Assessment of the occurrence of 455 pharmaceutical compounds in sludge according to their physical and chemical properties: A review.

Sludge agronomical reuse is of major interest due to the beneficial contribution of nutrients. However, it implies the introduction of unregulated pharmaceuticals into amended-soils and creates a controversial issue about sludge management. To limit their dissemination, it is essential to identify the compounds of interest and understand their attenuation mechanisms through the sludge processes. This paper summarizes the knowledge on 455 investigated pharmaceuticals among 32 therapeutical categories in amendable sludge matrices. It contributes to enlarging the list of commonly quantified compounds to 305 residues including 84 additional compounds compared to previous reviews. It highlights that sorption appears as the main mechanism controlling the occurrence of pharmaceuticals in sludge matrices and shows the considerable residual levels of pharmaceuticals reaching several mg/kg in dry weight. Antibiotics, stimulants, and antidepressants show the highest concentrations up to 232 mg/kg, while diuretics, anti-anxieties or anticoagulants present the lowest concentrations reaching up to 686 µg/kg. Collected data show the increase in investigated compounds as antifungals or antihistamines, and underline emerging categories like antidiabetics, antivirals, or antiarrhythmics. The in-depth analysis of the substantial database guides onto the pharmaceuticals that are the most likely to occur in these amendable matrices to assist future research.

Water stable isotopes and volumetric discharge rates to monitor the Rhône water's seasonal origin.

Along the 98 800 km2 Rhône catchment area, 3 million people depend on the river resource and its sustainability. Flow rate monitoring of the French rivers showed the importance of the Swiss part of the Rhône (measured at station 1), the Isere (station 2) and the Durance rivers (station 3) contribution into the Rhône downstream (station 4) during summer when other recharges are decreasing. While their contribution is only of 10-30 % during most of the year, those rivers could contribute to more than 60 % of the Rhône flow rate during the driest period. The current study aims at confirming the key role of Alpine rivers contribution to the Rhône downstream flow by investigating an alternative monitoring tool of high-altitude water contribution. As a suitable tracer of latitude and altitude especially in a contrasted morphology, such as the Rhône watershed, water stable isotopes can be relevant to trace the origin of the recharge contributing to the waterflow. This study is based on a full hydrological cycle survey of the Rhône downstream water isotopes signature complemented by the current flow rate monitoring program of the Alpine rivers. With a linear regression model between both parameters data, the current study evidences the relevance of using water isotope signature to trace the seasonal change of water's origin and evaluate the high altitude waters contribution (RQ AR) into the Rhône river downstream flow rate (δ2H = 26.0 x RQAR - 57.9 with R = 0.88, R2 = 0.79 and a p-value < 0.0001). It also confirms the key role of Alpine waters contribution to the Rhône River during summer with average value of 70 ± 6% and the importance to monitor the sustainability of their contribution in future drier period.

Sorption properties and behaviour at laboratory scale of selected pharmaceuticals using batch experiments.

Despite the increasing public concern about the frequent occurrence of pharmaceuticals in the water bodies, their transport and fate are not yet well known; in particular in groundwater. In this laboratory study, batch experiments were conducted to investigate the sorption behaviour of selected pharmaceuticals. The choice of compounds was motivated by their chemical properties as well as by their occurrence at the relevant field sites. It included: antipyrine, atenolol, caffeine, carbamazepine, ciprofloxacin, diclofenac, ketoprofen, ofloxacin, and sulfamethoxazole. Sorption behaviour has already been investigated for some of these compounds (e.g. carbamazepine), but for the others (e.g. antipyrine, ketoprofen), extensive studies are missing so far. For the experiments, artificial and actual aquifer materials from complementary field sites were selected: technical coarse quartz sand and sediments from alluvial Vistrenque Aquifer, France (sandy loam), and fluvio-deltaic Baix Fluvià Aquifer, Spain (sandy clay loam, clay, and medium sand). In these field sites occurrence of pharmaceuticals in groundwater was previously stated, and the presented laboratory experiments were complementary to the field investigations. Five concentration steps for determining the sorption isotherms were investigated. Correlation analysis showed dependencies of K-coefficients of individual compounds and sediment properties; however, no clear, universal patterns for all compounds were found. Batch experiments suggest that sorption behaviour was governed by compound-specific properties rather than by sediment properties. These results contribute to the understanding sorption behaviour of pharmaceuticals in heterogeneous sediments, although some inconsistencies were revealed between laboratory scale results and field scale observations.

Spatial distribution of triazine residues in a shallow alluvial aquifer linked to groundwater residence time.

At present, some triazine herbicides occurrence in European groundwater, 13 years after their use ban in the European Union, remains of great concern and raises the question of their persistence in groundwater systems due to several factors such as storage and remobilization from soil and unsaturated zone, limited or absence of degradation, sorption in saturated zones, or to continuing illegal applications. In order to address this problem and to determine triazine distribution in the saturated zone, their occurrence is investigated in the light of the aquifer hydrodynamic on the basis of a geochemical approach using groundwater dating tracers (3H/3He). In this study, atrazine, simazine, terbuthylazine, deethylatrazine, deisopropylatrazine, and deethylterbuthylazine are measured in 66 samples collected between 2011 and 2013 from 21 sampling points, on the Vistrenque shallow alluvial aquifer (southern France), covered by a major agricultural land use. The frequencies of quantification range from 100 to 56 % for simazine and atrazine, respectively (LQ = 1 ng L-1). Total triazine concentrations vary between 15 and 350 ng L-1 and show three different patterns with depth below the water table: (1) low concentrations independent of depth but related to water origin, (2) an increase in concentrations with depth in the aquifer related to groundwater residence time and triazine use prior to their ban, and (3) relatively high concentrations at low depths in the saturated zone more likely related to a slow desorption of these compounds from the soil and unsaturated zone. The triazine attenuation rate varies between 0.3 for waters influenced by surface water infiltration and 4.8 for water showing longer residence times in the aquifer, suggesting an increase in these rates with water residence time in the saturated zone. Increasing triazine concentrations with depth is consistent with a significant decrease in the use of these pesticides for the last 10 years on this area and highlights the efficiency of their ban.

Tracking natural and anthropogenic origins of dissolved arsenic during surface and groundwater interaction in a post-closure mining context: Isotopic constraints.

Arsenic contamination of stream waters and groundwater is a real issue in Au-As mine environments. At the Salsigne Au-As mine, southern France, arsenic contamination persists after closure and remediation of the site. In this study, natural and anthropogenic arsenic inputs in surface water and groundwater are identified based on (87)Sr/(86)Sr, and δ(18)O and δ(2)H isotopic composition of water. In the wet season, downstream of the remediated zone, the arsenic contents in stream water and alluvial aquifer groundwater are high, with values in the order of 36 µg/L and 40 µg/L respectively, while upstream natural background average concentrations are around 4 µg/L. Locally down-gradient of the reclaimed area, arsenic concentrations in stream water showed 2 peaks, one during an important rainy event (101 mm) in the wet season in May, and a longer one over the dry period, reaching 120 and 110 µg/L respectively. The temporal variations in arsenic content in stream water can be explained i) during the dry season, by release of arsenic stored in the alluvial sediments through increased contribution from base flow and decreased stream flow and ii) during major rainy events, by mobilization of arsenic associated with important surface runoff. The (87)Sr/(86)Sr ratios associated with increasing arsenic content in stream waters downstream of the reclaimed area are significantly lower than that of the natural Sr inherited from Variscan formations. These low (87)Sr/(86)Sr ratios are likely to be associated with the decontaminating water treatment processes, used in the past and still at present, where CaO, produced from marine limestone and therefore showing a low (87)Sr/(86)Sr ratios, is used to precipitate Ca3(AsO4)2. The low Sr isotope signatures will then impact on the Sr isotope ratio of (1) the Ca-arsenate stored in tailing dams, (2) effluent currently produced by water treatment process and (3) groundwater draining from the overall site. Furthermore, Δ(2)H shows that the low (87)Sr/(86)Sr ratio, arsenic rich water is characterized by an evaporated signature suggesting a potential influence of water impacted by evaporation during storage in decantation lagoons. This study shows the suitability of Sr and stable isotopes of water as tracers to differentiate natural and anthropogenic sources of arsenic release or other trace elements from mining context where CaO is used for water treatment.

Impact of climate changes during the last 5 million years on groundwater in basement aquifers.

Climate change is thought to have major effects on groundwater resources. There is however a limited knowledge of the impacts of past climate changes such as warm or glacial periods on groundwater although marine or glacial fluids may have circulated in basements during these periods. Geochemical investigations of groundwater at shallow depth (80-400 m) in the Armorican basement (western France) revealed three major phases of evolution: (1) Mio-Pliocene transgressions led to marine water introduction in the whole rock porosity through density and then diffusion processes, (2) intensive and rapid recharge after the glacial maximum down to several hundred meters depths, (3) a present-day regime of groundwater circulation limited to shallow depth. This work identifies important constraints regarding the mechanisms responsible for both marine and glacial fluid migrations and their preservation within a basement. It defines the first clear time scales of these processes and thus provides a unique case for understanding the effects of climate changes on hydrogeology in basements. It reveals that glacial water is supplied in significant amounts to deep aquifers even in permafrosted zones. It also emphasizes the vulnerability of modern groundwater hydrosystems to climate change as groundwater active aquifers is restricted to shallow depths.

High (36)Cl/Cl ratios in Chernobyl groundwater.

After the explosion of the Chernobyl Nuclear Power Plant in April 1986, contaminated material was buried in shallow trenches within the exclusion zone. A (90)Sr plume was evidenced downgradient of one of these trenches, trench T22. Due to its conservative properties, (36)Cl is investigated here as a potential tracer to determine the maximal extent of the contamination plume from the trench in groundwater. (36)Cl/Cl ratios measured in groundwater, trench soil water and leaf leachates are 1-5 orders of magnitude higher than the theoretical natural (36)Cl/Cl ratio. This contamination occurred after the Chernobyl explosion and currently persists. Trench T22 acts as an obvious modern point source of (36)Cl, however other sources have to be involved to explain such contamination. (36)Cl contamination of groundwater can be explained by dilution of trench soil water by uncontaminated water (rainwater or deep groundwater). With a plume extending further than that of (90)Sr, radionuclide which is impacted by retention and decay processes, (36)Cl can be considered as a suitable tracer of contamination from the trench in groundwater provided that modern release processes of (36)Cl from trench soil are better characterized.