Mercury mobilization in shrubland after a prescribed fire in NE Portugal: Insight on soil organic matter composition and different aggregate size.

Soils constitute the major reservoir of mercury (Hg) in terrestrial ecosystems, whose stability may be threatened by wildfires. This research attempts to look at the effect of prescribed fire on the presence of Hg in a shrubland ecosystem from NE Portugal, delving into its relationship with soil aggregate size and the molecular composition of soil organic matter (SOM). During the prescribed fire, on average 347 mg Hg ha-1 were lost from the burnt aboveground biomass of shrubs and 263 mg Hg ha-1 from the combustion of the soil organic horizon. Overall, Hg concentration and pools in the mineral soil did not show significant changes due to burning, which highlights their role as long-term Hg reservoirs. The higher Hg concentrations found in smaller aggregates (<0.2 mm) compared to coarser ones (0.5-2 mm) are favored by the higher degree of organic matter decomposition (low C/N ratio), rather than by greater total organic C contents. The Hg-enriched finest fraction of soil (<0.2 mm) could be more prone to be mobilized by erosion, whose potential arrival to water bodies increases the environmental concern for the Hg present in fire-affected soils. The SOM quality (molecular composition) and the main organic families, analyzed by Fourier-transform infrared spectroscopy in combination with multivariate statistical analysis, significantly conditioned the retention/emission of Hg in the uppermost soil layers. Thus, before the fire, Hg was strongly linked to lipid and protein fractions, while Hg appeared to be linked to aromatic-like compounds in fire-affected SOM.

Variation of Hg concentration and accumulation in the soil of maritime pine plantations along a coast-inland transect in SW Europe.

Climatic conditions have been shown as a major driver of the fate of Hg in forest ecosystems at a global scale, but less is known about climatic effects at shorter scales. This study assesses whether the concentration and pools of Hg in soils collected from seventeen Pinus pinaster stands describing a coastal-inland transect in SW Europe vary along a regional climatic gradient. In each stand, samples of the organic subhorizons (OL, OF + OH) and the mineral soil (up to 40 cm) were collected and some general physico-chemical properties and total Hg (THg) were analyzed. Total Hg was significantly higher in the OF + OH than in the OL subhorizons (98 and 38 µg kg-1, respectively), favored by a greater organic matter humification in the former. In the mineral soil, mean THg values decreased with depth, ranging from 96 µg kg-1 in the 0-5 cm layers to 54 µg kg-1 in the deepest layers (30-40 cm), respectively. The average Hg pool (PHg) was 0.30 mg m-2 in the organic horizons (92% accumulated in the OF + OH subhorizons), and 27.4 mg m-2 in the mineral soil. Changes in climatic factors, mainly precipitation, along the coast-inland transect resulted in a remarkable variation of THg in the OL subhorizons, consistent with their role as the first receiver of atmospheric Hg inputs. The high precipitation rate and the occurrence of fogs in coastal areas characterized by the oceanic influence would explain the higher THg found in the uppermost soil layers of pine stands located close to the coastline. The regional climate is key to the fate of mercury in forest ecosystems by influencing the plant growth and subsequent atmospheric Hg uptake, the atmospheric Hg transference to the soil surface (wet and dry deposition and litterfall) and the dynamics that determine net Hg accumulation in the forest floor.

Mercury in a birch forest in SW Europe: Deposition flux by litterfall and pools in aboveground tree biomass and soils.

Atmospheric mercury (Hg) is largely assimilated by vegetation and subsequently transferred to the soil by litterfall, which highlights the role of forests as one of the largest global Hg sinks within terrestrial ecosystems. We assessed the pool of Hg in the aboveground biomass (leaves, wood, bark, branches and twigs), the Hg deposition flux through litterfall over two years (by sorting fallen biomass in leaves, twigs, reproductive structures and miscellaneous) and its accumulation in the soil profile in a deciduous forest dominated by Betula alba from SW Europe. The total Hg pool in the aboveground birch biomass was in the range 532-683 mg ha-1, showing the following distribution by plant tissues: well-developed leaves (171 mg ha-1) > twigs (160 mg ha-1) > bark (159 mg ha-1) > bole wood (145 mg ha-1) > fine branches (25 mg ha-1) > thick branches (24 mg ha-1) > newly sprouted leaves (20 mg ha-1). The total Hg deposition fluxes through litterfall were 15.4 and 11.7 µg m-2 yr-1 for the two years studied, with the greatest contribution coming from birch leaves (73 %). In the soil profile, the pool of Hg in the mineral soil (37.0 mg m-2) was an order of magnitude higher than in the organic horizons (1.0 mg m-2), mostly conditioned by parameters such as soil bulk density and thickness, total C and N contents and the presence of certain Al compounds.

Needle age and precipitation as drivers of Hg accumulation and deposition in coniferous forests from a southwestern European Atlantic region.

Vegetation and climate are critical in the biogeochemical cycle of Hg in forest ecosystems. The study assesses the influence of needle age and precipitation on the accumulation of Hg in needle biomass and its deposition by litterfall in thirty-one pine plantations spread throughout two biogeographical regions in SW Europe. Well-developed branches of Pinus pinaster were sampled and pine needles were classified according to 4 age classes (y0, y1, y2, y3). The concentration of total Hg (THg) was analyzed in the samples and Hg content in needle biomass and its deposition by litterfall were estimated. The concentration of total Hg (THg) increased with needle age ranging from 9.1 to 32.7 µg Hg kg-1 in the youngest and oldest needles, respectively. The rate of Hg uptake (HgR) three years after needle sprouting was 10.2 ± 2.3 µg Hg kg-1 yr-1, but it decreased with needle age probably due to a diminution in photosynthetic activity as needles get older. The average total Hg stored in needle biomass (HgWt) ranged from 5.6 to 87.8 mg Hg ha-1, with intermediate needle age classes (y1 and y2) accounting for 70% of the total Hg stored in the whole needle biomass. The average deposition flux of Hg through needle litterfall (HgLt) was 1.5 µg Hg m-2 yr-1, with the y2 and y3 needles contributing most to the total Hg flux. The spatial variation of THg, HgWt and HgLt decreased from coastal pine stands, characterized by an oceanic climate, to inland pine stands, a feature closely related to the dominant precipitation regime in the study area. Climatic conditions and needle age are the main factors affecting Hg accumulation in tree foliage, and should be considered for an accurate assessment of forest Hg pools at a regional scale and their potential consequences in the functioning of terrestrial ecosystems.

Soil properties influencing Hg vertical pattern in temperate forest podzols.

Mercury content of twelve podzols from NW Spain was studied to elucidate the main soil properties involved in the Hg accumulation of these soils. The highest average Hg concentrations (HgT) were found in the Bh and Bs horizons (64 and 105 µg kg-1), whereas the lowest occurred in the E horizons (15 µg kg-1). Moderate values of HgT were obtained for the A and C horizons (38 and 52 µg kg-1). The Hg enrichment factors revealed that the predominant origin of Hg in these soils is the atmosphere instead of the parent material. As it was shown by the PCA performed (which explained 82% of the variance of the data), the main soil characteristics involved in the pedogenetic processes of the studied podzols are organic matter and Al and Fe compounds. The stepwise linear regressions made described between 54% and 84% of the predicted Hg depending on the soil horizon. Besides a complex ensemble of biogeochemical reactions involved in the balance between input and outputs of Hg, the most influencing variable in the A horizons was organic C, moderate stability Al-humus complexes in the E horizons, Fe-humus complexes and pHw in the Bh horizons, Al-humus compounds in the Bs horizons and crystalline Al and Fe compounds in the C horizons. Therefore, Hg is mobilized from the A and E horizons bound to dissolved organic matter and precipitated in the illuvial horizons due to the saturation of the organic matter with metals. The immobilization of Hg in the subsuperficial horizons of podzols leads to different environmental benefits derived from the removal of Hg from the A horizons, more exposed to climate-induced and land use/cover changes that could potentially modify the dynamics of Hg in those superficial horizons.

Modelling Hg mobility in podzols: Role of soil components and environmental implications.

A high-resolution soil sampling has been applied to two forest podzols (ACB-I and ACB-II) from SW Europe in order to investigate the soil components and processes influencing the content, accumulation and vertical distribution of Hg. Total Hg contents (THg) were 28.0 and 23.6 µg kg-1 in A horizons of ACB-I and ACB-II, then they strongly decreased in the E horizons and peaked in the Bhs horizons of both soils (55.3 and 63.0 µg kg-1). THg decreased again in BwC horizons to 17.0 and 39.8 µg kg-1. The Bhs horizons accounted for 46 and 38% of the total Hg stored (ACB-I and ACB-II, respectively). Principal component analysis (PCA) and principal components regression (PCR), i.e. using the extracted components as predictors, allowed to distinguish the soil components that accounted for Hg accumulation in each horizon. The obtained model accurately predicted accumulated Hg (R2 = 0.845) through four principal components (PCs). In A horizons, Hg distribution was controlled by fresh soil organic matter (PC4), whereas in E horizons the negative values of all PCs were consistent with the absence of components able to retain Hg and the corresponding very low THg concentrations. Maximum THg contents in Bhs horizons coincided with the highest peaks of reactive Fe and Al compounds (PC1 and PC2) and secondary crystalline minerals (PC3) in both soils. The THg distribution in the deepest horizons (Bw and BwC) seemed to be influenced by other pedogenetic processes than those operating in the upper part of the profile (A, E and Bhs horizons). Our findings confirm the importance of soils in the global Hg cycling, as they exhibit significant Hg pools in horizons below the uppermost O and A horizons, preventing its mobilization to other 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.

Controlling risks of P water pollution by sorption on soils, pyritic material, granitic material, and different by-products: effects of pH and incubation time.

Batch experiments were used to test P sorbent potential of soil samples, pyritic and granitic materials, mussel shell, mussel shell ash, sawdust, and slate waste fines for different pH and incubation times. Maximum P sorption varied in a wide range of pH: < 4 for pyritic material, 4-6 for forest soil, > 5 for slate fines, > 6 for shell ash, and pH 6-8 for mussel shell. P sorption was rapid (< 24 h) for forest soil, shell ash, pyritic material, and fine shell. On the opposite side, it was clearly slower for vineyard soil, granitic material, slate fines, pine sawdust, and coarse shell, with increased P sorption even 1 month later. For any incubation time, P sorption was > 90% in shell ash, whereas forest soil, pyritic material, and fine shell showed sorption rates approaching 100% within 24 h of incubation. These results could be useful to manage and/or recycle the sorbents tested when focusing on P immobilization or removal, in circumstances where pH changes and where contact time may vary from hours to days, thus aiding to diminish P pollution and subsequent eutrophication risks, promoting conservation and sustainability.

Chromium and fluoride sorption/desorption on un-amended and waste-amended forest and vineyard soils and pyritic material.

Using batch-type experiments, chromium (Cr(VI)) and fluoride (F-) sorption/desorption were studied in forest and vineyard soil samples, pyritic material, pine bark, oak ash, hemp waste and mussel shell, as well as on samples of forest and vineyard soil, and of pyritic material, individually treated with 48 t ha-1 of pine bark, oak ash, and mussel shell. Pine bark showed the highest Cr(VI) sorption (always > 97% of the concentration added) and low desorption (<1.5%). Pyritic material sorbed between 55 and 98%, and desorbed between 0.6 and 9%. Forest and vineyard soils, oak ash, mussel shell and hemp waste showed Cr(VI) sorption always < 32%, and desorption between 22 and 100%. Pine bark also showed the highest F- retention (sorption between 62 and 73%, desorption between 10 and 15%), followed by oak ash (sorption 60-69%, desorption 11-14%), forest soil (sorption 60-73%, desorption 19-36%), and pyritic material (sorption 60-67%, desorption 13-15%), whereas in vineyard sorption was 49-64%, and desorption 24-27%, and in hemp waste sorption was 26-36%, and desorption 41-59%. Sorption data showed better fitting to the Freundlich than to the Langmuir model, especially in the case of Cr(VI), indicating that multilayer sorption dominated. The addition of by-products to the forest and vineyard soils, and to the pyritic material, caused an overall increase in F- sorption, and decreased desorption. Furthermore, the pine bark amendment resulted in increases in Cr(VI) retention by both soils and the pyritic material. These results could be useful to favor the recycling of the by-products studied, aiding in the management of soils and degraded areas affected by Cr(VI) and F- pollution, and in the removal of both anions from polluted waters.

Modification of chemical properties, Cu fractionation and enzymatic activities in an acid vineyard soil amended with winery wastes: A field study.

The effects of adding two winery wastes, perlite waste (PW) and bentonite waste (BW), to an acid vineyard soil were assessed using some chemical and biological soil properties in a field study that lasted 18 months. The addition of PW (up to 81 Mg ha-1) had neither significant nor permanent effects on soil characteristics such as the pH, organic matter content or nutrient concentrations, the amounts of copper or zinc, or the electrical conductivity. Moreover, no persistent negative effects were found on the enzymatic activities after PW application. In contrast, soil that was amended with up to 71 Mg BW ha-1 showed increases in its soil pH values, exchangeable potassium and water soluble potassium and phosphorus contents. In addition, it caused significant increases in the electrical conductivity and water-soluble Cu. In addition, the phosphomonoesterase enzymatic activity decreased significantly (up to 28%) in response to the amendment with 71 Mg BW ha-1. These results showed that adding BW and PW to the soil may be a good agronomic practice for recycling these types of wastes. However, in the case of PW, its use as a soil amendment must be performed with caution to control its possible harmful effects.

As(V) Sorption/Desorption on Different Waste Materials and Soil Samples.

Aiming to investigate the efficacy of different materials as bio-sorbents for the purification of As-polluted waters, batch-type experiments were employed to study As(V) sorption and desorption on oak ash, pine bark, hemp waste, mussel shell, pyritic material, and soil samples, as a function of the As(V) concentration added. Pyritic material and oak ash showed high sorption (90% and >87%) and low desorption (<2% and <7%). Alternatively, hemp waste showed low retention (16% sorption and 100% desorption of the amount previously sorbed), fine shell and pine bark sorbed <3% and desorbed 100%, the vineyard soil sample sorbed 8% and released 85%, and the forest soil sample sorbed 32% and desorbed 38%. Sorption data fitted well to the Langmuir and Freundlich models in the case of both soil samples and the pyritic material, but only to the Freundlich equation in the case of the various by-products. These results indicate that the pyritic material and oak ash can be considered efficient As(V) sorbents (thus, useful in remediation of contaminated sites and removal of that pollutant), even when As(V) concentrations up to 6 mmol L-1 are added, while the other materials that were tested cannot retain or remove As(V) from polluted media.

Heavy metals fractionation and desorption in pine bark amended mine soils.

The European Community Bureau of Reference method (BCR) was used for evaluating the effects of pine bark amendment (0, 24 and 48 g kg-1) and ageing (1 and 30 days) on Cd, Cu, Ni, Pb and Zn fractionation, on samples from an acid mine soil. In addition, the stirred flow chamber technique was applied for analyzing heavy metals desorption from the unamended and pine bark amended mine soil. When the unamended soil were not subjected to ageing, the added heavy metals were mainly accumulated as soluble fraction (>90% for Cd, Ni and Zn; 71% for Cu; and 45% for Pb). Pine bark amendment and ageing had little effect on Cd, Ni and Zn fractionation, whereas important changes were detected for Cu and Pb in response to both pine bark amendment and ageing (decrease in the soluble fractions, and increase in less mobile fractions). Desorption experiments showed that both pine bark amendment and ageing decreased heavy metals release from the mine soil. The results of this study indicate that pine bark amendment could be used to increase heavy metals retention (especially in the case of Cu and Pb) in acid mine soils, thus reducing the risks of metal transfer to uncontaminated environmental zones.

As(V)/Cr(VI) retention on un-amended and waste-amended soil samples: competitive experiments.

Focusing on simultaneous arsenic and chromium pollution, we used batch-type experiments to study As(V)/Cr (VI) competitive sorption on soil samples, pyritic material, mussel shell, oak ash, pine bark and hemp waste, as well as on binary mixtures (50 % mussel shell and 50 % another material-oak ash, pine bark, or hemp waste), and on forest and vineyard soil samples and pyritic material amended with 48 t ha-1 of mussel shell, oak ash, pine bark, or hemp waste. Equal As(V) and Cr(VI) concentrations (0 to 6 mmol L-1) were added to the individual materials, binary mixtures, and 48 t ha-1 amended materials. The individual forest soil sample, pyritic material, and oak ash showed clearly higher As(V) sorption, whereas Cr(VI) sorption was higher on pine bark. Sorption was up to 50 % higher for As(V) than for Cr(VI) on the forest soil sample, oak ash, and pyritic material, while pine bark sorbed 95 % more Cr(VI). Regarding binary mixtures, the presence of mussel shell increased As(V) sorption on pine bark and Cr(VI) sorption on hemp waste. As regards the amendments, in the case of the forest soil sample, the amendments with oak ash and mussel shell increased As(V) sorption, while pine bark amendment increased Cr(VI) sorption; in the vineyard soil sample, the mussel shell amendment increased As(V) sorption; in the pyritic material, pine bark amendment increased Cr(VI) sorption. These results could be useful to appropriately manage the soils and individual or mixed by-products assayed when As(V) and Cr(VI) pollution occurs.

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.

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.

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.

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.

Cu retention in an acid soil amended with perlite winery waste.

The effect of perlite waste from a winery on general soil characteristics and Cu adsorption was assessed. The studied soil was amended with different perlite waste concentrations corresponding to 10, 20, 40 and 80 Mg ha(-1). General soil characteristics and Cu adsorption and desorption curves were determined after different incubation times (from 1 day to 8 months). The addition of perlite waste to the soil increased the amounts of organic matter as well as soil nutrients such as phosphorus and potassium, and these increments were stable with time. An increase in Cu adsorption capacity was also detected in the perlite waste-amended soils. The effect of perlite waste addition to the soil had special relevance on its Cu adsorption capacity at low coverage concentrations and on the energy of the soil-Cu bonds.

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.