Factors influencing the extraction of pharmaceuticals from sewage sludge and soil: an experimental design approach.

Pharmaceuticals can enter the environment when organic waste products are recycled on agricultural soils. The extraction of pharmaceuticals is a challenging step in their analysis. The very different extraction conditions proposed in the literature make the choice of the right method for multi-residue analysis difficult. This study aimed at evaluating, with experimental design methodology, the influence of the nature, pH and composition of the extraction medium on the extraction recovery of 14 pharmaceuticals, including 8 antibiotics, from soil and sewage sludge. Preliminary experimental designs showed that acetonitrile and citrate-phosphate buffer were the best extractants. Then, a response surface design demonstrated that many cross-product and squared terms had significant effects, explaining the shapes of the response surfaces. It also allowed optimising the pharmaceutical recoveries in soil and sludge. The optimal conditions were interpreted considering the ionisation states of the compounds, their solubility in the extraction medium and their interactions with the solid matrix. To perform the analysis, a compromise was made for each matrix. After a QuEChERS purification, the samples were analysed by online SPE-UHPLC-MS-MS. Both methods were simple and economical. They were validated with the accuracy profile methodology for soil and sludge and characterised for another type of soil, digested sludge and composted sludge. Trueness globally ranged between 80 and 120 % recovery, and inter- and intra-day precisions were globally below 20 % relative standard deviation. Various pharmaceuticals were present in environmental samples, with concentration levels ranging from a few micrograms per kilogramme up to thousands of micrograms per kilogramme. Graphical abstract Influence of the extraction medium on the extraction recovery of 14 pharmaceuticals. Influence of the ionisation state, the solubility and the interactions of pharmaceuticals with solid matrix. Analysis of different soils and organic waste products.

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.

A new extraction method to assess the environmental availability of ciprofloxacin in agricultural soils amended with exogenous organic matter.

Fluoroquinolone antibiotics such as ciprofloxacin can be found in soils receiving exogenous organic matter (EOM). Their long-term behavior in EOM-amended soils and their level of biodegradability are not well understood partly due to a lack of methods to estimate their environmental availability. We performed different aqueous extractions to quantify the available fraction of 14C-ciprofloxacin in soils amended with a compost of sewage sludge and green wastes or a farmyard manure contaminated at relevant environmental concentrations. After minimizing 14C-ciprofloxacin losses by adsorption on laboratory vessel tubes, three out of eleven different aqueous solutions were selected, i.e., Borax, Na2EDTA and 2-hydroxypropyl-ß-cyclodextrin. During 28 d of incubation, the non-extractable fractions were very high in all samples, i.e., 57-67% of the initial 14C-activity, and the availability of the antibiotic was very low, explaining its low biodegradation. A maximum of 6.3% of the initial 14C-activity was extracted from soil/compost mixtures with the Na2EDTA solution, and 7.2% from soil/manure mixtures with the Borax solution. The available fraction level was stable over the incubation in soil/compost mixtures but slightly varied in soil/manure mixtures following the organic matter decomposition. The choice of different soft extractants highlighted different sorption mechanisms controlling the environmental availability of ciprofloxacin, where the pH and the quality of the applied EOM appeared to be determinant.