Frederic Huneau

Pharmaceuticals in Rivers of Two Regions with Contrasted Socio-Economic Conditions: Occurrence, Accumulation, and Comparison for Ukraine and France

The goal of our study was to identify pharmaceuticals, their potential sources and consumption level in two different socioeconomic and geographical regions—Bordeaux, France and Kharkiv, Ukraine. These substances were monitored in rivers water during contrasted seasonal conditions with application of passive samplers. The 21 pharmaceuticals (psychiatric drugs: alprazolam, amitriptyline, diazepam, fluoxetine, nordiazepam, carbamazepine, bromazepam; analgesics: aspirin, paracetamol; broncholidator: clenbuterol, salbutamol, terbutaline; non-steroidal anti-inflammatory drug: diclofenac, ibuprofen, ketoprofen, naproxen; lipid regulator: gemfibrozil; stimulants: caffeine, theophylline) were identified in sites upstream and downstream of urban areas and discharge of wastewaters. Caffeine, carbamazepine, and diclofenac were relatively abundant into the surface water and could be considered as potential anthropogenic markers of wastewater discharges into rivers. A mass balance modeling has been applied to calculate approximate consumption rates for carbamazepine, diclofenac, and caffeine in both regions to assess socio-economic factors linked with pharmaceuticals behavior.

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

The research focuses on the monitoring of trace metals and pharmaceuticals as potential anthropogenic indicators of industrial and urban influences on surface water. This study includes analysis of tracers use for the indication of water pollution events and discussion of the detection method of these chemicals. The following criteria were proposed for the evaluation of indicators: specificity (physical chemical properties), variability (spatial and temporal), and practicality (capacity of the sampling and analytical techniques). The combination of grab and passive water sampling (i.e., diffusive gradient in the thin film and polar organic chemical integrated samplers) procedure was applied for the determination of dissolved and labile trace metals (Ag, Cd, Cr, Cu, Ni, Pb, and Zn) and pharmaceuticals (carbamazepine, diazepam, paracetamol, caffeine, diclofenac, and ketoprofen). Samples were analyzed using inductively coupled plasma mass spectrometry (MS; trace metals) and liquid chromatography–tandem MS electrospray ionization+/− (pharmaceuticals). Our results demonstrate the distinctive spatial and temporal patterns of trace elements distribution along an urban watercourse. Accordingly, two general groups of trace metals have been discriminated: “stable” (Cd and Cr) and “time varying” (Cu, Zn, Ni, and Pb). The relationship Cd ≫ Cu > Ag > Cr ≥ Zn was proposed as an anthropogenic signature of the industrial and urban activities pressuring the environment from point sources (municipal wastewaters) and the group Pb–Ni was discussed as a relevant fingerprint of the economic activity (industry and transport) mainly from non-point sources (runoff, atmospheric depositions, etc.). Pharmaceuticals with contrasting hydro-chemical properties of molecules (water solubility, bioaccumulation, persistence during wastewater treatment processes) were discriminated on conservative, labile, and with combined properties in order to provide information on wastewater treatment plant efficiency, punctual events (e.g., accidents on sewage works, runoff), and uncontrolled discharges. Applying mass balance modeling, medicaments were described as relevant socio-economic indicators, which can give a picture of main social aspects of the region.

Evaluation of pharmaceuticals in surface water: Reliability of PECs compared to MECs

Due to the current analytical processes that are not able to measure all the pharmaceutical molecules and to the high costs and the consumption of time to sample and analyze PhACs, models to calculate Predicted Environmental Concentrations (PECs) have been developed. However a comparison between MECs and PECs, taking into account the methods of calculations and peculiarly the parameters included in the calculation (consumption data, pharmacokinetic parameters, elimination rate in STPs and in the environment), is necessary to assess the validity of PECs. MEC variations of sixteen target PhACs [acetaminophen (ACE), amlodipine (AML), atenolol (ATE), caffeine (CAF), carbamazepine (CAR), doxycycline (DOX), epoxycarbamazepine (EPO), fluvoxamine (FLU), furosemide (FUR), hydrochlorothiazide (HYD), ifosfamide (IFO), losartan (LOS), pravastatin (PRA), progesterone (PROG), ramipril (RAM), trimetazidine (TRI)] have been evaluated during one hydrological cycle, from October 2011 to October 2012 and compared to PECs calculated by using an adaptation of the models proposed by Heberer and Feldmann (2005) and EMEA (2006). Comparison of PECs and MECS has been achieved for six molecules: ATE, CAR, DOX, FUR, HYD and PRA. DOX, FUR and HYD present differences between PECs and MECs on an annual basis but their temporal evolutions follow the same trends. PEC evaluation for these PhACs could then be possible but need some adjustments of consumption patterns, pharmacokinetic parameters and/or mechanisms of (bio)degradation. ATE, CAR and PRA are well modeled; PECs can then be used as reliable estimation of concentrations without any reserve.

Monitoring and flux determination of trace metals in rivers of the Seversky Donets basin (Ukraine) using DGT passive samplers

This paper reports the results of the in situ application of diffusive gradients in thin-films (DGT) passive samplers for trace metals (Cd, Co, Cr, Cu, Ni, Pb and Zn) monitoring in transboundary Udy and Lopan rivers of the Seversky Donets watershed in the Kharkiv region (Ukraine), which has a long history of industrial development. The research discusses potential sources of DGT-measured labile metals in water and seasonal variations. Our results demonstrate the application of DGT for identifying and measuring labile metal concentrations in contrasted climate conditions (cold snowy winter and hot summer) and appropriateness of such a tool for continuous water monitoring with the presence of an ice cover. Results show that DGT-measured concentrations of most of trace metals were much higher downstream of the wastewater treatment plants discharges than upstream; thus wastewater treatment plants seemed not able to reduce or to remove trace metals’ contaminations and become major sources of pollutants in the studied rivers. The calculation of the average metal fluxes based on the DGT-measured concentrations confirmed that the urban wastewater discharges significantly contribute to the metal fluxes into the Udy and the Lopan rivers during both low-flow and high-flow periods. Compared to the wastewaters inputs to the rivers, the transboundary effect is limited, but should be taken into account as the origin of some metals is from sources located on the adjacent Russian territory.

Strontium isotopes as tracers of water-rocks interactions, mixing processes and residence time indicator of groundwater within the granite-carbonate coastal aquifer of Bonifacio (Corsica, France)

This study aims at identifying the water-rock interactions and mixing rates within a complex granite-carbonate coastal aquifer under high touristic pressure. Investigations have been carried out within the coastal aquifer of Bonifacio (southern Corsica, France) mainly composed of continental granitic weathering products and marine calcarenite sediments filling a granitic depression. A multi-tracer approach combining physico-chemical parameters, major ions, selected trace elements, stable isotopes of the water molecule and 87Sr/86Sr ratios measurements is undertaken for 20 groundwater samples during the low water period in November 2014. 5 rock samples of the sedimentary deposits and surrounding granites are also analysed. First, the water-rock interactions processes governing the groundwater mineralization are described in order to fix the hydrogeochemical background. Secondly, the flow conditions are refined through the quantification of inter aquifer levels mixing, and thirdly, the kinetics of water-rock interaction based on groundwater residence time from a previous study using CFCs and SF6 are quantified for the two main flow lines. A regional contrast in the groundwater recharge altitude allowed the oxygene-18 to be useful combined with the 87Sr/86Sr ratios to differentiate the groundwater origins and to compute the mixing rates, revealing the real extension of the watershed and the availability of the resource. The results also highlight a very good correlation between the groundwater residence time and the spatial evolution of 87Sr/86Sr ratios, allowing water-rock interaction kinetics to be defined empirically for the two main flow lines through the calcarenites. These results demonstrate the efficiency of strontium isotopes as tracers of water-rock interaction kinetics and by extension their relevance as a proxy of groundwater residence time, fundamental parameter documenting the long term sustainability of the hydrosystem.

PaPRIKa, the French Multicriteria Method for Mapping the Intrinsic Vulnerability of Karst Water Resource and Source – Two Examples (Pyrenees, Normandy)

PaPRIKa is an updated intrinsic vulnerability mapping method derived from previous specialized works on karst groundwater. It assesses vulnerability by using four criteria: P for Protection (considering the most protective index that results from the combination of Soil cover, Unsaturated zone and Epikarst aquifer), R for Reservoir type, I for Infiltration and Ka for Karstification development. These criteria are chosen based on the structure and functioning of the karst aquifers. PaPRIKa distinguishes source and resource vulnerability, so it constitutes a common basis for hydrogeologists and French administration helping to delineate water catchments protection zones. Two test sites (a Pyrenean karstic system and a chalk karstified aquifer in the Paris basin) are here presented to illustrate its application.

Assessment of Trace Metals during Episodic Events using DGT Passive Sampler: A Proposal for Water Management Enhancement

The potential of the Diffusive Gradient Thin-Films (DGT) as a supplemental method for water quality monitoring was employed has been tested through 3 sampling campaigns to measure the trace metals (Cd, Co, Cr, Cu, Pb, Ni and Zn) present in the surface water of a highly urbanized river. Specifically, the study done in the Pasig River (Philippines) seeks to: assess the applicability of DGT passive sampler in an urban context exhibiting highly contrasted hydrological conditions (greatly influenced by episodic events) and sediment disturbance (dredging) and provide proposal for a better water management. The results indicate that: (1) DGT is highly recommended as part of a routine analysis for water quality monitoring; (2) DGT are able to capture the fluxes even in very contrasted flow regimes; (3) DGT are suitable to trace the labile fluxes of metals from the lake to the estuary; and (4) at the confluence of the Marikina River water management should be intensified. Moreover, recommendations were made for developing pertinent water monitoring protocol and management scheme.

Characterization of the aquifers of the Bangui urban area, Central African Republic, as an alternative drinking water supply resource

Abstract This paper presents the results of a survey carried out in 2010 aimed at evaluating the type and quality of the groundwater resources of the Bangui region of the Central African Republic. This work is the first step towards the development of groundwater resources in the Central African Republic in order to find alternatives to direct pumping from the Ubangi River and provide the population of the suburbs with a safer drinking water supply from deep boreholes. By combining both geological and hydrogeochemical approaches, it appears that the geology of Bangui is favourable to the development of a secure and sustainable water supply from groundwater provided that the conditions of exploitation would be constrained by the local authorities. The deep Precambrian carbonate aquifers, known as the Bimbo and Fatima formations, are identified as target resources in view of the relatively good quality of their water from the chemical point of view, and the semi-confined structure of the aquifers that prevents the mixing with shallow aquifers that are already strongly affected by domestic and industrial pollution. The main difficulty in terms of exploitation is to appreciate the depth of the resource and the more or less fractured/palaeo-karstified type of the porosity. Editor Z.W. Kundzewicz Citation Djebebe-Ndjiguim, C.L., Huneau, F., Denis, A., Foto, E., Moloto-a-Kenguemba, G., Celle-Jeanton, H., Garel, E., Jaunat, J., Mabingui, J., and Le Coustumer, P., 2013. Characterization of the aquifers of the Bangui urban area, Central African Republic, as an alternative drinking water supply resource. Hydrological Sciences Journal, 58 (8), 1760–1778.

Groundwater resources of Uzbekistan: an environmental and operational overview

As a result of the massive irrigation development during the Soviet Union era and intensive chemization of agriculture, the surface runoff quality has been degraded in this arid and endorheic region. Moreover hydraulically related groundwater has also been affected. Excessive irrigation has lead to land salinization, which now threatens the soil quality of significant areas where crop yields would be at risk in the future. Since the collapse of the Soviet Union, institutional changes have been undertaken for the management of natural resources and water infrastructure. At present, underdeveloped and inadequate systems have been practiced with respect to groundwater use and management. This paper analyzes the present extent of groundwater resources with consideration to their reserves, quality evolution, and to technical, institutional and transboundary management practices in Uzbekistan.

Contribution of {\text{P}}_{{{\text{CO}}_{ 2} {\text{eq}}}} and 13CTDIC Evaluation to the Identification of CO2 Sources in Volcanic Groundwater Systems: Influence of Hydrometeorological Conditions and Lava Flow Morphologies—Application to the Argnat Basin (Chaîne des Puys, Massif Central, France)

Mineralization of groundwater in volcanic aquifers is partly acquired through silicates weathering. This alteration depends on the dissolution of atmospheric, biogenic, or mantellic gaseous CO2 whose contributions may depend on substratum geology, surface features, and lava flow hydrological functionings. Investigations of \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}