Leaching and degradation of S-Metolachlor in undisturbed soil cores amended with organic wastes.

Organic waste (OW) reuse in agriculture is a common practice fostered by benefits in terms of waste recycling and crop production. However, OW amendments potentially affect the fate of pesticide spread on fields to protect the crops from pests and weeds. The influence of OW on the sorption, degradation, and leaching of pesticides is generally studied for each mechanism separately under artificial laboratory conditions. Our study aims at evaluating the balance of these mechanisms under more realistic conditions to clarify the influence of three common OW amendments on the fate, in soil, of the widely used herbicide S-Metolachlor. We performed leaching experiments in large undisturbed soil cores amended with raw sewage sludge, composted sludge, and digested pig slurry (digestate), respectively. We monitored S-Metolachlor and its two main metabolites MET-OA and MET-ESA in the leachates during a succession of 10 rainfall events over 126 days. We also quantified the remaining S-Metolachlor and metabolites in the soil at the end of the experiments. S-Metolachlor leaching didn't exceed 0.1% of the applied dose with or without OW amendment. Despite a soil organic carbon increase of 3 to 32%, OW amendments did not significantly affect the amount of S-Metolachlor that leached through the soil (0.01 to 0.1%) nor its transformation rate (6.0 to 8.6%). However, it affected the degradation pathways with an increase of MET-OA relative to MET-ESA formed after OW amendment (28 to 54%) compared to the controls (8%). Concentration of S-Metolachlor and metabolites in the leachates of all treatments greatly exceeded the regulatory limit for groundwater intended for human consumption in Europe. These high concentrations were probably the consequence of preferential macropore flow. Colloids had comparable levels in the leachates after S-Metolachlor application. Dissolved organic carbon was also comparable in the controls, digestate, and sludge treatments but was 65% higher in the compost-amended cores. These results, along with a great variability among replicates inherent to experiments performed under realistic conditions, partly explain the limited impact of OW on the transport of S-Metolachlor.

Fate and impacts of pharmaceuticals and personal care products after repeated applications of organic waste products in long-term field experiments.

Recycling organic waste products in agriculture is a potential route for the dispersion of pharmaceutical residues in the environment. In this study, the concentrations of thirteen pharmaceuticals and the personal care product triclosan (PPCPs) were determined in different environmental matrices from long-term experimental fields amended with different organic waste products (OWPs), including sludge, composted sludge with green wastes, livestock effluents and composted urban wastes applied at usual agricultural rates. PPCP concentrations were different in OWPs, varying from a few micrograms to milligrams per kilogram dry matter or per litre for slurry. OWPs from sludge or livestock effluents primarily contained antibiotics, whereas composted urban wastes primarily contained anti-inflammatory compounds. PPCP contents in soils amended for several years were less than a few micrograms per kilogram. The most persistent compounds (fluoroquinolones, carbamazepine) were quantified or detected in soils amended with sludge or composted sludge. In soils amended with composted municipal solid waste, carbamazepine was quantified, and fluoroquinolones, ibuprofen and diclofenac were sometimes detected. The small increases in fluoroquinolones and carbamazepine in soils after individual OWP applications were consistent with the fluxes from the applied OWP. The measured concentrations of pharmaceuticals in soil after several successive OWP applications were lower than the predicted concentrations because of degradation, strong sorption to soil constituents and/or leaching. Dissipation half-lives (DT50) were approximately 750-2500, 900 and <300days for fluoroquinolones, carbamazepine and ibuprofen, respectively, in temperate soils and <350 and <80days for fluoroquinolones and doxycycline, respectively, in tropical soils. Detection frequencies in soil leachates were very low (below 7%), and concentrations ranged from the limits of detection (0.002-0.03µg/L) and exceptionally to 0.27µg/L. The most frequently detected pharmaceuticals were carbamazepine and ibuprofen. Based on the risk quotient, the estimated ecotoxicological risks for different soil organisms were low.

Transport of organic contaminants in subsoil horizons and effects of dissolved organic matter related to organic waste recycling practices.

Compost amendment on agricultural soil is a current practice to compensate the loss of organic matter. As a consequence, dissolved organic carbon concentration in soil leachates can be increased and potentially modify the transport of other solutes. This study aims to characterize the processes controlling the mobility of dissolved organic matter (DOM) in deep soil layers and their potential impacts on the leaching of organic contaminants (pesticides and pharmaceutical compounds) potentially present in cultivated soils receiving organic waste composts. We sampled undisturbed soil cores in the illuviated horizon (60-90 cm depth) of an Albeluvisol. Percolation experiments were made in presence and absence of DOM with two different pesticides, isoproturon and epoxiconazole, and two pharmaceutical compounds, ibuprofen and sulfamethoxazole. Two types of DOM were extracted from two different soil surface horizons: one sampled in a plot receiving a co-compost of green wastes and sewage sludge applied once every 2 years since 1998 and one sampled in an unamended plot. Results show that DOM behaved as a highly reactive solute, which was continuously generated within the soil columns during flow and increased after flow interruption. DOM significantly increased the mobility of bromide and all pollutants, but the effects differed according the hydrophobic and the ionic character of the molecules. However, no clear effects of the origin of DOM on the mobility of the different contaminants were observed.

Multi-residue analysis of pharmaceuticals in aqueous environmental samples by online solid-phase extraction-ultra-high-performance liquid chromatography-tandem mass spectrometry: optimisation and matrix effects reduction by quick, easy, cheap, effective, rugged and safe extraction.

The aim of this study was to develop and optimise an analytical method for the quantification of a bactericide and 13 pharmaceutical products, including 8 antibiotics (fluoroquinolones, tetracyclines, sulfonamides, macrolide), in various aqueous environmental samples: soil water and aqueous fractions of pig slurry, digested pig slurry and sewage sludge. The analysis was performed by online solid-phase extraction coupled to ultra-high performance liquid chromatography with tandem mass spectrometry (online SPE-UHPLC-MS-MS). The main challenge was to minimize the matrix effects observed in mass spectrometry, mostly due to ion suppression. They depended on the dissolved organic carbon (DOC) content and its origin, and ranged between -22% and +20% and between -38% and -93% of the signal obtained without matrix, in soil water and slurry supernatant, respectively. The very variable levels of these matrix effects suggested DOC content cut-offs above which sample purification was required. These cut-offs depended on compounds, with concentrations ranging from 30 to 290mgC/L for antibiotics (except tylosine) up to 600-6400mgC/L for the most apolar compounds. A modified Quick, Easy, Cheap, Effective, Rugged and Safe (QuEChERS) extraction procedure was therefore optimised using an experimental design methodology, in order to purify samples with high DOC contents. Its performance led to a compromise, allowing fluoroquinolone and tetracycline analysis. The QuEChERS extraction salts consisted therefore of sodium acetate, sodium sulfate instead of magnesium sulfate, and sodium ethylenediaminetetraacetate (EDTA) as a ligand of divalent cations. The modified QuEChERS procedure employed for the extraction of pharmaceuticals in slurry and digested slurry liquid phases reduced the matrix effects for almost all the compounds, with extraction recoveries generally above 75%. The performance characteristics of the method were evaluated in terms of linearity, intra-day and inter-day precision, accuracy and limits of quantification, which reached concentration ranges of 5-270ng/L in soil water and sludge supernatant, and 31-2400ng/L in slurry and digested slurry supernatants, depending on the compounds. The new method was then successfully applied for the determination of the target compounds in environmental samples.