Use of waste materials to prevent tetracycline antibiotics toxicity on the growth of soil bacterial communities.

The increase of concentrations of tetracycline antibiotics in agricultural soils worldwide is of special concern, due to its potential toxic effects on soil bacterial communities. In the present work, the reuse of two waste/by-product materials as soil amendments was tested as a preventive practice for reducing tetracycline antibiotics toxicity in soils. Pine bark (PB), with high percentage of organic carbon, and crushed mussel shell (CMS), a frequent natural liming material, were added to 4 soils in doses 0, 6, 12 and 48 g of by-product per kg-1 of soil (dry weight) of each one (separately). The soils and soil-waste mixtures were then spiked with tetracycline (TC), oxytetracycline (OTC) and chlortetracycline (CTC). After one day of incubation, the bacterial growth was estimated in soils and soil-mixtures using the leucine incorporation technique. The addition of PB to the soils showed two different behaviors, depending on the antibiotics. The toxicity of TC and OTC decreased with the addition of PB (toxicities going from 6 to 25% and from 5 to 36%, respectively). However, CTC toxicity did not change, or even increased in response to the PB amendment. Regarding soil amendment with CMS, it was not effective to prevent the toxicity of any of the three antibiotics studied.

Valorization of biosorbent obtained from a forestry waste: Competitive adsorption, desorption and transport of Cd, Cu, Ni, Pb and Zn.

Bark from Pinus pinaster is one of the most abundant forestry wastes in Europe, and among the proposed technologies for its reutilization, the removal of heavy metals from wastewater has been gaining increasing attention. In this work, we have studied the performance of pine bark for heavy metal biosorption on competitive systems. Pb, Cu, Ni, Zn and Cd sorption and desorption at equilibrium were studied in batch experiments, whereas transport was studied in column experiments. Batch experiments were performed adding simultaneously different concentrations (0.08-3.15mM) of two or more metals in solution to pine bark samples. Column experiments were performed with 10mM solutions of two metals or a 5mM solution of the five metals. In general, the results under competitive conditions were different to those obtained in monoelemental experiments. The multi-metal batch experiments showed the adsorption sequence Pb≈Cu>Cd>Zn>Ni for lower metal doses, Pb>Cu>Cd>Zn>Ni for intermediate doses, and Pb>Cu>Cd≈Zn≈Ni for high metal doses. Desorption followed the sequence PbCu>Zn>Cd>Ni. The presence of a second metal affected the transport of all the elements studied except Pb, and confirmed the strong influence of Pb and Cu on the retention of the other metals. These results can help to appropriately design decontamination systems using this forestry waste.

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.

Lithological and land-use based assessment of heavy metal pollution in soils surrounding a cement plant in SW Europe.

We study the influence of phasing out a cement plant on the heavy metal (Hg, Pb and Cr) content in the surrounding soils, taking into account factors often neglected, such as contributions due to local lithology or land use. The range of total Hg was 10-144µg kg(-1), reaching up to 41 and 145mgkg(-1) for total contents of Pb and Cr, respectively. Forest soils showed higher concentration of Hg than prairie soils, indicating the importance of land use on the accumulation of volatile heavy metals in soils. In forest soils, total Hg showed a trend to decrease with soil depth, whereas in prairie soils the vertical pattern of heavy metal concentrations was quite homogeneous. In most cases, the distance to the cement plant was not a factor of influence in the soils content of the analyzed heavy metals. Total Pb and Cr contents in soils nearby the cement plant were quite similar to those found in the local lithology, resulting in enrichment factor values (EF's) below 2. This suggests that soil parent material is the main source of these heavy metals in the studied soils, while the contribution of the cement plant to Pb and Cr soil pollution was almost negligible. On the contrary, the soils surrounding the cement plant accumulate a significant amount of Hg, compared to the underlying lithology. This was especially noticeable in forest soils, where Hg EF achieved values up to 36. These results are of relevance, bearing in mind that Hg accumulation in soils may be an issue of environmental concern, particularly in prairie soils, where temporal flooding can favor Hg transformation to highly toxic methyl-Hg. In addition, the concurrence of acid soils and total-Cr concentrations in the range of those considered phytotoxic should be also stressed.

As(V) and P Competitive Sorption on Soils, By-Products and Waste Materials.

Batch-type experiments were used to study competitive As(V) and P sorption on various soils and sorbent materials. The materials assayed were a forest soil, a vineyard soil, pyritic material, granitic material, coarsely and finely ground mussel shell, calcinated mussel shell ash, pine sawdust and slate processing fines. Competition between As(V) and P was pronounced in the case of both soils, granitic material, slate fines, both shells and pine sawdust, showing more affinity for P. Contrary, the pyritic material and mussel shell ash showed high and similar affinity for As(V) and P. These results could be useful to make a correct use of the soils and materials assayed when focusing on As and P removal in solid or liquid media, in circumstances where both pollutants may compete for sorption sites.

Cr(VI) Sorption/Desorption on Pine Sawdust and Oak Wood Ash.

The objective of this work was to study Cr(VI) sorption/desorption on two by-products from the wood industry: pine sawdust and oak wood ash. The retention/release experiments were carried out using standard batch-type trials. In the sorption-phase experiments, pine sawdust showed 23% sorption when a concentration of 100 mg Cr(VI)ŸL-1 was added, whereas sorption on oak wood ash was 17%. In the desorption-phase, chromium release was clearly higher from pine sawdust than from oak wood ash (98% and 66%, respectively). Sorption curves were well fitted to the Freundlich and Lineal models. In view of the results, both materials can be considered of very limited value to remove Cr from polluted soil and water, which can be of relevance regarding its appropriate use as biosorbents and recycled by-products.

Kinetics of Hg(II) adsorption and desorption in calcined mussel shells.

The potential use of calcined mussel shells to purify water contaminated with mercury was evaluated. The Hg(II) adsorption and desorption kinetics were studied in batch-type and stirred-flow chamber experiments. The adsorption/desorption experiments revealed some differences between the batches of shells used. The batch of shells that displayed the greatest capacity to adsorb Hg(II), via a highly irreversible reaction, also contained more Fe and Al than the other batches. The results of the stirred-flow chamber experiments indicated a high degree of irreversibility in the process of Hg(II) adsorption in the mussel shell, and that Hg(II) was rapidly retained. The results of these experiments also revealed that the efficiency of depuration differed depending on the length of time that the system was used: when the system was operated for 55 min, depurating 162 mL of inflowing water g(-1) mussel shell, a 90% reduction in the initial concentration of Hg(II) was obtained; use of the system for 90 min, depurating 265 mL water g(-1) mussel shell, produced a 75% reduction in the initial Hg(II), and use of the system for 162.5 min, depurating 487 mL of water g(-1) mussel shell, resulted in a 50% reduction in the initial Hg(II).