Fate of 14C-acetyl sulfamethoxazole during the activated sludge process.

Compared to antibiotic parent molecule, human metabolites are generally more polar and sometimes not less toxic in wastewater. However, most researches focus on the fate of parent molecule. Therefore, behaviors of human metabolites are little known. Moreover, though much has been done on the fate of antibiotics during activated sludge process, there are still some limitations and gaps. In the present study, [Ring-14C] acetyl sulfamethoxazole (14C-Ac-SMX) was used to investigate the fate of human metabolite of SMX during activated sludge process at environmentally relevant concentration. At the end of 216 h, 3.1% of the spiked activity in the initial aqueous phase was mineralized, 50% was adsorbed onto the solid phase, and 36.5% still remained in the aqueous phase, indicating that adsorption, not biodegradation, was the main dissipation pathway. In the existence of microbial activities, accumulation into the solid phase was much higher, which was less bioavailable by chemical sequential extraction. The multimedia kinetic model simultaneously depicted the fate of Ac-SMX in the gas, aqueous, and solid phases, and demonstrated that microbially accelerated accumulation onto the solid phase was attributed to lower desorption rate from the solid phase to the aqueous phase, where adsorption rate was not the key factor. Therefore, Ac-SMX cannot be efficiently mineralized and remain in the aqueous or the solid phases. The accumulation in the solid phase is less bioavailable and is hard to be desorbed in the existence of microbial activities, and should not be easily degraded, and may lead to the development of antibiotic-resistant bacteria and genes after discharge into the environment.

Environmental availability of sulfamethoxazole and its acetylated metabolite added to soils via sludge compost or bovine manure.

The fate of antibiotics and their metabolites in soils after application of organic waste depends on their environmental availability, which depends on the quality and biodegradability of the added exogenous organic matter (EOM). This study aimed at better understanding the fate of sulfamethoxazole (SMX) and N-acetyl-sulfamethoxazole (AcSMX) metabolite added to soils via sludge compost or cow manure application, during a 28-day incubation. Experimental results obtained for mineralized, extractable, and non-extractable fractions as well as EOM mineralization were used to couple SMX and AcSMX dynamics to the EOM evolution using the COP-Soil model. According to various mechanisms of extraction, CaCl2, EDTA and cyclodextrin solutions extracted contrasted available fractions (31-96% on day 0), resulting in different sets of parameter values in the model. CaCl2 extraction was the best method to assess the sulfonamide availability, leading to low relative root mean squared errors and best simulations of SMX and AcSMX dynamics. The decrease of SMX and AcSMX availability over time went with the formation of non-extractable residues, mostly of physicochemical origin. Using the COP-Soil model, the co-metabolism was assumed to be responsible for the formation of biogenic non-extractable residues and the low mineralization of SMX and AcSMX.

Explaining the accelerated degradation of ciprofloxacin, sulfamethazine, and erythromycin in different soil exposure scenarios by their aqueous extractability.

Antibiotics are frequently introduced into agricultural soils with the application of sewage sludge or farm organic fertilizers. Repeated exposure of soils to a pollutant can enrich for microbial populations that metabolize the chemical, reducing its environmental persistence. In London, Canada, soils from a long-term field experiment have received different concentrations of antibiotics annually for several years. The purpose of the present study was to assess the bioavailability of sulfamethazine, erythromycin, or ciprofloxacin through aqueous extractions with borax or EDTA solutions and their biodegradation following different soil exposure scenarios. Control soils and soils treated annually in the field with 10 mg antibiotics per kg were sampled, supplemented in the laboratory with radiolabeled antibiotic either added directly or carried in dairy manure. Sulfamethazine and erythromycin were initially more bioavailable than ciprofloxacin, with aqueous extractabilities representing 60, 36, and 8%, respectively. Sulfamethazine and erythromycin were degraded in soils, with a larger fraction mineralized in the long-term exposed soil (20 and 65%, respectively) than in control soil (0.4 and 3%, respectively) after 7 days of incubation. In contrast, ciprofloxacin was not mineralized neither in control nor long-term exposed soils. The mineralized fractions were similar for antibiotics added directly to soil or carried in dairy manure.

Impact of sludge treatments on the extractability and fate of acetyl sulfamethoxazole residues in amended soils.

Sludge recycled in agriculture may bring antibiotics into cropped soils. The nature, total amount, and availability of the antibiotics in soil partly depend on the sludge treatments. Our paper compares the fate of N-acetyl sulfamethoxazole (AC-SMX) residues between soils incubated with the same sludge but submitted to different processes before being added in soil. The fate of 14C-AC-SMX residues was studied in mixtures of soil and sludges at different treatment levels: 1) activated and 2) centrifuged sludges, both enriched with 14C-AC-SMX, and 3) limed and 4) heat-dried sludges obtained by treating the previously contaminated centrifuged sludge. The evolution of the extractability of 14C residues (CaCl2, methanol) and their mineralization were followed during 119 days. More than 80% of the initial 14C-activity was no longer extractable after 14 days, except in soil with limed sludge. Liming and drying the centrifuged sludge decreased the mineralized 14C fraction from 5.7-6.4% to 1.2-1.8% and consequently, the corresponding soils contained more 14C residues after 119 days. Although 14C residues were more CaCl2-extractable in soil with limed sludge, they seemed to be poorly bioavailable for biodegradation. For all solid sludges, the mineralization rate of 14C-AC-SMX residues was strongly correlated to that of sludge organic carbon, with a coefficient three times lower for the limed and dried sludges than for the centrifuged sludge after 14 days.

Development of a soft extraction method for sulfamethoxazole and transformation products from agricultural soils: Effects of organic matter co-extraction on the environmental availability assessment.

The recycling of biosolids and livestock manure in agriculture may lead to the introduction of antibiotic residues, i.e., parent molecule and transformation products, into amended soils. Their fate in soils can be approached through the assessment of their environmental availability. In this work, the environmental availability of sulfamethoxazole (SMX) and three transformation products (N4-acetyl-SMX, 3-amino-5-methylisoxazole, aniline) was assessed in soils amended with sludge compost or cow manure throughout a three-month incubation, using soft extractions with CaCl2, EDTA or cyclodextrin solutions. First, the freeze-storage of soil samples was shown to decrease the SMX extractability. The SMX extractability depended on the initial concentration, the amendment type and the extracting solution at day 0. From 1.9% up to 63% of the SMX total content was initially extractable. The lowest fractions were quantified in EDTA extracts in which the dissolved organic matter was the most complex and responsible for high matrix effects in mass spectrometry compared to CaCl2 extracts. The purification of cyclodextrin extracts highly reduced the matrix effects, but CaCl2 was considered as the most suitable extractant. SMX extractability strongly decreased after the first 8days of incubation to finally reach 0.4-0.8% after 84days, whatever the initial conditions. This high decrease could be related to humification observed through the increasing complexity of extracted dissolved organic matter. Very low levels of transformation products were quantified throughout the incubation period. The low environmental availability of SMX was mainly due to its sorption on soil organic matter and resulted in its low biotransformation in these amended soils.

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.

Impact of liming and drying municipal sewage sludge on the amount and availability of (14)C-acetyl sulfamethoxazole and (14)C-acetaminophen residues.

Acetyl Sulfamethoxazole (AC-SMX) and acetaminophen (ACM) can be found in municipal sewage sludge, and their content and availability may be influenced by sludge treatments, such as drying and liming. A sludge similarly centrifuged with/without a flocculant was spiked with (14)C-labelled AC-SMX or ACM. Then, it was either limed (20% CaO) or/and dried under different laboratory conditions (1 week at ambient temperature; and 48 h at 40 or 80 °C). The total amount and distribution of the (14)C-compounds among several chemical fractions, based on the sludge floc definition, were assessed at the end of the treatments. All the (14)C-activity brought initially was recovered in the limed and/or dried sludges for AC-SMX but only between 44.4 and 84.9% for ACM, with the highest rate obtained for the limed sludge. Drying at 80 °C or liming increased the percentage of the sludge total organic carbon recovered in the extracts containing soluble extracellular polymeric substances (S-EPS) and the percentage of the total (14)C-activity extracted simultaneously. The non-extractable residues represented only 3.9-11.6% of the total (14)C-activity measured in the treated sludges for AC-SMX and 16.9-21.8% for ACM. The presence of AC-SMX and ACM residues in the treated sludges, after liming and drying under different conditions, was shown using some (14)C-labelled molecules. At this time scale and according to the extraction method selected, most of the (14)C-residues remained soluble and easily extractable for both compounds. This result implies that certain precautions should be taken when storing sludges before being spread on the field. Sludge piles, particularly the limed sludge, should be protected from rain to limit the production of lixiviates, which may contain residues of AC-SMX and ACM.

Modeling the release of organic contaminants during compost decomposition in soil.

Composts, incorporated in soils as amendments, may release organic contaminants during their decomposition. COP-Soil is presented here as a new model to simulate the interaction between organic contaminants and compost, using one module for organic matter and one for organic pollutants, with these modules being linked by several assumptions. Published results of laboratory soil incubations using labeled carbon pollutants from compost were used to test the model for one polycyclic aromatic hydrocarbon (PAH), two surfactants and one herbicide. Several simulation scenarios were tested using (i) the organic pollutant module either alone or coupled to the organic matter module, (ii) various methods to estimate the adsorption coefficients (Kd) of contaminants on organic matter and (iii) different degrading biomasses. The simulations were improved if the organic pollutant module was coupled with the organic matter module. Multiple linear regression model for Kd as a function of organic matter quality yielded the most accurate simulation results. The inclusion of specific biomass in the model made it possible to successfully predict the PAH mineralization.

Fate of (14)C-organic pollutant residues in composted sludge after application to soil.

Organic micropollutants may be present in biosolids, leading to soil contamination when they are recycled in agriculture. A sludge spiked with (14)C-labelled glyphosate (GLY), sodium linear dodecylbenzene sulphonate (LAS), fluoranthene (FLT) or 4-n-nonylphenol (NP) was composted with green waste and the fate of the (14)C-micropollutant residues remaining after composting was assessed after the compost application to the soil. (14)C-residues were mineralised in the soil and represented after 140d 20-32% of the initial activity for LAS, 16-25% for GLY, 6-9% for FLT and 4-7% for NP. The (14)C-residues at the end of composting that could not be extracted with methanol or ammonia were minimally remobilised or even increased for FLT. After 140d, non-extractable residues represented 38-52% of all of the (14)C-residues remaining in the soil for FLT, 50-67% for GLY, 91-92% for NP and 94-97% for LAS and in most cases, less than 1% of the (14)C-residues were water soluble, suggesting a low direct availability for leaching and microbial or plant assimilation. FLT was identified as the main compound among the methanol-extractable (14)C-residues that may be potentially available. The fate of the (14)C-organic pollutant residues in composts after application to soil could be assessed through a sequential chemical extraction scheme and depended on the chemical nature of the pollutant.

Simultaneous simulations of uptake in plants and leaching to groundwater of cadmium and lead for arable land amended with compost or farmyard manure.

The water budget of soil, the uptake in plants and the leaching to groundwater of cadmium (Cd) and lead (Pb) were simulated simultaneously using a physiological plant uptake model and a tipping buckets water and solute transport model for soil. Simulations were compared to results from a ten-year experimental field study, where four organic amendments were applied every second year. Predicted concentrations slightly decreased (Cd) or stagnated (Pb) in control soils, but increased in amended soils by about 10% (Cd) and 6% to 18% (Pb). Estimated plant uptake was lower in amended plots, due to an increase of K(d) (dry soil to water partition coefficient). Predicted concentrations in plants were close to measured levels in plant residues (straw), but higher than measured concentrations in grains. Initially, Pb was mainly predicted to deposit from air into plants (82% in 1998); the next years, uptake from soil became dominating (30% from air in 2006), because of decreasing levels in air. For Cd, predicted uptake from air into plants was negligible (1-5%).