Models to Estimate Volatile Organic Hazardous Air Pollutant Emissions from Municipal Sewer Systems

Abstract

Emissions from municipal sewers are usually omitted from hazardous air pollutant (HAP) emission inventories. This omission may result from a lack of appreciation for the potential emission impact and/or from inadequate emission estimation procedures. This paper presents an analysis and comparison of the models available to estimate volatile organic HAP (VOHAP) emissions from sewers. Comparisons were made between the different theoretical foundations of the models, as well as between the emissions predicted by the models for a single sewer component. Sewer gas concentrations predicted by the models were also compared to measured sewer gas concentrations reported in the literature. Two of the models were compared in their ability to estimate sewer VOHAP emissions for a large U. S. city using National Pollution Discharge Effluent System data for the influent wastewater to the city's municipal wastewater treatment facilities. This estimate showed that, regardless of the model used, sewer emissions are a potentially significant source of VOHAP emissions in the urban environment. The choice of model, however, is thought to be less critical to sewer emission estimates than the source of sewer wastewater VOHAP concentration data.     

Alkylphenolic compounds and bisphenol A contamination within a heavily urbanized area: case study of Paris

This study evaluates the influence of a heavily urbanized area (Paris Metropolitan area), on receiving water contamination by both bisphenol A (BPA) and alkylphenol ethoxylate (APE) biodegradation product. The study began by investigating concentrations within urban sources. In addition to the more commonly studied wastewater treatment plant effluent, wet weather urban sources (including combined sewer overflows, urban runoff, and total atmospheric fallout) were considered. The initial results highlight a significant contamination of all urban sources (from a few nanograms per liter in atmospheric fallout to several micrograms per liter in the other sources) with clearly distinguishable distribution patterns. Secondly, concentration changes along the Seine River from upstream of the Paris Metropolitan area to downstream were investigated. While the concentrations of BPA and nonylphenoxy acetic acid (NP₁EC) increase substantially due to urban sources, the 4-nonylphenol concentrations remain homogeneous along the Seine. These results suggest a broad dissemination of 4-nonylphenol at the scale of the Seine River basin. Moreover, the relationship between pollutant concentrations and Seine River flow was assessed both upstream and downstream of the Paris conurbation. Consequently, a sharp decrease in dissolved NP₁EC concentrations relative to Seine River flow underscores the influence of single-point urban pollution on Seine River contamination. Conversely, dissolved 4-nonylphenol concentrations serve to reinforce the hypothesis of its widespread presence at the Seine River basin scale.     

Temporal evolution in PPCP removal from urban wastewater by constructed wetlands of different configuration: a medium-term study

Pharmaceuticals and personal care products (PPCPs) are widely distributed in urban wastewaters and can be removed to some extent by constructed wetlands (CWs). The medium-term (3-5 years) behaviour of these systems regarding PPCP removal is still unknown. Seven mesocosm-scale (1 m²) CWs of different configurations were operated outdoors for 39 months under the same conditions to assess their PPCP removal ability and temporal evolution. CWs differed in some design parameters, namely plant presence, species chosen (Typha angustifolia vs Phragmites australis), flow configuration and presence/absence of gravel bed (floating macrophytes surface flow, FM-SF; free-water surface flow, FW-SF; free-water subsurface flow, FW-SSF; or conventional horizontal subsurface flow, SSF). PPCP efficiencies decreased throughout time and performance differences among CWs disappeared with the systems aging. This could be due to a homogenization process in the systems caused by detrimental factors like saturation, clogging and shading. Winter efficiencies were lower than summer ones for salicylic acid, caffeine, methyl dihydrojasmonate, galaxolide and tonalide, and seasonal biological activities seem key factors to explain this fact. Maximal removal efficiencies were achieved in an unplanted-FW-SSF for ketoprofen (47-81%), naproxen (58-81%) and salicylic acid (76-98%); in an unplanted-SSF for caffeine (65-99%); in a Phragmites-FM-SF for ibuprofen (49-96%) and diclofenac (16-68%); in a Typha-FM-SF for carbamazepine (35-71%); and in a Typha-FW-SSF for methyl dihydrojasmonate (71-96%), galaxolide (67-82%) and tonalide (55-74%). Photodegradation could be involved in ketoprofen, naproxen, ibuprofen and diclofenac removal. Carbamazepine and diclofenac were moderately removed by the most efficient CWs studied. Carbamazepine might be eliminated by vegetal uptake.     

Toxicity of water and sediment in a small urban river (Store Vejleå, Denmark)

The urban stream Store Vejle? (Denmark), which receives discharges of urban runoff, was investigated using a combination of biological toxicity tests and chemical analysis. The urban stormwater and road runoff gave low, but statistically significant, effects on the reproduction of the alga Pseudokirchneriella subcapitata. In all pre-concentrated water samples toxic effects were found and differences in toxicity depending on time and location of sampling were identified. Undiluted pore water samples from sediments collected in the stream were all toxic towards the algae and dilutions from 4 to 14 times were needed compared to a pore water sample from an unpolluted stream where a dilution factor of only 1.6 was required. A qualitative correlation between the toxicity of the pore water and the degree of pollution as evidenced by the metal concentration was observed, but statistically significant correlations could not be established by ranking procedures of, e.g. metal content or PAH-concentrations versus the observed toxicity.     

山地城市合流污水特细砂来源

对三峡库区山地城市合流制污水特细砂、管道沉积物、本地土壤等进行矿物成分分析表明,污水中特细砂矿物成分以石英、方解石,长石类为主,并含有少量云母、赤铁矿和石膏等矿物;认为特细砂主要来自周边砂壤质地土壤、风化岩石和地表沉积物;山地城市合流制管网（污水常规收集方式）,山涧、边沟和冲沟（污水特殊收集方式）是细砂迁移的途径;生活污水和雨水是细砂迁移的载体;中亚热带湿润季风气候,加速成土母质主要是侏罗系紫色砂质岩、泥岩和石灰岩风化,而山地、丘陵地貌特征和充沛的雨量强化合流雨污水冲刷作用,导致水土流失加剧。因此,对于山地城市合流污水特细砂的治理,需要从合流制管网建设完善、水土流失防治、生活小区统一规划和污水处理厂除砂系统优化等多个方面进行控制。     

Assessment of the contribution of sewer deposits to suspended solids loads in combined sewer systems during rain events

Within the French observatories network SOERE “URBIS,” databases of continuous turbidity measurements accumulating hundreds of events and many dry weather days are available for two sites with different features (Clichy in Paris and Ecully in Lyon). These measurements, converted into total suspended solids (TSS) concentration using TSS–turbidity relationships and combined with a model of runoff event mean concentration, enable the assessment of the contribution of sewer deposits to wet weather TSS loads observed at the outlet of the two watersheds. Results show that the contribution of sewer deposits to wet weather suspended solid’s discharges is important but variable (between 20 and 80 % of the mass at the outlet depending on the event), including a site allegedly free of (coarse) sewer deposits. The uncertainties associated to these results are assessed too.     

Forensic Applications of Nitrogen and Oxygen Isotopes in Tracing Nitrate Sources in Urban Environments

Ground and surface waters in urban areas are susceptible to nitrate contamination from septic systems, leaking sewer lines, and fertilizer applications. Source identification is a primary step toward a successful remediation plan in affected areas. In this respect, nitrogen and oxygen isotope ratios of nitrate, in conjunction with hydrologic data and water chemistry, have proven valuable in urban studies from Austin, Texas, and Tacoma, Washington.In Austin, stream water was sampled during stremflow and baseflow conditions to assess surface and subsurface sources of nitrate, respectively. In Tacoma, well waters were sampled in adjacent sewered and un-sewered areas to determine if locally high nitrate concentrations were caused by septic systems in the un-sewered areas. In both studies, sewage was identified as a nitrate source and mixing between sewage and other sources of nitrate was apparent. In addition to source identification, combined nitrogen and oxygen isotopes were important in determining the significance of denitrification, which can complicate source assessment by reducing nitrate concentrations and increasing δ¹⁵N values. The two studies illustrate the value of nitrogen and oxygen isotopes of nitrate for forensic applications in urban areas.     

Cost optimization of integrated wastewater drainage and treatment systems

This paper presents the cost optimization of an urban drainage and wastewater treatment system. The mixed sewer urban drainage (including combined sewer overflows and retention basins), the activated sludge wastewater treatment plant (WWTP), and the permissible loading of the receiving water were optimized simultaneously by the nonlinear programming approach. For this purpose, the integrated optimization model OPTIMALWWT was developed. The economic objective function of the defined investment and operational costs is subjected to rigorous design and ecological constraints. A practical example of the cost optimization of an existing urban drainage and WWTP, located in Slovenia, is presented to demonstrate the efficiency of the proposed method. For each of the two different design approaches, three different optimization cases were carried out for three different technological alternatives. As a result, the optimal technological process was finally selected for the reconstruction of the system, as a result of its suitable costs and operational safety.     

Lake eutrophication at the urban fringe,Seattle region,USA

Nutrient pollution and associated eutrophication of freshwaters threaten the ecological integrity and the services provided to humans by lakes. We examined how human residential development influenced the level of lake eutrophication in the Seattle, WA, USA, region. We surveyed 30 lakes and measured 3 indicators of eutrophication: concentrations of chlorophyll-a and phosphorus, and the proportion of algae that are inedible to zooplankton. We classified lakes based on the waste-treatment method for shoreline homes: septic, sewer, and undeveloped lakes. Septic lakes occurred along the urban-rural fringe while sewer lakes occurred near urban centers. Septic lakes were more eutrophic than sewer lakes and undeveloped lakes, as indicated by higher levels of phosphorus and chlorophyll-a. These results suggest that septic systems contribute to the high levels of eutrophication in lakes at the urban-rural fringe. Lakes at the urban-rural fringe represent an opportunity for proactive management of urban expansion to minimize lake eutrophication.     

Occurrence and fate of PPCPs and correlations with water quality parameters in urban riverine waters of the Pearl River Delta, South China

The occurrence and fate of eight PPCPs was studied in river waters from upstream to downstream of the three rivers in the Pearl River Delta, China. The correlations of PPCP levels and water quality parameters were also investigated. The analytes of the highest concentrations were caffeine, acetaminophen, and ciprofloxacin. Carbamazepine and erythromycin-H₂O were detected at the lowest concentrations. The highest concentrations of PPCPs were found in the Shijing River, with 865 ng/L caffeine, 339 ng/L acetaminophen, and 304 ng/L ciprofloxacin. In general, the levels of PPCPs in the Zhujiang River were higher at sites where the metropolitan city Guangzhou is located and decreased from the epicenter along the river. Low levels of PPCPs were generally found in the Beijiang River. Positive correlations were found between PPCP levels, total nitrogen, ammonium nitrogen, and cumulative fluorescence excitation-emission matrix (EEM) volume. Among the four PPCPs evaluated (caffeine, acetaminophen, ciprofloxacin, and sulfamethoxazole), caffeine had the best correlations with the correlation coefficients ranging from 0.62 to 0.98. The prediction of PPCP concentrations at specified locations can be substantially simplified.     

Physico-chemical characterization of grease interceptors with and without biological product addition

Hardened and insoluble fat, oil, and grease (FOG) deposits are the primary cause of sewer line blockages leading to sanitary sewer overflows (SSOs). However, there have been very few long-term assessments of the physico-chemical characteristics of full-scale grease interceptors (GIs), the first "line of defense" against FOG buildup in sewer lines. In this study, we assessed the physico-chemical characteristics of two full-scale GIs (at a restaurant and a retirement community kitchen) over a one-year period. Statistically significant differences between bioaugmented and untreated cycles were detected for several chemical and physical properties. The treated cycles had lower BOD and COD at the grease interceptor outlet. While the combined data for all treated cycles did not show lower FOG concentrations in the GI outlet compared to the combined data for all untreated cycles, comparison of specific individual treated and untreated cycles show a positive effect due to the addition of product.     

Delivery and frequency distributions of combined wastewater collection system wet and dry weather loads

Combined wastewater collection systems continue to serve as a common urban conveyance method in urban areas of Europe and older urban areas of the United States. This study uses combined wastewater collection system monitoring data from the urbanizing Liguori catchment and channel in Cosenza (Italy) to illustrate event-based delivery and distribution of conveyed pollutant indices. Motivated by recent European Union (EU) discharge control legislation, this study specifically differentiates the event-based delivery of these indices between dry and wet-weather flows. Although the relatively steady to diurnal-variable delivery phenomena in dry weather flows are known, transport limiting phenomena for wet-weather hydrology and mass delivery typically are not known for the same catchment. Limiting categories of transport for a pollutant phase are generated by variables such as flow volume and duration, stream power, hydrograph parameters, and previous dry hours (PDH). Transport limitations of wet and dry weather events from the 414-ha catchment were analyzed and characterized as limited by mass indices (first-order, first flush transport) or limited by flow (zero-order transport). Results indicated significant concentration differences between mass- and flow-limited events. Higher concentrations were associated with mass-limited events. Frequency distributions of flow, total suspended solids (TSS), chemical oxygen demand (COD), and five-day biochemical oxygen demand (BOD5) were consistently exponential for wet-weather and mass-limited events. In contrast, flow, TSS, and BOD5 concentrations were distributed normally for flow-limited events. Results indicated a reasonable linear relationship between discharged TSS, COD, and BOD5 (biochemical oxygen demand) for Liguori Channel discharges into the Crati River. Wet-weather event transport was predominately mass-limited for TSS, COD, and BOD5.     

Reduction of pharmaceutically active compounds by a lagoon wetland wastewater treatment system in Southeast Louisiana

A number of pharmaceutically active compounds (PhACs) have been detected in the aquatic environment as a result of discharges of municipal wastewater. In the state of Louisiana, USA, many municipalities treat wastewater using natural systems, such as lagoons and wetlands, rather than conventional wastewater treatment technologies. Nearly all research to date has focused on the fate of PhACs in conventional treatment plants, not constructed and natural wetlands. In the wastewater treatment plant (WWTP) for Mandeville, Louisiana, USA, wastewater flows of 7600 m³ d⁻¹ are treated in a series of aeration lagoons (basins), followed by a constructed wetland and UV disinfection, before being discharged into a natural forested wetland (i.e. Bayou Chinchuba) and eventually, Lake Pontchartrain. Thirteen out of the 15 PhACs investigated were detected in the wastewater inflow to the treatment plant. Only 9 of the 13 compounds were above the detection limits at the treatment plant effluent. The concentrations of most compounds were reduced by greater than 90% within the plant, while carbamazepine and sotalol were only reduced by 51% and 82%, respectively. The percent reductions observed in the Mandeville system were greater than reduction rates reported for conventional WWTPs; perhaps due to the longer treatment time (30 days). Most target PhACs were not completely removed before discharge into Lake Pontchartrain, although their collective annual loading was reduced to less than 1 kg and down to ppb with significant potential for dilution in the large lake.     

An evaluation of the urban stormwater pollutant removal efficiency of catch basin inserts.

In a storm sewer system, the catch basin is the interface between surface runoff and the sewer. Responding to the need to improve the quality of stormwater from urban areas and transportation facilities, and spurred by Phase I and II Stormwater Rules from the U.S. Environmental Protection Agency, several companies market catch basin inserts as best management practices for urban water quality management. However, little data have been collected under controlled tests that indicate the pollutant removal efficiency of these inserts when the inflow is near what can be expected to occur in the field. A stormwater simulator was constructed to test inserts under controlled and replicable conditions. The inserts were tested for removal efficiency of total suspended solids (TSS) and total petroleum hydrocarbons (TPH) at an inflow rate of 757 to 814 L/min, with influent pollutant concentrations of 225 mg/L TSS and 30 mg/L TPH. These conditions are similar to stormwater runoff from small commercial sites in the southeastern United States. Results from the tests indicate that at the test flowrate and pollutant concentration, average TSS removal efficiencies ranged from 11 to 42% and, for TPH, the removal efficiency ranged from 10 to 19%.     

Sources of priority substances entering an urban wastewater catchment--trace organic chemicals

The implementation of new legislation such as the Water Framework Directive (WFD) requires Member States to gain a better understanding of priority substances entering surface waters. This will include inputs from wastewater treatment works as well as from other urban, industrial and agricultural sources. There is currently a lack of available data regarding the magnitude and sources of organic priority substances entering treatment works. As a consequence the concentrations of organic priority substances including PAHs, surfactants, polybrominated diphenylethers (PBDEs), diethylhexyl phthalate (DEHP), pesticides and solvents were determined in the wastewater from an urban catchment located in the UK, as part of a project undertaken for UK Water Industry Research (UKWIR). Most organic priority substances were detected in the microg/l range. Significant variations in the concentration of linear alkylbenzene sulphonate (LAS), DEHP, PBDEs and nonylphenol ethoxylates (NPEOs), in particular, were observed for the different sources. The greatest differences were evident between new and older domestic discharges. Solvent levels varied considerably reflecting use and production within the catchment. Chloroform levels were highest in domestic effluent, while trichloroethene and tetrachloroethene were detected only in commercial samples.     

Evaluation of PPCPs removal in a combined anaerobic digester-constructed wetland pilot plant treating urban wastewater

The removal efficiency of 16 pharmaceuticals and personal care products (PPCPs) from urban wastewater (dissolved and particulate phases) was evaluated for the first time in a hybrid pilot plant consisting of an upflow anaerobic sludge blanket reactor followed by two sequentially connected horizontal flow constructed wetlands: a surface flow wetland (SF CW) and a subsurface flow wetland (SSF CW). Whereas the PPCP removal associated with the dissolved phase exhibited a seasonal pattern, the fraction associated with the suspended solids showed less seasonality. In the dissolved phase, the overall removal efficiency in summer ranged from 70% to 85% for salicylic acid (SAL), methyl dihydrojasmonate, caffeine (CAF), ketoprofen and triclosan, whereas in winter it declined for most of the PPCPs to between 30% and 50%, except for CAF and SAL (>80%) and carbamazepine and butylated hydroxyl toluene (11-18%). In the suspended solids, the removal exceeded 80% for most of the target PPCPs. The efficiency of the different treatment steps was also compound-dependent, but the SF CW generally exhibited the highest removal efficiency for most of the contaminants analyzed. The characterization of the organic matter retained in the wetland gravel beds revealed the occurrence of hydrophobic contaminants such as phthalate esters and fragrances at moderate concentrations (i.e., up to 3.5 μg kg⁻¹), which declined strongly over the course of the different treatment steps. In the SF CW, the net mass accumulation rates of tonalide and galaxolide were 4 and 23 g y⁻¹ respectively, whereas in the SSF CW they were 0.3 and 1.8 g y⁻¹ respectively.     

Occurrence and distribution of selected pharmaceuticals and personal care products in aquatic environments: a comparative study of regions in China with different urbanization levels

Purpose

We analyzed and compared the distributions of 13 target pharmaceuticals in different water samples from the Hangzhou metropolitan area and Linan County, Southeast China.

Methods

Sampling was conducted in five hospitals, two wastewater treatment plants (WWTPs), and Qiantang River. Samples were concentrated by solid-phase extraction and PPCP concentrations were determined by UPLC-MS/MS.

Results and discussion

Trimethoprim, erythromycin A dihydrate, norfloxacin, ofloxacin, diclofenac sodium, and atenolol were the most frequently detected pharmaceuticals in hospital effluents. Most of the pharmaceutical concentrations in hospital effluents were higher than those in the WWTP influents. Although both WWTPs adopt the anaerobic?Caerobic?Canoxic treatment process, the removal rates for pharmaceuticals, such as trimethoprim and diclofenac sodium, were completely different. Meanwhile, erythromycin A dihydrate, ofloxacin, penicillin-G, cephalexin, cefazolin, ibuprofen, and diclofenac sodium were detected in Qiantang River.

Conclusions

These results indicate that hospitals are more concentrated sources of pharmaceuticals than WWTPs, and the WWTPs are not the only route of entry of pharmaceuticals into aquatic environments in these two regions.     

The carbon-sequestration potential of municipal wastewater treatment

The lack of proper wastewater treatment results in production of CO(2) and CH(4) without the opportunity for carbon sequestration and energy recovery, with deleterious effects for global warming. Without extending wastewater treatment to all urban areas worldwide, CO(2) and CH(4) emissions associated with wastewater discharges could reach the equivalent of 1.91 x 10(5) t(CO2)d(-1) in 2025, with even more dramatic impact in the short-term. The carbon sequestration benefits of wastewater treatment have enormous potential, which adds an energy conservation incentive to upgrading existing facilities to complete wastewater treatment. The potential greenhouse gases discharges which can be converted to a net equivalent CO(2) credit can be as large as 1.91 x 10(5) t(CO2)d(-1) in 2025 by 2025. Biomass sequestration and biogas conversion energy recovery are the two main strategies for carbon sequestration and emission offset, respectively. The greatest potential for improvement is outside Europe and North America, which have largely completed treatment plant construction. Europe and North America can partially offset their CO(2) emissions and receive benefits through the carbon emission trading system, as established by the Kyoto protocol, by extending existing technologies or subsidizing wastewater treatment plant construction in urban areas lacking treatment. This strategy can help mitigate global warming, in addition to providing a sustainable solution for extending the health, environmental, and humanitarian benefits of proper sanitation.     

Source identification and risk assessment of heavy metal contaminations in urban soils of Changsha,a mine-impacted city in Southern China

The urban soils suffered seriously from heavy metal pollutions with rapid industrialization and urbanization in China. In this study, 54 urban soil samples were collected from Changsha, a mine-impacted city located in Southern China. The concentrations of heavy metals (As, Cd, Co, Cu, Mn, Ni, Pb, and Zn) were determined by ICP-MS. The pollution sources of heavy metals were discriminated and identified by the combination of multivariate statistical and geostatistical methods. Four main sources were identified according to the results of hierarchical cluster analysis (HCA), principal component analysis (PCA), and spatial distribution patterns. Co and Mn were primarily derived from soil parent material. Cu, Pb, and Zn with significant positive relationships were associated with mining activities and traffic emissions. Cd and Ni might be affected by commercial activities and industrial discharges. As isolated into a single group was considered to have correlation with coal combustion and waste incineration. Risk assessment of heavy metals in urban soils indicated an overall moderate potential ecological risk in the urban region of Changsha.     

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.