Georges Merlina

Mutagenic impact on fish of runoff events in agricultural areas in south-west France.

When heavy rainfall follows herbicide application, the intense surface runoff causes stream water contamination. Aquatic organisms are then briefly exposed to a complex mixture of contaminants. The aim of the present study is to investigate the genotoxic impact of such events on fish. A model fish, the Crucian carp (Carassius carassius) was exposed in controlled conditions, for 4 days, to water sampled daily in the Save River (France). The watershed of this stream is representative of agricultural areas in south-west France. Three hydrological conditions were compared: basal flow, winter flood, and spring flood. Chemical analysis of the water samples confirmed the higher contamination of the spring flood water, mainly explained by a peak of metolachlor. Genotoxicity was evaluated by micronucleus (MN) test and comet assay in peripheral erythrocytes. A significant increase in DNA breakdowns compared to controls was detected by the comet assay for all conditions. Exposure to spring flood water resulted in the highest damage induction. Moreover, induced chromosomal damage was only detected in this condition. In addition, fish were exposed, for 4 days, to an experimental mixture of 5 herbicides representative of the spring flood water contamination. Fish exhibited moderate DNA damage induction and no significant chromosomal damage. The mutagenicity induced by field-collected water is then suspected to be the result of numerous interactions between contaminants themselves and environmental factors, stressing the use of realistic exposure conditions. The results revealed a mutagenic impact of water contamination during the spring flood, emphasizing the need to consider these transient events in water quality monitoring programs.

Evaluation of a TiO2 photocatalysis treatment on nitrophenols and nitramines contaminated plant wastewaters by solid-phase extraction coupled with ESI HPLC–MS

Nitration reactions of aromatic compounds are commonly involved in different industrial processes for pharmaceutical, pesticide or military uses. For many years, most of the manufacturing sites used lagooning systems to treat their process effluents. In view of a photocatalytic degradation assay, the wastewater of a lagoon was investigated by using HPLC coupled with mass spectrometry. The wastewater was highly concentrated in RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine), HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine) and two herbicides Dinoterb (2-tert-butyl-4,6-dinitrophenol) and Dinoseb (2-sec-butyl-4,6-dinitrophenol). First of all, an analytical method using solid-phase extraction (SPE) combined with HPLC ESI MS/MS was put in work for identification and titration of RDX, HMX and the two dinitrophenols in a complex natural matrix. Then, the UV/TiO2 treatment was investigated for pollutants removal. Dinitrophenolic compounds were significantly degraded after a 8-h-exposition of the wastewater/TiO2 suspension, whereas RDX and HMX were poorly affected.

Assessment of average exposure to organochlorine pesticides in southern Togo from water, maize (Zea mays) and cowpea (Vigna unguiculata)

Drinking water, cowpea and maize grains were sampled in some potentially exposed agro-ecological areas in Togo and analysed for their contamination by some common organochlorine pesticides. A total of 19 organochlorine pesticides were investigated in ten subsamples of maize, ten subsamples of cowpea and nine subsamples of drinking water. Analytical methods included solvent extraction of the pesticide residues and their subsequent quantification using gas chromatography-mass spectrometry (GC/MS). Estimated daily intakes (EDIs) of pesticides were also determined. Pesticides residues in drinking water (0.04–0.40 µg l−1) were higher than the maximum residue limit (MRL) (0.03 µg l−1) set by the World Health Organization (WHO). Dieldrin, endrin, heptachlor epoxide and endosulfan levels (13.16–98.79 µg kg−1) in cowpea grains exceeded MRLs applied in France (10–50 µg kg−1). Contaminants’ levels in maize grains (0.53–65.70 µg kg−1) were below the MRLs (20–100 µg kg−1) set by the Food and Agriculture Organization (FAO) and the WHO. EDIs of the tested pesticides ranged from 0.02% to 162.07% of the acceptable daily intakes (ADIs). Population exposure levels of dieldrin and heptachlor epoxide were higher than the FAO/WHO standards. A comprehensive national monitoring programme on organochlorine pesticides should be undertaken to include such other relevant sources like meat, fish, eggs and milk.

Evaluation of an aerobic treatment for olive mill wastewater detoxification

Olive mill wastewater (OMWW) is a by-product of the olive oil extraction industry. Its dumping creates severe environmental problems in the Mediterranean countries. The phytoxicity of OMWW is due to the phenolic substances and is evaluated through a genotoxicity method. An aerobic treatment of OMWW was conducted during 45 days. Different concentrations of raw and treated OMWW were tested using the Vicia faba micronuclei test. Results showed that raw OMWW induced significant micronuclei formation at 10% of OMWW dilution. At 20% of dilution, no mitosis was recorded. The 45 days aerobic treatment OMWW showed an important decrease in the genotoxicity and also in the toxicity that was observed at 10% and 20% OMWW dilution. This could be correlated with the biodegradation of 76% of the total phenols. Indeed, qualitative analysis by high performance liquid chromatography shows the disappearance of the majority of phenolic compounds after 45 days of treatment. This study was completed by an agricultural test with V. faba plant. Data showed significant growth yield of 36.3% and 29.9% after being irrigated with 5 and 10 t/ha, respectively. These results supported the positive role of aerobic treatment on OMWW and their capacity to ameliorate the agronomic potential of these effluents.

Toxicity effects of an environmental realistic herbicide mixture on the seagrass Zostera noltei

Worldwide seagrass declines have been observed due to multiple stressors. One of them is the mixture of pesticides used in intensive agriculture and boat antifouling paints in coastal areas. Effects of mixture toxicity are complex and poorly understood. However, consideration of mixture toxicity is more realistic and ecologically relevant for environmental risk assessment (ERA). The first aim of this study was to determine short-term effects of realistic herbicide mixture exposure on physiological endpoints of Zostera noltei. The second aim was to assess the environmental risks of this mixture, by comparing the results to previously published data. Z.xa0noltei was exposed to a mixture of four herbicides: atrazine, diuron, irgarol and S-metolachlor, simulating the composition of typical cocktail of contaminants in the Arcachon bay (Atlantic coast, France). Three stress biomarkers were measured: enzymatic activity of glutathione reductase, effective quantum yield (EQY) and photosynthetic pigment composition after 6, 24 and 96xa0h. Short term exposure to realistic herbicide mixtures affected EQY, with almost 100% inhibition for the two highest concentrations, and photosynthetic pigments. Effect on pigment composition was detected after 6xa0h with a no observed effect concentration (NOEC) of 1xa0μg/L total mixture concentration. The lowest EQY effect concentration at 10% (EC10) (2xa0μg/L) and pigment composition NOEC with an assessment factor of 10 were above the maximal field concentrations along the French Atlantic coast, suggesting that there are no potential short term adverse effects of this particular mixture on Z.xa0noltei. However, chronic effects on photosynthesis may lead to reduced energy reserves, which could thus lead to effects at whole plant and population level. Understanding the consequences of chemical mixtures could help to improve ERA and enhance management strategies to prevent further declines of seagrass meadows worldwide.

Chemical Composition and Insecticidal Activity of Ocimum canum Essential Oil Against Coffee Berry Borer, Hypothenemus hampei (Ferrari) (Coleoptera: Scolytidae)

Abstract The chemical compositions of the essential oils of Ocimum canum Sims (Lamiaceae) areal part cultivated in Togo were investigated by GC-MS and tested for possible insecticidal activity against the coffee berry borer, Hypothenemus hampei (Ferrari) (Coleoptera: Scolytinae) under laboratory. Eighteen constituents (98.5 % of the total oil) were identified in the volatile oil of O. canum leaf. The main constituents found in the oil were terpineol-4 (34.7 %), linalool (22.7 %), λ-terpinene (7.3 %), trans-thujan-4-ol (5.9 %), trans-α-bergamotene (4.9 %) and caryophyllene (4.6 %). Other components were also identified by at minor concentrations ranging from 0.12 % (Thymol) to 2.7 % (Limonene). In the insecticidal activity test, crude essential oil of O. canum emulsions of exhibited adulticidal activity against coffee berry borer and response was being dose-related. The LD50 were 320 ppm for O. canum essential oil and 450 ppm for endosulfan and the conventional insecticide used as standard, respectively. The results indicate that the O. canum essential oil has a potential insecticidal activity and can be used as active ingredient in natural and sustainable pesticide within an Integrated Pest Management approach to combat the coffee berry borer.

Chemical Composition and Insecticidal Activity of Aeollanthus pubescens Essential Oil Against Coffee Berry Borer (Hypothenemus hampei Ferrari) (Coleoptera: Scolytidae)

Abstract Essential oil extracted from aerial parts of Aeollanthus pubescens was analysed for its chemical composition and investigated for possible insecticidal activity against Hypothenemus hampei (Ferrari), the major pest of coffee throughout the world. The GC and GC-MS analyses indicated that linalool (56.4 %) and fenchone (28.6 %) were the main components of the tested A. pubescens oil sample. Emulsions of crude essential oil of A. pubescens exhibited adulticidal activity against coffee berry borer and response was being dose-related. The LD50 were respectively 220 ppm for A. pubescens essential oil and 450 ppm for endosulfan, the conventional insecticide used as standard. These preliminary findings indicate that the tested volatile oil have a potential insecticidal activity and can be used as active ingredient in natural and sustainable pesticide within an Integrated Pest Management approach to combat coffee berry borer.

Identification and assay of microbial fatty acids during co-composting of active sewage sludge with palm waste by TMAH-thermochemolysis coupled with GC-MS

The fatty acids of two composts of active sludge with palm tree waste were investigated by thermochemolysis coupled to gas chromatography-mass spectrometry. This method (tetramethylammonium hydroxide-pyrolysis-gas chromatography-mass spectrometry) allowed the direct determination of total fatty acids (analysed as fatty acid methyl esters: FAMEs) present in the organic matter of the samples without any separation procedures. Mixture A was 1/3 sludge+2/3 palm waste and mixture B was 1/2 sludge+1/2 palm waste. The level of FAMEs rose by 8.4–33.3% and 10.8–13.4% in mixtures A and B, respectively, after 6 months of co-composting. Branched FAMEs of bacterial origin (iC15:0) rose during the thermophilic phase, in mixture A the aC17:0/aC15:0 ratio increased during the co-composting process, also in mixture B the aC16:0/C16:0 ratio rose but only during the thermophilic phase. All the FAMEs identified showed a drop at the end of co-composting except for C18:0 and C16:0. The stabilisation phase was characterised by a significant rise in the length of the aliphatic chains; the carbon preference index thus increased at the end of the composting process, indicating that the final product was proportionally richer in fatty acids of plant origin.

Human and veterinary antibiotics during composting of sludge or manure: Global perspectives on persistence, degradation, and resistance genes

Wastewater treatment plant effluent, sludge and manure are the main sources of contamination by antibiotics in the whole environment compartments (soil, sediment, surface and underground water). One of the major consequences of the antibiotics discharge into the environment could be the prevalence of a bacterial resistance to antibiotic. In this review, four groups of antibiotics (Tetracyclines, Fluoroquinolones, Macrolides and Sulfonamides) were focused for the background on their wide spread occurrence in sludge and manure and for their effects on several target and non-target species. The antibiotics concentrations range between 1 and 136,000 μg kg-1 of dry matter in sludge and manure, representing a potential risk for the human health and the environment. Composting of sludge or manure is a well-known and used organic matter stabilization technology, which could be effective in reducing the antibiotics levels as well as the antibiotic resistance genes. During sludge or manure composting, the antibiotics removals range between 17-100%. The deduced calculated half-lives range between 1-105 days for most of the studied antibiotics. Nevertheless, these removals are often based on the measurement of concentration without considering the matter removal (lack of matter balance) and very few studies are emphasized on the removal mechanisms (biotic/abiotic, bound residues formation) and the potential presence of more or less hazardous transformation products. The results from the few studies on the fate of the antibiotic resistance genes during sludge or manure composting are still inconsistent showing either decrease or increase of their concentration in the final product. Whether for antibiotic or antibiotic resistance genes, additional researches are needed, gathering chemical, microbiological and toxicological data to better understand the implied removal mechanisms (chemical, physical and biological), the interactions between both components and the environmental matrices (organic, inorganic bearing phases) and how composting process could be optimized to reduce the discharge of antibiotics and antibiotic resistance genes into the environment.

A pressurized liquid extraction approach followed by standard addition method and UPLC-MS/MS for a fast multiclass determination of antibiotics in a complex matrix

In this work a fast analytical method for the determination of macrolides, tetracyclines and fluoroquinolones in a compost originating from a mixture of sewage sludge, palm waste and grass was developed by ultra-high performance liquid chromatography coupled to mass spectrometry (U-HPLC/MS). Antibiotics were extracted from compost by using the accelerated solvent extraction (ASE). The chromatographic separation was carried out on a T3 Cortecs C18 column using a mobile phase gradient mixture of water acidified with 1% of formic acid and acetonitrile. Recoveries of 24-30%, 53-93%, 33-57%, 69-135% and 100-171% were obtained for roxithromycin (ROX), chlortetracycline (CTC), oxytetracycline (OTC), enrofloxacin (ENR) and ciprofloxacin (CIP), respectively. As the most part of antibiotics showed significant matrix effect (ME), the method was validated using the standard addition method (SAM) to correct the observed ME. Instrumental variation, of LC/MS system, showed that 93.75% of the relative standard deviation (RSD %) are below 15%, although the organic load of extracts. This analytical method was applied to assess the fate of antibiotics during composting. Two composting experiments were conducted separately after spiking sludge at 2 different concentrations levels. The resulting elimination rates were of 52-76, 69-100, 100 and 24-50% for ROX, CTC, OTC and CIP, respectively. These results suggest that composting process contributes to the removal of residuals concentrations of macrolides and tetracyclines while the fluoroquinolones persist in the final compost product.