Combining sequential extraction and 3D fluorescence to investigate the behavior of antibiotic and polycyclic aromatic hydrocarbons during solar drying of sewage sludge.

Solar drying and liming are commonly used for sludge treatment, but little is known about their efficiency on antibiotics and Polycyclic Aromatic Hydrocarbons (PAHs) removal. This study aimed to investigate the removal of antibiotics and PAHs during solar drying of Limed Sludge (LS) and Non-Limed Sludge (NLS). Thus, organic matter fractionation and 3D fluorescence were used to assess the accessibility and the complexity of organic matter. 2 experiments have been conducted using LS and NLS for 45 days of drying in a pilot scale tunnel. Physicochemical results indicated significant decrease of water content (90%) for both sludge samples within 15 days of drying. For both treatments, the removal of total organic carbon and total nitrogen was low and similar for both treatments. Through this study, it has been confirmed that liming and drying contributed to a strong modification of the organic matter quality with an increase of its accessibility. On the other hand, drying alone increased the less accessible compartments, while the presence of lime affected the interconnexion between the organic matter pools. 3D fluorescence confirmed the obtained results and indicated that LS leads to obtaining more simple molecules in the most accessible compartments, while NLS leads to obtaining more complex molecules in the less accessible compartments. In addition, solar radiations and leaching may contribute to the significant removal (p < 0.01) of roxithromycin, benzo(a)anthracene, chrysene, benzo[k]fluoranthene, benzo[a]pyrene, and benzo(g, h, i) perylene in the presence of lime. Furthermore, the evolution of organic matter pools in terms of accessibility and complexity may drive the bioavailability of these pollutants, leading to their significant removal.

Assessment of the genotoxicity of antibiotics and chromium in primary sludge and compost using Vicia faba micronucleus test.

The objective of this study was to investigate chemical, biological and eco-toxicological parameters of a compost produced through the co-composting of dewatered primary sludge (DPS) and date palm waste to evaluate in which extent it can exploited as a bio-fertilizer. DPS and date palm waste were co-composted in aerobic conditions for 210 days. Physico-chemical parameters were evaluated during composting (total organic carbon, total nitrogen, pH, available forms of phosphorus). Furthermore, heavy metals (Cd, Cu, Cr, Pb, Ni, Zn) and antibiotics (fluoroquinolones, macrolides and tetracyclines) content were analyzed in the DPS. To evaluate the genotoxicity of substrates, Vicia faba micronucleus test was carried out. Single and combined toxicities of a mixture of antibiotics (ciprofloxacin, enroflxacin, nalidixic acid, roxithromycin and sulfapyridin) and chromium (Cr2 (SO4)3 and K2Cr2O7) were examined. Although the final compost product showed a significant decrease of the genotoxicity, almost 50% of the micronucleus frequency still remained, which could be explained by the persistence of several recalcitrant compounds such as chromium and some antibiotics. Overall, the presence of antibiotics and chromium showed that some specific combination of contaminants represent an ecological risk for soil health and ecosystems even at environmentally negligible concentrations.

Fate of antibiotics present in a primary sludge of WWTP during their co-composting with palm wastes.

Antibiotics persistence in the primary sludge can contribute to the emergence of these molecules in the environment and limit the agricultural recycling of sludge without any preliminary treatment. Composting is a widely used process for recycling sludges and then can contribute to the antibiotics removal. However, little interest is actually given to the evaluation of the persistence of some antibiotics families after the sludge co-composting and more particularly to the final compost valorization. In this work, antibiotics concentrations of ßeta-lactams, Macrolides, Lincosamide, Tetracyclines, Sulfonamides and Fluoroquinolones were checked in the primary sludge of the wastewater treatment plants (WWTP) of Marrakesh (Morocco) before its co-composting. The results showed a final high amount of the fluoroquinolones family (4.21 and 2.92 µg/kg DM for Ciprofloxacin and Ofloxacin respectively) compared to the other studied families. To assess the fate of antibiotics, the primary sludge and palm waste were windrowed and composted during 120 days. The final compost showed a high level of organic matter decomposition (52%) and a C/N ratio of 12 which insure the compost quality. The assessment of antibiotics concentrations during co-composting showed that clarithromycin is more degraded particularly during the stabilization stage (43%), the degradation of lincomycin and tetracyclines is more significant during the maturation stage (36 and 75% respectively). Ampicillin and trimethoprim were degraded all along the process of co-composting (46 and 35% respectively). By the way, the persistence of the fluoroquinolones family was observed. This persistence could be a limiting key factor for the composted sludge valorization. So, more knowledge is needed to understand fluoroquinolones behavior and, then, to optimize their composting conditions.

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.

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.

Evaluation of the antibiotics effects on the physical and chemical parameters during the co-composting of sewage sludge with palm wastes in a bioreactor.

The objective of this study was to investigate thermal and physicochemical parameters of sewage sludge-palm waste mixtures contaminated by different families of antibiotics (tetracyclines, macrolides and fluoroquinolones) during co-composting. Sludge was spiked with chlortetracycline (CTC), oxytetracycline (OTC), roxithromycin (RXY), enrofloxacin (ENR) and ciprofloxacin (CIP). Antibiotics were spiked at a low level, medium level, high level and a control without antibiotics was conducted. The results showed that the organic matter degradation was delayed and the carbon/nitrogen (C/N) ratio was affected by an increase of the antibiotics concentration. The presence of antibiotics, especially at high level, delayed the coming of the temperature maxima, and disturbed the thermophilic phase. The calorific model showed that the heat release is affected during the thermophilic phase when high antibiotics concentrations were used. In addition, the microbiological approach showed that the adsorption of antibiotics on the rachis could be probably responsible of the fungi inhibition especially during the maturation phase. Therefore, the medium and high levels of antibiotics affected the thermal, physical and chemical parameters as well as the compost quality.

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. noltei 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 96 h. 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 6 h with a no observed effect concentration (NOEC) of 1 µg/L total mixture concentration. The lowest EQY effect concentration at 10% (EC10) (2 µg/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. noltei. 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.

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.

New insight into pesticide partition coefficient Kd for modelling pesticide fluvial transport: application to an agricultural catchment in south-western France.

Pesticides applied on crops are leached with rainfall to groundwater and surface water. They threat the aquatic environment and may render water unfit for human consumption. Pesticide partitioning is one of the pesticide fate processes in the environment that should be properly formalised in pesticide fate models. Based on the analysis of 7 pesticide molecules (alachlor, atrazine, atrazine's transformation product deethylatrazine or DEA, isoproturon, tebuconazole and trifluralin) sampled from July 2009 to October 2010 at the outlet of the river Save (south-western France), the objectives of this study were (1) to check which of the environmental factors (discharge, pH, concentrations of total suspended matter (TSM), dissolved organic carbon (DOC) and particulate organic carbon (POC) could control the pesticide sorption dynamic, and (2) to establish a relationship between environmental factors, the partition coefficient Kd and the octanol/water distribution coefficient Kow. The comparison of physico-chemical parameters values during low flow and high flow shows that discharge, TSM and POC are the factors most likely controlling the pesticide sorption processes in the Save river network, especially for lower values of TSM (below 13mgL(-1)). We therefore express Kd depending on the widely literature-related variable Kow and on the commonly simulated variable TSM concentration. The equation can be implemented in any model describing the fluvial transport and fate of pesticides in both dissolved and sorbed phases, thus, Kd becomes a variable in time and space. The Kd calculation method can be applied to a wide range of catchments and organic contaminants.

Occurrence of metolachlor and trifluralin losses in the Save river agricultural catchment during floods.

Rising pesticide levels in streams draining intensively managed agricultural land have a detrimental effect on aquatic ecosystems and render water unfit for human consumption. The Soil and Water Assessment Tool (SWAT) was applied to simulate daily pesticide transfer at the outlet from an agriculturally intensive catchment of 1110 km(2) (Save river, south-western France). SWAT reliably simulated both dissolved and sorbed metolachlor and trifluralin loads and concentrations at the catchment outlet from 1998 to 2009. On average, 17 kg of metolachlor and 1 kg of trifluralin were exported at outlet each year, with annual rainfall variations considered. Surface runoff was identified as the preferred pathway for pesticide transfer, related to the good correlation between suspended sediment exportation and pesticide, in both soluble and sorbed phases. Pesticide exportation rates at catchment outlet were less than 0.1% of the applied amount. At outlet, SWAT hindcasted that (i) 61% of metolachlor and 52% of trifluralin were exported during high flows and (ii) metolachlor and trifluralin concentrations exceeded European drinking water standards of 0.1 µg L(-1) for individual pesticides during 149 (3.6%) and 17 (0.4%) days of the 1998-2009 period respectively. SWAT was shown to be a promising tool for assessing large catchment river network pesticide contamination in the event of floods but further useful developments of pesticide transfers and partition coefficient processes would need to be investigated.

Can we predict community-wide effects of herbicides from toxicity tests on macrophyte species?

Macrophyte communities play an essential role in the way freshwater ecosystems function. It is thus of great concern to understand how environmental factors, especially anthropogenic ones, influence their composition and diversity. The aim of this study was to examine whether the effects of a herbicide mixture (50% atrazine, 35% isoproturon, 15% alachlor) on single macrophyte species can be used to predict its impact at a community level. In a first experiment we tested the sensitivity of six species (Azolla filiculoides, Ceratophyllum demersum, Elodea canadensis, Lemna minor, Myriophyllum spicatum and Vallisneria spiralis) grown separately and exposed to 0.6-600 µg L(-1) of the herbicide mixture. In a second experiment, conducted in microcosms, we tested the effects of herbicides on macrophyte assemblages composed of the same six species exposed to 0, 6 or 60 µg L(-1) of the herbicide mixture. Species grown separately exhibited growth inhibition at 60 and 600 µg L(-1). At 600 µg L(-1) the sensitivity differed significantly between species. V. spiralis was the most resistant species, C. demersum, M. spicatum and E. canadensis exhibited intermediate sensitivities, and A. filiculoides and L. minor were the most sensitive species. In microcosms, community biomass and Shannon evenness index were reduced after 8 weeks at 60 µg L(-1). Communities also exhibited changes in their composition: the relative and absolute abundance of C. demersum increased at 6 µg L(-1), while the relative abundance of V. spiralis increased at 60 µg L(-1). These results are in agreement with the individual responses of these species to the herbicides. It is therefore concluded that short-term effects of herbicides on simple macrophyte communities can be predicted from the sensitivity of individual species. However, further investigations are required to examine whether longer term effects can be predicted as well, especially in more complex communities.

Influence of in situ biological activity on the vertical profile of pre-emergence herbicides in sediment.

The in situ effect of biological activity on herbicide degradation was studied in sediment. Early diagenesis indicators of organic matter (OM) was selected to provide information on the presence and the kinetics of the various biotic and abiotic processes involved in the degradation of fresh organic matter, the vector of herbicides in sediment. Two tandem-coring samples were taken in the Malause reservoir, one in the hyperoxic zone (Tarn confluence, MT core) and the other in the central part, under the exclusive influence of the Garonne River (MG core), after having crossed a zone where the high intensity of abiotic processes is proven. At each site, analysis of the vertical profile of the herbicides was coupled with compounds associated with early diagenesis of OM. The MT core proved nearly seven times more contaminated than the MG core. DEA played a minor role in sediment contamination. Biological activity only seems to influence herbicide degradation indirectly. Neither oxygen concentration nor the level of labile carbon indicated any correlation between the consumption of fresh organic matter and substrate degradation. Herbicide transformation thus does not seem to depend on the consortia studied but on physicochemical parameters such as hydrolysis, leading to the long half-life of herbicides in sediment and hence their long-term presence in the aquatic environment.

Herbicide accumulation and evolution in reservoir sediments.

The aim of the present study was to understand the effect of reservoir configurations on sediment pesticide fate. Two dams were selected on the River Garonne, in southwest France: Carbonne and Golfech, both with reservoirs subject to accumulation of herbicide-contaminated sediment. They are situated upstream and downstream respectively of an agricultural and urban area: the Mid-Garonne. The results presented include pesticide concentrations and C/N ratios in the smaller sediment particles (<2 mm) and values of oxygenation and herbicide concentrations in the water. The dynamic behaviour of sediment in the reservoirs is discussed. The present study shows that the theoretical lifespan (weak remanence in vitro) and the results actually observed in the sediment are conflicting. Pesticide contamination in Carbonne indicates conservation, even accumulation, of herbicide molecules while in Golfech transformation processes clearly dominate. The hydromorphological position of Golfech reservoir, i.e. located at the junction of two rivers with contrasting hydrological regimes and very different oxygenation conditions, leads to accelerated pesticide desorption or degradation. Unfortunately, this configuration is rare.

Multi-residues analysis of pre-emergence herbicides in fluvial sediments: application to the mid-Garonne River.

Contamination of man and ecosystems by pesticides has become a major environmental concern. Whereas many studies exist on contamination from agriculture, the effects of urban sources are usually omitted. Fluvial sediment is a complex matrix of pollutants but little is known of its recent herbicide content. This study proposes a method for a fast and reliable analysis of herbicides by employing the accelerated solvent extractor (ASE). The aim of the study is to show the impact of a major town (Toulouse) on the herbicide content in the river. In this study, three herbicide families (i.e.s-triazine, substituted ureas and anilides) were analysed in fluvial sediment fractions at 11 sampling sites along the mid-Garonne River and its tributaries. River water contamination by herbicides is minor, except for at three sites located in urban areas. Among the herbicidal families studied, urban and suburban areas are distinguished from rural areas and were found to be the most contaminated sites during the study period, a winter low-water event. The herbicide content of the coarse sediment fractions is about one third of that found in the fine fractions and usually ignored. The distribution of pesticide concentrations across the whole range of particle sizes was investigated to clarify the role of plant remains on the significant accumulation in the coarse fractions.

Sequential extraction of heavy metals during composting of sewage sludge.

The major limitation of soil application of sewage sludge compost is the total heavy metal contents and their bioavailability to the soil-plant system. This study was conducted to determine the heavy metal speciation and the influence of changing the physico-chemical properties of the medium in the course of composting on the concentrations, bioavailability or chemical forms of Cu, Zn, Pb and Ni in sewage sludge. Principal physical and chemical properties and FTIR spectroscopical characterization of sludge compost during treatment show the stability and maturity of end product. The total metal contents in the final compost were much lower than the limit values of composts to be used as good soil fertilizer. Furthermore, it was observed by using a sequential extraction procedure in sludge compost at different steps of treatment, that a large proportion of the heavy metals were associated to the residual fraction (70-80%) and more resistant fractions to extraction X-NaOH, X-EDTA, X-HNO3 (12-29%). Less than 2% of metals bound to bioavailable fractions X-(KNO3+H2O). Heavy metal distribution and bioavailability show some changes during composting depending on the metal itself and the physico-chemical properties of the medium. Bioavailable fractions of all elements tend to decrease except Ni-H2O. Zn and mainly Cu present more affinity to organic and carbonate fractions. In contrast, Pb is usually preferentially bound to sulfide forms X-HNO3. Nickel shows a significant decrease of organic form. Significant degrees of correlation were found between heavy metal fractions and changes of some selected variables (e.g. pH, ash, organic matter, humic substance) during the course of composting. Mobile fractions of metals are poorly predictable from the total content. The R2 value was significantly increased by the inclusion of other variables such as the amount of organic matter (OM) and pH.