Marc Chevreuil

Occurrence and fate of antibiotics in the Seine River in various hydrological conditions.

Occurrence and fate of 17 antibiotics were investigated in the aqueous phase of river water under different hydrological conditions at 5 sampling locations in the Seine River inner estuary. The target analytes belonged to 4 groups: quinolones, sulfonamides, nitro-imidazoles and diaminopyrimidines. This six-month survey (from January to June 2006) showed that different compounds were occurring at individual concentrations reaching 544 ng L(-)(1) (sulfamethoxazole). All 17 compounds were detected at least once in the survey. Sulfamethoxazole was detected in every sample, and showed the highest concentrations. Norfloxacin and flumequine were found to be the most ubiquitous quinolones, with detection frequencies of 33 and 75% respectively at the most contaminated site (Poses). Investigations concerning the origins of this contamination were made by means of a longitudinal profile along the Seine River between Paris and Poses. It showed large inputs of norfloxacin, ofloxacin, trimethoprim and sulfamethoxazole from wastewater treatment plants, with an increase in norfloxacin and sulfamethoxazole concentrations of 84% and 70% respectively, both reaching 155 ng L(-)(1) in the river, downstream from a wastewater outlet. The detected compounds showed different dissipation patterns and behaviours under different hydrological conditions. Higher inputs of norfloxacin were found in low flow conditions, which were rapidly attenuated along the stream. In contrast, sulfamethoxazole inputs were increasing in high flow conditions, and dissipation of this compound was found to be slow. Similar behaviour was observed for the synergist trimethoprim. Flumequine was also frequently detected and its input increased during flood events.

Partitioning behaviour of perfluorinated alkyl contaminants between water, sediment and fish in the Orge River (nearby Paris, France)

This paper reports on the partitioning behaviour of 15 perfluorinated compounds (PFCs), including C(4)-C(10) sulfonates and C(5)-C(14) carboxylic acids, between water, sediment and fish (European chub, Leuciscus cephalus) in the Orge River (nearby Paris). Total PFC levels were 73.0 ± 3.0 ng L(-1) in water and 8.4 ± 0.5 ng g(-1) in sediment. They were in the range 43.1-4997.2 ng g(-1) in fish, in which PFC tissue distribution followed the order plasma > liver > gills > gonads > muscle. Sediment-water distribution coefficients (logK(d)) and bioaccumulation factors (logBAF) were in the range 0.8-4.3 and 0.9-6.7, respectively. Both distribution coefficients positively correlated with perfluoroalkyl chain length. Field-based biota-sediment accumulation factors (BSAFs) are also reported, for the first time for PFCs other than perfluorooctane sulfonate. logBSAF ranged between -1.3 and 1.5 and was negatively correlated with the perfluoroalkyl chain length in the case of carboxylic acids.

Phthalate removal throughout wastewater treatment plant: case study of Marne Aval station (France).

The fate of six phthalates: dimethyl phthalate (DMP), diethyl phthalate (DEP), di-n-butyl phthalate (DnBP), butyl benzyl phthalate (BBP), bis (2-ethylhexyl) phthalate (DEHP) and di-n-octyl phthalate (DnOP) was investigated throughout wastewater treatment processes in the wastewater treatment plant (WWTP) of Marne Aval (France). That plant treats wastewater from a highly populated area and was used as a pilot station for development of nitrification processes. In wastewater, at each step of treatment, DEHP was always the major compound (9 to 44 microg L(-1)), followed by DEP (1.6 to 25 microg L(-1)). Other phthalates averaged 1 microg L(-1) and DnOP remained close to the detection limit in nearly all cases. In sludge, the prevailing compound was also DEHP (72 microg g(-1)) which is consistent with its tendency to get sorbed upon suspended matter (SM). DnOP came in third, in relation with its resistance to biodegradation. For the studied period, the removal efficiency of DEHP from wastewater was about 78%. That removal seemed to proceed rather from particle settling than from biodegradation. A highly significant correlation (p<0.001) was found between DEHP and SM concentrations throughout treatment processes. The other compounds: DMP, DEP, DnBP and BBP, displayed satisfactory efficiencies ranging from 68 to over 96% for the lighter ones obviously more easily degraded. Under rainy periods, the plant discharge impact upon Marne River quality in terms of phthalate fluxes, appeared to be minor as compared to the amount brought by the storm overflows in the same area. Downstream of the WWTP discharge, DEHP concentration remained under the European norm for surface water (NQE: 1.3 microg L(-1)). Our study documents the behaviour of phthalate esters throughout a WWTP which treatment device is used by 55% of the WWTP in the river Seine basin.

Measurement of trace levels of antibiotics in river water using on-line enrichment and triple-quadrupole LC–MS/MS

This study presents the development of an automated on-line solid phase extraction (SPE)-liquid chromatography-tandem mass spectrometry (LC-MS/MS) method for the determination of 23 antibiotics in environmental water samples. After optimisation of LC-MS/MS conditions, SPE parameters such as sorbent type, sample pH or sample volume were optimised. Antibiotic recoveries ranged from 64% to 98% and compared favourably with those achieved using off-line SPE. Limits of detection were in the range 0.5-13.7 ng L(-1). This on-line SPE-LC-MS/MS procedure was applied to the analysis of water samples taken in three rivers within the Seine River basin, near Paris (France). The obtained results revealed the occurrence of 12 antibiotics, including tylosin, erythromycin, tetracycline, amoxicillin, trimethoprim, sulfamethoxazole, oxolinic acid, flumequine, norfloxacin, ciprofloxacin, ofloxacin, and vancomycin (2-1435 ng L(-1)).

Transfer of glyphosate and its degradate AMPA to surface waters through urban sewerage systems.

A study of glyphosate and aminomethyl phosphonic acid (AMPA) transfer in the Orge watershed (France) was carried out during 2007 and 2008. Water samples were collected in surface water, wastewater sewer, storm sewer and wastewater treatment plant (WWTP). These two molecules appeared to be the most frequently detected ones in the rivers and usually exceeded the European quality standard concentrations of 0.1microg L(-1) for drinking water. The annual glyphosate estimated load was 1.9 kg year(-1) upstream (agricultural zone) and 179.5 kg year(-1) at the catchment outlet (urban zone). This result suggests that the contamination of this basin by glyphosate is essentially from urban origin (road and railway applications). Glyphosate reached surface water prevalently through storm sewer during rainfall event. Maximum concentrations were detected in storm sewer just after a rainfall event (75-90 microg L(-1)). High concentrations of glyphosate in surface water during rainfall events reflected urban runoff impact. AMPA was always detected in the sewerage system. This molecule reached surface water mainly via WWTP effluent and also through storm sewer. Variations in concentrations of AMPA during hydrological episodes were minor compared to glyphosate variations. Our study highlights that AMPA and glyphosate origins in urban area are different. During dry period, detergent degradation seemed to be the major AMPA source in wastewater.

Origin and distribution of polyaromatic hydrocarbons and polychlorobiphenyls in urban effluents to wastewater treatment plants of the Paris area (France)

Polyaromatic hydrocarbons (PAHs) and polychlorobiphenyls (PCBs), were investigated in urban effluents to wastewater treatment plants in the Paris area (France), under different meteorological conditions. The Achères plant was considered with special attention because of its particular features. Wastewater PAH concentration level was 6 fold higher than that of PCBs. In March, PCB concentrations did not vary whatever the meteorological conditions whereas, for PAHs, they were markedly higher during rainy episodes. In September, concentrations of both pollutants increased due to rainy weather. The rise was 30 fold stronger for PAHs. Daily fluxes displayed the same trends. This suggests that the contribution of atmospheric wet deposition to wastewater contamination prevails for PCBs. In contrast, PAHs appeared to originate mainly from urban runoff processes.

Occurrence of organochlorines (PCBs, pesticides) and herbicides (triazines, phenylureas) in the atmosphere and in the fallout from urban and rural stations of the Paris area

The concentrations of organochlorines (PCBs, pesticides) and herbicides (triazines, phenylureas) were determined in the atmosphere. The total fallout in the Paris area in 1992 and in 1993 was measured. Fallout was investigated at two stations, urban and rural and the gaseous phase was studied at the rural one. PCB concentrations (0.3-4.9 ng/m3) and compositions in the atmosphere and in the fallout (20-520 ng/l) varied, according to the local emission, with the temperature and the direction of wind. Compared to our first results in 1986, there were no changes of pollution levels by organochlorines in that area. Pesticide concentrations in the atmosphere and in the fallout reached maximal values after the local agricultural treatments in spring. No phenylurea was detected in any of the gaseous or liquid samples. Lindane, atrazine and simazine were the main pesticides found. Their levels in the vapour phase, expressed as ng/m3, were: lindane 0.3-6.3, atrazine < 0.03-2, simazine < 0.03-3; in the fallout, expressed as ng/l they were: lindane 5-350, atrazine 5-380, simazine 5-650. In relative terms, the Parisian area is very small. No difference in the diversity and in the abundance of the micropollutants introduced by the atmosphere was observed between the rural and the urban stations. The pollution level of atrazine was close to that found in Europe and in North America, while the organochlorine and the simazine levels were higher.

Assessing the fate of antibiotic contaminants in metal contaminated soils four years after cessation of long-term waste water irrigation

Spreading of urban wastewater on agricultural land may lead to concomitant input of organic and inorganic pollutants. Such multiple pollution sites offer unique opportunities to study the fate of both heavy metals and pharmaceuticals. We examined the occurrence and fate of selected antibiotics in sandy-textured soils, sampled four years after cessation of 100 years irrigation with urban wastewater from the Paris agglomeration. Previous studies on heavy metal contamination of these soils guided our sampling strategy. Six antibiotics were studied, including quinolones, with a strong affinity for organic and mineral soil components, and sulfonamides, a group of more mobile molecules. Bulk samples were collected from surface horizons in different irrigation fields, but also in subsurface horizons in two selected profiles. In surface horizons, three quinolones (oxolinic acid, nalidixic acid, and flumequine) were present in eight samples out of nine. Their contents varied spatially, but were well-correlated one to another. Their distributions showed great similarities regarding spatial distribution of total organic carbon and heavy metal contents, consistent with a common origin by wastewater irrigation. Highest concentrations were observed for sampling sites close to irrigation water outlets, reaching 22 μg kg(-1) for nalidixic acid. Within soil profiles, the two antibiotic groups demonstrated an opposite behavior: quinolones, found only in surface horizons; sulfamethoxazole, detected in clay-rich subsurface horizons, concomitant with Zn accumulation. Such distribution patterns are consistent with chemical adsorption properties of the two antibiotic groups: immobilization of quinolones in the surface horizons ascribed to strong affinity for organic matter (OM), migration of sulfamethoxazole due to a lower affinity for OM and its interception and retention in electronegative charged clay-rich horizons. Our work suggests that antibiotics may represent a durable contamination of soils, and risks for groundwater contamination, depending on the physicochemical characteristics both of the organic molecules and of soil constituents.

Seasonal transport of herbicides (Triazines and Phenylureas) in a small stream draining an agricultural basin: Melarchez (France)

Abstract The transportation of triazines (atrazine, simazine, ametryne and cyanazine) was investigated in an experimental catchment basin situated in an agricultural area. It focused on the surface and groundwaters from March 1991 to December 1993. In addition, the phenylureas (isoproturon, linuron, diuron and chlortoluron) were studied in the surface waters from January 1992 to December 1993. So as to assess the evolution of water contamination by triazines and phenylureas during the survey period, the herbicide concentrations were considered together with the characteristic parameters of the catchment basin: types of cultivations, flows and precipitations. The main herbicides found in the stream of Fosse Rognon during our study were the atrazine (30–2450 ng/l), the simazine (10–1880 ng/l) and the isoproturon (10–1800 ng/l). The results, obtained from the stream, show that the contamination overstepped the application periods. The precipitations play a major part in the herbicide leaching after their application. In the groundwaters, the atrazine concentration (5–1700 ng/l) and the simazine concentration (5–1120 ng/l) were higher than those found in 1977, despite a reduction of the corn cultivated areas. The only degradation product of atrazine found in both the surface and the groundwaters was desethylatrazine (10–850 ng/l). It appears that the groundwaters were the main incoming sources of desethylatrazine to surface waters. The exportation balances by the stream of Fosse Rognon, expressed as a percentage of the applied amounts, were for atrazine, simazine and isoproturon, in 1992: 0.085, 0.18 and 0.035, and in 1993: 0.28, 0.3 and 0.083, respectively.

Behaviour and spatial and temporal variations of polychlorinated biphenyls and lindane in the urban atmosphere of the Paris area, France

Abstract This paper presents the results of a five year study (1986–1991) of the contamination of the Paris area atmosphere by polychlorinated biphenyls (PCBs) and lindane. The main processes affecting their behaviour and fate such as vapour/particle partitioning and washout are described and modelled. The spatial and temporal variations of the concentrations of the compounds are assessed. PCBs did not exhibit a clear seasonal cycle, whilst lindane showed systematically higher concentrations in Spring, reflecting the agricultural use of this pesticide. The mean annual concentration of lindane in the atmosphere was stable during the period of study. PCBs concentrations showed a twofold decrease since 1986, presumably in part because of the effectiveness of pollution prevention measures. Recent spatial variations in PCBs or lindane were not very important and the most recent concentrations recorded (2–6 ng m −3 for PCBs and 1.5 ngm −3 for lindane) were in line with levels commonly reported in the literature. PCBs as a whole were predominantly in the vapour phase (78% on top of the St Jacques Tower in 1989–1990). The amount associated with the particle phase was linked to temperature and increased during winter. The behaviour of individual components showed wide differences reflecting their varying physico-chemical properties: IUPAC no. 18 was not detectable in the particle phase whilst no. 180 was for 70% in the particle phase. Lindane was found only in the vapour phase. The overall washout ratio W (ng m −3 rain/ngm −3 air) was 34 × 10 3 for total PCBs and 79 × 10 3 for lindane. It varied between 21 × 10 3 for component IUPAC no. 28 to 235 × 10 3 for n 180. Dry deposition amounted to 35% of the total deposition for PCBs and 1 % for lindane. The associated deposition velocity for Aroclor 1254 was 0.12 cm s −1 .