Recycling of EDTA solution after soil washing of Pb, Zn, Cd and As contaminated soil

Soil washing with EDTA is known to be an effective means of removing toxic metals from contaminated soil. A practical way of recycling of used soil washing solution remains, however, an unsolved technical problem. We demonstrate here, in a laboratory scale experiment, the feasibility of using acid precipitation to recover up to 50% of EDTA from used soil washing solution obtained after extraction of Pb (5330 mg kg⁻¹), Zn (3400 mg kg⁻¹), Cd (35 mg kg⁻¹) and As (279 mg kg⁻¹) contaminated soil. Up to 100% of EDTA residual in the washing solution and 100%, 97%, 98% and 100% of initial Pb, Zn, Cd and As concentration in the solution, respectively, were removed in an electrolytic cell using a graphite anode. We employed the recovered EDTA and treated washing solution to prepare recycled soil washing solution with the same potential for extracting toxic metals from soil as the original. The efficiency of soil washing depends on the EDTA concentration. Using twice recycled 30 mmol EDTA kg⁻¹ soil, we removed 44%, 20%, 53% and 61% of Pb, Zn, Cd and As, respectively, from contaminated soil.     

Anaerobic incorporation of the radiolabeled explosive TNT and metabolites into the organic soil matrix of contaminated soil after different treatment procedures

Four bioreactor designs were performed to evaluate the level of incorporation of 14C-labeled 2,4,6-trinitrotoluene (TNT) and metabolites into the organic soil matrix of different anaerobically treated contaminated soils. The contaminated soils were amended with molasses slivers (80:20% per weight) as auxiliary substrate to enhance microbial activity. After 5 weeks (bioreactors 1 and 2), 8 weeks (bioreactor 3) and 12 weeks (bioreactor 4) of anaerobic incubation, we determined 41%, 58%, 72%, and 54%, respectively, of the initially applied radioactivity immobilized in various soil fractions. After alkaline hydrolyses of the solvent-extracted soils, low quantities of radiolabel were found in the humic and fulvic acid fractions, whereas the bulk of 14C activity was found to be strongly bound to the humin fraction (solid soil residues). The amounts of solvent extractable radioactivity were 53%, 40%, 16%, and 29% for bioreactors 1, 2, 3, and 4, respectively. The level of TNT transformation at the end of the experiments was within 90-94%. Regarding the results presented in this study, we can assume that there is the possibility of high incorporation levels of TNT metabolites into the soil organic matrix mediated by microbial cometabolism under strictly anoxic conditions.     

The two-phase leaching of Pb, Zn and Cd contaminated soil using EDTA and electrochemical treatment of the washing solution

The feasibility of a novel two-phase method for remediation of Pb (1374 mg kg(-1)), Zn (1007 mg kg(-1)), and Cd (9.1 mg kg(-1)) contaminated soil was evaluated. In the first phase we used EDTA for leaching heavy metals from the soil. In the second phase we used an electrochemical advanced oxidation process (EAOP) for the treatment and reuse of washing solution for soil rinsing (removal of the soil-retained, chelant-mobilized metallic species). In EAOP, a boron-doped diamond anode was used for the generation of hydroxyl radicals and oxidative decomposition of EDTA-metal complexes at a constant current density (15 mA cm(-2)). The released metals were removed from the solution by filtration as insoluble participate and by electro-deposition on the cathode. Four consecutive additions of 5.0 mm ol kg(-1) EDTA (total 20 mmol kg(-1)) removed 44% Pb, 14% Zn and 35% Cd from the soil. The mobility of the Pb, Zn and Cd (Toxicity Characteristic Leaching Procedure) left in the soil after remediation was reduced by 1.6, 3.4 and 1.5 times, respectively. The Pb oral availability (Physiologically Based Extraction Test) in the simulated stomach phase was reduced by 2.4 and in the intestinal phase by 1.7 times. The discharge solution was clear, almost colorless, with pH 7.73 and 0.47 mg L(-1) Pb, 1.03 mg L(-1) Zn, bellow the limits of quantification of Cd and 0.023 mM EDTA. The novel method enables soil leaching with small water requirements and no wastewater generation or other emissions into the environment.     

Evaluation of the effectiveness of phosphate treatment for the remediation of mine waste soils contaminated with Cd, Cu, Pb, and Zn

The effectiveness of phosphate treatment for Cd, Cu, Pb, and Zn immobilization in mine waste soils was examined using batch conditions. Application of synthetic hydroxyapatite (HA) and natural phosphate rock (FAP) effectively reduced the heavy metal water solubility generally by about 84-99%. The results showed that HA was slightly superior to FAP for immobilizing heavy metals. The possible mechanisms for heavy metal immobilization in the soil involve both surface complexation of the metal ions on the phosphate grains and partial dissolution of the phosphate amendments and precipitation of heavy metal-containing phosphates. HA and FAP could significantly reduce Cd, Cu, Pb, and Zn availability in terms of water solubility in contaminated soils while minimizing soil acidification and potential risk of eutrophication associated with the application of highly soluble phosphate sources.     

Comparative kinetic desorption of 60Co, 85Sr and 134Cs from a contaminated natural silica sand column: influence of varying physicochemical conditions and dissolved organic matter

In order to determine the mechanisms of the retention of 60Co, 85Sr and 134Cs in natural silica sand columns, desorption experiments were performed by changes of pH and ionic strength and by injection of natural organic matter (NOM). Injection of KCl (0.1 M) resulted in a high release of 60Co (60-100%) and 85Sr (72-100%) but a smaller release of 134Cs (31-66%). Only limited release of 60Co (66%) and 85Sr (71%) and no release of 134Cs were observed by injection of NOM. The different percentages of desorption were related to the chemical characteristics of the organic colloids previously retained in columns before the desorption step. The results evidenced different sorption processes on energetically heterogeneous surface sites. According to the initial conditions, the binding of the radionuclides to the solid phase resulted from weak and easily reversible sorption processes to strong association probably by inner sphere complexes. The rather weak release of 134Cs by KCl was attributed to the strong retention of 134Cs by clay coatings on the natural silica sand surfaces.     

Toxicological characterization of the landfill leachate prior/after chemical and electrochemical treatment: A study on human and plant cells

In this research, toxicological safety of two newly developed methods for the treatment of landfill leachate from the Piškornica (Croatia) sanitary landfill was investigated. Chemical treatment procedure combined chemical precipitation with CaO followed by coagulation with ferric chloride and final adsorption by clinoptilolite. Electrochemical treatment approach included pretreatment with ozone followed by electrooxidation/electrocoagulation and final polishing by microwave irradiation. Cell viability of untreated/treated landfill leachate was examined using fluorescence microscopy. Cytotoxic effect of the original leachate was obtained for both exposure periods (4 and 24 h) while treated samples showed no cytotoxic effect even after prolonged exposure time. The potential DNA damage of the untreated/treated landfill leachate was evaluated by the comet assay and cytokinesis-block micronucleus (CBMN) assay using either human or plant cells. The original leachate exhibited significantly higher comet assay parameters compared to negative control after 24 h exposure. On the contrary, there was no significant difference between negative control and chemically/electrochemically treated leachate for any of the parameters tested. There was also no significant increase in either CBMN assay parameter compared to the negative control following the exposure of the lymphocytes to the chemically or electrochemically treated landfill leachate for both exposure periods while the original sample showed significantly higher number of micronuclei, nucleoplasmic bridges and nuclear buds for both exposure times. Results suggest that both methods are suitable for the treatment of such complex waste effluent due to high removal efficiency of all measured parameters and toxicological safety of the treated effluent.     

Characterization of organic matter in pristine and contaminated coastal marine sediments using solid-state 13C NMR, pyrolytic and thermochemolytic methods: a case study in the San Diego harbor area.

Chemical composition of coastal marine sedimentary organic matter (SDOM) is a function of natural and anthropogenic inputs to the system. In this study a combination of analytical techniques: 13C nuclear magnetic resonance (NMR), pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) and tetramethylammonium hydroxide thermochemolysis-gas chromatography/mass spectrometry (TMAH thermochemolysis-GC/MS) were used to study the contribution of hydrophobic organic contaminants and terrestrial OM to the SDOM. Sediments were collected from two sites in the San Diego Bay: Paleta Creek, which is contaminated, and Coronado Cayes, which is relatively pristine. Concentrations of polycyclic aromatic hydrocarbons (PAHs) at both sites, as determined by ultrasonically assisted lipid extraction are found to be higher in the surface layer, to generally decrease with depth, and to be present at about two orders of magnitude higher concentration at the contaminated site as compared to the pristine site. The sediment samples were partially deashed with HF/HCI treatment before further analysis. 13C-NMR spectra of the Paleta Creek samples show a higher aromatic carbon content and a distinct phenolic carbon peak. This suggests a large input from terrestrial carbon (lignin). Data from both Py-GC/MS and TMAH thermochemolysis-GC/MS support this and indicate the presence of lignin-derived residues, primarily of the guaiacyl type at the contaminated site. In contrast, SDOM at the Coronado Cayes site exhibits less terrestrial input. In general, the SDOM resembles soil OM rather than typical marine SDOM. Chemical analyses of the lipid-extracted, partially deashed sediments, does not reveal the presence of any PAHs.     

超声波处理剩余污泥有机物、氮和磷的释放特性研究

以生活污水处理厂污泥为研究对象.采用超声波技术研究了污泥破解过程中有机物、氮和磷的释放规律.结果表明,在声能密度为0.167、0.330、0.500 W/mL的条件下,污泥中的有机物、氮和磷的释放均随超声时间而增加;破解后污泥释放出的有机物以分子量(MW)≤2 000的物质为主,且上清液BOD5/COD>0.33;所释放的氮以有机氮为主,其次是氨氮,污泥破解液COD/凯氏氮平均值为11,适合于生物法脱氮;污泥破解所释放的正磷酸盐约占污泥总磷质量的6.0%～18.2%.利用沉淀结晶法将其回收,可减轻原污水处理工艺的磷负荷.     

The conversion of chicken manure to biooil by fast pyrolysis I. Analyses of chicken manure, biooils and char by 13C and 1H NMR and FTIR spectrophotometry

Fast pyrolysis of chicken manure produced two biooils (Fractions I and II) and a residual char. All four materials were analyzed by chemical methods, 13C and 1H Nuclear Magnetic Resonance Spectrometry (13C and 1H NMR), and Fourier Transform Infrared Spectrosphotometry (FTIR). The char showed the highest C content and the highest aromaticity. Of the two biooils Fraction II was higher in C, yield and calorific value but lower in N than Fraction I. The S and ash content of the two biooil fractions were low. The Cross Polarization Magic Angle Spinning (CP-MAS) 13C NMR spectrum of the initial chicken manure showed it to be rich in cellulose, which was a major component of sawdust used as bedding material. Nuclear Magnetic Resonance (NMR) spectra of the two biooils indicated that Fraction I was less aromatic than Fraction II. Among the aromatics in the two biooils, we were able to tentatively identify N-heterocyclics like indoles, pyridines, and pyrazines. FTIR spectra were generally in agreement with the NMR data. FTIR spectra of both biooils showed the presence of both primary and secondary amides and primary amines as well as N-heterocyclics such as pyridines, quinolines, and pyrimidines. The FTIR spectrum of the char resembled that of the initial chicken manure except that the concentration of carbohydrates was lower.     

The conversion of chicken manure to biooil by fast pyrolysis I. Analyses of chicken manure,biooils and char by 13C and 1H NMR and FTIR spectrophotometry

Fast pyrolysis of chicken manure produced two biooils (Fractions I and II) and a residual char. All four materials were analyzed by chemical methods, ¹³C and 1H Nuclear Magnetic Resonance Spectrometry (¹³C and 1H NMR), and Fourier Transform Infrared Spectrosphotometry (FTIR). The char showed the highest C content and the highest aromaticity. Of the two biooils Fraction II was higher in C, yield and calorific value but lower in N than Fraction I. The S and ash content of the two biooil fractions were low. The Cross Polarization Magic Angle Spinning (CP-MAS) ¹³C NMR spectrum of the initial chicken manure showed it to be rich in cellulose, which was a major component of sawdust used as bedding material. Nuclear Magnetic Resonance (NMR) spectra of the two biooils indicated that Fraction I was less aromatic than Fraction II. Among the aromatics in the two biooils, we were able to tentatively identify N-heterocyclics like indoles, pyridines, and pyrazines. FTIR spectra were generally in agreement with the NMR data. FTIR spectra of both biooils showed the presence of both primary and secondary amides and primary amines as well as N-heterocyclics such as pyridines, quinolines, and pyrimidines. The FTIR spectrum of the char resembled that of the initial chicken manure except that the concentration of carbohydrates was lower.     

Long-term characterization, lagoon treatment and migration potential of landfill leachate: a case study in an active Italian landfill

The elaboration of 10 years of monitoring of leachate quality and quantity, leachate treatment and degree of contamination of soil and surface waters at the Tre Monti site--an active, 4-million-m(3) landfill in Northern Italy--is presented in this study. A hydrological model of leachate production is applied, with a good match of the experimental data. The concentrations of all leachate components except sulfate are characterized by fluctuations over a constant or increasing value. Different ways of interpreting leachate quality data are discussed; the elaboration indicates that the pollutant load on the leachate treatment facility will remain basically constant as long as waste will be added to the landfill. The analysis of the data relative to 10 years of leachate pre-treatment in the adjoining, non-aerated lagoon system indicates that a significant removal is achieved for most leachate components; the operational conditions of the plant are described, and the removal mechanisms are discussed. Finally, the potential for contamination of soil and surface waters is examined by analyzing long-term quality trends of the sub-superficial waters sampled near the lagoons and by means of an analytical campaign conducted on clay cores sampled near and underneath the treatment ponds. The experimental values indicate that the clay layer located under the entire site offers an effective barrier to the migration of leachate contaminants.     

猪粪经蝇蛆生态处理后粪臭素和排污量的变化

观察家蝇幼虫 (蝇蛆 )生态处理猪粪后 ,猪粪中粪臭素和排污量的变化。以养猪场的猪粪为试验材料 ,经当地蝇蛆处理的猪粪作为处理组 ,未经蝇蛆处理的猪粪为对照组 ,测定两组猪粪样本中粪臭素 ( 3 -甲基吲哚 ,简称 3 -MI)、CODCr、BOD5和 NH3-N的质量浓度。经蝇蛆处理后每 kg猪粪中的 3 -MI、CODCr、BOD5和 NH3-N分别为 2 .76× 10 - 3、5 6.3 6、14 .84和 3 .41g;对照组中上述物质分别为 3 8.5 8× 10 - 3、12 3 .0 1、60 .0 7和 3 .64 g。经蝇蛆处理后的猪粪中的 3 -MI、CODCr和 BOD5分别减少了 92 .8%、5 4.2 %和75 .3 %;而 NH3-N的含量仅减少 6.3 %。蝇蛆生态处理猪粪可有效减少粪臭素和有机污染物 ,有利于改善环境     

O3、H2O2／O3及UV／O3在焦化废水深度处理中的应用

采用O3、H2O2／O3及UV／O3等高级氧化技术（AOPs）对某焦化公司的生化出水进行深度处理,考察了O3与废水的接触时间、溶液pH、反应温度等因素对废水COD去除率的影响,确定出O3氧化反应的最佳工艺参数为：接触时间40min,溶液pH8．5,反应温度25℃,此条件下废水COD及UV254的去除率最高可达47．14％和73．47％;H2O2／O3及UV／O3两种组合工艺对焦化废水COD及UV254的去除率均有一定程度的提高,但H2O2／O3系统的运行效果取决于H2O2的投加量。研究结论表明,单纯采用COD作为评价指标,并不能准确反映出O3系列AOPs对焦化废水中有机污染物的降解作用。     

Environmental exposure of pharmaceuticals and musk fragrances in the Somes River before and after upgrading the municipal wastewater treatment plant Cluj-Napoca,Romania

Background, aim, and scope

Pharmaceutically active substances are a class of emerging contaminants, which has led to increasing concern about potential environmental risks. After excretion, substantial amounts of unchanged pharmaceuticals and their metabolites are discharged into domestic wastewaters. The absence of data on the environmental exposure in Eastern Europe is significant, since use patterns and volumes differ from country to country. In Romania, the majority of wastewater, from highly populated cities and industrial complex zones, is still discharged into surface waters without proper treatment or after inefficient treatment. In respect to this, it is important to determine the environmental occurrence and behavior of pharmaceuticals and personal care products (PPCPs) in wastewaters and surface waters. The objective of the present study was to investigate the occurrence of selected PPCPs during the transport in the Somes River by mass flow analysis before and after upgrading a municipal wastewater treatment plant (WWTP) in Cluj-Napoca, which serves 350,000 inhabitants and is the largest plant discharging into the Somes River. The concentrations of PPCPs at Cluj-Napoca can be correlated with the high population and a high number of hospitals located in the catchment area leading to higher mass flows. The results of this study are expected to provide information, with respect to the Romanian conditions, for environmental scientists, WWTP operators, and legal authorities. The data should support the improvement of existing WWTPs and implementation of new ones where necessary and, therefore, minimize the input of contaminants into ambient waters.

Materials and methods

The PPCPs were selected on the basis of consumption at the regional scale, reported aquatic toxicity, and the suitability of the gas chromatography/mass spectrometry (GC/MS) method for the determination of the compounds at trace levels. The studied PPCPs, caffeine (stimulant), carbamazepine (antiepileptic), pentoxifylline (anticoagulant), cyclophosphamide (cytostatic), ibuprofen (analgesic), and galaxolide (musk fragrance), were determined in samples of the Somes River. The analytes were enriched by solid-phase extraction and subsequently determined by GC/MS. Caffeine, pentoxifylline, and galaxolide were determined underivatized, whereas the acidic pharmaceuticals carbamazepine, cyclophosphamide, and ibuprofen were determined after derivatization with N-methyl-N-(trimethylsilyl)-trifluoroacetamide.

Results and discussion

The concentrations in the Somes River varied from below 10 ng/L up to 10 μg/L. A substantial decrease of the exposure in the Somes River could be observed due to the upgrade of the municipal WWTP in Cluj-Napoca. The loads in the river stretch between Cluj-Napoca and Dej (Somes Mic) varied strongly: caffeine (400–2,000 g/day), carbamazepine (78–213 g/day), galaxolide (140–684 g/day), ibuprofen (84–108 g/day). After the upgrade of the WWTP Cluj-Napoca, the concentrations in the Somes of caffeine, pentoxifylline, cyclophosphamide, galaxolide, and tonalide were significantly reduced (over 75%). One might be cautious comparing both studies because the relative efficiency of the WWTP’s removal of PPCP was not evaluated. However, the significantly lower concentrations of most compounds after the upgrade of the WWTP Cluj-Napoca allow one to infer that the technical measures at the source substantially reduced inputs of contaminants to the receiving river. Dej loads of the poorly biodegradable substance carbamazepine increased by a factor of 2–3 as a result of wastewater discharges into the river. The disproportionate increase in caffeine loads by a factor of 4 below Cluj-Napoca indicates inputs of untreated wastewater from the Somes Mare due to the discharge of untreated wastewater derived from Bistrita, Nasaud, and Beclean (115,000 inhabitants).

Conclusions

The relative contribution of treated and untreated wastewater in surface water might be assessed by measuring chemical markers. Recalcitrant pharmaceuticals like carbamazepine are suitable as chemical markers for estimating the relative contribution of wastewater in surface water. The easily degradable caffeine might be a good indicator for raw sewage and hardly treated wastewaters.

Recommendations and perspectives

Municipal WWTPs have the potential of a significant contribution in reducing the load of contaminants to ambient waters. The efficiency of the wastewater treatment in Cluj-Napoca improved considerably after the upgrade of the WWTP. Therefore, it is crucial that several WWTPs must be implemented or improved in the Somes Valley Watershed in order to reduce the discharge of contaminants in the Somes River from these point sources.

     

Environmental exposure of pharmaceuticals and musk fragrances in the Somes River before and after upgrading the municipal wastewater treatment plant Cluj-Napoca, Romania

Background, aim, and scope  

Pharmaceutically active substances are a class of emerging contaminants, which has led to increasing concern about potential environmental risks. After excretion, substantial amounts of unchanged pharmaceuticals and their metabolites are discharged into domestic wastewaters. The absence of data on the environmental exposure in Eastern Europe is significant, since use patterns and volumes differ from country to country. In Romania, the majority of wastewater, from highly populated cities and industrial complex zones, is still discharged into surface waters without proper treatment or after inefficient treatment. In respect to this, it is important to determine the environmental occurrence and behavior of pharmaceuticals and personal care products (PPCPs) in wastewaters and surface waters. The objective of the present study was to investigate the occurrence of selected PPCPs during the transport in the Somes River by mass flow analysis before and after upgrading a municipal wastewater treatment plant (WWTP) in Cluj-Napoca, which serves 350,000 inhabitants and is the largest plant discharging into the Somes River. The concentrations of PPCPs at Cluj-Napoca can be correlated with the high population and a high number of hospitals located in the catchment area leading to higher mass flows. The results of this study are expected to provide information, with respect to the Romanian conditions, for environmental scientists, WWTP operators, and legal authorities. The data should support the improvement of existing WWTPs and implementation of new ones where necessary and, therefore, minimize the input of contaminants into ambient waters.     

Environmental exposure of pharmaceuticals and musk fragrances in the Somes River before and after upgrading the municipal wastewater treatment plant Cluj-Napoca,Romania

Background, aim, and scope

Pharmaceutically active substances are a class of emerging contaminants, which has led to increasing concern about potential environmental risks. After excretion, substantial amounts of unchanged pharmaceuticals and their metabolites are discharged into domestic wastewaters. The absence of data on the environmental exposure in Eastern Europe is significant, since use patterns and volumes differ from country to country. In Romania, the majority of wastewater, from highly populated cities and industrial complex zones, is still discharged into surface waters without proper treatment or after inefficient treatment. In respect to this, it is important to determine the environmental occurrence and behavior of pharmaceuticals and personal care products (PPCPs) in wastewaters and surface waters. The objective of the present study was to investigate the occurrence of selected PPCPs during the transport in the Somes River by mass flow analysis before and after upgrading a municipal wastewater treatment plant (WWTP) in Cluj-Napoca, which serves 350,000 inhabitants and is the largest plant discharging into the Somes River. The concentrations of PPCPs at Cluj-Napoca can be correlated with the high population and a high number of hospitals located in the catchment area leading to higher mass flows. The results of this study are expected to provide information, with respect to the Romanian conditions, for environmental scientists, WWTP operators, and legal authorities. The data should support the improvement of existing WWTPs and implementation of new ones where necessary and, therefore, minimize the input of contaminants into ambient waters.

Materials and methods

The PPCPs were selected on the basis of consumption at the regional scale, reported aquatic toxicity, and the suitability of the gas chromatography/mass spectrometry (GC/MS) method for the determination of the compounds at trace levels. The studied PPCPs, caffeine (stimulant), carbamazepine (antiepileptic), pentoxifylline (anticoagulant), cyclophosphamide (cytostatic), ibuprofen (analgesic), and galaxolide (musk fragrance), were determined in samples of the Somes River. The analytes were enriched by solid-phase extraction and subsequently determined by GC/MS. Caffeine, pentoxifylline, and galaxolide were determined underivatized, whereas the acidic pharmaceuticals carbamazepine, cyclophosphamide, and ibuprofen were determined after derivatization with N-methyl-N-(trimethylsilyl)-trifluoroacetamide.

Results and discussion

The concentrations in the Somes River varied from below 10 ng/L up to 10 μg/L. A substantial decrease of the exposure in the Somes River could be observed due to the upgrade of the municipal WWTP in Cluj-Napoca. The loads in the river stretch between Cluj-Napoca and Dej (Somes Mic) varied strongly: caffeine (400–2,000 g/day), carbamazepine (78–213 g/day), galaxolide (140–684 g/day), ibuprofen (84–108 g/day). After the upgrade of the WWTP Cluj-Napoca, the concentrations in the Somes of caffeine, pentoxifylline, cyclophosphamide, galaxolide, and tonalide were significantly reduced (over 75%). One might be cautious comparing both studies because the relative efficiency of the WWTP’s removal of PPCP was not evaluated. However, the significantly lower concentrations of most compounds after the upgrade of the WWTP Cluj-Napoca allow one to infer that the technical measures at the source substantially reduced inputs of contaminants to the receiving river. Dej loads of the poorly biodegradable substance carbamazepine increased by a factor of 2–3 as a result of wastewater discharges into the river. The disproportionate increase in caffeine loads by a factor of 4 below Cluj-Napoca indicates inputs of untreated wastewater from the Somes Mare due to the discharge of untreated wastewater derived from Bistrita, Nasaud, and Beclean (115,000 inhabitants).

Conclusions

The relative contribution of treated and untreated wastewater in surface water might be assessed by measuring chemical markers. Recalcitrant pharmaceuticals like carbamazepine are suitable as chemical markers for estimating the relative contribution of wastewater in surface water. The easily degradable caffeine might be a good indicator for raw sewage and hardly treated wastewaters.

Recommendations and perspectives

Municipal WWTPs have the potential of a significant contribution in reducing the load of contaminants to ambient waters. The efficiency of the wastewater treatment in Cluj-Napoca improved considerably after the upgrade of the WWTP. Therefore, it is crucial that several WWTPs must be implemented or improved in the Somes Valley Watershed in order to reduce the discharge of contaminants in the Somes River from these point sources.