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.

Competitive adsorption and desorption of three tetracycline antibiotics on bio-sorbent materials in binary systems.

Batch-type experiments were used to study competitive adsorption/desorption for the antibiotics tetracycline (TC), oxytetracycline (OTC), and chlortetracycline (CTC), onto by-products from forest and food industries (oak ash, pine bark, and mussel shell). These antibiotics are frequently present in manures and slurries spread on agrosystems. Binary competitive systems were performed by setting the dose of one antibiotic to 200 µmol L-1, and varying the concentration of a second antibiotic from 50 to 600 µmol L-1. In the cases where a concentration of 200 µmol L-1 was used for each antibiotic, the results of the binary experiments were also compared with those obtained in parallel tests corresponding to simple and ternary systems using the same concentration. The results indicated that pine bark can adsorb most of the antibiotics added, with desorption being less than 5% in most cases. Oak ash showed high adsorption for all three antibiotics in the simple systems (100% of CTC, 90% of TC, and 80% of OTC), but clearly decreased in the binary systems (up to values below 40%), especially for higher antibiotics concentrations, although desorption was generally less than 5%. Mussel shell showed adsorption results lesser than 25% for OTC and CT in simple systems, while increased up to 65% in binary systems in which CTC was present at high concentrations, but desorption was generally very high. CTC was the antibiotic with the highest adsorption onto all three by-products, and the one showing less decrease for its adsorption in the binary systems. Overall, the smallest differences among the various competitive systems were obtained when the adsorbent used was pine bark, and especially for the CTC antibiotic. These results could aid to develop management practices, based on the use of low-cost bio-sorbents, which would decrease risks of pollution due to tetracycline antibiotics spread in agroecosystems and affecting the environment.

Adsorption/desorption of three tetracycline antibiotics on different soils in binary competitive systems.

Taking into account environmental and public health issues due to emerging pollutants, and specifically to antibiotics spread into environmental compartments, this work focused on the competition among three tetracycline antibiotics (tetracycline, CT; oxytetracycline, OTC; and chlortetracycline, CTC) for adsorption sites in six different soils. Batch-type adsorption/desorption tests were carried out, with 24 h as contact time. The six soils were from two different farming areas, and were selected according to pH values and organic matter contents. Binary systems (pairs of antibiotics present simultaneously) were used to study competition, setting the dose of one antibiotic at 200 µmol L-1, and varying the concentration of another from 50 to 600 µmol L-1. In the case of the concentration of 200 µmol L-1, the results of the binary systems were also compared with those obtained in simple and ternary systems. The results showed that those soils with the highest organic matter content (soils 50AL and 71S) adsorbed 100% of the three antibiotics, with desorption being <10% in all cases. The other four soils showed some degree of competition for adsorption sites in binary systems, with adsorption decreasing between 25 and 47% compared to simple systems, and with desorption increasing, especially in soils with higher pH and less organic matter. This competition was even more pronounced in ternary systems, affecting to these same soils, while the effects were very scarce in soils with higher organic matter content. The results indicate that most of the studied soils have high adsorption capacity for tetracycline antibiotics, retaining them with high energy even in the case of multiple systems. It was also shown that hysteresis affected adsorption/desorption processes. These results have relevance at environmental and social levels, given the growing concern regarding antibiotics pollution, and the need of promoting their retention and inactivation when spread in environmental compartments.

Competitive adsorption/desorption of tetracycline, oxytetracycline and chlortetracycline on pine bark, oak ash and mussel shell.

We studied competitive adsorption for the tetracycline antibiotics (TCs) tetracycline (TC), oxytetracycline (OTC), and chlortetracycline (CTC) on three bio-adsorbents (mussel shell, oak wood ash, and pine bark). The results were compared for individual systems (with antibiotics added separately) and ternary systems (with all three antibiotics added simultaneously). In all cases batch-type experiments were carried out, with 24 h of contact time. In the individual systems, concentrations of 200 µmol L-1 were used for each of the three antibiotics, separately. In the ternary system, all three TCs were added simultaneously, using the following total concentrations: 50, 100, 200, 400, 600 µmol L-1, each antibiotic being 1/3 of the total. Taking into account that ionic strength of a solution is related to a measure of the concentration of ions in that solution, the use of individual and ternary systems allows to compare, for each antibiotic, systems having equal concentrations and similar ionic strength (concentrations of 200 µmol L-1), and systems having different concentrations and ionic strength (200 µmol L-1 in the individual systems, and 600 µmol L-1 in the ternary systems, resulting from the sum of 200 µmol L-1 corresponding to each of the three antibiotics). Adsorption/desorption results indicated that these processes were in all cases closely related to pH values, and to carbon and non-crystalline minerals contents in the bio-adsorbents. Both oak ash and pine bark adsorbed close to 100% of TCs in individual and ternary systems, with desorption <4% for oak ash, and <12% for pine bark. However, mussel shell gave clearly poorer results, only relatively acceptable for CTC, with adsorption <56% and desorption even >30% for TC and OTC. In view of the results, oak ash and pine bark can be recommended as effective bio-adsorbents for the three TCs studied, and could be useful to retain/inactive them in wastes, and soil or liquid media receiving these emerging pollutants, thus reducing risks of damage for public health and the environment.

Competitive adsorption of tetracycline, oxytetracycline and chlortetracycline on soils with different pH value and organic matter content.

Antibiotics spread into the environment can cause soil and water degradation. Specifically, tetracycline antibiotics (TCs) are among those most consumed in veterinary medicine, and near 90% of the doses administered to animals are excreted as original compounds, due to poor absorption. In this study we investigated competitive soil adsorption/desorption for three tetracycline antibiotics (tetracycline: TC, oxytetracycline: OTC, and chlortetracycline: CTC), usually spread on soils by slurry fertilization, affecting to soil degradation due to chemical pollution. The study was carried out on six soils selected according to their pH values (4.49-7.06), and organic matter contents (1.07-10.92%). The competitive experiments were performed in ternary systems (adding all three TCs simultaneously, using five equal and increasing concentrations, from 17 to 200 µmol L-1). The results were compared with those obtained in simple systems (adding individual antibiotics separately), for the same final concentration (in this case, 200 µmol L-1) and for different concentrations (200 µmol L-1 in the simple systems, versus 600 µmol L-1 in the ternary systems, resulting from the sum of 200 µmol L-1 of each of the three antibiotics). In all cases, batch-type adsorption/desorption experiments were carried out, with 24 h as contact time. Those soils with higher organic matter content adsorbed 100% of the TCs, with desorption being always lower than 3%. In soils with less organic matter, adsorption decreased as the dose of added antibiotic increased, due to competition for adsorption sites. CTC was the most retained among the three TCs (up to 20% more than the other when high doses of antibiotic were added). In the simple systems, percentage adsorption was always high (>85%) for the three TCs; however, percentage adsorption decreased in the ternary systems, reaching just 65% and 40% (for equal and different ionic strength, respectively) in soils with low organic matter contents. These results show the environmental and public health relevance of competition among the three TCs. In fact, the highest risk of entering the food chain takes place when these antibiotics are spread together on soils with low organic matter content, especially in the case of TC and CTC, which are the least adsorbed and the most desorbed molecules.

As(V)/Cr(VI) pollution control in soils, hemp waste, and other by-products: competitive sorption trials.

We study As(V)/Cr(VI) competitive sorption on a forest soil, a vineyard soil, pyritic material, mussel shell, pine bark, oak ash, and hemp waste, adding variable As(V) and Cr(VI) concentrations or displacing each pollutant with the same concentration of the other. When using variable concentrations, As(V) showed more affinity than Cr(VI) for sorption sites on most materials (sorption up to >84 % on oak ash and pyritic material). The only exception was pine bark, with clearly higher Cr(VI) sorption (>90 %) for any Cr(VI)/As(V) concentration added. Regarding the displacement experiments, when As(V) was added and reached sorption equilibrium, the subsequent addition of equal Cr(VI) concentration did not cause relevant As displacement from oak ash and pyritic material, indicating strong As bindings, and/or low competitive effects. When Cr(VI) was added and reached sorption equilibrium, the subsequent addition of equal As(V) concentration caused Cr(VI) displacement from all materials except pine bark, indicating weak Cr bindings. In view of these results, oak ash and the pyritic material could be used to remove As(V) in concentrations as high as 6 mmol L(-1), even in the presence of a wide range of Cr(VI) concentrations, whereas pine bark could be used to remove Cr(VI) concentrations as high as 6 mmol L(-1). The other materials assayed (including hemp waste, studied for the first time as As(V) and Cr(VI) bio-sorbent) cannot be considered appropriate to remove As(V) and/or Cr(VI) from polluted media.

F sorption/desorption on two soils and on different by-products and waste materials.

We used batch-type experiments to study F sorption/desorption on a forest soil, a vineyard soil, pyritic material, granitic material, finely and coarsely ground mussel shell, mussel shell calcination ash, oak wood ash, pine-sawdust, slate processing fines, and three different mixtures that included three components: sewage sludge, mussel shell ash, and calcined mussel shell or pine wood ash. The three waste mixtures, forest soil, pyritic material, and shell ash showed high sorption capacity (73-91 % of added F) and low desorption, even when 100 mg F L(-1) was added. All these materials (and to a lower extent wood ash) could be useful to remove F from polluted media (as certain soils, dumping sites, and contaminated waters). The vineyard soil, the granitic material, mussel shell, slate fines, and pine-sawdust were less effective in F removal. In most cases, sorption data fitted better to the Freundlich than to the Langmuir equation. These results can be useful to program the correct management of the soils, by-products, and waste materials assayed, mostly in situations where F concentrations are excessive and F removal should be promoted.