF(砂滤)工艺对该废水进行净化处理。通过试验研究,得到了BAF工艺合适的运行参数,取得了满意的试验结果。经BAF工艺处理后,出水COD和油平均浓度分别为9.78mg/L和0.24mg/L,再经SF工艺进一步去除SS后,出水SS平均浓度为3.8mg/L,系统处理出水完全达到工业回用水水质要求。试验证明:BAF工艺是一种高效的处理方法,适合炼油厂轻污染水的净化处理。     

浸没式超滤膜替代砂滤处理东江水的中试研究

针对传统饮用水处理工艺的升级改造问题,通过中试实验,系统考察浸没式超滤膜替代砂滤处理东江水的出水水质并研究高通量条件下的膜运行条件。结果表明,浸没式超滤膜出水浊度不受原水水质条件影响,均保持在0.1 NTU以下,与砂滤出水相比具有优势,但有机物去除率与砂滤相差不大。膜系统在高通量条件下运行时,过滤周期应作适当的缩短,采用合理的物理清洗来缓解膜污染,并辅助以有效的在线化学清洗可保证膜过滤的长期稳定运行。     

Sample preparation for GC analysis of selected pesticides in surface water.

A new isolation procedure for the determination of nitrogen/phosphorous containing pesticides and organochlorine pesticides in water was tested, and statistical evaluation of the recoveries was performed. The procedure, designed specifically for the analysis of semi-volatile compounds in water containing Suspended Particulate Matter (SPM), utilizes a specially designed filtration vessel coupled directly to an SPE cartridge. The studies were based on surface water samples (from the Vistula River) spiked with pesticides. SPM separation and analyte isolation/concentration were carried out in a special filtration vessel. Pesticides were sorbed both on the SPE cartridge and on the suspended matter. The cartridge and the filter with the suspended matter were extracted separately with a solvent, which enabled the determination of analyte distribution between the two. For organochlorine pesticides, between 3 and 60% of the initial amount was found on the filter, while the recoveries in the filtrate ranged from 30 to 98%. Total recoveries of organochlorine pesticides from surface water samples spiked with pesticides using the method described were high, ranging from 90 to 101%. The amounts of nitrogen/phosphorus containing pesticides recovered from the filter were lower than 2%, while those from the filtrate ranged from 69 to 92%. Total recoveries of nitrogen/phosphorus containing pesticides from surface water samples were high, ranging from 71 to 92%.     

Arsenic accumulation in duckweed (Spirodela polyrhiza L.): a good option for phytoremediation

Some unavoidable drawbacks of traditional technologies have made phytoremediation a promising alternative for removal of arsenic from contaminated soil and water. In the present study, the potential of an aquatic macrophyte Spirodela polyrhiza L. for phytofiltration of arsenic, and the mechanism of the arsenic uptake were investigated. The S. polyrhiza L. were grown in three test concentrations of arsenate and dimethylarsinic acid (DMAA) (i.e. 1.0, 2.0 and 4.0microM) with 0 (control), 100 or 500microM of phosphate. One control treatment was also set for each test concentrations of arsenic. The PO(4)(3-) concentration in control treatment was 0.02microM. When S. polyrhiza L. was cultivated hydroponically for 6d in culture solution containing 0.02microM phosphate and 4.0microM arsenate or DMAA, the arsenic uptake was 0.353+/-0.003micromolg(-1) and 7.65+/-0.27nmolg(-1), respectively. Arsenic uptake into S. polyrhiza L. was negatively (p<0.05) correlated with phosphate uptake when arsenate was applied to the culture solutions owing to similar in the sorption mechanism between AsO(4)(3-) and PO(4)(3-), and positively (p<0.05) correlated with iron uptake due to adsorption of AsO(4)(3-) onto iron oxides. Thus, the S. polyrhiza L. accumulates arsenic by physico-chemical adsorption and via the phosphate uptake pathway when arsenate was added to the solutions. These results indicate that S. polyrhiza L. would be a good arsenic phytofiltrator. In contrast, DMAA accumulation into S. polyrhiza L. was neither affected by the phosphate concentration in the culture nor correlated (p>0.05) with iron accumulation in plant tissues, which indicates that S. polyrhiza L. uses different mechanisms for DMAA uptake.     

利用生物曝气滤池修复受污染水源

利用生物曝气滤池(BAF)对微污染水源水去除氨氮及有机物进行了试验研究。试验表明,在进水氨氮为6mg／L左右时,BAF可在8m／h的滤速下运行,氨氮去除率大于88％;在氨氮进水为2mg／L时,BAF可在16m／h的滤速下运行,氨氮去除率大于84％。BAF对水中的三氯甲烷前体物去除率较低(16％),对AOC的去除率为58％。BAF中载体上的生物膜主要聚集在表面的凹陷和孔洞处,不能完全覆盖载体表面。     

Dissipation of sulfosulfuron in water - bioaccumulation of residues in fish - LC-MS/MS-ESI identification and quantification of metabolites

Dissipation study of sulfosulfuron in natural water and its bioaccumulation in fish was conducted at 25+/-2 degrees C and at two different concentration levels 1mgl(-1) and 2mgl(-1). The dissipation data in water showed the DT50 and DT90 values 67-76 and 222-253 days and followed first order kinetics. Bioaccumulation of sulfosulfuron in fish was conducted under static conditions exposing the fish at one-tenth of sub-lethal concentration 9mgl(-1) and at double the concentration 18mgl(-1), for a period of 56 days. On different occasions fish samples were collected and analyzed. A HPLC-RF method was used for the quantification of sulfosulfuron and aminopyrimidine with the limit of quantification 0.001microg ml(-1). Results showed the accumulation of residues of sulfosulfuron in fish over the concentration range 0.009-0.496microg g(-1). Both in water and fish samples, identified the presence of metabolites aminopyrimidine, desmethyl sulfosulfuron, guanidine, sulfonamide, ethyl sulfone and rearranged amine. The formations of these metabolites are confirmed by LC-MS/MS analysis. An LC-MS/MS electro spray ionization technique was used for this purpose. One of the metabolite Aminopyrimidine was identified at higher concentration levels (0.01-0.1microg ml(-1)) when compared with other metabolites. Subsequently dissipation of aminopyrimidine in water and its bioaccumulation was also studied at the concentration level 1mgl(-1) and 2mgl(-1). The calculated DT50 and DT90 values are 66-68 days and 218-226 days, respectively. This followed first order kinetics. Three hundred days after the exposure complete demineralization was observed.     

Analysis of chlorothalonil and degradation products in soil and water by GC/MS and LC/MS

We present a method using gas chromatography (GC) and liquid chromatography (LC) coupled to a mass selective detector to measure concentrations of the fungicide chlorothalonil and several of its metabolites in soil and water. The methods employed solid-phase extraction using a hydrophobic polymeric phase for the isolation of analytes. In lake water, average analyte recoveries ranged from 70% to 110%, with exception of pentachloronitrobenzene that gave low recoveries (23%). The method detection limits were determined to be in the range of 1 and 0.1microg l(-1) for the LC and GC methods, respectively. In soil samples, recoveries ranged from 80% to 95% for 4-hydroxy-2,5,6-trichloroisophthalonitrile (metabolite II) and 1,3-dicarbamoyl-2,4,5,6-tetrachlorobenzene (metabolite III). Limits of detection (LOD) were 0.05 and 0.02microg g(-1), respectively. Chlorothalonil and other metabolites were analyzed by GC giving recoveries ranging from 54% to 130% with LOD of 0.001-0.005microg g(-1).     

自洁式三级串联的水样在线过滤系统的研制和应用

基于玻璃纤维对小颗粒物的截留和微孔过滤,以及超声波辅助清洗等方法原理,设计和制作了带反冲洗自洁功能的三级串联在线过滤系统,将滤网（初级）、超声波作用下装填有玻璃纤维的过滤器（二级）、微孔滤管（三级）串联,对较高浊度的环境水样进行在线过滤。评估了模拟水样和实际水样中浊度的去除效果,证明该系统对水样中颗粒物有很好的去除并大幅降低水样浊度。在优化的条件下,原始浊度范围在4～100NTU的水样经过滤后,浊度均能降至1NTU以下。以标准方法测定的典型水质指标（活性磷、铵氮、亚硝酸盐氮和硝酸盐氮）的浓度为基准,计算水样经所设计的过滤系统处理后,这4种营养盐的回收率一般在85％-130％之间,说明本系统的使用基本不影响目标物的测定。     

叠式曝气生物滤池在给水预处理中的挂膜启动

针对低污染原水进行叠式曝气生物滤池的自然挂膜启动实验。在HRT为20～30 min,温度为28～33℃,气水比为0.5,滤速为12.5 m/h的条件下,研究分析叠式曝气生物滤池在自然挂膜启动过程中各项水质指标的变化情况与生物膜生长之间的相互关系,判断挂膜启动的进程。结果表明,在南方夏季,叠式曝气生物滤池能够进行快速启动,经过7 d左右自然挂膜启动完成,对CODMn的平均去除率为33%,对氨氮的平均去除率达到85.5%,对亚硝酸盐氮的去除率为82.9%。     

Degradation behaviour of pyrazosulfuron-ethyl in water as affected by pH

Pyrazosulfuron-ethyl, a new herbicide belonging to the sulfonylurea group, is used for weed control in rice crops growing in areas varying from acidic to alkaline soils. This study was undertaken to determine the degradation behaviour of pyrazosulfuron-ethyl in distilled water and buffer solutions at pH 4, 7 and 9. Degradation was pH-dependent and herbicide was least persistent in acidic pH followed by alkaline and neutral pH. The half-life of pyrazosulfuron-ethyl varied from 2.6 days (pH 4) to 19.4 days (pH 7) and half-life in distilled water was comparable to half-life at pH 7 buffer. HPLC analysis of different pH samples showed the formation of three metabolites viz., 5-(aminosulfonyl)-1-methyl-1H-pyrazole-4-carboxylic acid; ethyl 5-(aminosulfonyl)-1-methyl-1H-pyrazole-4-carboxylate and 2-amino-4,6-dimethoxy pyrimidine. The formation of pyrazosulfuron acid [5-([([(4,6-dimethoxy-2 pyrimidinyl)-amino]-carbonyl) amino]-sulfonyl)-1-methyl-1H-pyrazole-4-carboxylic acid] was not observed at any pH. The study indicated that the herbicide was least stable under acidic conditions and the predominant degradation route of pyrazosulfuron-ethyl in water is hydrolysis of sulfonamide linkage.     

Degradation in soil and water and ecotoxicity of rimsulfuron and its metabolites.

The degradation and ecotoxicity of sulfonylurea herbicide rimsulfuron and its major metabolites were examined in batch samples of an alluvial sandy loam and in freshwater. An HPLC-DAD method was adapted to simultaneously identify and quantify rimsulfuron and its metabolites, which was successfully validated by GC-MS analysis. In aqueous solutions, pure rimsulfuron was rapidly hydrolyzed into metabolite 1 (N-(4,6-dimethoxypyrimidin-2-yl)-N-(3-(ethylsulfonyl)-2-pyridinylurea)), which itself was transformed into the more stable metabolite 2 (N-((3-(ethylsulfonyl)-2-pyridinyl)-4,6-dimethoxy-2-pyrimidineamine)), with half-life (t(1/2)) values of 2 and 2.5 days, respectively. Hydrolysis was instantaneous under alkaline conditions (pH = 10). In aqueous suspensions of the alluvial soil (pH = 8), formulated rimsulfuron had a half-life of 7 days, whereas that of metabolite 1 was similar to that in water (about 3.5 days). The degradation of the two major metabolites was also studied in soil suspensions with the pure compounds at concentrations ranging from 1 to 10 mg l(-1). The half-life of metabolite 1 ranged from 3.9 to 5 days, close to the previous values. Metabolite 2 was more persistent and its degradation is strongly dependent on the initial concentration (C0): half-life values ranged from 8.1 to 55 days at 2-10 mg l(-1), respectively. These values are higher than those determined from the kinetics of metabolite 1 transformation into metabolite 2 (t(1/2) = 8-19 days). The ecotoxicity of the three chemicals was evaluated through their effect on Daphnia magna and Vibrio fischeri (Microtox bioassay). No effect was observed on D. magna with 24 and 48 h acute toxicity tests. Similarly, no toxic effect was observed with the Microtox test for the three chemicals in the range of concentrations tested that included the field application dose. Thus, being of low persistence and lacking acute toxicity, these chemicals present a low environmental risk. However, chronic effects should be studied in order to confirm the safety of rimsulfuron and its major metabolites.