Laura Cutillas-Barreiro

Pine bark as bio-adsorbent for Cd, Cu, Ni, Pb and Zn: Batch-type and stirred flow chamber experiments

The objective of this work was to determine the retention of five metals on pine bark using stirred flow and batch-type experiments. Resulting from batch-type kinetic experiments, adsorption was rapid, with no significant differences for the various contact times. Adsorption was between 98 and 99% for Pb(2+), 83-84% for Cu(2+), 78-84% for Cd(2+), 77-83% for Zn(2+), and 70-75% for Ni(2+), and it was faster for low concentrations, with Pb suffering the highest retention, followed by Cu, Cd, Ni and Zn. The fitting to the Freundlich and Langmuir models was satisfactory. Desorption increased in parallel to the added concentrations, with Pb always showing the lowest levels. Stirred flow chamber experiments showed strong hysteresis for Pb and Cu, sorption being mostly irreversible. The differences affecting the studied heavy metals are mainly due to different affinity for the adsorption sites. Pine bark can be used to effectively remove Pb and Cu from polluted environments.

Study of metal transport through pine bark for reutilization as a biosorbent.

The potential utilization of pine bark as a biosorbent for the treatment of metal-contaminated soils and waters has been evaluated in transport experiments using laboratory columns. Solutions containing the metals Cu, Pb, Zn, Ni or Cd, each one individually and at three different concentrations (2.5, 10 and 25 mM) were tested. Pine bark affected metal transport and the breakthrough curves, producing a reduction of their concentrations in the solution and a clear retardation with respect to an inert tracer. At metal concentrations equal to 2.5 mM, 100% of the assayed elements were removed from the solution in the pine bark column. At the 10 mM metal concentration, the percentage of metals retained fell to 38-67% of the amount added, whereas at the 25 mM metal concentration, only 16-43% was retained. In all cases, the highest retention capacity corresponded to Pb, and the lowest to Zn, whereas Cu, Cd and Ni produced intermediate comparable results. The analysis of the pine bark within the columns after the transport experiment showed that the metals entering the column adsorb progressively until a saturation concentration is reached in the whole column, and only then they can be released at significant concentrations. This saturation concentration was approximately 70 mmol kg(-1) for Cd, Ni and Zn, 100 mmol kg(-1) for Cu, and 125 mmol kg(-1) for Pb. Overall, our experiments have shown the high effectiveness of pine bark to retain the assayed metals in stable forms of low mobility.

Competitive adsorption and transport of Cd, Cu, Ni and Zn in a mine soil amended with mussel shell

Batch type and column experiments were used to study competitive adsorption-desorption and transport for Cd, Cu, Ni and Zn in a mine soil, both un-amended and amended with mussel shell. Batch type experiments showed that adsorption was affected by the added concentration of the metals, generally following the sequence Cu>Zn>Cd≈Ni. Metal desorbed was a function of the dose of metal added, as well as of the dose of shell amendment, being relevant that even when the highest dose of metal (2300 μM) was added, the 24 g kg(-1) shell amendment caused a drastic diminution in the amount of metal desorbed. Column experiments showed that even the lowest dose of the shell amendment (6 g kg(-1)) caused a strong retention of the 4 heavy metals assayed, whereas using the 24 g kg(-1) shell amendment no metal was detected in the effluent during the time of the experiment. The mass of metal retained in the un-amended soil was very different for the various metals assayed, but the amendment with 6 g kg(-1) shell increased this retention in all cases, and the 24 g kg(-1) amendment caused almost 100% retention for all 4 metals. The retardation factor (R) suffered an overall increase as a function of the shell dose; the profile distribution of the 4 heavy metals was homogeneous through the un-amended soil into the column, but the shell amendment clearly decreased the solute transport affecting these metals, causing its concentration in the first centimeters of the soil profile.

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 (EFs) 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.

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 Pb<Cd<Cu<Zn<Ni for the lowest metal doses, and Pb<Cu<Zn<Cd<Ni for the highest ones. The bi-metal batch experiments indicated that Cu and Pb suffered the highest retention, with high capacity to displace Cd, Ni and Zn from adsorption sites on pine bark. The transport experiments produced comparable results to those obtained in the batch experiments, with pine bark retention capacity following the sequence Pb>Cu>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.

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)·L−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.

Heavy metals in pastureland soils situated in A Pastoriza (NW Spain) treated with cattle slurry and NPK fertilizers

In Galicia (NW Spain), pasturelands cover a broad extension and are mainly used to feed cattle. Farms are managed in an intensive manner, using cattle slurry and inorganic fertilizers to increase pasture production, but also increasing risks of heavy metal pollution. In this work we studied the influence of fertilization practices on total concentrations and in-depth distribution of heavy metals and related elements (As, Cd, Cr, Cu, Mn, Ni, Pb and Zn) in two forest soils (SN1, SN2) and five pastureland soils (P1-P5) fertilized with cattle slurry and NPK, in a broadly exploded farmland area (A Pastoriza, Lugo). Soils SN2 and P4 were developed over slate, whereas soils SN1, P1, P2, P3 and P5 evolved on Candana quartzite. Forest soils presented acid pH (4.58-4.68), high Al saturation (75-90%), and low available P concentration (4.78-11.96 mg kg -1 ), whereas those parameters exhibited better scores in the pastureland soils, due to previous amendment and fertilization practices, thus giving pH 5.17-7.02, Al saturation 0.58-59.24%, and available P 5.24-42.07 mg kg -1 . Regarding heavy metals, soil depth did not affect significantly to total concentrations, contrary to that happening with parent material, with higher As, Cu, Fe, and Ni concentrations found in soils over slate (possibly due to the presence of pyritic materials). In most cases, heavy metal total concentrations were lower than that considered as reference background levels for soils developed over each of the parent materials, and were always lower than that considered phyto-toxic. In this study, natural soils usually presented heavy metal total contents similar or even higher than that of the fertilized soils (unless Zn in the P4 pastureland), thus indicating that the spread doses of fertilizers did not influence significantly their concentration levels.