Characteristic occurrence patterns of micropollutants and their removal efficiencies in industrial wastewater treatment plants

The concentrations and removal efficiencies of various kinds of micropollutants were investigated and the relationships between the input sources of industrial wastewater and occurrence patterns of each micropollutant were identified at nine on-site industrial wastewater treatment plants (WWTPs). The distribution pattern of each compound varied according to the WWTP type and several micropollutants were significantly related with specific industries: chlorinated phenols (ClPhs) with paper and metal industries, polycyclic aromatic hydrocarbons (PAHs) with petrogenic- and pyrogenic-related industries, polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) with the paper industry, and chlorinated benzenes (ClBzs) with dye-related industries. The activated sludge (AS) process was very efficient in the removal of ClPhs and PAHs, and the filtration process in the removal of PCDD/Fs and 1,4-dioxane. Generally, the removal efficiencies of each micropollutant varied according to the WWTP type.     

Occurrence and fate of androgens, estrogens, glucocorticoids and progestagens in two different types of municipal wastewater treatment plants

The occurrence and fate of fourteen androgens, four estrogens, five glucocorticoids and five progestagens were investigated in two different types of wastewater treatment plants (Plant A: activated sludge with chlorination, and Plant B: oxidation ditch with UV) of Guangdong province, China. 14, 14, and 10 of 28 target compounds were detected in the influent, effluent and dewatered sludge samples with the concentrations ranging from below 1.2 ± 0.0 ng L(-1) (stanozolol) to 1368 ± 283 ng L(-1) (epi-androsterone), below 1.0 ± 0.0 ng L(-1) (progesterone) to 23.1 ± 1.0 ng L(-1) (5α-dihydrotestosterone), 1.0 ± 0.1 ng g(-1) (estrone) to 460 ± 4.4 ng g(-1) (5α-dihydrotestosterone), respectively. The concentrations of total androgens (1554-1778 ng L(-1) in influent, 13.3-47.8 ng L(-1) in effluent, 377-923 ng g(-1) in dewatered sludge) were much higher than those of total estrogens (41.5-60.2 ng L(-1) in influent, 5.6-13.5 ng L(-1) in effluent, 13.9-57.8 ng g(-1) in dewatered sludge), glucocorticoids (171-192 ng L(-1) in influent, 2.2-6.3 ng L(-1) in effluent, N.D.-4.4 ng g(-1) in dewatered sludge), and progestagens (39.6-40.5 ng L(-1) in influent, 6.9-12.1 ng L(-1) in effluent, N.D. in dewatered sludge) in these two WWTPs. According to mass balance analysis, the removal rates of most target steroids in Plant A had exceeded 90%, while those in Plant B for nearly half of detected target steroids were lower than 80%. It is obvious that the treatment capacity of the activated sludge system (Plant A) is superior to the oxidation ditch (Plant B) in the degradation of steroids in sewage treatment systems. Androgens, estrogens and progestagens were mainly removed by sorption and degradation, while the reduction of glucocorticoids was primarily due to degradation.     

Organophosphate flame retardants and plasticisers in wastewater treatment plants

Previous studies have revealed that chlorinated and non-chlorinated organophosphorous flame retardants and plasticisers are important contaminants in German surface waters and it has been demonstrated that wastewater treatment plants contribute to the emission of these substances. In this study temporal development as well as elimination efficiency were determined in two wastewater treatment plants (STP) in the Ruhr/Rhine area at different stages of the wastewater treatment process. The samples were analysed for the non-chlorinated organophosphate esters tri-n-butylphosphate (TnBP), tri-iso-butylphosphate (TiBP), tris-(butoxyethyl)-phosphate (TBEP) and triphenylphosphate (TPP) and the chlorinated organophosphate esters tris-(2-chloro, 1-methylethyl)-phosphate (TCPP), tris-(2-chloro-, 1-chloromethylethyl)-phosphate (TDCP) and tris-(2-chloroethyl)-phosphate (TCEP). The study showed that there were significant differences in the elimination of chlorinated and non-chlorinated organophosphorous flame retardants. The elimination rates ranged from 57-86% for TiBP, TnBP and TBEP at both STP's. No elimination of the chlorinated flame retardants TCPP, TDCP and TCEP was observed in any of the sampled STPs. At both STPs the first treatment steps and the final filtration did not contribute to the elimination of the non-chlorinated organophosphorous flame retardants while the aeration step did. At both STPs the efficiency of the cleaning process concerning the flame retardants was comparable. Thus the type of construction of the STP was not relevant for the elimination of these substances. Additionally a strong day-to-day variation was observed, while in one STP a temporal trend for TCPP during the week was found.     

The fate of steroid estrogens: partitioning during wastewater treatment and onto river sediments

The partitioning of steroid estrogens in wastewater treatment and receiving waters is likely to influence their discharge to, and persistence in, the environment. This study investigated the partitioning behaviour of steroid estrogens in both laboratory and field studies. Partitioning onto activated sludge from laboratory-scale Husmann units was rapid with equilibrium achieved after 1 h. Sorption isotherms and Kd values decreased in the order 17??-ethinyl estradiol > 17??-estradiol > estrone > estriol without a sorption limit being achieved (1/n?>1). Samples from a wastewater treatment works indicated no accumulation of steroid estrogens in solids from primary or secondary biological treatment, however, a range of steroid estrogens were identified in sediment samples from the River Thames. This would indicate that partitioning in the environment may play a role in the long-term fate of estrogens, with an indication that they will be recalcitrant in anaerobic conditions.     

Occurrence,removal and health risk assessment of phthalate esters in the process streams of two different wastewater treatment plants in Lagos and Ogun States,Nigeria

Phthalate esters (PEs) are one of the environmentally active organic pollutants capable of causing endocrine disruption. The levels of PE congeners were determined in the influent and effluent from Covenant Oxidation Pond (COP) and Ikeja Wastewater Treatment Plant (IWWTP). Standard methods were adopted for determining the physical and chemical parameters of the water samples. The water samples for PE congener’s determination were collected, acidified and stored at 4 °C prior to liquid-liquid extraction and analysis by gas chromatograph. The possible health risk associated with the usage of effluent-polluted river water was also investigated. The pH and temperature ranges were within the Federal Ministry of Environment (FME) 2001 guideline limits while the dissolved oxygen, biochemical oxygen demand and chemical oxygen demand were above the limits. The IWWTP performed better at removing PEs at 54% compared to 43.3% on average at COP. The health risk of individual PE congener showed no non-cancer effects (HQ) as the values varied from 5.01E?05 (DAP) to 1.52E?02 (DEHP) for adults and 1.17E?04 (DAP) to 3.76E?03 (DBP) for children at COP, while at IWWTP, it ranged from 8.06E?05 (DIBP) to 1.09E?02 (DEHP) for adults and 5.68E?04 (MMP) to 2.54E?02 (DEHP) for children. Notwithstanding, the usage of effluent-polluted river water by local communities downstream may result in carcinogenic effects due to the cumulative effects of the PE congeners as the values obtained for adults and children for the ingestion and dermal routes for the two waste process streams ranged from 4.67E?06 (IWWTP) to 6.22E?05 (IWWTP) and 2.18E?05 (IWWTP) to 7.18E?05 (COP), respectively.     

The antibacterial effects of engineered nanomaterials: implications for wastewater treatment plants

Nanotechnology is currently at the forefront of scientific research and technological developments that have resulted in the manufacture of novel consumer products and numerous industrial applications using engineered nanomaterials (ENMs). With the increasing number of applications and uses of ENMs comes an increasing likelihood of nanoscale materials posing potential risks to the environment and engineered technical systems such as wastewater treatment plants (WWTPs). Recent scientific data suggests that ENMs that are useful in, for example, medical applications due to their novel physicochemical properties, may also cause adverse effects to the bacterial populations used in wastewater treatment systems. In this review, the toxicological effects of titanium nanoparticles (nTiO(2)), zinc oxide (nZnO), carbon nanotubes (CNTs), fullerenes (C(60)) and silver nanoparticles (AgNPs) to bacteria were examined. The results suggest that the potential ENMs risks to bacteria are non-uniform (need to be assessed case-by-case), and are dependent on numerous factors (e.g. size, pH, surface area, natural organic matter). Currently available data are therefore insufficient for evaluating the risks that ENMs pose in WWTPs. To fill these knowledge gaps, we recommend scenario specific studies aimed at improving our understanding on: (i) estimated volumes of ENMs in effluents, (ii) the antibacterial sensitivity of cultures within WWTPs towards selected ENMs, and (iii) processes improving the stability of ENMs in solutions. Two factors that merit consideration for elucidating the potential risks systematically are the toxicity mechanisms of ENMs to bacteria, and the influencing factors based on inherent physicochemical properties and environmental factors. Furthermore, the complexity of behaviour and fate of ENMs in real WWTPs requires case studies for assessing the ENMs risks to bacteria in vivo. The current laboratory results derived using simplified exposure media do not reflect actual environmental conditions.     

Occurrence and fate of steroid estrogens in the largest wastewater treatment plant in Beijing, China

Concern over steroid estrogens has increased rapidly in recent years due to their adverse health effects. Effluent discharge from wastewater treatment plants (WWTPs) is the main pollutant source for environmental water. To understand the pollutant level and fate of steroid estrogens in WWTPs, the occurrence of estrone (E1), 17-β-estradiol (E2), estriol (E3), and 17-β-ethinylestradiol (EE2) was investigated in the Gaobeidian WWTP in Beijing, China. Water samples from influent as well as effluent from second sedimentation tanks and advanced treatment processes were taken monthly during 2006 to 2007. In influent, steroid estrogen concentrations varied from 11.6 to 1.1?×?10(2)?ng/l, 3.7 to 1.4?×?10(2)?ng/l, no detection (nd) to 7.6×10(2)?ng/l and nd to 3.3?×?10(2)?ng/l for E1, E2, E3, and EE2, respectively. Compared with documented values, the higher steroid estrogen concentrations in the WWTP influent may be due to higher population density, higher birthrate, less dilution, and different sampling time. Results revealed that a municipal WWTP with an activated sludge system incorporating anaerobic, anoxic, and aerobic processes could eliminate natural and synthetic estrogens effectively. The mean elimination efficiencies were 83.2%, 96.4%, 98.8%, and 93.0% for E1, E2, E3, and EE2, respectively. The major removal mechanism for natural estrogens and synthetic estrogen EE2 were biodegradation and sorption on the basis of mass balance in water, suspension particles, and sludge. In the WWTP effluent, however, the highest concentrations of E1, E2, E3, and EE2 attained were 74.2, 3.9, 5.1, and 4.6?ng/l, respectively. This is concerning as residual steroid estrogens in WWTP effluent could lead to pollution of the receiving water. Advanced flocculation treatment was applied in the WWTP and transformed the residual estrogen conjugates to free species, which were reduced further by filtration with removal shifting from 32% to 57% for natural estrogen, although no EE2 was removed.     

Polyfluoroalkyl compounds in the aquatic environment: a review of their occurrence and fate

The occurrence and fate of polyfluoroalkyl compounds (PFCs) in the aquatic environment has been recognized as one of the emerging issues in environmental chemistry. PFCs comprise a diverse group of chemicals that are widely used as processing additives during fluoropolymer production and as surfactants in consumer applications for over 50 years. PFCs are known to be persistent, bioaccumulative and have possible adverse effects on humans and wildlife. As a result, perfluorooctane sulfonate (PFOS) has been added to the persistent organic pollutants (POPs) list of the Stockholm Convention in May 2009. However, their homologues, neutral precursor compounds and new PFCs classes continue to be produced. In general, several PFCs from different classes have been detected ubiquitously in the aqueous environment while the concentrations usually range between pg and ng per litre for individual compounds. Sources of PFCs into the aqueous environment are both point sources (e.g., wastewater treatment plant effluents) and nonpoint sources (e.g., surface runoff). The detected congener composition in environmental samples depends on their physicochemical characteristics and may provide information to their sources and transport pathways. However, the dominant transport pathways of individual PFCs to remote regions have not been conclusively characterised to date. The objective of this article is to give an overview on existing knowledge of the occurrence, fate and processes of PFCs in the aquatic environment. Finally, this article identifies knowledge gaps, presents conclusions and recommendations for future work.     

Techno-economical efficiency and productivity change of wastewater treatment plants: the role of internal and external factors

Efficiency and productivity are important measures for identifying best practice in businesses and optimising resource-use. This study analyses how these two measures change across the period 2003-2008 for 196 wastewater treatment plants (WWTPs) in Spain, by using the benchmarking methods of Data Envelopment Analysis and the Malmquist Productivity Index. To identify which variables contribute to the sustainability of the WWTPs, differences in efficiency scores and productivity indices for external factors are also investigated. Our results indicate that both efficiency and productivity decreased over the five years. We verify that the productivity drop is primarily explained by technical change. Furthermore, certain external variables affected WWTP efficiency, including plant size, treatment technology and energy consumption. However, plants with low energy consumption are the only ones which improve their productivity. Finally, the benchmarking analyses proved to be useful as management tools in the wastewater sector, by providing vital information for improving the sustainability of plants.     

Occurrence and removal of titanium at full scale wastewater treatment plants: implications for TiO2 nanomaterials

Titanium dioxide nanoparticles increasingly will be used in commercial products and have a high likelihood of entering municipal sewage that flows to centralized wastewater treatment plants (WWTPs). Treated water (effluent) from WWTPs flows into rivers and lakes where nanoparticles may pose an ecological risk. To provide exposure data for risk assessment, titanium concentrations in raw sewage and treated effluent were determined for 10 representative WWTPs that use a range of unit processes. Raw sewage titanium concentrations ranged from 181 to 1233 μg L(-1) (median of 26 samples was 321 μg L(-1)). The WWTPs removed more than 96% of the influent titanium, and all WWTPs had effluent titanium concentrations of less than 25 μg L(-1). To characterize the morphology and presence of titanium oxide nanoparticles in the effluent, colloidal materials were isolated via rota-evaporation, dialysis and lyophilization. High resolution transmission electron microscopy and energy dispersive X-ray analysis indicated the presence of spherical titanium oxide nanoparticles (crystalline and amorphous) on the order of 4 to 30 nm in diameter in WWTP effluents. This research provides clear evidence that some nanoscale particles will pass through WWTPs and enter aquatic systems and offers a methodological framework for collecting and analyzing titanium-based nanomaterials in complex wastewater matrices.     

Analysis of the usefulness of biological parameters for the control of activated sludge wastewater treatment plants in an interlaboratory study context

The quality of the sludge in Wastewater Treatment Plants (WWTPs) depends on the suitable colonization of the flocs by microorganisms. Due to the functional importance of these biological constituents, several biological or biological-related parameters have been commonly used for the control of depuration efficiency. According to national and international water regulation recommendations, interlaboratory studies have a great relevance to determine which parameters are more reliable for their extensive application in routine control. However, these studies are also very useful to demonstrate consistency in results from multiple laboratories and to develop reliable and reproducible methodologies which might be necessary for protocol validation and also for accreditation issues to meet regulatory environmental requirements. The main purpose of this work was to assess the results obtained in consecutive interlaboratory assays in order to determine the concordance degree in the application of biological parameters by participating laboratories. Following the international recommendations about these studies, a common working protocol was proposed. Statistical tests indicated that Sludge Index and several routine physical-chemical analyses [V30, Mixed Liquor Suspended Solids (MLSS), Mixed Liquor Volatile Solids (MLVS) and Sludge Volumetric Index (SVI)] show low variability and therefore are suitable tools for laboratory control. Shannon Index and Sludge Biotic Index also presented low variability although a more precise protocol would be necessary, in particular the methodology to count small flagellates. The abundance and identification of protist species showed low concordance among laboratories and three factors were responsible for the low reliability of data: population density, size and morphological distinguishable characters of the specimens.     

Polycyclic aromatic hydrocarbons in effluents from wastewater treatment plants and receiving streams in Tianjin, China

Surface water, suspended particulate matter, pore water, and sediment samples were collected and analyzed for polycyclic aromatic hydrocarbons (PAHs) in Yongding New River, South Drainage Canal and North Drainage Canal, which receive most of wastewater from industrial city of Tianjin. PAH concentrations in effluent samples of wastewater treatment plants (WTP) discharging into the South Drainage Canal and North Drainage Canal were quantified for the first time. The results showed that the discharge of the WTPs recently only contributed to the PAH contamination in the canals near the outlets of the WTPs. PAH levels in sediments of the streams were greatly higher than those in soils by riverbank probably due to receiving large amounts of untreated wastewater. Unusually high benz[a] anthracene concentration strongly influenced the seasonal and spatial variation of total PAH concentrations in South Drainage Canal. Paired samples t test of ??Nap, Fl, Phe, Fluo and ??Nap, Phe, Fluo, Chry concentrations, which were dominant components in the air samples from non-heating and heating season, respectively, in the suspended particulate matters from the streams showed that PAH source from air deposition was more important for Yongding New River than that for South Drainage Canal and North Drainage Canal. Source apportionment based on PAH profiles indicated that coal combustion was the major PAH contamination source, and coke oven sources and wood combustion also contributed to the PAH contamination of the streams. This was further indicated by organic petrography analysis.     

Occurrence and distribution of polycyclic aromatic carbons in sludges from wastewater treatment plants in Guangdong, China

In this study, the occurrence and distribution of polycyclic aromatic hydrocarbons (PAHs) were investigated in six sludge samples collected from Guangdong Province, China. Concentrations of PAHs varying from 2,534.1 to 6,926.6 μg kg^???1 (dry sludge) were observed in three municipal wastewater treatment plants with phenanthrene (Phe), fluoranthene, and pyrene being the main compounds. In addition, 682.6 μg kg^???1 PAHs were detected in one sludge sample from a food processing plant, with fluorene, Phe, and chrysene being the main components. No PAHs were detected in sludge samples obtained from two cosmetic plants. The levels and distributional characteristics of PAHs, polychlorinated biphenyls (PCBs), and polycyclic musks (PMs) from the samples were also compared. The results of this comparison indicated that petrochemical refineries and road traffic played important roles in the PAH loads in sludge, while PMs primarily originated from domestic wastewater and industrial wastewater from cosmetic plants. Finally, the presence of 98.8 μg kg^???1 PCBs in sludge suggested diffusional emission sources from electrical components containing PCBs.     

Heavy metal concentration and speciation of seven representative municipal sludges from wastewater treatment plants in Northeast China

The analysis of heavy metals is very important for assessing the feasibility of the agricultural utilization for the municipal sludge. In this paper, a four-step sequential extraction method was applied to extract heavy metals (Cu, Zn, Mn, Cr, and Ni) in municipal sludges from seven individual wastewater treatment plants located in Jilin and Heilongjiang Province, China, for estimating the mobility and bioavailability of the metal ions in the agricultural application. The total concentrations of heavy metals and their chemical fractions after the sequential extraction were determined. Principal component analysis (PCA) was applied to analyze the relations of heavy metals fractions in the municipal sludges. Experimental results indicated that the total concentrations of Cu, Zn, Cr, and Ni in all sludge samples were below the threshold values set out by the Chinese legislation (GB18918-2002). Specially, Zn had a high bioavailability and mobility, Cu and Cr had potential bioavailability, while Mn mainly existed in the residual fraction of municipal sludge. On the other hand, Ni had different mobility in different municipal sludge. PCA results were confirmed by the environmental behavior of heavy metals.     

Speciation of heavy metals in biosolids of wastewater treatment plants at Mysore,Karnataka, India

Urban wastewater treatment leads to the generation of large quantities of biosolids. Accumulation of biosolids is a problem of environmental relevance due to the existence of heavy metals in the biosolids. Determination of total metal in biosolid provides information relating pollution levels. Determination of their mobilization capacity and behaviour in the environment is an important task. An experimental approach commonly used for studying the mobility, transport and bioavailability of metal in biosolids is the use of selective sequential extraction procedure. In the present study an attempt has been made to study the heavy metal properties in biosolid samples collected from urban wastewater treatment plants located at Mysore, Karnataka. Few heavy metals selected for the present study are cadmium, chromium, copper, iron, nickel and zinc. The concentration of these metals in biosolids and their partition in different fractions are studied. The speciation of metals based on the sequential extraction scheme was carried out. The concentration of heavy metals is lower than that established by European legislation. The residual fraction has the maximum percentage of heavy metals whereas, only a small fraction of heavy metals (Fe, Zn and Cd) are extracted in the most soluble fractions, exchangeable and carbonate fractions.     

Quantitative assessment of polycyclic aromatic hydrocarbons in sewage sludge from wastewater treatment plants in Qingdao, China

In this study, 16 polycyclic aromatic hydrocarbons (PAHs) were detected in sewage sludge samples from four wastewater treatment plants (WWTPs) in Qingdao, China. These WWTPs differ in the type of treatment used and in the origin of the wastewater. The total amounts of PAHs in digested sludges ranged from 1.9645 to 6.5752 mg/kg, which did not exceed the projected European Union cut-off limits (6 mg/kg) for sludge found in farmland, except for the Haibohe WWTP. Significant differences were observed in overall PAH values between WWTPs receiving domestic effluents and those receiving industrial effluents. The total amounts of PAHs in digested sludge from the Licunhe and Haibohe WWTPs, which mainly received industrial effluents, were markedly higher than those of the Tuandao and Huangdao WWTPs, which received only domestic effluents. The distribution of PAH compounds in digested sludges were analysed. At the Tuandao, Huangdao and Licunhe WWTPs, 2-, 3-, 4-benzene rings were predominant, accounting for 100%, 99.8% and 99.0% of the sum concentration of 16 PAHs (∑PAHs), respectively. At the Haibohe WWTP, a large number of high molecular weight PAHs (5-, 6-benzene rings) were observed, accounting for 30% of the ∑PAHs. The sum of seven carcinogenic PAHs (∑PAHs-c) ranged from 0.8694 to 3.0389 mg/kg in four WWTPs. The highest value was found in the Haibohe WWTP. Moreover, the PAH concentrations in sludges from the different treatment processes in the Licunhe and Tuandao WWTPs are discussed.     

Pharmaceuticals and personal care products in effluent matrices: A survey of transformation and removal during wastewater treatment and implications for wastewater management

Pharmaceuticals and personal care products (PPCPs) represent pollutants of emerging concern, originating in surface and drinking waters largely from their persistence in wastewater effluent. Accordingly, a wealth of recent investigations has examined PPCP fate during wastewater treatment, focusing on their removal during conventional (e.g., activated sludge) and advanced (e.g., ozonation and membrane filtration) treatment processes. Here, we compile nearly 1500 data points from over 40 published sources pertaining to influent and effluent PPCP concentrations measured at pilot- and full-scale wastewater treatment facilities to identify the most effective series of technologies for minimizing effluent PPCP levels. Available data suggest that at best a 1-log(10) concentration unit (90%) of PPCP removal can be achieved at plants employing only primary and secondary treatment, a performance trend that is maintained over the range of reported PPCP influent concentrations (ca. 0.1-10(5) ng L(-1)). Relatively few compounds (15 of 140 PPCPs considered) are consistently removed beyond this threshold at facilities using solids removal and conventional activated sludge (CAS), and most PPCPs are removed to a far lesser extent. Further, increases in CAS hydraulic retention time or sludge retention time do not appreciably increase removal beyond this limit. In contrast, plants employing advanced treatment methodologies, particularly ozonation and/or membranes, remove the vast majority of PPCPs beyond 1-log(10) concentration unit and oftentimes to levels below analytical detection limits in effluent. Data also indicate that passive approaches for tertiary treatment (e.g., wetlands and lagoons) represent promising options for PPCP removal. We conclude by addressing future challenges and frontiers in wastewater management posed by PPCPs including analytical needs for their real-time measurement, energy demands associated with advanced treatment technologies, and byproducts arising from transformation of PPCPs during treatment.     

A one year investigation of the occurrence of illicit drugs in wastewater from Brussels, Belgium

Daily 24 hour composite influent wastewater samples were collected from the wastewater treatment plant of Brussels-North (Belgium) for eight months to study variations in the concentrations and mass loads of nine illicit drugs and metabolites: cocaine (COC) and its metabolites benzoylecgonine (BE) and ecgonine methyl ester (EME), amphetamine (AMP), methylenedioxymethamphetamine (MDMA), methamphetamine (METH), methadone (MTD) and its metabolite 2-ethylidene-1,5-dimethyl-3,3-diphenylpyrrolidine (EDDP) and the specific metabolite of heroin, 6-monoacetylmorphine (6-MAM). Samples were analyzed using a validated analytical method based on solid-phase extraction and hydrophilic interaction liquid chromatography coupled to tandem mass spectrometry. The selected compounds could be detected and quantified in all samples. The measured concentrations were in agreement with earlier published concentrations, when available. All illicit drugs showed significant differences in mass loads between months. Daily variations were observed for MDMA, AMP and COC and metabolites, with higher mass loads observed during the weekend. This is probably related to their recreational consumption pattern and was further confirmed when holiday periods (New Year's Eve, Belgian national holiday) were in detail investigated. For METH, 6-MAM, MTD and EDDP, stable and consistent amounts were observed during the week. In all samples, the ratio of the concentration of the parent compound to its metabolite(s) was calculated to evaluate whether measured concentrations reflect human excretion of the illicit drugs. For MTD, the ratio of parent compound/metabolite was in agreement with the excretion pattern, while for COC some deviations were observed, resulting from excretion pattern uncertainties, and stability and discharge issues.