Understanding the origins of herbicides metabolites in an agricultural watershed through their spatial and seasonal variations.

The aim of this study is to understand the spatial and seasonal variations of persistent herbicides metabolites and to determine their origins in the Vilaine River watershed, Britany-France. Improving knowledge on herbicides metabolites sources and seasonality is important for drinking water resource management. Data were collected at 13 sampling stations during five sampling campaigns in 2016 and 2017. Relations between water quality parameters, herbicides and metabolites were analyzed using statistical methods. The influence of land use and wastewater treatment plants (WWTP) on streams water quality has been identified. Cluster Analysis revealed that two groups of sampling stations can be described as "urban" with stations downstream the urban area and as "agricultural" with stations located downstream of the watershed. Chloroacetamids metabolites have been associated together with nitrates and agricultural areas as could be expected. Thus, the drinking water treatment plant located in the estuary of the Vilaine River is exposed to high metolachlor ESA and nitrate loads all year long. Aminomethylphosphonic acid (AMPA) is associated to anthropogenic urban contamination and nutrient loads. AMPA has its major sources in both glyphosate and phosphonate detergents issued from WWTP. This can help to adapt surface water treatment process and water management policies concerning herbicides metabolites.

Heavy Rainfall Impacts on Trihalomethane Formation in Contrasting Northwestern European Potable Waters.

There is emerging concern over the impact of extreme events such as heavy rainfall on the quality of water entering the drinking water supply from aboveground sources, as such events are expected to increase in magnitude and frequency in response to climate change. We compared the impact of rainfall events on streamwater quality in four contrasting upland (peatland and mineral soil) and lowland agricultural catchments used to supply drinking water in France (Brittany) and the United Kingdom (North Wales) by analyzing water samples collected before, during, and after specific events. At all four streams, heavy rainfall led to a considerable rise in organic matter concentration ranging from 48 to 158%. Dissolved organic carbon (DOC) quality, as determined using specific ultraviolet absorbance, changed consistently at all sites during rainfall events, with a greater proportion of aromatic and higher molecular weight compounds following the onset of rainfall. However, the change in DOC quality and quantity did not significantly alter the trihalomethane formation potential. We observed small increases in trihalomethane (THM) generation only at the Welsh peatland and agricultural sites and a small decrease at the Brittany agricultural site. The proportion of brominated THMs in chlorinated waters was positively correlated with bromide/DOC ratio in raw waters for all sites and hydrological conditions. These results provide a first indication of the potential implications for surface-based drinking water resources resulting from expected future increases in rainfall event intensity and extension of dry periods with climate changes.

Indoor Carbon Dioxide, Fine Particulate Matter and Total Volatile Organic Compounds in Private Healthcare and Elderly Care Facilities.

Poor indoor air quality can have adverse effects on human health, especially in susceptible populations. The aim of this study was to measure the concentrations of dioxide carbon (CO2), fine particulate matter (PM2.5) and total volatile organic compounds (TVOCs) in situ in private healthcare and elderly care facilities. These pollutants were continuously measured in two rooms of six private healthcare facilities (general practitioner's offices, dental offices and pharmacies) and four elderly care facilities (nursing homes) in two French urban areas during two seasons: summer and winter. The mean CO2 concentrations ranged from 764 ± 443 ppm in dental offices to 624 ± 198 ppm in elderly care facilities. The mean PM2.5 concentrations ranged from 13.4 ± 14.4 µg/m3 in dental offices to 5.7 ± 4.8 µg/m3 in general practitioner offices. The mean TVOC concentrations ranged from 700 ± 641 ppb in dental offices to 143 ± 239 ppb in general practitioner offices. Dental offices presented higher levels of indoor air pollutants, associated with the dental activities. Increasing the ventilation of these facilities by opening a window is probably an appropriate method for reducing pollutant concentrations and maintaining good indoor air quality.

Quantitative Health Risk Assessment of the Chronic Inhalation of Chemical Compounds in Healthcare and Elderly Care Facilities.

Previous studies have described the chemical pollution in indoor air of healthcare and care facilities. From these studies, the main objective of this work was to conduct a quantitative health risk assessment of the chronic inhalation of chemical compounds by workers in healthcare and elderly care facilities (hospitals, dental and general practitioner offices, pharmacies and nursing homes). The molecules of interest were 36 volatile and 13 semi-volatile organic compounds. Several professional exposure scenarios were developed in these facilities. The likelihood and severity of side effects that could occur were assessed by calculating the hazard quotient for deterministic effects, and the excess lifetime cancer risk for stochastic effects. No hazard quotient was greater than 1. Three compounds had a hazard quotient above 0.1: 2-ethyl-1-hexanol in dental and general practitioner offices, ethylbenzene and acetone in dental offices. Only formaldehyde presented an excess lifetime cancer risk greater than 1 × 10-5 in dental and general practitioner offices (maximum value of 3.8 × 10-5 for general practitioners). The health risk for chronic inhalation of most compounds investigated did not appear to be of concern. Some values tend to approach the acceptability thresholds justifying a reflection on the implementation of corrective actions such as the installation of ventilation systems.

Indoor air quality in two French hospitals: Measurement of chemical and microbiological contaminants.

In addition to being influenced by the environment, the indoor air pollution in hospitals may be associated with specific compounds emitted from various products used, health care activities and building materials. This study has enabled assessment of the chemical and microbiological concentrations of indoor air in two French hospitals. Based on an integrated approach, the methodology defined aims to measure concentrations of a wide range of chemical compounds (>50 volatile and semi-volatile organic compounds), particle concentrations (PM10 and PM2.5), microorganisms (fungi, bacteria and viruses) and ambient parameters (temperature, relative humidity, pressure and carbon dioxide). Chemical and microbiological air concentrations were measured during two campaigns (winter and summer) and across seven rooms (for spatial variability). The results have shown that indoor air contains a complex mixture of chemical, physical and microbiological compounds. Concentrations in the same order of magnitude were found in both hospitals. Compared to dwelling indoor air, our study shows low, at least equivalent, contamination for non-hospital specific parameters (aldehydes, limonene, phthalates, aromatic hydrocarbons), which is related to ventilation efficiency. Chemical compounds retrieved at the highest concentration and frequencies are due to healthcare activities, for example alcohol - most commonly ethanol - and hand rubbing (median concentration: ethanol 245.7 µg/m3 and isopropanol 13.6 µg/m3); toluene and staining in parasitology (highest median concentration in Nancy laboratory: 2.1 µg/m3)).

AminoMethylPhosphonic acid (AMPA) in natural waters: Its sources, behavior and environmental fate.

The widely occurring degradation product aminomethylphosphonic acid (AMPA) is a result of glyphosate and amino-polyphosphonate degradation. Massive use of the parent compounds leads to the ubiquity of AMPA in the environment, and particularly in water. The purpose of this review is to summarize and discuss current insights into AMPA formation, transport, persistence and toxicity. In agricultural soils, AMPA is concentrated in the topsoil, and degrades slowly in most soils. It can reach shallow groundwater, but rarely managed to enter deep groundwater. AMPA is strongly adsorbed to soil particles and moves with the particles towards the stream in rainfall runoff. In urban areas, AMPA comes from phosphonates and glyphosate in wastewater. It is commonly found at the outlets of Wastewater Treatment Plants (WWTP). Sediments tend to accumulate AMPA, where it may be biodegraded. Airborne AMPA is not negligible, but does wash-out with heavy rainfall. AMPA is reported to be persistent and can be biologically degraded in soils and sediments. Limited photodegradation in waters exists. AMPA mainly has its sources in agricultural leachates, and urban wastewater effluents. The domestic contribution to urban loads is negligible. There is a critical lack of epidemiological data - especially on water exposure - to understand the toxicological effects, if any, of AMPA on humans. Fortunately, well operated water treatment plants remove a significant proportion of the AMPA from water, even though there are not sufficient regulatory limits for metabolites.

Improving microcystin monitoring relevance in recreative waters: A regional case-study (Brittany, Western France, Europe).

Cyanobacteria and their toxins are known as a health hazard in recreative and distributed waters. Monitoring data from 2004 to 2011 were collected at regional scale to characterize exposition parameters to microcystins in Brittany (Western France). The data show that cyanobacteria populations are experiencing a composition shift leading to a longer duration of cell densities higher than WHO alert levels 2 and 3. Microcystins however appear to be more frequently detected with subacute concentrations in low cell density samples than in high cell density samples or during bloom episodes. Positive relations are described between microcystin concentrations, detection frequencies and cyanobacteria biovolumes, allowing for a novel definition of alert levels and decision framework following WHO recommendations.

Learning from 8 years of regional cyanobacteria observation in Brittany in view of sanitary survey improvement.

Cyanobacteria and cyanotoxins have been more and more studied during the last decades with regard to environment and health issues. More recently the consequences of climate change reinforced the need for research in view of a better management of cyanobacteria blooms. In this context the exploitation of the water quality survey of 26 recreational lakes in Brittany (north western France) between 2004 and 2011 is reported in this paper in order to encompass spatial and interannual patterns of cyanobacteria development at a regional scale. Starting from weekly data principally acquired during summertime, the links between cyanobacteria cell densities, toxin occurrences and interannual meteorological factors can give insights on the potential evolution of cyanobacterial crisis in the future. This study is part of a project aiming at a better understanding of potentially toxic cyanobacteria crisis occurrences in recreational waters, in order to improve predictive monitoring routines.

Geographical patterns in cyanobacteria distribution: climate influence at regional scale.

Cyanobacteria are a component of public health hazards in freshwater environments because of their potential as toxin producers. Eutrophication has long been considered the main cause of cyanobacteria outbreak and proliferation, whereas many studies emphasized the effect of abiotic parameters (mainly temperature and light) on cell growth rate or toxin production. In view of the growing concerns of global change consequences on public health parameters, this study attempts to enlighten climate influence on cyanobacteria at regional scale in Brittany (NW France). The results show that homogeneous cyanobacteria groups are associated with climatic domains related to temperature, global radiation and pluviometry, whereas microcystins (MCs) occurrences are only correlated to local cyanobacteria species composition. As the regional climatic gradient amplitude is similar to the projected climate evolution on a 30-year timespan, a comparison between the present NW and SE situations was used to extrapolate the evolution of geographical cyanobacteria distribution in Brittany. Cyanobacteria composition should shift toward species associated with more frequent Microcystins occurrences along a NW/SE axis whereas lakes situated along a SW/NE axis should transition to species (mainly Nostocales) associated with lower MCs detection frequencies.

Microbial contamination detection in water resources: interest of current optical methods, trends and needs in the context of climate change.

Microbial pollution in aquatic environments is one of the crucial issues with regard to the sanitary state of water bodies used for drinking water supply, recreational activities and harvesting seafood due to a potential contamination by pathogenic bacteria, protozoa or viruses. To address this risk, microbial contamination monitoring is usually assessed by turbidity measurements performed at drinking water plants. Some recent studies have shown significant correlations of microbial contamination with the risk of endemic gastroenteresis. However the relevance of turbidimetry may be limited since the presence of colloids in water creates interferences with the nephelometric response. Thus there is a need for a more relevant, simple and fast indicator for microbial contamination detection in water, especially in the perspective of climate change with the increase of heavy rainfall events. This review focuses on the one hand on sources, fate and behavior of microorganisms in water and factors influencing pathogens' presence, transportation and mobilization, and on the second hand, on the existing optical methods used for monitoring microbiological risks. Finally, this paper proposes new ways of research.

A decision support system for drinking water production integrating health risks assessment.

The issue of drinking water quality compliance in small and medium scale water services is of paramount importance in relation to the 98/83/CE European Drinking Water Directive (DWD). Additionally, concerns are being expressed over the implementation of the DWD with respect to possible impacts on water quality from forecast changes in European climate with global warming and further anticipated reductions in north European acid emissions. Consequently, we have developed a decision support system (DSS) named ARTEM-WQ (AwaReness Tool for the Evaluation and Mitigation of drinking Water Quality issues resulting from environmental changes) to support decision making by small and medium plant operators and other water stakeholders. ARTEM-WQ is based on a sequential risk analysis approach that includes consideration of catchment characteristics, climatic conditions and treatment operations. It provides a holistic evaluation of the water system, while also assessing human health risks of organic contaminants potentially present in treated waters (steroids, pharmaceuticals, pesticides, bisphenol-a, polychlorobiphenyls, polycyclic aromatic hydrocarbons, petrochemical hydrocarbons and disinfection by-products; n = 109). Moreover, the system provides recommendations for improvement while supporting decision making in its widest context. The tool has been tested on various European catchments and shows a promising potential to inform water managers of risks and appropriate mitigative actions. Further improvements should include toxicological knowledge advancement, environmental background pollutant concentrations and the assessment of the impact of distribution systems on water quality variation.

State of knowledge and concerns on cyanobacterial blooms and cyanotoxins.

Cyanobacteria are ubiquitous microorganisms considered as important contributors to the formation of Earth's atmosphere and nitrogen fixation. However, they are also frequently associated with toxic blooms. Indeed, the wide range of hepatotoxins, neurotoxins and dermatotoxins synthesized by these bacteria is a growing environmental and public health concern. This paper provides a state of the art on the occurrence and management of harmful cyanobacterial blooms in surface and drinking water, including economic impacts and research needs. Cyanobacterial blooms usually occur according to a combination of environmental factors e.g., nutrient concentration, water temperature, light intensity, salinity, water movement, stagnation and residence time, as well as several other variables. These environmental variables, in turn, have promoted the evolution and biosynthesis of strain-specific, gene-controlled metabolites (cyanotoxins) that are often harmful to aquatic and terrestrial life, including humans. Cyanotoxins are primarily produced intracellularly during the exponential growth phase. Release of toxins into water can occur during cell death or senescence but can also be due to evolutionary-derived or environmentally-mediated circumstances such as allelopathy or relatively sudden nutrient limitation. Consequently, when cyanobacterial blooms occur in drinking water resources, treatment has to remove both cyanobacteria (avoiding cell lysis and subsequent toxin release) and aqueous cyanotoxins previously released. Cells are usually removed with limited lysis by physical processes such as clarification or membrane filtration. However, aqueous toxins are usually removed by both physical retention, through adsorption on activated carbon or reverse osmosis, and chemical oxidation, through ozonation or chlorination. While the efficient oxidation of the more common cyanotoxins (microcystin, cylindrospermopsin, anatoxin and saxitoxin) has been extensively reported, the chemical and toxicological characterization of their by-products requires further investigation. In addition, future research should also investigate the removal of poorly considered cyanotoxins (ß-methylamino-alanine, lyngbyatoxin or aplysiatoxin) as well as the economic impact of blooms.

Contribution to surface water contamination understanding by pesticides and pharmaceuticals, at a watershed scale.

This study aims at understanding the presence of regulated and emerging micropollutants, particularly pesticides and pharmaceuticals, in surface water, regarding spatial and temporal influences at a watershed scale. The study of relations between micropollutants and other water quality and hydroclimatic parameters was carried out from a statistical analysis on historical and experimental data of different sampling sites from the main watershed of Brittany, western France. The outcomes point out the influence of urban and rural areas of the watershed as well as the impact of seasons on contamination variations. This work contributes to health risk assessment related to surface water contamination by micropollutants. This approach is particularly interesting in the case of agricultural watersheds such as the one studied, where more than 80% of surface water is used to produce drinking water.

Impacts of rainfall events on runoff water quality in an agricultural environment in temperate areas.

Since a rise in dissolved organic carbon (DOC) concentrations has been observed for surface waters at least over the last two decades, a change in weather conditions (temperature and precipitations) has been proposed to partly explain this increase. While the majority of DOC delivery from soils to stream occurs during rainfall events, a better understanding of the rainfall influence on DOC release is needed. This study has been conducted in Brittany, western France, on agricultural experimental plots receiving either cattle manure (CM) or pig slurry (PS) as fertilizers in accordance with local practices. Each plot was instrumented with a flow meter and an auto sampler for runoff measurements. The results show that export of DOC during high intensity events is higher than during lower intensity rainfalls. Fertilization has a noticeable impact on total organic carbon (TOC) fluxes with an increase of five to seven folds for PS and CM respectively. If TOC shock load occurs shortly after the rainfall peak, DOC maximum appears with the first flush of the event. Organic carbon (OC) is mainly under colloidal (41.2%) and soluble (23.9%) forms during the first stage of a rainfall event and a control of rainfall intensity on OC colloidal transport is suggested. These findings highlight the potential risk of receiving water quality degradation due to the increase of heavier rainfall events with climate change in temperate areas.

Fast characterization of non domestic load in urban wastewater networks by UV spectrophotometry.

Urban wastewater treatment plant efficiency, as well as biosolid quality, depends on urban wastewater quality, which can be affected by non domestic discharges (industrial, commercial etc.). The characterization of wastewater quality and non domestic discharge is complex, expensive and time consuming. However, these discharges must be controlled and reduced if possible. The development of a simple and fast methodology, namely based on alternative methods such as UV spectrophotometry, has been carried out and applied to different areas of a medium sized town of Southern Québec (Canada). Several autosamplers and on line/on site measurements have been used in critical control points of the network areas, for a dry weather campaign in four areas (industrial, commercial, hospital and university). The flow rate study, completed by the exploitation of conductivity measurements and the qualitative examination of UV spectra allows the discrimination of non domestic loads and their variability study from one point to another. The identification of critical discharges and organic shock loads has been possible with low investment, and mitigation actions have been proposed.