Azithromycin removal using pine bark, oak ash and mussel shell.

Adsorption is considered an interesting option for removing antibiotics from the environment because of its simple design, low cost, and potential efficiency. In this work we evaluated three by-products (pine bark, oak ash, and mussel shell) as bio-adsorbents for the antibiotic azithromycin (AZM). Furthermore, they were added at doses of 48 t ha-1 to four different soils, then comparing AZM removal for soils with and without bio-adsorbents. Batch-type experiments were used, adding AZM concentrations between 2.5 and 600 µmol L-1 to the different bio-adsorbents and soil + bio-adsorbent mixtures. Regarding the bio-adsorbents, oak ash showed the best adsorption scores (9600 µmol kg-1, meaning >80% retention), followed by pine bark (8280 µmol kg-1, 69%) and mussel shell (between 3000 and 6000 µmol kg-1, 25-50% retention). Adsorption data were adjusted to different models (Linear, Freundlich and Langmuir), showing that just mussel shell presented an acceptable fitting to the Freundlich equation, while pine bark and oak ash did not present a good adjustment to any of the three models. Regarding desorption, the values were always below the detection limit, indicating a rather irreversible adsorption of AZM onto these three by-products. Furthermore, the results showed that when the lowest concentrations of AZM were added to the not amended soils they adsorbed 100% of the antibiotic, whereas when the highest concentrations of AZM were spread, the adsorption decreased to 55%. However, when any of the three bio-adsorbents was added to the soils, AZM adsorption reached 100% for all the antibiotic concentrations used. Desorption was null in all cases for both soils with and without bio-adsorbents. These results, corresponding to an investigation carried out for the first time for the antibiotic AZM, can be seen as relevant in the search of low-cost alternative treatments to face environmental pollution caused by this emerging contaminant.

Adsorption of antibiotics on bio-adsorbents derived from the forestry and agro-food industries.

Antibiotic consumption at high levels in both human and veterinary populations pose a risk to their eventual entry into the food chain and/or water bodies, which will adversely affect the health of living organisms. In this work, three materials from forestry and agro-food industries (pine bark, oak ash and mussel shell) were investigated as regards their potential use as bio-adsorbents in the retention of the antibiotics amoxicillin (AMX), ciprofloxacin (CIP) and trimethoprim (TMP). Batch adsorption/desorption tests were conducted, adding increasing concentrations of the pharmaceuticals individually (from 25 to 600 µmol L-1), reaching maximum adsorption capacities of ≈ 12000 µmol kg-1 for the three antibiotics, with removal percentages of ≈ 100% for CIP, 98-99% adsorption for TMP onto pine bark, and 98-100% adsorption for AMX onto oak ash. The presence of high calcium contents and alkaline conditions in the ash favored the formation of cationic bridges with AMX, whereas the predominance of hydrogen bonds between pine bark and TMP and CIP functional groups explain the strong affinity and retention of these antibiotics. The Freundlich's model provided the best prediction for AMX adsorption onto oak ash and mussel shell (heterogeneous adsorption), whereas the Langmuir's model described well AMX adsorption onto pine bark, as well as CIP adsorption onto oak ash (homogeneous and monolayer adsorption), while all three models provided satisfactory results for TMP. In the present study, the results obtained were crucial in terms of valorization of these adsorbents and their subsequent use to improve the retention of antibiotics of emerging concern in soils, thereby preventing contamination of waters and preserving environment quality.

Clarithromycin as soil and environmental pollutant: Adsorption-desorption processes and influence of pH.

Antibiotics pollution is a growing environmental issue, as high amounts of these compounds are found in soil, water and sediments. This work studies the adsorption/desorption of the macrolide antibiotic clarithromycin (CLA) for 17 agricultural soils with different edaphic characteristics. The research was carried out using batch-type experiments, with an additional assessment of the specific influence of pH for 6 of the soils. The results show that CLA adsorption reaches between 26 and 95%. In addition, the fit of the experimental data to adsorption models provided values between 1.9 and 19.7 Ln µmol1-n kg-1 for the KF, Freundlich affinity coefficient, and between 2.5 and 10.5 L kg-1 for Kd, distribution constant of Linear model. Regarding the linearity index, n, it varied between 0.56 and 1.34. Desorption showed lower scores than adsorption, with an average of 20%, and with values of 3.1 and 93.0 Ln µmol1-n kg-1 for KF(des) and 4.4 and 95.0 L kg-1 for Kd(des). The edaphic characteristics with the highest influence on adsorption were the silt fraction content and the exchangeable Ca content, while in the case of desorption, they were the total nitrogen, organic carbon, and exchangeable Ca and Mg contents. Regarding the pH, within the range studied (between 3 and 10), its value did not decisively affect the adsorption/desorption process. Overall, the set of these results could be of help to program appropriate measures leading to the retention/elimination of this antibiotic when it reaches the environment as a pollutant.

Influence of pH on the adsorption-desorption of doxycycline, enrofloxacin, and sulfamethoxypyridazine in soils with variable surface charge.

In this research, the adsorption/desorption of the antibiotics doxycycline (DC), enrofloxacin (ENR), and sulfamethoxypyradazine (SMP) was studied in 6 agricultural soils with predominance of variable charge, both before and after removing organic matter by calcination. DC adsorption was high at acidic pH, and decreased at pH values above 8. Removal of organic matter with calcination caused just a slight decrease in adsorption, and even in some soils adsorption was similar to that in non-calcined samples. The adsorption coefficients (Kd) were higher for the DC- species compared to DC+, DC0 and DC2-. Regarding DC desorption, the values were very low throughout the pH range covered in the study (2-12), both in the calcined samples and in those not subjected to calcination. ENR showed a similar behavior to DC regarding the effect of pH, since ENR adsorption also decreased at basic pH, but the effect of removing organic matter was different, as it caused a clear decrease in ENR adsorption. The species with the highest Kd was in this case ENR0, although ENR+ is also quantitatively important as regards Kd value in calcined samples. For this antibiotic, no differences in desorption were observed between calcined and non-calcined samples. Finally, SMP adsorption also decreased as pH increased, and, in addition, similarly to what happened with ENR, in general, there was a strong decrease in SMP adsorption when organic matter was removed. The species with the highest Kd in this case was SMP+ in non-calcined samples, but SMP0 and SMP- become more relevant in calcined samples. The percentages of SMP desorption were higher than those for the other two antibiotics, and an increase occurs at intermediate pH values, being higher for calcined samples. These results can be considered relevant in terms of increasing the knowledge as regards the possible evolution and fate of the three antibiotics studied. Specifically, for different pH conditions and with different organic matter contents, when they reach soils and other environmental compartments after being discharged as contaminants. This could have important repercussions on public health and the overall environment.

Ciprofloxacin and Trimethoprim Adsorption/Desorption in Agricultural Soils.

The current research focuses on the adsorption/desorption characteristics of the antibiotics ciprofloxacin (CIP) and trimethoprim (TRI) taking place in 17 agricultural soils, which are studied by means of batch-type experiments. The results show that adsorption was higher for CIP, with Freundlich KF values ranging between 1150 and 5086 Ln µmol1-n kg-1, while they were between 29 and 110 Ln µmol1-n kg-1 in the case of TRI. Other parameters, such as the Langmuir maximum adsorption capacity (qm(ads)), as well as the Kd parameter in the linear model and also the adsorption percentages, follow the same trend as KF. Desorption was lower for CIP (with KF(des) values in the range 1089-6234 Ln µmol1-n kg-1) than for TRI (with KF(des) ranging between 26 and 138 Ln µmol1-n kg-1). The higher irreversibility of CIP adsorption was also confirmed by its lower nF(des)/nF(ads) ratios, compared to TRI. Regarding soil characteristics, it was evidenced that nitrogen and carbon contents, as well as mineral fractions, had the highest influence on the adsorption/desorption process. These results can be considered relevant as regards the fate of both antibiotics when they reach the environment as pollutants and therefore could be considered in assessment procedures focused on environmental and public health aspects.

Amoxicillin Retention/Release in Agricultural Soils Amended with Different Bio-Adsorbent Materials.

The antibiotic amoxicillin (AMX) may reach soils and other environmental compartments as a pollutant, with potential to affect human and environmental health. To solve/minimize these hazards, it would be clearly interesting to develop effective and low-cost methods allowing the retention/removal of this compound. With these aspects in mind, this work focuses on studying the adsorption/desorption of AMX in different agricultural soils, with and without the amendment of three bio-adsorbents, specifically, pine bark, wood ash and mussel shell. For performing the research, batch-type experiments were carried out, adding increasing concentrations of the antibiotic to soil samples with and without the amendment of these three bio-adsorbents. The results showed that the amendments increased AMX adsorption, with pine bark being the most effective. Among the adsorption models that were tested, the Freundlich equation was the one showing the best fit to the empirical adsorption results. Regarding the desorption values, there was a decrease affecting the soils to which the bio-adsorbents were added, with overall desorption not exceeding 6% in any case. In general, the results indicate that the bio-adsorbents under study contributed to retaining AMX in the soils in which they were applied, and therefore reduced the risk of contamination by this antibiotic, which can be considered useful and relevant to protect environmental quality and public health.

Photodegradation of Ciprofloxacin, Clarithromycin and Trimethoprim: Influence of pH and Humic Acids.

In view of the rising relevance of emerging pollutants in the environment, this work studies the photodegradation of three antibiotics, evaluating the effects of the pH of the medium and the concentration of dissolved organic matter. Simulated light (with a spectrum similar to that of natural sunlight) was applied to the antibiotics Ciprofloxacin (Cip), Clarithromycin (Cla) and Trimethoprim (Tri), at three different pH, and in the presence of different concentrations of humic acids. The sensitivity to light followed the sequence: Cip > Cla > Tri, which was inverse for the half-life (Tri > Cla > Cip). As the pH increased, the half-life generally decreased, except for Cla. Regarding the kinetic constant k, in the case of Cip and Tri it increased with the rise of pH, while decreased for Cla. The results corresponding to total organic carbon (TOC) indicate that the complete mineralization of the antibiotics was not achieved. The effect of humic acids was not marked, slightly increasing the degradation of Cip, and slightly decreasing it for Tri, while no effect was detected for Cla. These results may be relevant in terms of understanding the evolution of these antibiotics, especially when they reach different environmental compartments and receive sunlight radiation.

Pica asociada con ascariasis: presentación de un caso / Pica associated with ascariasis: report of a case

Se presenta una niña de 8 años que come piedras como manifestación típica de una pica asociada con una ascariasis moderada. Se exponen los pocos hallazgos clínicos y la ventaja de la anamnesis con la ayuda de la radiología para llegar al diagnóstico. Se comparan los datos de nuestra paciente con lo informado por la literatura médica internacional. Se hace una revisión bibliográfica y se menciona la posible causa, las complicaciones y se exponen las posibilidades terapéuticas, señalándose que el tratamiento y curación resultan de difícil control médico, aunque 6 meses después del tratamiento la paciente se encontraba asintomática

Pica asociada con ascariasis: presentación de un caso

Se presenta una niña de 8 años que come piedras como manifestación típica de una pica asociada con una ascariasis moderada. Se exponen los pocos hallazgos clínicos y la ventaja de la anamnesis con la ayuda de la radiología para llegar al diagnóstico. Se comparan los datos de nuestra paciente con los informado por la literatura médica internacional. Se hace una revisión bibliográfica y se menciona la posible causa, las complicaciones y se exponen las posibilidades terapéuticas, señalándose que el tratamiento y curación resultan de difícil control médico, aunque 6 meses después del tratamiento la paciente se encontraba asintomática(AU)