Comparison of by-products as adsorbents for the removal of the antibiotics ciprofloxacin, trimethoprim and clarithromycin.

Antibiotics in the environment are considered emerging pollutants, with special relevance and concern due to the proliferation of antibiotic-resistant bacteria and genes. Therefore, finding ways to remediate antibiotics-contaminated soil and water through the use of bio-adsorbents is imperative. In this research, we investigate three by-products (hemp waste, oak ash, and mussel shell) as potential low-cost bio-adsorbents for the antibiotics Ciprofloxacin (CIP), Clarithromycin (CLA), and Trimethoprim (TRI), using batch-type and stirred flow chamber experiments to study their retention and release. The results indicate that hemp waste has higher sorption capacity for CIP and TRI (20891.8 and 2481.6 µmol L-1, respectively), while oak ash yields the highest retention for CLA (3078.4 µmol L-1). In addition, it was shown that the pH value significantly influences the sorption of these pollutants onto hemp waste. Among the three antibiotics, CLA was the most mobile, given the release experiments (903.9-1758.9 µmol kg-1), while ciprofloxacin (440.3-542.4 µmol kg-1) and trimethoprim (639.4-1652.1 µmol kg-1) are released less. Overall, the results of this research (the first of this kind including these antibiotics and sorbents simultaneously) suggest that while the individual antibiotics retention on each of the three by-products may not be entirely satisfactory, its potential combination (among them and/or with other low-cost sorbents) could significantly contribute to addressing antibiotics environmental pollution, favouring recycling and promoting a circular economy, which is a matter of global relevance.

Natural and modified clays as low-cost and ecofriendly materials to remove salinomycin from environmental compartments.

Antibiotics in the environment represent a substantial pollution threat. Among these emerging pollutants, ionophore anticoccidials are of special concern due to their potential ecological impact, persistence in the environment, and role in promoting antimicrobial resistance. To investigate the adsorption/desorption of the ionophore antibiotic salinomycin (SAL) on/from raw and modified clay adsorbents, batch-type experiments were performed using 0.5 g of clay adsorbent mixed with 10 mL of increasing doses of SAL solutions for each sample, at room temperature, with a contact time of 24 h. All measurements were conducted in triplicate employing HPLC-UV equipment. Three different natural (raw) and modified clay samples were investigated, which were denominated as follows: AM (with 51% calcite), HJ1 (with 32% kaolinite), and HJ2 (with 32% microcline). The experiments were carried out using three pH ranges: between 3.33 and 4.49 for acid-activated clays, 8.39-9.08 for natural clays, and 9.99-10.18 for base-activated clays. The results indicated that, when low concentrations of the antibiotic were added (from 5 to 20 µmol L-1), more than 98% of SAL was strongly adsorbed by almost all clays, irrespective of the physicochemical and mineralogical composition of the clays or their pH values. When higher SAL concentrations were added (40 and 100 µmol L-1), the adsorption of the antibiotic showed pH-dependent ligand adsorption mechanisms: (i) highly decreased as the pH raised (for the raw and base-activated AM and HJ1 clays), while (ii) slightly decreased as the pH decreased (on the acid-activated clays). Among the adsorption equations tested (Freundlich, Langmuir, and Linear), the Freundlich model was identified as the most suitable for fitting the data corresponding to SAL adsorption onto the studied clays. SAL desorption from clays was consistently below 10% for all the clay samples, especially for the acid-activated clays, due to cation bridging adsorption mechanisms, when the lowest concentration of the antibiotic was added. Additionally, it should be stressed that the desorption values can increase with rising SAL concentrations, but they always remain below 20%. Overall, the clays here investigated (both raw and modified) provide a cost-effective and efficient alternative for the removal of the veterinary anticoccidial antibiotic SAL, with potential positive and practical implications in environmental remediation and antibiotic pollution management, particularly by serving as amendments for contaminated soils to enhance their adsorption capacities against SAL. Additionally, using these clays in water treatment processes could improve the efficiency of mitigating antibiotic contamination in aquatic systems.

Removal of the Highly Toxic Anticoccidial Monensin Using Six Different Low-Cost Bio-Adsorbents.

The anticoccidial monensin (MON) is a high-concern emerging pollutant. This research focused on six low-cost bio-adsorbents (alfa, cactus, and palm fibers, and acacia, eucalyptus, and zean oak barks), assessing their potential for MON removal. Batch adsorption/desorption tests were carried out, and the results were fitted to the Freundlich, Langmuir, Linear, Sips, and Temkin models. The concentrations adsorbed by the six materials were very similar when low doses of antibiotic were added, while they differed when adding MON concentrations higher than 20 µmol L-1 (adsorption ranging 256.98-1123.98 µmol kg-1). The highest adsorption corresponded to the sorbents with the most acidic pH (<5.5) and the highest organic matter and effective cation exchange capacity values (eucalyptus bark and acacia bark, reaching 92.3% and 87.8%), whereas cactus and palm fibers showed the lowest values (18.3% and 10.17%). MON desorption was below 8.5%, except for cactus and palm fibers. Temkin was the model showing the best adjustment to the experimental data, followed by the Langmuir and the Sips models. The overall results indicate that eucalyptus bark, alfa fiber, and acacia bark are efficient bio-adsorbents with potential for MON removal, retaining it when spread in environmental compartments, reducing related risks for human and environmental health.

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.

Experimental data and modeling of sulfadiazine adsorption onto raw and modified clays from Tunisia.

In recent years, the increasing detection of emerging pollutants (particularly antibiotics, such as sulfonamides) in agricultural soils and water bodies has raised growing concern about related environmental and health problems. In the current research, sulfadiazine (SDZ) adsorption was studied for three raw and chemically modified clays. The experiments were carried out for increasing doses of the antibiotic (0, 1, 5, 10, 20, and 40 µmol L-1) at ambient temperature and natural pH with a contact time of 24 h. The eventual fitting to Freundlich, Langmuir and Linear adsorption models, as well as residual concentrations of antibiotics after adsorption, was assessed. The results obtained showed that one of the clays (HJ1) adsorbed more SDZ (reaching 99.9 % when 40 µmol L-1 of SDZ were added) than the other clay materials, followed by the acid-activated AM clay (which reached 99.4 % for the same SDZ concentration added). The adsorption of SDZ followed a linear adsorption isotherm, suggesting that hydrophobic interactions, rather than cation exchange, played a significant role in SDZ retention. Concerning the adsorption data, the best adjustment corresponded to the Freundlich model. The highest Freundlich KF scores were obtained for the AM acid-treated and raw HJ1 clays (606.051 and 312.969 Ln µmol1-n kg-1, respectively). The Freundlich n parameter ranged between 0.047 and 1.506. Regarding desorption, the highest value corresponded to the AM clay, being generally <10 % for raw clays, <8 % for base-activated clays, and <6 % for acid-activated clays. Chemical modifications contributed to improve the adsorption capacity of the AM clay, especially when the highest concentrations of the antibiotic were added. The results of this research can be considered relevant as regard environmental and public health assessment since they estimate the feasibility of three Tunisian clays in SDZ removal from aqueous solutions.

Tetracycline adsorption/desorption by raw and activated Tunisian clays.

Clay-based adsorbents have applications in environmental remediation, particularly in the removal of emerging pollutants such as antibiotics. Taking that into account, we studied the adsorption/desorption process of tetracycline (TC) using three raw and acid- or base-activated clays (AM, HJ1 and HJ2) collected, respectively, from Aleg (Mazzouna), El Haria (Jebess, Maknessy), and Chouabine (Jebess, Maknessy) formations, located in the Maknessy-Mazzouna basin, center-western of Tunisia. The main physicochemical properties of the clays were determined using standard procedures, where the studied clays presented a basic pH (8.39-9.08) and a high electrical conductivity (446-495 dS m-1). Their organic matter contents were also high (14-20%), as well as the values of the effective cation exchange capacity (80.65-97.45 cmolckg-1). In the exchange complex, the predominant cations were Na and Ca, in the case of clays HJ1 and AM, while Mg and Ca were dominant in the HJ2 clay. The sorption experimental setup consisted in performing batch tests, using 0.5 g of each clay sample, adding the selected TC concentrations, then carrying out quantification of the antibiotic by means of HPL-UV equipment. Raw clays showed high adsorption potential for TC (close to 100%) and very low desorption (generally less than 5%). This high adsorption capacity was also present in the clays after being activated with acid or base, allowing them to adsorb TC in a rather irreversible way for a wide range of pH (3.3-10) and electrical conductivity values (3.03-495 dS m-1). Adsorption experimental data were studied as regards their fitting to the Freundlich, Langmuir, Linear and Sips isotherms, being the Sips model the most appropriate to explain the adsorption of TC in these clays (natural or activated). These results could help to improve the overall knowledge on the application of new low-cost methods, using clay based adsorbents, to reduce risks due to emerging pollutants (and specifically TC) affecting the environment.

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.

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.

Cu and As(V) Adsorption and Desorption on/from Different Soils and Bio-Adsorbents.

This research is concerned with the adsorption and desorption of Cu and As(V) on/from different soils and by-products. Both contaminants may reach soils by the spreading of manure/slurries, wastewater, sewage sludge, or pesticides, and also due to pollution caused by mining and industrial activities. Different crop soils were sampled in A Limia (AL) and Sarria (S) (Galicia, NW Spain). Three low-cost by-products were selected to evaluate their bio-adsorbent potential: pine bark, oak ash, and mussel shell. The adsorption/desorption studies were carried out by means of batch-type experiments, adding increasing and individual concentrations of Cu and As(V). The fit of the adsorption data to the Langmuir, Freundlich, and Temkin models was assessed, with good results in some cases, but with high estimation errors in others. Cu retention was higher in soils with high organic matter and/or pH, reaching almost 100%, while the desorption was less than 15%. The As(V) adsorption percentage clearly decreased for higher As doses, especially in S soils, from 60−100% to 10−40%. The As(V) desorption was closely related to soil acidity, being higher for soils with higher pH values (S soils), in which up to 66% of the As(V) previously adsorbed can be desorbed. The three by-products showed high Cu adsorption, especially oak ash, which adsorbed all the Cu added in a rather irreversible manner. Oak ash also adsorbed a high amount of As(V) (>80%) in a rather non-reversible way, while mussel shell adsorbed between 7 and 33% of the added As(V), and pine bark adsorbed less than 12%, with both by-products reaching 35% desorption. Based on the adsorption and desorption data, oak ash performed as an excellent adsorbent for both Cu and As(V), a fact favored by its high pH and the presence of non-crystalline minerals and different oxides and carbonates. Overall, the results of this research can be relevant when designing strategies to prevent Cu and As(V) pollution affecting soils, waterbodies, and plants, and therefore have repercussions on public health and the environment.

Competitive adsorption and desorption of tetracycline and sulfadiazine in crop soils.

In view of the environmental issues caused by antibiotics, this research studies competitive adsorption/desorption for tetracycline (TC) and sulfadiazine (SDZ) in agricultural soils. Competitive adsorption was studied in binary systems (adding equal concentrations of both antibiotics). In addition, it was compared with results from simple systems. In all cases, batch-type adsorption/desorption experiments were carried out. In the binary systems, for the highest antibiotic concentration added, adsorption percentages were always higher for TC (close to 100%) than for SDZ (10-90%). In these systems, TC desorption was lower than 5% for all soils, and generally <10% for SDZ. Comparing TC and SDZ adsorption for the different systems, SDZ was clearly affected by the presence of TC, with SDZ adsorption percentages being was much higher (with differences generally above 65%) in the binary than in the simple systems. On the contrary, comparing the results of TC adsorption in simple and binary systems, TC was not affected by the presence of SDZ, obtaining similar adsorption percentages in both systems. Kd and KF values (in the Linear and Freundlich models), were higher in the simple systems in the case of TC, which could be due to competition with SDZ, while for SDZ Kd and KF were higher in the binary systems, with a synergistic effect of TC favoring SDZ adsorption. Regarding desorption, it reached 100% for SDZ in some soils in simple systems, dropping to 10% in the presence of TC. TC desorption was <4%, not affected by SDZ. The results indicate that environmental risks would be higher for SDZ, showing differences when both antibiotics are present. This can be considered relevant as regards public health and environmental preservation, in view of direct toxicities and the promotion of resistance to antibiotics associated with the presence of these contaminants in the environment.

Potential of low-cost bio-adsorbents to retain amoxicillin in contaminated water.

Sewage sludge as agricultural amendment is the main route of human-medicine antibiotics to enter soils. When reaching environmental compartments, these compounds can cause significant risks to human and ecological health. Specifically, the antibiotic amoxicillin (AMX) is highly used in medicine, and the fact that more than 80% of the total ingested is excreted increases the chances of causing serious environmental and public health problems. As the use of low-cost bio-adsorbents could help to solve these issues, this research focuses on the retention of AMX onto four by-products of the forestry industry (eucalyptus leaf, pine bark, pine needles, and wood ash) and one from food industry (mussel shell). To carry out this study, batch-type tests were performed, where increasing concentrations of the antibiotic (0, 2.5, 5, 10, 20, 30, 40 and 50 µmol L-1) were added to samples of 0.5 g of each bio-adsorbent. Eucalyptus leaf, pine needle and wood ash showed adsorption scores higher than 80%, while it was up to 39% and 48% for pine bark and mussel shell, respectively. For pine bark, wood ash and mussel shell, adsorption data showed good adjustment to the Freundlich and Linear models, while pine needles and eucalyptus leaf did not fit to any model. There was not desorption when the maximum concentration of AMX (50 µmol L-1) was added. Overall, eucalyptus leaf, pine needles and wood ash can be considered good bio-adsorbents with high potential to retain AMX, which has significant implications regarding their eventual use to reduce risks of environmental pollution by this antibiotic.

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.

Relevance of sorption in bio-reduction of amoxicillin taking place in forest and crop soils.

The fate of antibiotics reaching soils is a matter of concern, given its potential repercussions on public health and the environment. In this work, the potential bio-reduction of the antibiotic amoxicillin (AMX), affected by sorption and desorption, is studied for 17 soils with clearly different characteristics. To carry out these studies, batch-type tests were performed, adding increasing concentrations of AMX (0, 2.5, 5, 10, 20, 30, 40, and 50 µmol L-1) to the soils. For the highest concentration added (50 µmol L-1), the adsorption values for forest soils ranged from 90.97 to 102.54 µmol kg-1 (74.21-82.41% of the amounts of antibiotic added), while the range was 69.96-94.87 µmol kg-1 (68.31-92.56%) for maize soils, and 52.72-85.40 µmol kg-1 (50.96-82.55%) for vineyard soils. When comparing the results for all soils, the highest adsorption corresponded to those more acidic and with high organic matter and non-crystalline minerals contents. The best adjustment to adsorption models corresponded to Freundlich's. AMX desorption was generally <10%; specifically, the maximum was 6.5% in forest soils, and 16.9% in agricultural soils. These results can be considered relevant since they cover agricultural and forest soils with a wide range of pH and organic matter contents, for an antibiotic that, reaching the environment as a contaminant, can pose a potential danger to human and environmental 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.

SARS-CoV-2 and other main pathogenic microorganisms in the environment: Situation in Galicia and Spain.

In the context of the current COVID-19 pandemic, and mostly taking a broad perspective, it is clearly relevant to study environmental factors that could affect eventual future outbreaks due to coronaviruses and/or other pathogenic microorganisms. In view of that, the authors of this manuscript review the situation of SARS-CoV-2 and other main pathogenic microorganisms in the environment, focusing on Galicia and Spain. Overall, in addition to showing local data, it is put in evidence that, summed to all efforts being carried out to treat/control this and any other eventual future epidemic diseases, both at local and global levels, a deep attention should be paid to ecological/environmental aspects that have effects on the planet, its ecosystems and their relations/associations with the probability of spreading of eventual future pandemics.