Monitoring of Trace Metals and Pharmaceuticals As Anthropogenic and Socio- Economic Indicators of Urban and Industrial Impact on Surface Waters

See discussions, stats, and author profiles for this publication at: https://www.researchgate.net/publication/235768706

Monitoring of trace metals and pharmaceuticals as anthropogenic and socio- economic indicators of urban and industrial impact on surface waters

Article in Environmental Monitoring and Assessment · April 2013 DOI: 10.1007/s10661-012-2811-x · Source: PubMed

CITATIONS READS 50 301

3 authors:

Yuliya Vystavna Philippe Le Coustumer Biology Centre CAS University of Bordeaux

102 PUBLICATIONS 658 CITATIONS 192 PUBLICATIONS 3,167 CITATIONS

SEE PROFILE SEE PROFILE

Frederic Huneau Université de Corse Pascal Paoli

189 PUBLICATIONS 1,758 CITATIONS

SEE PROFILE

Some of the authors of this publication are also working on these related projects:

Використання джерельних вод для питного водопостачання в умовах надзвичайних ситуацій у Східній Україні / Spring groundwater utilization for drinking water supply in emergency in East Ukraine View project

Nanomaterials - nanoparticles analysis and behaviours for different applications such as medical, biotechnology and environmental ones View project

All content following this page was uploaded by Yuliya Vystavna on 05 June 2014.

The user has requested enhancement of the downloaded file. Environ Monit Assess DOI 10.1007/s10661-012-2811-x

Monitoring of trace metals and pharmaceuticals as anthropogenic and socio-economic indicators of urban and industrial impact on surface waters

Y. Vystavna & P. Le Coustumer & F. Huneau

Received: 30 March 2012 /Accepted: 25 July 2012 # Springer Science+Business Media B.V. 2012

Abstract The research focuses on the monitoring of for the determination of dissolved and labile trace metals trace metals and pharmaceuticals as potential anthropo- (Ag, Cd, Cr, Cu, Ni, Pb, and Zn) and pharmaceuticals genic indicators of industrial and urban influences on (carbamazepine, diazepam, paracetamol, caffeine, diclo- surface water. This study includes analysis of tracers use fenac, and ketoprofen). Samples were analyzed using for the indication of water pollution events and discus- inductively coupled plasma mass spectrometry (MS; sion of the detection method of these chemicals. The trace metals) and liquid chromatography–tandem MS following criteria were proposed for the evaluation of electrospray ionization+/− (pharmaceuticals). Our results indicators: specificity (physical chemical properties), demonstrate the distinctive spatial and temporal patterns variability (spatial and temporal), and practicality (ca- of trace elements distribution along an urban water- pacity of the sampling and analytical techniques). The course. Accordingly, two general groups of trace metals combination of grab and passive water sampling (i.e., have been discriminated: “stable” (Cd and Cr) and “time diffusive gradient in the thin film and polar organic varying” (Cu, Zn, Ni, and Pb). The relationship Cd≫Cu chemical integrated samplers) procedure was applied >Ag>Cr≥Zn was proposed as an anthropogenic signature of the industrial and urban activities pressuring the Y. Vystavna : P. Le Coustumer environment from point sources (municipal wastewaters) Université de Bordeaux, EA 4592 Géoressources and the group Pb–Ni was discussed as a relevant finger- & Environnement, ENSEGID, print of the economic activity (industry and transport) 1 Allée F. Daguin, mainly from non-point sources (runoff, atmospheric dep- 33607 Pessac, France ositions, etc.). Pharmaceuticals with contrasting hydro- Y. Vystavna (*) chemical properties of molecules (water solubility, bio- Department of Environmental Engineering accumulation, persistence during wastewater treatment and Management, National Academy of Municipal processes) were discriminated on conservative, labile, Economy at Kharkiv, vul. Revolutsii 12, and with combined properties in order to provide infor- Kharkiv 61002, Ukraine mation on wastewater treatment plant efficiency, punc- e-mail: [email protected] tual events (e.g., accidents on sewage works, runoff), and uncontrolled discharges. Applying mass balance model- F. Huneau Laboratoire d’Hydrogéologie, ing, medicaments were described as relevant socio- Université de Corse Pascal Paoli, economic indicators, which can give a picture of main Campus Grimaldi, BP 52, 20250 Corte, France social aspects of the region.

F. Huneau . . CNRS, Keywords Water monitoring Pharmaceuticals Trace UMR 6134 SPE, BP 52, 20250 Corte, France metals . DGT. POCIS . Indicators . Ukraine Environ Monit Assess

Introduction Trace metals are inorganic compounds issued from natural and anthropogenic sources (e.g., Schäfer et al. The contamination of urban water by trace elements 2009). Two general features discriminate metals from (i.e., detected at the level<1 μgL−¹) is associated with other trace pollutants: (1) they are not biodegradable regional environmental and socio-economic factors and thus are able to accumulate in sediments and (Dickenson et al. 2011). Climate, hydrological, living organisms; (2) their bioavailability and potential hydro-, and geochemical regional specificity is re- toxicity are largely controlled by present physical sponsible for the accumulation, dilution, complexa- chemical forms (Alonso et al. 2004) affecting their tion, and degradation of chemicals and what can accumulation and distribution along water courses derive from point (i.e., treated and untreated dis- (Baalousha et al. 2006). Ability of trace metals to charges of municipal wastewater treatment plants, in- deposit in the sediments is widely used for the reflec- dustrial manufacturing processes, leaky sewers, tion of local industrial, mining, and agricultural pres- combined sewer overflow, and onsite wastewater sys- sures on the area and for describing long-term tems) and nonpoint (diffusive) sources (i.e., runoff, pollution influences (Sanchez-Cabeza and Druffel precipitation; Daughton and Ternes 1999; Rowsell et 2009; Lepland et al. 2010). Trace metals were previ- al. 2010; Dickenson et al. 2011). Inputs and distribu- ously proposed as indicators (Christophoridis et al. tion of chemicals in urban waters are also linked to 2009; Schäfer et al. 2009) of the economic sector population density, consumption patterns, economic (industrial and transport: e.g., Ni and Pb for the indi- structure, and water use rate (Dickenson et al. 2011). cation of pollution by fossil fuel combustion and oil Other important issues are physical chemical proper- refinery processes by Soldi et al. (1996) and Mazzei et ties of elements (i.e., speciation and solubility), which al. (2008)) and urban activity (e.g., Ag as the tracer of can be responsible for their behavior and fate in the urban effluents by Guevara et al. (2005) and Lanceleur environment (i.e., accumulation complexation and et al. (2011)). biodegradation). Knowledge on impact factors and Pharmaceuticals are organic compounds signing properties of certain tracers in the environment can anthropogenic origin, produced, consumed and/or ex- be useful for the indication of changes in the environ- creted by humans and animals, or used in household ment (Dale and Bayeler 2001), assessing the degree of products. They relate to the consumption level, high industrial and urban pressures on the natural water, detection frequency, and already currently developed and source identification (McGeoch 1998; Duelli and monitoring and analytical techniques for the identifi- Obrist 2003). cation in the environment (Buerge et al. 2003; Clara et Our study focuses on the perspectives of the applica- al. 2004; Bartelt-Hunt et al. 2009;Froehneretal. tion of trace metals and pharmaceuticals with distinctive 2010). Pharmaceuticals are previously considered as properties and origin, as regional anthropogenic and good anthropogenic indicators of water contamination socio-economic indicators of industrial and urban pres- with treated and untreated domestic discharges (Clara sures on watercourses. et al. 2004; Nakada et al. 2008; Kasprzyk-Hordern et Trace metals and pharmaceuticals (TMP) have been al. 2009a) and as prospective anthropogenic markers previously considered as potential indicators of anthro- (Clara et al. 2004; Sankararamakrishnan and Guo pogenic inputs in natural waters (Kasprzyk-Hordern et 2005;Buergeetal.2006; Nakada et al. 2008; al. 2009a, b; Dickenson et al. 2011). Compared to Bahlmann et al. 2009) of the social activity (i.e., drug biological markers, the TMP have the following advan- consumption rate) (Bendz et al. 2005; Kasprzyk- tages: (1) their physical chemical properties (i.e., persis- Hordern et al. 2009a, b). tence, solubility, and degradation) are know as they are Selected tracers (trace metals: Ag, Cd, Cr, Cu, Ni, linked to industrial or domestic pollution processes Pb, Zn; pharmaceuticals: caffeine, carbamazepine, di- (Dickenson et al. 2011); (2) monitoring of TMP typical- azepam, diclofenac, ketoprofen, and paracetamol) ly requires less sample preparation and time for the were monitored in the urban Udy River of the analysis (Bull et al. 2002; Hagedorn and Weisberg Seversky Donets watershed, in the Kharkiv region, 2009); and (3) data on their occurrence can be used as Ukraine. Previous research carried out in the studied socio-economic indicators in multidisciplinary studies watershed (Vystavna et al. 2010, 2012a, b, c) revealed (Kasprzyk-Hordern et al. 2009b). that discharges of wastewater effluents are responsible Environ Monit Assess for the urban water contamination by trace metals and Ukraine, where the watercourse is used for recreation, pharmaceuticals. The reason was the mixing of do- drinking and industrial water supply, irrigation and mestic and industrial effluents of the Kharkiv agglom- fishing, and receives municipal wastewaters from the eration on the municipal wastewater treatment works, Kharkiv city (Vasenko et al. 2006). The mean annual low efficiency of used techniques, and weak dilution discharge of the Udy River is 6.8 m3 s−1 in winter and in the natural water bodies (Vystavna et al. 2012a). 2.5 m3 s−1 in summer in the site located upstream of The general tasks of this research were: (1) ana- the Kharkiv city (Vasenko et al. 2006). The river is lyzed particular properties of trace metals and pharma- partly covered by ice from the end of November to the ceuticals in the environment using the specified end of March. Subsurface geological structures of the criteria; (2) proceeded the water monitoring on the catchment area are dated from Paleocene and consist pilot study area with the application of conventional mainly of sedimentary rocks like sandstone, marl, and and innovative passive sampling techniques; and (3) chalk. The Udy River generally feeds by precipitation provided a mass balance modeling for the application (Vasenko et al. 2006), so the influence of ground- of pharmaceuticals as indicators of the social activity waters (Seiler et al. 1999; Einsiedl et al. 2010) on the (i.e., medicaments consumption). water quality can be neglected. There are two main wastewater treatment plants (WWTP) in the Kharkiv region discharging treated Study area wastewater effluents into the Udy River (Suchkova et al. 2010; Vystavna et al. 2012c): WWTP The Udy River in the Kharkiv region (c.a. 3,000,000 “ Bezludivka” (WWTP “ B ” ) and WWTP inhabitants) has been selected as a model water body “Dykanivka” (WWTP “D”). The WWTP “B” (c.a. − to identify principal trace elements contaminant, their 250,000 m3 day 1) discharges directly into the studied − distribution and sources of origin (Vystavna et al. river and WWTP “D” (c.a. 600,000 m3 day 1) dis- 2012a) on the industrial, agricultural, and urban ag- charges into the Lopan River at 500 m upstream of the glomeration of Eastern Ukraine (Table 1). Udy–Lopan confluence (Fig. 1). Both WWTPs pro- The Udy River is the main tributary of the Seversky cess mixed industrial (25 % of total wastewaters) and Donets River. This alluvial transboundary river takes domestic wastewaters (75 % of total wastewaters) of source in the Belgorod region, Russia, and flows the Kharkiv city and the sub-urban area, serving ap- through rural and urban areas of the Kharkiv region, proximately 1.3 millions of population (89 % of the

Table 1 Socio-economic characteristics of the Kharkiv region Indicator Value (2009) Population total 2,780,300 persons Urban population 80 % Incomes of population 2,200 USD person−1 year−1 Economic structure Industry: 50 % of gross regional production Heavy industry (metallurgy, machine building, coal 28 % combustion, smelters, electroplating, etc.) Food production 30 % Chemical industry (pigments, plastics, pharmaceuticals, etc.) 6 % Process industry (gas, oil, wood, sand) 5 % Building materials 4 % Light industry 4 % Other 23 % Agriculture 5 % of gross regional production Gaz, energy, heat, water production, and supply 17 % of gross regional production Other (transport, trade, education, service, etc.) 28 % of gross regional production Environ Monit Assess

Fig. 1 The location of the sampling sites on the Udy River

regional urban population). During the low-flow period effluents in the city area, what can be contaminated (August–September), the volume of wastewaters can be from discharges of untreated wastewaters of rural 21 times more than the river’s flow. The wastewater communities and treated wastewaters of the local ther- treatment includes mechanical (mills and grit chambers, mal power station; (3) U06 is in the urban area, up- pre-aerator, primary, and secondary clarifiers) and bio- stream of the Lopan–Udy confluence and upstream logical (aerobic treatment with the activated sludge) from the outlet of both WWTPs—selected for the processes with a final chlorination. Treatment of munic- identification of urban area impact on natural water ipalsludgeiscarriedoutatWWTP“B” (about and in order to compare upstream/downstream river 3,000 m3 day−1), where sewage sludge is passed parts from WWTP inputs; (4) U07 is downstream through thickeners, decanters, and store at the land field from the discharge of the WWTP “B” and the (Suchkova et al. 2010). Lopan–Udy Rivers confluence—the river flow is contaminated by pollutants from the urban and industrial area of the Kharkiv region (Fig. 1). Materials and method The dissolved and diffusive gradient in the thin film (DGT) labile trace elements, i.e., priority pollutants: Data collection Cd, Cr, Cu, Ni, Pb, and Zn (EU 2008) in water, were measured with the duplicated samples (n, number of The sampling sites were chosen taking into account samples taken during the monitoring048 for DGT and the location of potential sources of substances (i.e., n048 for grab samples) in contrasted hydrological con- wastewaters discharge), possible access to sites in ditions: high flow in May and low flow in August from different climate conditions and the risk of vandalism 2008 to 2010. The concentration of trace metals (Cd, Cr, towards installed passive sensors. Cu, Ni, Pb, Zn, and the urban tracer Ag) in the sediments Sampling sites were: (1) U01 is in the agricultural was determined in the sampling campaign in May and rural area of the Kharkiv region, Ukraine, 1 km down- August 2009 (n016). Pharmaceuticals (i.e., carbamaze- stream from the Russian border—selected for the up- pine, diazepam, caffeine, paracetamol, ketoprofen, and stream baseline overview; (2) U04 is upstream of the diclofenac) were monitored using the duplication of Kharkiv urban area—chosen for the identification of polar organic chemical integrated samplers (POCIS) Environ Monit Assess samplers (n072) in contrasted seasonal conditions: cold laboratory, samples were dried at 50 °C to the constant season in January, warm high flow season in May and weight, powdered, homogenized, and stored in closed warm low flow season in August from 2008 to 2010. polyacrylate containers. After the digestion at 110 C and cooling, samples were brought to 10 mL using

Samples collection and analysis 250 μLHNO3 (14 M, suprapure) and double- deionized (Milli-Q®) water. Dissolved metal concen- Trace metals in water and sediments trations in water samples and sediment digests were measured by ICP-MS (X7, Thermo). The results were The dissolved (0.22 μm) fraction of trace metals, that consistent within the range of certified values for all includes free hydrated ions, readily dissociable (labile) CRM (SLRS-4 river water; IAEA405 and LGC 6187 complexes, species adsorbed on inorganic, and organ- sediments) and the analytical error (relative standard ic colloids and elements strongly bound to inorganic deviation) generally less than 5 % for concentrations and organic complexes, was sampled at 1 m from the 10 times higher than the detection limits. The proce- bank and at 0.2 m depth using an acid-cleaned 50-ml dure and results were in accordance with previous syringe and immediately filtered through 0.2 μm with studies performed in the analytical laboratory used polycarbonate filters (Nucleopore®) (Lanceleur et al. (e.g., Schäfer and Blanc 2002; Audry et al. 2004).

2011), acidified (HNO3, ultrapure; 1/1,000v/v), as described by Masson et al. (2009) and stored in acid Pharmaceuticals in water cleaned 16 ml polypropylene tubes at 4 °C in the dark place before being analyzed. The POCIS with the Oasis HLB sorbent were purchased The labile metal fraction was sampled using the from Exposmeter (Tavelsjö, Sweden). After 21 days of DGT—passive samplers to be installed at same sites exposure, each individual POCIS device was removed and the period with the extraction of grab water sam- from the water and briefly rinsed with ultrapure water. ples. According to the DGT theory, these devices The POCIS extraction and analysis have been per- measure mobile, and bioavailable fraction of the ele- formed in the laboratory of the University of ment, which are in the labile equilibrium with species Bordeaux, France according to previously developed that can bind to the binding agent of the sampler protocols (Togola and Budzinski 2007; Vystavna et al. (Zhang and Davison 1995). The DGT devices with a 2012b). The surface membrane was detached and rinsed 0.4 mm resin gel layer, a 0.8 mm diffusive gel layer with the ultrapure water. Phases of the each POCIS have and a 0.45 μm pore-size filter, were deployed at a been transferred into an empty SPE tube by 5 mL of 0.20–0.25 m water depth to avoid turbulent flow ultrapure water per each membrane, through cartridges zones. After 15 days, DGT samplers were retrieved with cleaned Teflon frits, and dried under vacuum for and kept humid at 4 °C until the analysis. Trace metals 1 h. The sorbent was eluted using 10 mL of each accumulated in the binding phase of the DGT probes solution: methanol; methanol/dichloromethane mixture (3.14 cm2) were eluted by immersion into 1 mL of (50:50) and dichloromethane and spiked with internal 13 HNO3 (1 M) for 48 h (Zhang and Davison 1995). The standards: c3-caffeine, d4-diclofenac, d5-diazepam, d3- parallel blank elution was performed in the laboratory. ketoprofen, and d4-paracetamol (Budzinski et al. 2009; DGT measured dissolve labile concentrations of Cd, Vystavna et al. 2012b). The obtained extracts were Cr, Cu, Ni, Pb, and Zn were analyzed by inductively evaporated using a nitrogen flux and transferred into coupled plasma mass spectrometry (ICP-MS). The injection vials 50 μL of acetonitrile. Blanks were per- blank corrected concentrations of DGT-labile metal formed in the laboratory concurrently with water sam- in water were estimated using the temperature- ples. All targeted compounds were found below the dependent diffusion coefficient as proposed by the limits of the detection in blank samples. Recovery rates DGT manufacturer (DGT Research 2002). The de- were determined by spike samples (n03 for the each tailed procedure of the DGT sampling in severe con- chemical) and vary from 81 to 89 % of the spiked ditions (approach and analysis) has been published in amount (Table 2). After the extraction step, the mass Vystavna et al. (2012a). of sorbent was measured by the gravimetry for the each Sediments weres collected close to the riverbank POCIS. The prepared samples, spikes, and blanks were and stored in sterile capped containers. In the analyzed on the Agilent 6410 Triple Quadropole LC/ Environ Monit Assess

MS/MS system (USA) with an electrospray (ESI+/−) (flow conditions is 0.21 ms−1, installation is during ionization source. Electrospray ionization with the pos- 14 days, temperature is 15–25 °C), which were closest itive ion mode was used for the detection of paracetamol to those in the field, than rates found in other previously (PARA), caffeine (CAF), carbamazepine (CBZ), diaze- mentioned studies. The sampling rate is independent pam (DZP), and the negative ion mode was applied for from the aqueous concentration of analytes (Togola diclofenac (DICLO) and ketoprofen (KETO) by multi- and Budzinski 2007), it shows insignificant variation ple reaction monitoring (MRM) with nitrogen collision depending on the presence of organic matter (Li et al. gas. The Agilent 1200 series Binary Pump and Column 2011) and at the range of pH from 7 to 9 (Li et al. 2011). SL G1312B USA (50×2.1 mm, 1.8 μm, 30 °C) system A previous study (Togola and Budzinski 2007)conclud- was used for the separation at a flow rate of ed the influence of the water temperature on the uptake 0.6 mL min−1 with a gradient of acetonitrile and 0.1 % of molecules in the POCIS membrane. The most pro- formic acid in water. Source conditions were: capillarity nounced effect was observed for KETO, which shows a 3,000 V, gas flow at 11 Lmin−1, gas temperature 300 °C twofold growing level of the sampling rate with the and nebulizer 30 psi. The limit of the detection was increasing of water temperature (Togola and Budzinski determined by measuring the coincident instrumental 2007). The temperature effect on the uptake of CAF, response of standard solutions and spiked blank CBZ, and DICLO is relatively small (less than 1.5-fold) POCIS extracts. Environmental time weight average (Togola and Budzinski 2007;Lietal.2010). So, their (TWA) concentrations of molecules were determined sampling rates were not adjusted to water temperature using the standard equation (Togola and Budzinski (Li et al. 2010; Munaron et al. 2011). The correction of 2007)(Eq.1): the TWA concentration according to water temperature has not been done in this study, but the results on the TWA C ¼ C M =R t ð1Þ w s s s during cold (winter) and warm (spring and summer) was where Cw and Cs are the concentration of the compound interpreted with the precaution, especially for KETO. in the aqueous and sorbent phase (nanograms per liter), respectively, Ms is the mass of sorbent (grams), Rs is the General physico-chemical water parameters sampling rate (liters per day) and t is the exposure time (days). Among the suitable sampling rates (Alvarez et Water temperature, conductivity, and pH were measured al. 2004; MacLeod et al. 2007; Togola and Budzinski in the field with a WTW© Multiline P4 meter before 2007;Lietal.2010), we used sampling rates of CAF, and after passive samplers deployment. Total organic DZP, and PARA obtained by Miège et al. (2011) and for carbon (TOC; Vystavna et al. 2012a) was determined CBZ, DICLO, and the sampling rate of KETO was from spot unfiltered samples, taken at the same time as determined by Budzinski et al. (2009;Table2). the installation of passive samplers, and analyzed by Sampling rates were identified in laboratory conditions. TOC-5000, Schimadzu© automated analyzer following The selection of these values were considered similar to ISO 10694. Water flow rates were obtained from the the type used for POCIS and environmental parameters Kharkiv Hydro-meteorological Agency.

Table 2 Targeted pharmaceuticals (PPs) detected by POCIS and analytical method performance

PPs CAS no Therapeutic class Retention MRM Collision Cone voltage LOD Recovery Sampling −1 −1 time (min) energy (V) (V) (ng g ) (n03), % rate, (Rs Lday )

Mean RSD

Caffeine 58-08-2 Stimulant 4.01 196>139 20 130 1 88 4.1 0.13 Carbamazepine 298-46-4 Sedative 6.52 237>192 20 120 1 86 21 0.29 Diazepam 439-14-15 Antidepressant 7.82 285>154 28 120 1 86 4.9 0.40 Diclofenac 15307-86-5 Non-steroidal anti- 18.55 294>214 18 80 1 81 9.6 0.15 inflammatory drug Ketoprofen 22071-15-4 Non-steroidal anti- 14.41 253>212 1 60 1 89 3.9 0.13 inflammatory drug Paracetamol 103-90-2 Analgesic 2.95 152>93 26 110 1 87 3.3 0.03 Environ Monit Assess

Criteria for the selection of an indicator have more pronounced seasonal and hydrological patterns, but also it can depend on the seasonal economic The application of trace metals and pharmaceuticals as activity (i.e., agriculture) (Vystavna et al. 2012a). indicators were described according to the following The trace metal variability in waters was estimated criteria (e.g., Hagedorn and Weisberg 2009): specific- using the following ratio (Sangi et al. 2002; Balistrieri ity, variability, and practicality. and Blank 2008): Specificity was accessed based on the form, physi- K ¼ C =C ð3Þ cal chemical properties, and links to metabolism relat- dgt dis ed and/or industrial discharges. Trace metals were where Cdgt is the concentration measured using the selected for the characterization of economic sector integration time (within 15-day installation period) of activity (industry, transport, and agriculture) on the DGT samplers; Cdis is the dissolved fraction concen- urban water. tration (0.22 μm permeate) measured from the stan- Trace metals in the sediments were chosen for the dard grab sampling. indication of accumulation processes in urban water The variability of pharmaceuticals was assessed (Schäfer and Blanc 2002; Audry et al. 2004;Yangand using the coefficient of variation (CV rsd, %) Rose 2005) and were evaluated by the enrichment factor (Shridhar et al. 2010) calculated for contrasted hydro- (EF) using the following equation (Liaghati et al. 2004): logical and seasonal periods: ! ðÞ¼EF ðÞC =C =ðÞC =C ð2Þ pPffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi x Th sample x Th bas n ðÞCx Cx CV rsd ¼ 100 i¼1 i =Cx ð4Þ n 1 where (Cx/CTh)sample is the ratio of measured concentration of the element (Cx) in the sediment sample upon Th concentration (CTh), and (Cx/CTh)bas is the respective where Cxi is the concentration of the pharmaceutical baseline ratio (Fateev and Pashenko 1999) also normal- during i study period, Cx is the mean measured con- ized by Th. Researchers of the Ukrainian Academy of centration of pharmaceutical in all periods, and n is the Science determined the mentioned baseline ratio consid- number of measurements. ering the crust value proposed by Vinogradov (1962)and Practicality means the capacity of the available local hydrological and hydro-chemical characteristics of sampling and analytical techniques to monitor and the Udy River, what were identified during 5 years of the analyze the indicator with the high precision (low monitoring. Thorium was used as a normalizer in order to detection limit, high reproducibility, and accuracy). compensate the variability of trace elements in sediments The practicality of indicators was assessed using the resulting from the grain size distribution and the sam- detection ratio (DR), which was previously proposed pling procedure (Coynel et al. 2007). by Sedlak et al. (2004): The dissolved and DGT-labile fractions of trace DR ¼ C =LOQ ð5Þ metals in water were used for the indication of current med inputs of elements and the representation of certain where Cmed is the median concentration (nanograms per sources. The following specificity of pharmaceuticals liter) and LOQ is the analytical detection limit (nano- has been taken into account: persistence during waste- grams per liter) of the compound. The ratio shows the water treatment processes (removal efficiency, per- capability of analytical tools to screen changes and cent), water solubility (milligrams per liter), and quantify selected compounds with the precision. bioaccumulation, using octanol–water partition coefficient (log Kow) (Girard 2005; Kasprzyk-Hordern et al. Principle component analysis 2009a, b; USEPA 2011). Variability means that indicators have defined tem- The principle component analysis (PCA, e.g., Saporta poral (i.e., seasonal, hydrological periods, economic 1990) has been used in order to estimate the linear activity) and spatial (urban and rural area, regions, correlation between DGT-labile trace metals and phar- countries) patterns. Therefore, trace metals in the sedi- maceuticals. These parameters have been sampled using ments represent the persistent and low-variable model the passive method and also considered as mobile frac- compare to dissolved and DGT-labile metals, which tions in the water (Zhang and Davison 1995;Alvarezet Environ Monit Assess al. 2004; Vystavna et al. 2012a). The PCA allows us to On a PCA plot, where the first axis describes the describe the correlation between sampled fractions of most significant correlation, the maximum attention was inorganic and organic compounds and find similar and given to the point close to the circle centered at (0; 0) diverse patterns of their distribution in the Udy River in and whose radius is equal to 1. Points, which are close May—high flow and August—low-flow periods. The one to another, indicate the existence of a linear positive data of the mean values (2008–2010) of 12 targeted correlation between parameters and the radical opposi- TMP (Cd, Cr, Cu, Ni, Pb, and Zn; CAF, PARA, tion between points shows the negative correlation of DICLO, KETO, DZP, and CBZ) have been used for the elements. Two points located on perpendicular diame- projection for sites located in the urban area (U04, U06, ters indicate an independency between values. and U07). Trace metals have been represented in the DGT-labile concentration in micrograms per liter. In order to exclude the potential influence of various param- Results eters on the estimation of the exact concentration of pharmaceuticals, but also the risk associated with the General environmental parameters selection of sampling rate, these compounds have been considered in the POCIS—contamination value in nano- According to water temperature and flow rate variations grams of contaminant per gram of the OASIS sorbent of (Table 3), the following contrasted hydrological, and the sampler (Vystavna et al. 2012b)forthePCA. seasonal patterns of the Udy River have been

Table 3 Measured environmental parameters of the Udy River (mean of n03±SD, 2008–2010)

Sites and parameter May August January Warm high flow Warm low flow Cold low flow

U01 Water flow, m3 s−1 1.92±0.60 0.28±0.08 2.91±0.3 Water temperature, °C 17±1 18±1 2±0.5 pH 7.80±0.10 7.61±0.07 7.27±0.48 Conductivity, μScm−1 865±19 885±41 832±100 TOC, mg L−1 nd 87±3 nd U04 Water flow, m3 s−1 2.15±0.49 0.32±0.06 2.98±0.18 Water temperature, °C 18±1 21±1 3±1 pH 8.20±0.14 7.65±0.46 7.55±0.16 Conductivity, μScm−1 930±54 966±10 1,010±180 TOC, mg L−1 nd 68±9 nd U06 Water flow, m3 s−1 7.8±1.0 1.1±0.09 8.5±1.6 Water temperature, °C 19±1 21±1 4±1 pH 7.82±0.08 7.37±0.01 7.77±0.09 Conductivity, μScm−1 1,077±61 1,113±105 1,227±68 TOC, mg L−1 nd 73±5 nd U07 Water flow, m3 s−1 14.6±1.01 7.48±0.93 12.9±0.85 Water temperature, °C 20±1 22±1 7±1 pH 7.38±0.10 7.35±0.08 7.27±0.10 Conductivity, μScm−1 1,243±81 1,184±59 1,282±130 TOC, mg L−1 nd 53±9 nd Environ Monit Assess discriminated: warm high flow period in May, warm highest levels upstream of releases. Variation of trace low-flow period in August, and cold high flow period metals during high and low flows period showed other in January. The water flow in May was about 10 times patterns. Dissolved Cd, Cr, Cu, and Zn presented a less higher than in August for sites upstream of wastewater than twofold difference between May and August. In influences (U1, U4 and U06), and two times higher than contrast, Ni and Pb had distinctive displays with a signif- the summer values in the downstream sites (U07). The icant decrease of dissolved Ni and increase of dissolved flow rate in January was approximately at the same level Pb in August. At the same time, DGT-labile Pb declined (CV, ±18 %) as in May. The difference in the water flow during the low-flow period. This situation revealed rate between seasons mainly related to precipitations, higher temporal mobility of Pb and Ni in comparison to which were 55, and 7 mm (mean value of 2008–2010, other metals on the urban area. Therefore, the presence of obtained in the Kharkiv Hydro-Meteorological Agency these metals in the Udy River was largely influenced by for the Kharkiv “Osnova” Airport Meteorological sta- environmental (i.e., organic carbon) and anthropogenic tion) in May and August correspondingly. During mon- (i.e., distinctive pollution sources) factors. The estimation itored summer and spring months, water temperature had of K ratio (Eq. 3) confirmed the significant temporal low variation (CV, ±12 %) at the sites, but in January the variation (K ratioismorethan5)ofPbandNi(Fig.3) water temperature decreased to 2–4°Cinupstreamand in rainy and dry periods; moreover, Pb had a higher K to 7–8 °C in downstream city sites. Water flow rate and value in the city center and in contrast, Ni had the water temperature were increasing from upstream to maximum K value in the site downstream of WWTP. In downstream sites, considering the influence of the urban addition, Cu and Zn were found to have noticeable area on instream environmental parameters of the river. temporal variation (K ratio is less than 5) downstream The conductivity was growing (in more than 1.5 times) of discharges (Fig. 3). from rural to urban territories, showing additional inputs In sediments, the highest spatial variation was deter- along the watercourse (Table 3).ThepHhadlowtem- mined for Cr, Cu, and Zn (Fig. 2). It was found that poral and spatial variations (CV, <10 %). Measured total concentrations of Ag, Cd, Cr, Cu, and Zn increased organic carbon was slightly decreasing from upstream to downstream of municipal wastewaters discharges (site downstream sites. U07). Concurrent with the water concentration patterns, the Pb and Ni showed a significant contamination in the Anthropogenic indicators of the river pollution sites (U04 and U06) upstream of the WWTPs. The analysis of the accumulation level of trace metals in sediments Trace metals revealed that the EF>10 was observed for the group Cd≫ Cu>Ag>Cr≥Zn in the site downstream of the urban The determined concentration of dissolved and DGT- wastewater discharges (Fig. 3) that is associated with labile trace metals (Fig. 2) and their detection frequency discharges from household, industry, and construction (Table 4) displayed spatial and temporal variations of (e.g., Sörme and Lagerkvist 2002)oftheKharkivregion. selected compounds in the studied river, confirming the The distribution and accumulation patterns allowed influence of environmental and anthropogenic factors on us to discriminate two principle groups of trace metals the river geochemistry. Significant spatial variation was in terms of variation and potential sources: observed for DGT-labile and dissolved Zn during May “Stable” metals (Cd and Cr), which were enriched in and August (Fig. 2), confirming the presence of various the sediments (EF is more than 10 in U07) and show low sources of this element in the river. In this study, dis- (K ratio was less than 1) spatial and temporal variations solved fraction of targeted trace metals have exhibited during both contrasted hydrological periods in water. higher dimensional differences, compared to the deter- Presence of Cd and Cr can reflect to long-term discharges mined DGT-labile one (Fig. 2), that can be explained by and generally associates with point sources, as their sig- instream processes such as complexation, sedimentation nificant enrichment (EF is 5–20 times higher in U07 and/or diverse sources of trace metals along the river. compared to U06) was found downstream of urban waste- Maximum water concentration of all monitored metals water discharges (Fig. 3) potentially indicating the histor- was found in the urban area of the Kharkiv agglomera- ical and long-term river pollution by these elements. tion,withpeaksofCd,Cr,Cu,andZndownstreamof “Time-varying” metals (Cu, Ni, Pb, and Zn) municipal wastewater discharges. Ni and Pb had their exhibited spatial and temporal variations. The Pb and Environ Monit Assess

Fig. 2 Measured DGT- labile, dissolved (0.22μm) and sediments concentration of trace metals in the Udy River (minimum, mean and maximum values)

Ni demonstrated the higher temporal variations (K ratio (Mazzei et al. 2008; Peltier et al. 2009). Possibly, the was more than 5) compared to Cu and Zn (K ratio was contribution of Cu and Zn from the point source (i.e., from 1 to 5), but presented the lower enrichment value wastewaters discharge) was higher than non-point sour- downstream of the WWTP (EF is less than 10) than Cu ces (i.e., runoff, deposition from the atmosphere, illegal and Zn. It seems that, Pb and Ni can link to the non- discharges etc.). point pollution sources (i.e., transport activity and atmo- Using this approach, we suggest that the relation- spheric depositions from the fossil fuel burning) and/or ship of the enrichment value Cd≫Cu>Ag>Cr≥Zn can illegal discharges of the contaminated wastewaters be used as a anthropogenic signature of the industrial Environ Monit Assess

Table 4 The frequency of detection (FD, percent) and detec- Tracer FD, % DR Technique tion ratio (DR) of tracers in the Udy River Sampling Analysis

Metals (n048) Cd 58 9 DGT ICP-MS Cr 88 55 DGT ICP-MS Cu 100 335 DGT ICP-MS Ni 100 311 DGT ICP-MS Pb 92 68 DGT ICP-MS Zn 100 736 DGT ICP-MS Pharmaceuticals (n072) Caffeine 100 618 POCIS LC/MS/MS Carbamazepine 88 600 POCIS LC/MS/MS Diclofenac 100 2,116 POCIS LC/MS/MS Diazepam 63 3 POCIS LC/MS/MS Ketoprofen 50 15 POCIS LC/MS/MS Paracetamol 75 16 POCIS LC/MS/MS and urban activities pressuring the environment (de upstream of the municipal wastewater discharges (U06)

Miguel et al. 2005) from point sources (municipal and DICLO38>CBZ30>CAF18>KETO12>DZP1 > wastewaters) of Kharkiv urban area. The other group PARA1 for the site located downstream of municipal Pb–Ni can be a relevant fingerprint of the economic wastewater discharges. Thus, the distribution patterns in activity (industry and transport) mainly from non- the site located at U06 was similar to those found at the point sources (runoff, atmospheric depositions, etc.). U04 site, however, at the downstream part (U07), the order of monitored pharmaceuticals changed signifi- Pharmaceuticals cantly. Therefore, the spatial distribution of substances indicated the presence of various sources of these com- Pharmaceuticals had varying frequencies of detection pounds in the environment, which are not only related to (Table 4) and only DICLO and CAF were detected in the municipal wastewater discharges. all selected sampling sites, indicating pathways of these Temporal distribution of targeted pharmaceuticals also tracers along the river. Significant contamination of showed various seasonal patterns. KETO exhibited sig- DICLO, CAF, KETO, and PARA was found in sites nificant seasonal variations (CV rsd>100 %; Fig. 5). The upstream of wastewater effluents (U04 and U06; Fig. 4), seasonal variation of KETO can be less pronounced in displaying that these compounds can enter natural the case if considering water temperature dependent on stream with the runoff (Bartelt-Hunt et al. 2009)and/or sampling rate, but the sampling rate for most chemicals is untreated illegal discharges or during accidents on the not available for the particular parameters. CBZ and wastewater treatment plants. CBZ was also found at the DICLO had lowest seasonal variation (CV rsd<30 %; trace level (1–2ngL−1) in the upstream sites, represent- Fig. 5). As observed, the seasonality of pharmaceuticals ing contaminated discharges at this site of the river. DZP links to various factors such as: medicament consumption was measured at a detectable level (8–13 ng L−1)only patterns, bioaccumulation, and degradation under the downstream of the WWTP. influence of environmental factors (i.e., temperature, The comparison of the presence of pharmaceuticals UV radiation, etc.), but can also be associated with phys- in different river’s parts was described by the following ical chemical properties of compounds. Thus, targeted order (as percent of the sum of mean concentration): pharmaceuticals were projected using three main param-

CAF80>KETO19.5>PARA8>DICLO2>CBZ0.5 for the eters that can have a strong impact on the environment: site upstream of the urban area (U04); CAF52> bioaccumulation factor or Kow, the water solubility factor PARA44>DICLO3>CBZ1 for the urban area at the site or Ks, and the removal efficiency (RE; Fig. 6). Environ Monit Assess

May - city centre May - downstream WWTPs 300 10 Pb 250 Pb 8 200

6 150

100 4 K - time variation K - time variation Zn 50 2 Cd 0 Ni Cu Cr Zn Cu Ni Cd 0 Cr 1,0 1,2 1,4 1,6 1,8 2,0 2,2 2,4 2,6 2,8 3,0 3,2 0102030405060 EF - accumulation EF - accumulation

August - city centre August - downstream WWTPs 7 16 Ni 14 6 Ni

12 5 10 4 8 3 6 2 K - time variation K - time variation 4 1 Cu Zn 2 Cd 0 CuCr Pb Cd Zn 0 Pb Cr

1,0 1,2 1,4 1,6 1,8 2,0 2,2 2,4 2,6 2,8 3,0 3,2 010203040506070 EF - accumulation EF - accumulation

Fig. 3 The accumulation (EF) and temporal (K) distribution of trace metals in the Udy River

−1 As the result, monitored pharmaceuticals were di- solubility (Ks is more than 10,000 mg L ), low vided into three groups: accumulation (log Kow is less than 0.5) and high efficiency of treatment (RE is more than 60 % of Labile (non-conservative) pharmaceuticals: CAF removal) by a conventional wastewater treatment and PAR. These compounds have high water processes (active sludge). In our study, these ele-

250

200

150

CV rsd,CV % 100

0 PARA CAF CBZ DZP KETO DICLO

Fig. 4 Determined concentration of pharmaceuticals (nano- Fig. 5 The coefficient of variation (CV rsd, %) of pharmaceut- grams per liter, ±SD) in the Udy River icals downstream WWTPs (May, August, and January) Environ Monit Assess

Fig. 6 Physicochemical characteristics of pharmaceuticals

ments dominated in sites located at the upstream fecal wastewaters or runoff, as there were no reported part of the city, the municipal wastewater dis- discharges of the human origin wastewaters in this charges (Fig. 4), and had high frequency of the section of the river. At the same time, conservative detection (Table 4). compounds are typical for the sites located down- Conservative pharmaceuticals: DZP and CBZ. stream of the wastewater discharges and can indicate

This group shows low water solubility (Ks is less the sources of urban effluents. −1 than 1,000 mg L ), a high accumulation (logKow Results of the principle component analysis of is more than 3) and a low efficiency of treatment DGT-labile trace metals and pharmaceuticals (Fig. 7) (RE is less than 20 % of removal) on the conven- presented the strong correlation between conservative tional wastewater treatment plant (active sludge). organic compounds and metals, especially with the In our research, these molecules dominated in the group of “stable” metals, which mainly associated to site downstream of the municipal wastewater municipal wastewater effluents. At the same time, effluents (Fig. 4) had small frequency of the de- “time-varying” metals and pharmaceuticals presented tection (Table 4) and exhibited low seasonal var- distinctive patterns during contrasted hydrological iation (Fig. 5). conditions. Pharmaceuticals with combined (mixed) properties: DICLO and KETO. These molecules Anthropogenic indicators of the socio-economic have low water solubility (Ks is less than processes 1,000 mg L−1), a high accumulation coefficient

(logKow is more than 3). But the treatment efficien- Conservative properties of some compounds gave us cy of these compounds is relatively good (RE is an opportunity to apply targeted molecules as socio- 40–60 % of removal from raw wastewaters on the economic indicators. The regional data on the drug conventional wastewater treatment plant), what consumption are difficult to estimate as medicaments associates with other properties, e.g., photodegrada- can be prescribed or not, used, or stored. Moreover, tion, (Nakada et al. 2008; Daneshvar et al. 2010), there are different ways for drug delivery (legal and and additional factors influencing the presence and illegal market), especially for specific medicaments behavior of these molecules. such as psychotropic substances (e.g., carbamazepine, diazepam). In this case, the water monitoring data can Consequently, we resumed, that the occurrence of be used for the calculation of the preliminary data on the labile pharmaceuticals upstream of the city was the regional drug consumption using the mass balance probably limited to continuous discharges of untreated approaches (Vystavna et al. 2012b). Environ Monit Assess

Fig. 7 The principle component analysis of DGT-labile metals and pharmaceuticals in the Udy River (2008–2010) (May, F1074.62 %; F2025.38 % and August, F1078.04 %; F2021.96 %)

To estimate the pharmaceuticals consumption rate, we data on the drugs excretion are used proposed to take into account the physical chemical prop- (Kasprzyk-Hordern et al. 2009b; Froehner et erties of substances using the following formula (Eq. 5): al. 2010). Due to the limitation of the used chemical and analytical protocols, metabolites ¼ ðÞ =ðÞ ðÞ Mc QwCw QuCu K1 K1K2 5 of targeted compounds have not been included in the research. where K2 is the efficiency of wastewater treatment Mc is drug consumption rate in a studied processes, which was estimated from the part settlement, served by a sewage system of the pharmaceutical not removed during the (grams per day) treatment (grams per gram). The efficiency K1 is drug excretion rate (a part of a hasbeenusedfrompreviouslypublished pharmaceutical component entering the works taking into account the type of sewage system under unchanged form in treatment processes (Table 5).

the human excretion; grams per gram). Cu is the concentration of the pharmaceuticals Pharmacokinetics represents a very complex in the upstream part (grams per cubic meter)

process depending on metabolism, age, Qw, Qu are water flow rates in the river, activity, etc. In this study, previously reported downstream and upstream of WWTPs

Table 5 The calculated con- a,b sumption rate of pharmaceuti- Pharmaceutical Metabolism Treatment Fluxes from the Consumption −1 a,b,c −1 cals in the Kharkiv city (g g ) efficiency Kharkiv city (g day /1,000 (g g−1) (g day−1) people)

May January May January a Kasprzyk-Hordern et al. Carbamazepine 0.31 0.04 94.6 157.3 0.21 0.35 (2009a) Diazepam 0.05 0.04 5.7 5.0 0.08 0.07 bZhang et al. (2008) Diclofenac 0.02 0.12 107.3 196.5 4.07 7.44 cKNAPPE (2008) Environ Monit Assess

The daily drug consumption rate per person (D) structure, health problems of the population, and reg- was estimated as Eq. 6: ulation of the medicament market and welfare. The other reason of the variation of pharmaceuticals be- D ¼ M =P ð6Þ c tween countries can be the difference in wastewater where P is the number of people that use the municipal treatment efficiency during particular climate condi- sewage system, inhabitants. tions (cold snowy winter and hot dry summer). Consequently, for the conservative substances In spite of the lower medicaments consumption rate (CBZ and DZP), as the compound with high accumu- in Ukraine, compared to USA, Canada, EU countries, lative ability, we took into account upstream influents and Australia, wastewater-receiving rivers were found (the distance between sites U06 and U07 is less than to be more contaminated by tracers because of non 5 km). Hence, we assumed that the conservative sub- sufficient dilution and treatment of wastewaters, but stances from the upstream part of the river are able to also due to discharge of untreated and uncontrolled reach the downstream parts. For DICLO, the pharma- inputs to water bodies. ceuticals with mixed properties, the upstream inputs were also taken into account, because these medicaments presented properties, which are close to the Discussion conservative substances (Figs. 6 and 7). The results of our mass balance calculation showed Results of our research revealed several patterns of the estimated data on some medicaments consumption in variation and behavior of trace metals and pharma- the Kharkiv region, Ukraine. The comparison on med- ceuticals. Existence of these displays depends on icaments consumption data in Ukraine with other forms and physical chemicals properties of com- countries has been done using the officially reported pounds, environmental instream parameters, diverse data on the drugs consumption and data, which was sources of chemicals, but also the consumption pat- also calculated by the mass balance approach (Buerge terns. Using these environmental and anthropogenic et al. 2003; Miao et al. 2005;Zhangetal.2008; factors, we assumed the perspectives to apply certain Kasprzyk-Hordern et al. 2009b). substances as indicators of the regional anthropic and The estimated consumption of carbamazepine was socio-economic activity (Table 6). comparable to the world wide measurements, (0.45 g − − day 1/1,000 people), Canada (0.2 gday 1/1,000 people; Trace metals as anthropogenic indicators adapted from Miao et al. 2005) and USA data (0.34 g − day 1/1,000 people), but lower than in EU countries Considering the obtained outputs, we suggested the − (1.8–2.6 gday 1/1,000 people; adapted from Zhang et possibility to use Cd and Ag as the indicators of the al. 2008). The calculated consumption rate of diclofenac long-term industrial pressure on the urban watershed. − was two to three times more than in Wales (0.9 gday 1/ In our study, Cd found to have the highest enrichment 1,000 people; Kasprzyk-Hordern et al. 2009b), Australia (up to 60; Fig. 3), indicating the long-term industrial − (0.6 gday 1/1,000 people), but close to the data of influence on the urban area (Yu et al. 2010). This − Finland (3.0 gday 1/1,000 people) and Germany (2.9 g element finds pathways to the environment generally − day 1/1,000 people; adapted from Zhang et al. (2008)). through heavy industrial processes, e.g., coal combus- The mass balance results showed that the level of tion, smelters, iron and still mills, electroplating, and medicaments consumption in Ukraine was lower than chemicals production (Reimann and de Caritat 1998) in the economically developed countries like USA, which are prevailing in the economic structure of the Canada, and EU members. The general reason was Kharkiv region (Table 1). Compared to Cd, Ag has the the combination between the high price of pharma- lower crustal abundance (Lanceleur et al. 2011), but ceuticals and weak medical service with the lack of a also showing the high enrichment in the sediments well-established mechanism of social insurance. Thus, (EF014±2) in the part of the river located along most of people adopt a self-treatment strategy using industrial and urban areas (site U07). The natural path- alternative methods rather than prescribed ones. ways of Ag in the environment are not well docu- Additionally, such discrepancy in drug consump- mented (Reimann and de Caritat 1998). Various tion between countries reflects differences in the age, anthropogenic sources on urban area, e.g., Environ Monit Assess

Table 6 Perspectives of trace metals and pharmaceuticals as anthropogenic and socio-economic indicators

Compound Fraction/properties Type of the indicator

Anthropogenic Socio-economic

Trace metals DGT-labile Time varying events (diffusive sources; Components of the regional economic accidents, illegal discharges) activity (transport, industry, agriculture, Dissolved Continuous effluents urban, etc.) Sediments Long-term and historical pollution Industrial structure Pharmaceuticals Conservative Sources determination : treated and Regional consumption patterns untreated inputs Non conservative Untreated inputs (domestic wastewaters, Presence of prohibited and illicit runoff, accidents) medicaments Mixed Efficiency of the wastewater treatment in Development of regional pharmaceuticals contrasted seasons market photographic industry, coins and jewelry production, instream chemistry, especially pH, conductivity, and batteries, brazing alloys, electroplating, electrical con- organic matters which influence on the mobility and trols and conductors, medical service, nanotechnologies complexation of metallic compounds in natural waters and paints (Reimann, and de Caritat 1998; Kaegi et al. (e.g., Mendiguchía et al. 2007). 2010) are typifying on the economy of the Kharkiv city and region (Table 1). In this case, Ag can be considered Pharmaceuticals as anthropogenic and socio-economic also as an indicator of the urban pressure on the envi- indicators ronment (Lanceleur et al. 2011). Using the ratio Cd/Ag, the industrial influence on the urban area can be pointed Labile pharmaceuticals were previously identified as out. Thereby, in the Udy River, the ratio Cd/Ag changed good tracers of untreated wastewaters of the human from 1.2 at the river’s source (U01) to 2.6 in the city origin (Buerge et al. 2003). The detection of caffeine center (U06) and reach 5.3 in the site downstream of the and carbamazepine in upstream and downstream sites industrial and urban water discharges (U07), demon- brought us to assume that WWTPs are not the main strating the industrial pressure on the surface water of source of labile pharmaceuticals. Potentially these com- the urban region. Other studied metals, such as Cu and pounds can enter the water flow with runoff (Bartelt- Cr have high abundance and various natural pathways, Hunt et al. 2009) and/or untreated illegal discharges or e.g., rock weathering, geogenic dust, animal waste during accidence on the wastewater treatment plants. (Reimann and de Caritat 1998), which limits their use The main risk to use caffeine as anthropogenic marker as efficient indicators of the urban and industrial pollu- is the presence of this compound in the nature, e.g in tion in comparison to Ag and Cd. some plants (Buerge et al. 2003). So, in the case of an Metals, with their temporal and spatial patterns, have application of caffeine as an anthropogenic marker, the the perspectives to be used as indicators of non-point background concentration of caffeine should be estimat- (e.g., urban runoff and atmospheric deposits) and point ed (Froehner et al. 2010). The paracetamol, with a pure sources (e.g., wastewaters from WWTP) and character- human origin, can be a more efficient indicator of do- ize the industrial pressure on the environment. For ex- mestic inputs than caffeine. Moreover paracetamol has ample, based on the accumulation and distribution of almost the same physical chemical properties (water trace elements into the Udy River, the economic profile solubility, bioaccumulation, removal efficiency) as caf- of the Kharkiv region impacting or pressuring the envi- feine (Fig. 6). ronment can be described as industry prevalence, fol- Conservative substances, like carbamazepine (Zhou lowed by the transport and a moderate impact from the et al. 2011) and diazepam, have been reported as effi- agriculture that was in agreement with the documented cient tracers of both untreated and treated waters (Clara regional socio-economic indicators (Table 1). et al. 2004;Miaoetal.2005;Moldovanetal2009; But the application of trace metals variation pat- Gasser et al. 2011; Segura et al. 2011;Wölzetal. terns should be considered in the relation to the water 2011). Due to their properties (Fig. 4), they are able to Environ Monit Assess accumulate in the natural environment. These substan- tracers in recent researches. For example, artificial sweet- ces have no natural sources and they point only anthro- ener acesulfame (Wolf et al. 2012), atrazine (Segura et al. pogenic inputs. It appears that CBZ is a more efficient 2011), 17β estradiol, 4-nonylphenolpolyethoxylates, and marker of wastewaters than DZP, but also easier to 4-nonylphenolpolyethoxycarboxylate (Writer et al. identify by different sampling and analytical techniques 2012) have been used as tracers of wastewaters in natural (Table 4). Other advantages of the CBZ is related to its aquatic systems and treatment facilities, indicating the low seasonal variation (CV rsd<30 %, Fig. 5;Moldovan continuous development of emerging compounds appli- et al. 2009) which is helpful for the indication during cation as indicators of water pollution. contrasted seasons. In recent studies (Gasser et al. 2011; Segura et al. 2011;Wölzetal.2011; Daneshvar et al. 2012), CBZ has been reported as a tracer of cumulative Conclusions and perspectives urban wastewater discharges and sewage leakages into natural waters, as it can be used as an independent The analysis of distinctive properties and patterns of marker (Gasser et al. 2011) or in caffeine/carbamazepine tracers revealed that in term of specificity, variability, ratio (Daneshvar et al. 2012), which indicate the contri- and practicality, trace metals and pharmaceuticals in bution of raw sewage versus treated wastewaters. But urban water can indicate not only a pollution event, further use of CBZ as a tracer should be considered in but also reflect the regional socio-economic aspects. relation with the regional consumption dynamics, due to Trace metals (i.e., Ag, Cd, Cr, Cu, Ni, Pb, and Zn) possible reduction of CBZ application in the medical were proposed as anthropogenic indicators of the indus- practice and the growing use of other medicaments. trial impact on the urban water system. Trace metals in Pharmaceuticals with combined properties were less the sediments are useful for the indication of the “histor- often promoted as anthropogenic markers than conser- ical pollution processes” by regional economic activities. vative and labile (Kasprzyk-Hordern et al. 2009a, b; So, the group of elements—Cd≫Cu>Ag >Cr≥Zn (order Nakada et al. 2008). Nevertheless, the specific usage by the EF) was proposed as an anthropogenic fingerprint of ketoprofen, as a veterinary product, can be applied for of industrial pressure on urban area and ratio Cd/Ag were tracking pollutants not only urban, but also from rural discussed as the relevant indicator of the industrial com- areas, applying as a labile marker of the pollutants from ponent on the urban territory. The dissolved and dis- the rural area. The KETO as an anthropogenic indicator solved labile metals in the water were found convenient should be balanced with the seasons (Daneshvar et al. for the indication of time-varying influences on the en- 2010). Typically, in winter, it shows the ability to accu- vironment. Thus, the group Pb–Ni can represent the river mulate in the environment and act as a conservative pollution by non-point sources, e.g., urban runoff and tracer, while in summer it behaves as labile indicator atmospheric deposits from different economic sectors of inputs from rural and urban areas. Diclofenac can be (industry and traffic) in this regional study. also considered as a potential anthropogenic marker Depending on physical chemical properties, con- (Kasprzyk-Hordern et al. 2009a, b), due to low biode- sumption patterns, seasonal variability, pharmaceutical gradability and ability to accumulate in the aqueous molecules were identified as anthropogenic indicators environment. This study pointed out the presence of of wastewater treatment efficiency and uncontrolled the noticeable level of diclofenac in all samples contaminated discharges. In that way, three groups of (Table 4 and Fig. 4). The most probable reason comes pharmaceuticals have been classified: conservative from the wide use of the medicament prescribed and (i.e., carbamazepine and diazepam), labile (i.e., caf- non-prescribed as an anti- inflammatory in Ukraine, due feine and paracetamol) and with combined properties to the low price and a broad local production. But (i.e., ketoprofen and diclofenac). Due to accumulative DICLO has a good removal efficiency by the WWTPs abilities, conservative substances were discussed as (RE is 30–60 %), reducing it application as conservative efficient tracers of treated and untreated wastewaters, environmental indicator, however, gives some opportu- revealing the long-term impact of urban wastewaters nity to use it as a potential indicator of the domestic on the river and surface waters. The labile substances wastewater treatment efficiency. were considered as anthropogenic indicators of un- As well as pharmaceuticals, other organic emerging treated wastewaters undergoing other influences pollutants also showed their applicability as wastewater (e.g., accidents on sewage works, runoff). Environ Monit Assess

The chemicals with combined properties were Servetnyk from National Academy of Municipal Economy at found to act as conservative and labile tracers depend- Kharkiv, Ukraine are greatly acknowledged. Special thanks to Victoria Nicole Deycard from the Université de Bordeaux, for ing on the seasons and usage patterns. According to the English language improvement and correction. this specificity, they can be potential indicators of multi-varying influences (e.g., human and veterinary) and report the treatment efficiency of wastewaters. References It was described that pharmaceuticals can also provide additional data on the social aspects in the region. Alonso, E., Santos, A., Gallejon, M., & Jimenez, J. C. (2004). In this manner, the mass balanced modeling was ap- Speciation as a screening tool for the determination of plied for the identification of the regional drug con- heavy metal surface water pollution in the Guadiamar river – sumption patterns, current wastewater treatment basin. Chemosphere, 56, 561 570. Alvarez, D. A., Petty, J. D., Huckins, J. N., Jones-Lepp, T. L., technologies, dilution processes, etc., which needs Getting, D. T., Goddard, J. P., et al. (2004). Development additional research and monitoring. of a passive, in situ, integrative sampler for hydrophilic Concerning the monitoring approach, it was found organic contaminants in aquatic environments. Environ- – that the combination of passive and conventional sam- mental Toxicology and Chemistry, 23(7), 1640 1648. Audry, S., Schäfer, J., Blanc, G., Bossy, C., & Lavaux, G. pling technique is a convenient tool for environmental (2004). Anthropogenic components of heavy metal (Cd, data obtaining. Zn, Cu, Pb) budgets in the Lot–Garonne fluvial system This research is a pilot for the Kharkiv region, (France). Applied Geochemistry, 19, 769–786. Ukraine and some aspects such as (1) seasonal and Baalousha, M., Motelica-Heino, M., & Coustumer, P. L. (2006). Conformation and size of humic substances: effects of temporal behavior of micro-pollutants in the con- major cation concentration and type, pH, salinity and res- trasted conditions; (2) discrimination of the point and idence time. Colloids and Surfaces A: Physicochemical non point sources; (3) mathematical modeling in order and Engineering Aspects, 272(1), 48–55. to integrate environmental and socio-economic data Bahlmann, A., Weller, M. G., Panne, U., & Scheider, R. J. (2009). Monitoring carbamazepine in surface and wastewaters by an needs future development. The database on emerging immunoassay based on a monoclonal antibody. Analytical pollutants should be expanded in terms of the regular and Bioanalytical Chemistry, 395,1809–1820. sample collection and analysis, but also the inclusion Balistrieri, L. S., & Blank, R. G. (2008). Dissolved and labile of other groups of micro-pollutants (e.g., illicit drugs, concentrations of Cd, Cu, Pb and Zn in the South Fork Coeur d’Alene River, Idaho: comparisons among chemical nanoparticles, surfactants, etc). equilibrium models and implications for biotic ligand mod- In perspective, anthropogenic indicators can be ap- els. Applied Geochemistry, 23, 3355–3371. plied for the multi-disciplinary tasks, i.e., identification Bartelt-Hunt, S. L., Snow, D. D., Damon, T., Shockley, J., & of uncontrolled discharges, definition of consumption of Hoagland, K. (2009). The occurrence of illicit and therapeutic pharmaceuticals in wastewater effluent and surface waters illicit and regulated drugs in the community, analysis of in Nebraska. Environmental Pollution, 157,786–791. the market, and sales of drug without prescription, and Bendz, D., Paxeus, N., Ginn, T., & Loge, F. (2005). Occurrence identification of the disposal of drugs leading to the and fate of pharmaceutically active compounds in the en- overestimation of usage. Other applications of these vironment, a case study: Hoje River in Sweden. Journal of Hazardous Materials, 122, 195–204. anthropogenic indicators are the identification of the Budzinski, H., Soulier, C., Lardy, S., Capdeville, M.J., Tapie, type of the human settlements (urban, industrial and N., Vrana, B., Miege, C., & Ait Aissa, S. (2009). Passive rural), and presence of the animal farms (monitoring of sampler for chemical substance monitoring and associated the veterinary medicaments). toxicity assessment in water. Abstract presented at the International Conference on Xenobiotics in the Urban Wa- ter Cycle, 11–13 March 2009, Cyprus. Acknowledgments This research was conducted in the frame- Buerge, I. J., Poiger, T., Muller, M. D., & Buser, H. R. (2003). work of the International Collaborative Program “Partenariat Caffeine, an anthropogenic marker for wastewater contami- Hubert Curien DNIPRO” (grant no 19744VJ 2009/2010) with nation of surface waters. Environmental Science and Tech- the financial support of both the French Ministry of Foreign nology, 37,691–700. Affairs and the Ukrainian Ministry of Education and Science. Buerge, I. J., Poiger, T., Muller, M. D., & Buser, H.-R. (2006). Some authors have been granted by the European Union through Combined sewer overflows to surface waters detected by the ERASMUS MUNDUS External Cooperation Window Pro- the anthropogenic marker caffeine. Environmental Science gram (Lot 6/7—Belarus, Moldova, and Ukraine), by the Embassy and Technology, 40, 4096–4102. of France to Ukraine (Bourse de Court Séjour de Recherche) and Bull,I.D.,Lockheart,M.J.,Elhmmali,M.M.,Roberts,D.J.,& Eiffel Scholarship (France). The technical support and help of Yuri Evershed, R. P. (2002). The origin of faeces by means of Vergeles, Iulija Rusko, Volodymyr Grynenko, and Maria biomarker detection. Environment International, 27,647–654. Environ Monit Assess

Christophoridis, C., Dedepsidis, P., & Fytianos, K. (2009). Brazil using biomarkers. Water, Air, and Soil Pollution, Occurrence and distribution of selected heavy metals in 210,33–41. the surface sediments of Thermaikos Gulf, N. Greece. Gasser, G., Rona, M., Voloshenko, A., Shelkov, R., Lev, O., Assessment using pollution indicators. Journal of Hazard- Elhanany, S., Lange, F. T., Scheurer, M., & Pankratov, I. ous Materials, 168, 1082–1091. (2011). Evaluation of micropollutant tracers. II. carbama- Clara, M., Strenn, B., & Kreuzinger, N. (2004). Carbamazepine zepine tracer for wastewater contamination from a nearby as possible anthropogenic marker in the aquatic environ- water recharge system and from non-specific sources. De- ment: investigations on the behavior of carbamazepine in salination, 273(2–3), 398–404. wastewater treatment and during groundwater infiltration. Girard, J. E. (2005). Principles of environmental chemistry (p. Water Research, 38, 947–954. 320). U.S: Jones and Barlett. Coynel, A., Schäfer, J., Blanc, G., & Bossy, C. (2007). Scenario Guevara, S. R., Arribere, M., Bubach, D., Vigliano, P., Rizz, A., of particulate trace metal transport during a major flood Alonso, M., & Sancher, R. (2005). Silver contamination on event inferred from transient geochemical signals. Applied abiotic and biotic compartments of Nahuel Huapi National Geochemistry, 22, 821–836. Park lakes, Patagonia, Argentina. Science of the Total En- Dale, V. H., & Bayeler, S. C. (2001). Challenges in the devel- vironment, 336,119–134. opment and use of ecological indicators. Ecological Indi- Hagedorn, C., & Weisberg, S. B. (2009). Chemical based fecal cators, 1,3–10. source tracking methods: current status and guidelines for Daneshvar, A., Svanfelt, J., Kronberg, L., & Weyhenmeyer, G. evaluation. Review in Environmental Science and Biotech- A. (2010). Winter accumulation of acidic pharmaceuticals nology, 8, 275–287. in a Swedish river. Environmental Science and Pollution Kaegi, P., Sinnet, B., Zuleeg, S., Hagendorter, H., Mueller, E., Research, 17, 908–916. Vonbank, R., et al. (2010). Release of silver nanoparticles from Daneshvar, A., Aboulfadl, K., Viglino, L., Broséus, R., Sauvé, outdoor facades. Environmental Pollution, 158(9), 2900–2905. S., Madoux-Humery, A.-S., Weyhenmeyer, G. A., & Pré- Kasprzyk-Hordern, B., Dinsdale, R. M., & Guwy, A. J. (2009a). vost, M. (2012). Evaluating pharmaceuticals and caffeine Illicit drugs and pharmaceuticals in the environment–fo- as indicators of fecal contamination in drinking water rensic applications of environmental data, part 2: pharma- sources of the Greater Montreal region. Chemosphere, 88 ceuticals as chemical markers of fecal water contamination. (1), 131–139. Environmental Pollution, 157, 1778–1786. Daughton, C. G., & Ternes, T. A. (1999). Pharmaceuticals and Kasprzyk-Hordern, B., Dinsdale, R. M., & Guwy, A. J. (2009b). personal care products in the environment: agents of subtle Illicit drugs and pharmaceuticals in the environment–forensic change. Environmental Health Perspective, 107, 907–938. applications of environmental data, part 1: estimation of the de Miguel, E., Charlesworth, S., Ordonez, A., & Seijas, E. usage of drugs in local communities. Environmental Pollu- (2005). Geochemical fingerprints and controls in the sedi- tion, 157,1778–1786. ments of an urban river: River Manzanares, Madrid KNAPPE. (2008) D. 2.1.: Report on the limitations of conven- (Spain). Science of the Total Environment, 340, 137–148. tional treatment processes of the most resistant PPs and DGT Research. (2002). DGT for measurements in water, soils new development. In D. Buncher (Ed.), (pp. 45–57). and sediments. Lancaster: DGT Research. anceleur, L., Schäfer, J., Bossy, C., Coynel, A., Larrose, A., Dickenson, E. R. V., Snyder, S. A., Sedlak, D. L., & Drewes, J. Masson, M., & Blanc, G. (2011). Silver fluxes to the Gironde E. (2011). Indicator compounds for assessment of waste- estuary—eleven years (1999–2009) of monitoring at the water effluent contribution to flow and water quality. Water watershed scale. Applied Geochemistry, 26,797–808. Research, 45, 1199–1212. Lepland, A., Andersen, T. J., Lepland, A., Arp, H. P. H., Alve, Duelli, P., & Obrist, M. K. (2003). Biodiversity indicators: the E., Breedveld, G. D., & Rindby, A. (2010). Sedimentation choice of values and measures. Agriculture, Ecosystems and chronology of heavy metal pollution in Oslo Harbor, and Environment, 98,87–98. Norway. Marine Pollution Bulletin, 60, 1512–1522. Einsiedl, F., Radke, M., & Maloszewski, P. (2010). Occurrence Li, H., Helm, P. A., & Metcalf, C. D. (2010). Sampling in the and transport of pharmaceuticals in a karst groundwater great lakes for pharmaceuticals, personal care products, system affected by domestic wastewater treatment plants. and endocrine-disrupting substances using the passive po- Journal of Contaminant Hydrology, 117,26–36. lar integrative sampler. Environmental Toxicology and EU. (2008). EU, Directive 2008/105/EC of the European Par- Chemistry, 29(11), 2517–2529. liament and of the Council of 16 December 2008 on Li, H., Helm, P., Paterson, G., & Metcalf, C. D. (2011). The environmental quality standards in the field of water policy, effect of dissolved organic matter and pH on sampling rates amending and subsequently repealing Council Directives for polar organic chemical integrative samplers (POCIS). 82/176/EEC, 83/513/EEC, 84/156/EEC, 84/491/EEC, 86/ Chemosphere, 83, 271–280. 280/EEC and amending Directive 2000/60/EC of the Eu- Liaghati, T., Preda, M., & Cox, M. (2004). Heavy metal distri- ropean Parliament and of the Council. Official Journal of bution and controlling factors, within coastal plain sedi- the European Union, 348(2008), 84–97. ments, Bells Creek Catchment, Southeast Queensland, Fateev, A. I., & Pashenko, Y. V. (1999). Research report. The Australia. Environment International, 29(7), 935–948. background contents of trace metals in soils of Ukraine (p. MacLeod, S. L., McClure, E. L., & Wong, C. S. (2007). Labo- 145). Kharkiv: Institute of Soil Science of the National ratory calibration and field deployment of the polar organic Academy of Sciences of Ukraine. in Ukrainian. chemical integrative sampler for pharmaceuticals and per- Froehner, S., Scuza, D. B., Machado, K. S., & da Rosa, E. C. sonal care products in wastewater and surface water. Envi- (2010). Tracking anthropogenic inputs in Barigui River, ronmental Toxicology and Chemistry, 26, 2517–2529. Environ Monit Assess

Masson, M., Schäfer, J., Blanc, G., Dabrin, A., Castelle, S., & Saporta, G. (1990). Probability, data analysis and statistics. Lavaux, G. (2009). Behavior of arsenic and antimony in the French: Gulf Publishing. fresh water reaches of a highly turbid estuary, the Gironde Schäfer, J., & Blanc, G. (2002). Relationship between ore Estuary, France. Applied Geochemistry, 24,1747–1759. deposits in river catchments and geochemistry of sus- Mazzei, F., D’Alessandro, A., Lucarelli, F., Nava, S., Prati, P., pended particulate matter from six rivers in southwest Valli, G., et al. (2008). Characterization of particulate mat- France. Science of the Total Environment, 298, 103–118. ter sources in an urban environment. Science of the Total Schäfer, J., Norra, S., Klein, D., & Blanc, G. (2009). Mobility of Environment, 401(1–3), 81–89. trace metals associated with urban particles exposed to McGeoch, M. (1998). The selection, testing and application of natural waters of various salinities from the Gironde Estu- terrestrial insects as bioindicators. Biological Reviews, 73, ary, France. Journal of Soils and Sediments, 9, 374–392. 181–201. Sedlak, D. L., Huang, C. Y., & Pinkston, K. E. (2004). Strategies Mendiguchía, C., Moreno, C., & García-Vargas, M. (2007). for selecting pharmaceuticals to assess attenuation during Evaluation of natural and anthropogenic influences on the indirect potable water reuse. In K. Kummerer (Ed.), Pharma- Guadalquivir river (Spain) by dissolved heavy metals and ceuticals in the environment. Berlin: Springer. nutrients. Chemosphere, 69(10), 1509–1517. Segura, P. A., MacLeod, S. L., Lemoine, P., Sauvé, S., & Miao, X. S., Yang, J. J., & Metcalf, C. D. (2005). Carbamaze- Gagnon, C. (2011). Quantification of carbamazepine and pine and its metabolites in wastewater and in biosolids in atrazine and screening of suspect organic contaminants in municipal wastewater treatment plant. Environmental Sci- surface and drinking waters. Chemosphere, 84(8), 1085– ence and Technology, 39, 7469–7475. 1094. Miège, C., Budzinski, H., Jacquet, R., Soulier, C., Pelte, T., & Seiler, R. L., Zaugg, S. D., Thomas, J. M., & Harcroft, D. L. Coquery, M. (2011). Passive sampling using pocis. applica- (1999). Caffeine and pharmaceuticals as indicators of tion for monitoring organic micropollutants in wastewater wastewater contamination in wells. Ground Water, 37, effluent and in surface water. [L’échantillonnage intégratif 405–410. par Pocis Application pour la surveillance des micropolluants Shridhar, V., Khillare, P. S., Agarwal, T., & Ray, S. (2010). organiques dans les eaux résiduaires traitées et les eaux de Metallic species in ambient particulate matter at rural and surface] Techniques-Sciences-Methodes (1–2), 80–94. urban location of Delhi. Journal of Hazardous Materials, Moldovan, Z., Chiza, R., & Alder, C. (2009). Environmental 175, 600–607. exposure of pharmaceuticals and musk fragrances in the Soldi, T., Riolo, C., Alberti, G., Gallorini, M., & Peloso, G. F. Somes River before and after upgrading the municipal (1996). Environmental vanadium distribution from an in- wastewater treatment plant Cluj-Napoca, Romania. Envi- dustrial settlement. Science of the Total Environment, 18, ronmental Science and Pollution Research, 16, S46–S54. 45–50. Munaron, D., Tapie, N., Budzinski, N., Andrai, B., & Gonzalez, Sörme, L., & Lagerkvist, R. (2002). Sources of heavy metals in J. L. (2011). Pharmaceuticals, alkylphenols and pesticides urban wastewater in Stockholm. Science of the Total Envi- in Mediterranean coastal waters: results from a pilot survey ronment, 298(1–3), 131–145. using passive samplers. Estuarian, Coastal and Shelf Sci- Suchkova, N., Darakas, E., & Ganoulis, J. (2010). Phytoreme- ence. doi:10.1016/j.ecss.2011.09.009. diation as a prospective method for rehabilitation of areas Nakada, N., Kiri, K., Shinohara, H., Harada, A., Kuroda, K., contaminated by long-term sewage storage: a Ukrainian– Takizawa, S., & Takada, H. (2008). Evaluation of pharma- Greek case study. Ecological Engineering, 36(4), 373–378. ceuticals and personal care products as water-soluble mo- Togola, A., & Budzinski, H. (2007). Development of polar organic lecular markers of sewage. Environmental Science and integrative samplers for analysis of pharmaceuticals in aquat- Technology, 42, 6347–6353. ic systems. Analytical Chemistry, 79,6734–6741. Peltier,R.E.,Hsu,S.-I.,Lall,R.,&Lippman,M.(2009). USEPA (2011). US Environmental Protection Agency. Chemicals Residual oil combustion: a major sources of airborne nickel profile: www.pbtprofiler.net. Accessed on 1 July 2011. in New York City. Journal of Exposure Science & Envi- Vasenko, O. G., Lungu, M. L., Iljevska, Y. A., Klymov, O. V., et ronmental Epidemiology, 19(6), 603–612. al. (2006). Research report. The integrated field research Reimann, C., & de Caritat, P. (1998). Chemical elements in the of environmental conditions of water bodies of the Udy environment: factsheets for the geochemists and environ- water basins (sub-basin of the Seversky Donets River) (p. mental scientist (p. 400). Berlin: Springer. 156). Kharkiv: Rayder. in Ukrainian. Rowsell, V. F., Tangney, P., Hunt, C., & Voulvoulis, N. (2010). Vinogradov, A. P. (1962). Average element abundances in main Estimating levels of micropollutants in municipal waste- types of eruptive rocks in the Earth’s crust. Geokhimiya, 7, water. Water, Air, and Soil Pollution, 206(1–4), 357–368. 555–571 (in Russian). Sanchez-Cabeza, J.-A., & Druffel, E. R. M. (2009). Environmen- Vystavna, Y., Le Coustumer, P., & Huneau, F. (2010). The tal records of anthropogenic impacts on coastal ecosystems: distribution and accumulation of emerging pollutants in an introduction. Marine Pollution Bulletin, 59(4–7), 87–90. urban waters of Eastern Ukraine. Abstract volume. World Sangi, M. R., Halstead, M. J., & Hunter, K. A. (2002). Use of Water Week in Stockholm, September 5–11, 2010 (pp. 420– diffusion gradient thin film method to measure trace metals 421). Sweden: Stockholm International Water Institute. in fresh waters at low ionic strength. Analytica Chimica Vystavna, Y., Huneau, F., Motelica-Heino, M., Le Coustumer, Acta, 456, 241–251. P., Vergeles, Y., & Stolberg, F. (2012a). Monitoring and Sankararamakrishnan, N., & Guo, Q. (2005). Chemical tracers flux determination of trace metals in rivers of the Seversky as indicator of human fecal coliforms at atorm water out- Donets basin (Ukraine) using DGT passive samplers. En- falls. Environment International, 31(8), 1133–1140. vironmental Earth Sciences, 65, 1715–1725. Environ Monit Assess

Vystavna, Y., Huneau, F., Grynenko, V., Vergeles, Y., Celle- Writer, J. H., Ryan, J. N., Keefe, S. H., & Barber, L. B. (2012). Jeanton, H., Tapie, N., Budzinski, H., & Le Coustumer, Fate of 4-nonylphenol and 17β-estradiol in the redwood P. (2012b). Pharmaceuticals in rivers of two regions with river of minnesota. Environmental Science and Technolo- contrasted socio-economic conditions: occurrence, accu- gy, 46(2), 860–868. mulation and comparison for Ukraine and France. Water Yang, H., & Rose, N. (2005). Trace element pollution records in Air and Soil Pollution, 223(5), 2111–2124. some UK lake sediments, their history, influence factors and Vystavna, Y., Huneau, F., Schafer, J., Motelica-Heino, M., regional differences. Environment International, 31(1), 63–75. Blanc, G., Larrose, A., Vergeles, Y., Diadin, D., & Le Yu, C., Ling, Q., Yan, S., Lia, J., Chen, Z., & Peng, Z. (2010). Coustumer, P. (2012c). Distribution of trace elements in Cadmium contamination in various environmental materi- waters and sediments of the Seversky Donets transboun- als in an industrialized area, Hangzhou, China. Chemical dary watershed (Kharkiv region, Eastern Ukraine). Applied Speciation and Bioavailability, 22,35–42. Geochemistry. doi:10.1016/j.apgeochem.2012.05.006. Zhang, H., & Davison, W. (1995). Performance characteristics Wolf, L., Zwiener, C., & Zemann, M. (2012). Tracking artificial of diffusive gradients in thin films for in situ measurement sweeteners and pharmaceuticals introduced into urban of trace metals in aqueous solution. Analytical Chemistry, groundwater by leaking sewer networks. Science of the 67(19), 3391–3400. Total Environment, 430,8–19. Zhang, Y., Geiben, S. U., & Gal, C. (2008). Carbamazepine and Wölz, J., Grosshans, K., Streck, G., Schulze, T., Rastall, A., diclofenac: removal in wastewater treatment plants and Erdinger, L., Brack, W., Fleig, M., Kuhlers, D., Braunbeck, occurrence in water bodies. Chemosphere, 73, 1151–1161. T., & Hollert, H. (2011). Estrogen receptor mediated activ- Zhou, X. F., Dai, C. M., Zhang, Y. L., Surampalli, R. Y., & ity in bankside groundwater, with flood suspended partic- Zhang, T. C. (2011). A preliminary study on the occurrence ulate matter and floodplain soil—an approach combining and behavior of carbamazepine (CBZ) in aquatic environ- tracer substance, bioassay and target analysis. Chemo- ment of Yangtze River Delta, China. Environmental Mon- sphere, 85(5), 717–723. itoring and Assessment, 173(1–4), 45–53.

View publication stats