Polar organic chemical integrative samplers as an effective tool for chemical monitoring of surface waters - Results from one-year monitoring in France.

In an effort to support European Union Water Framework Directive goals, we have set up a national demonstrator project to identify the advantages and limitations of passive samplers for regulatory monitoring of polar contaminants in surface waters. Here we carried out successive 14 day-deployments of polar organic chemical integrative samplers (POCIS) for one year at three sites. In parallel, we used the passive sampler deployment/retrieval operations to collect spot water samples for comparative analysis. We observed that frequency of quantification was significantly higher in POCIS than spot samples for 29 contaminants, similar for 15, and lower for one, because POCIS lowered the limits of quantification for most contaminants (median value factor of 11). We built a database of sampling rates (Rs) according to quality indices to convert concentrations in POCIS to concentrations in water (23 contaminants with a high-quality median Rs value, 20 with an approximate Rs and two with no usable Rs). Several phenomena were observed over one-year monitoring period. For example, after a flood episode, dilution phenomenon in rivers is correctly observed by using POCIS sampling whereas significant concentration increased due to soil leaching is observed with both passive and spot sampling. Cases of episodic contamination that were missed by spot sampling were observed with POCIS as it was able to capture contamination of short duration but sufficient intensity. Contamination by pharmaceuticals was found to come from wastewater treatment plant discharges and showed relatively little variation over the course of the year in both POCIS and spot samples. POCIS enables more reliable annual monitoring of pesticide and pharmaceutical contamination than spot sampling. Furthermore, POCIS also improves the environmental quality standards based assessment of chemical status and on annual average concentrations compared to spot sampling. This study demonstrates the value and practicability of POCIS-based chemical monitoring for use in regulatory control networks.

Sense of coherence, self-esteem, and health locus of control in subjects with type 1 diabetes mellitus with/without satisfactory metabolic control.

BACKGROUND: Despite intensive training, a few individuals with Type 1 diabetes mellitus (T1DM) fail to reach the desired metabolic targets. AIM: To evaluate the association between disease-related emotional and cognitive aspects and metabolic control in subjects with T1DM. SUBJECTS AND METHODS: Health locus of control (HLOC), sense of coherence (SOC), and self-esteem were assessed in T1DM subjects using validated questionnaires. Sixty-seven consecutive subjects who did not attain the desired HbA1c target (mean HbA1c, 8.3% [67 mmol/mol]) were compared with 30 cases in satisfactory metabolic control (HbA1c levels <7%-53 mmol/mol). RESULTS: In the overall population, SOC was negatively associated with BMI and average HbA1c, as was the association of self-esteem with HbA1c. Subjects attaining the desired metabolic target were characterized by higher SOC scores, higher Internal HLOC and prevalent Internal vs. Powerful-others HLOC. Compared to subjects in good metabolic control, subjects with unsatisfactory control had lower scores of SOC, Internal HLOC and Self-esteem, with no difference in Powerful others, or Chance HLOC. In the same group, SOC in the upper tertile was significantly associated with self-esteem (OR 1.35; 95% CI 1.08-1.69) and PHLOC (OR 1.24; 95% CI 1.03-1.49), after adjustment for age, sex, educational level, and comorbidities. CONCLUSIONS: Patients who fail to reach a satisfactory metabolic control tend to rely on significant others, trusting in the physicians' skills or on the efficiency of the health-care system. Strategies aimed at increasing self-efficacy and SOC, based on personal ability, are eagerly awaited to help patients improve diabetes care.

Field application of passive SBSE for the monitoring of pesticides in surface waters.

Spot sampling lacks representativeness for monitoring organic contaminants in most surface waters. Passive sampling has emerged as a cost-effective complementary sampling technique. We recently developed passive stir bar sorptive extraction (passive SBSE), with Twister from Gerstel, for monitoring moderately hydrophilic to hydrophobic pesticides (2.18 < log K ow < 5.11) in surface water. The aims of the present study were to assess this new passive sampler for the determination of representative average concentrations and to evaluate the contamination levels of two French rivers. Passive SBSE was evaluated for the monitoring of 16 pesticides in two rivers located in a small vineyard watershed during two 1-month field campaigns in spring 2010 and spring 2011. Passive SBSE was applied for periods of 1 or 2 weeks during the field campaigns and compared with spot sampling and weekly average automated sampling. The results showed that passive SBSE could achieve better time-representativeness than spot sampling and lower limits of quantification than automated sampling coupled with analytical SBSE for the pesticides studied. Finally, passive SBSE proved useful for revealing spatial and temporal variations in pesticide contamination of both rivers and the impact of rainfall and runoff on the river water quality.

Genetic and physiological responses of three freshwater diatoms to realistic diuron exposures.

This study examined the effects of diuron on strains of three major freshwater diatom species, Eolimna minima, Nitzschia palea and Planothidium lanceolatum. These species are frequently recorded in the Morcille River, where diuron runs off during phytosanitary treatments of the vineyards around. Here, there were three diatom exposure groups for each species: 0, 1 and 10 µg/L diuron during a 14-day laboratory assessment. Diuron water concentration, cell number, photosynthetic activity and gene expression were assessed at 6 h and 2, 7 and 14 days after contamination. Diuron exposure altered photosynthetic activity in that the optimal quantum yield of photosystem II (PSII) decreased between 40 and 50% and, for P. lanceolatum at 10 µg/L, there was complete inhibition. Genetic responses indicated diuron effects on both photosystem II and mitochondrial metabolism in all three species at both diuron exposure levels. Thus, analysis of the expression of psaA, d1, cox1, nad5 and 12s could be an early biomarker to detect pesticide pollution. Overall, this study revealed differences in diuron sensitivity among the three species: E. minima and N. palea appeared to be more tolerant than P. lanceolatum. These results suggest that the development of molecular tools, and more precisely of biomarkers, will aid in early assessment of contamination and water quality.

Risk assessment of herbicides and booster biocides along estuarine continuums in the Bay of Vilaine area (Brittany, France).

A 2-year study was implemented to characterize the contamination of estuarine continuums in the Bay of Vilaine area (NW Atlantic Coast, Southern Brittany, France) by 30 pesticide and biocide active substances and metabolites. Among these, 11 triazines (ametryn, atrazine, desethylatrazine, desethylterbuthylazine, desisopropyl atrazine, Irgarol 1051, prometryn, propazine, simazine, terbuthylazine, and terbutryn), 10 phenylureas (chlortoluron, diuron, 1-(3,4-dichlorophenyl)-3-methylurea, fenuron, isoproturon, 1-(4-isopropylphenyl)-3-methylurea, 1-(4-isopropylphenyl)-urea, linuron, metoxuron, and monuron), and 4 chloroacetanilides (acetochlor, alachlor, metolachlor, and metazachlor) were detected at least once. The objectives were to assess the corresponding risk for aquatic primary producers and to provide exposure information for connected studies on the responses of biological parameters in invertebrate sentinel species. The risk associated with contaminants was assessed using risk quotients based on the comparison of measured concentrations with original species sensitivity distribution-derived hazardous concentration values. For EU Water Framework Directive priority substances, results of monitoring were also compared with regulatory Environmental Quality Standards. The highest residue concentrations and risks for primary producers were recorded for diuron and Irgarol 1051 in Arzal reservoir, close to a marina. Diuron was present during almost the all survey periods, whereas Irgarol 1051 exhibited a clear seasonal pattern, with highest concentrations recorded in June and July. These results suggest that the use of antifouling biocides is responsible for a major part of the contamination of the lower part of the Vilaine River course for Irgarol 1051. For diuron, agricultural sources may also be involved. The presence of isoproturon and chloroacetanilide herbicides on some dates indicated a significant contribution of the use of plant protection products in agriculture to the contamination of Vilaine River. Concentration levels and associated risk were always lower in estuarine sites than in the reservoir, suggesting that Arzal dam reduces downstream transfer of contaminants and favors their degradation in the freshwater part of the estuary. Results of the additional monitoring of two tidal streams located downstream of Arzal dam suggested that, although some compounds may be transferred to the estuary, their impact was probably very low. Dilution by marine water associated with tidal current was also a major factor of concentration reduction. It is concluded that the highest risks associated to herbicides and booster biocides concerned the freshwater part of the estuary and that its brackish/saltwater part was exposed to a moderate risk, although some substances may sometimes exhibit high concentration but mainly at low tide and on an irregular basis.

Linking diatom community structure to pesticide input as evaluated through a spatial contamination potential (Phytopixal): a case study in the Neste river system (South-West France).

A large-scale field survey was undertaken in the Neste system (South-West France) to investigate the impact of pesticide inputs on the structure of riverine benthic diatom communities. A total of 18 sites in the "Coteaux de Gascogne" study area were sampled during periods of pesticide use over two consecutive years (2005-2006). The typology of the diatoms collected was determined using artificial neural networks generating patterns in diatom community composition that indicated the species influenced by pesticide inputs, combined with organic pollution. Small, pioneer species of the Achnanthales group were more frequent in the pesticide-contaminated assemblages, whereas slower colonizers were more often found in the sites where disturbance was lower. The Phytopixal approach, a means to assess the spatial contamination potential, provided valuable information about pesticide exposure and was a successful means of discriminating diatom assemblages, suggesting that a global estimate of pesticide pollution risk, although rough, would be more appropriate and more representative than sporadic pesticide analyses.

Sensitivity of freshwater periphytic diatoms to agricultural herbicides.

The biomonitoring of pesticide pollution in streams and rivers using algae such as diatoms remains difficult. The responses of diatom communities to toxic stress in stream water are disturbed by the variations of environmental parameters. In this study, periphytic algae collected in situ were exposed under controlled conditions to two major herbicides used in French agriculture (isoproturon and s-metolachlor). Three exposure regimes were tested: 5 and 30 microg L(-1) for 6 days and 30 microg L(-1) for 3 days followed by a recovery period of 3 days. The algal biomasses were assessed from pigment concentrations (chlorophyll a and c) and from live cell density. The highest concentration (30 microg L(-1)) of isoproturon inhibited the biomass increase statistically significantly. In periphyton exposed to 5 and 30 microg L(-1) of s-metolachlor, chlorophyll c concentration and live cell density were also statistically significantly lower than in the control. Periphyton left to recover after reduced exposure duration (3 days) showed higher growth rates after treatment with s-metolachlor than with isoproturon. Taxonomic identifications showed that species like Melosira varians, Nitzschia dissipata and Cocconeis placentula were not affected by the herbicide exposure. Other species like Eolimna minima and Navicula reichardtiana were more sensitive. Studying diatoms according to their trophic mode showed that facultative heterotroph species were statistically significantly favoured by isoproturon exposure at the highest concentration. Results obtained with s-metolachlor exposure showed a disturbance of cell multiplication rather than that of photosynthesis. These results suggest that photosynthesis inhibitors like isoproturon favour species able to survive when the autotroph mode is inhibited.

Investigation of the matrix effects on a HPLC-ESI-MS/MS method and application for monitoring triazine, phenylurea and chloroacetanilide concentrations in fresh and estuarine waters.

In this work, the effects of matrix interferences on the analytical performance of a new multiresidue method based on off-line solid phase extraction followed by reversed-phase liquid chromatographic separation and electrospray triple quadrupole mass spectrometric detection were investigated. This technique allows the simultaneous determination of 30 triazines, phenylureas and chloroacetanilides, extracted from freshwaters, in 40 minutes. Quantifications were performed with the use of appropriate internal standards (i.e. atrazine D5, diuron D6 and metolachlor D6). The limits of quantification were from 1 to 32 ng L(-1) for the triazines, from 5 to 59 ng L(-1) for the phenylureas and from 13 to 54 ng L(-1) for the chloroacetanilides. The matrix effects were studied by spiking various waters (i.e. tap, river, pond and sea waters) with the chemicals of interest. The results showed that the samples with the highest conductivity (i.e. seawater) and the most abundant dissolved organic matter content (i.e. pond water) exhibited important matrix effects with signal suppressions and high imprecision, respectively. These matrix effects were strongly minimized by performing appropriate internal standardizations. Afterward, this analytical method was applied for analyzing environmental samples from either river or estuarine waters and for monitoring herbicide input in a freshwater-seawater interface.

Effects of crude oil on phospholipid fatty acid compositions of marine hydrocarbon degraders: estimation of the bacterial membrane fluidity.

In this study, we investigated, in vitro, the effects of petroleum hydrocarbons on the phospholipid ester-linked fatty acid composition of Corynebacterium sp. Strain 8. The usual ratio of monounsaturated fatty acids E/Z (or trans/cis) was calculated. This ratio led to unexpected results because we found similar values for growths on either a hydrophobic substrate (crude oil) or a soluble carbon source (rich medium). The use of such an indicator seemed limited for monitoring an environmental stress, so we proposed an index based on the homeoviscous adaptation theory. A membrane viscosity index was defined and applied to Corynebacterium sp. Strain 8 (in vitro growth) and to a sedimentary community (in situ experiment). The results allowed us to estimate the membrane fluidity of both an isolated strain and a bacterial community in accordance with the medium hydrophobicity.