Removal of anionic pollutants by pine bark is influenced by the mechanism of retention

Chemosphere, 167, 2017, 139–145

http://dx.doi.org/10.1016/j.chemosphere.2016.09.158

The use of organic biosorbents for anion removal from water has been less studied than for cationic compounds. In this work, the removal capacity of pine bark for potential anionic pollutants (fluoride, phosphate, arsenate and dichromate) was assessed in column experiments, designed to study the process of transport. The results showed that pine bark has a very low retention capacity for phosphate, arsenate or fluoride, and in turn, very high for dichromate, with retention values close to 100% and less than 2% desorption of the adsorbed dichromate. The large differences observed between anions suggest that differences in the retention mechanism of each anion exist. In the case of phosphate and arsenate, electrostatic interactions with the mostly negatively charged functional groups of the pine bark determine the low retention capacity. Dichromate retention might proceed through reduction of chromium (VI) to chromium (III), what improves the efficiency of the removal.

Copper, Chromium, Nickel, Lead and Zinc levels and pollution degree in firing rage soils

Land Degrad. Develop. 27: 1721–1730 (2016)

DOI: 10.1002/ldr.2497

Small-arms firing ranges are an important source of metal contaminants in the ecosystems located near these facilities, owing to the constant fall and alteration of the ammunition remnants on the soil, particularly in nearby berms. The objectives of this study were to analyse the pollution of chromium (Cr), copper (Cu), nickel (Ni), lead (Pb) and zinc (Zn) in rifle/pistol shooting range soils, to estimate their availability and to evaluate the influence of the ammunition used. The concentrations of Pb, Zn, Cu, Cr and Ni range from 55 to 6·309, 34 to 264, 19 to 98, 40 to 79 and 11 to 33 mg kg 1, respectively. The moderate acidity and organic matter content favour the availability of Pb, followed by Cu > Zn > Ni > Cr. The values of different contamination indexes (Igeo, pollution index and integrated pollution index) suggest that Pb soil contamination is moderate to heavy, especially in the berm area and moderate for Cu and Zn. Lead ammunition is the main source of pollution, but another one was identified owing to the concentrations of Fe, Cr and Ni detected. Further studies are needed to verify their long-term potential adverse effects.

TOF-SIMS and FE-SEM/EDS to verify the heavy metal fractionation in serpentinite quarry soils

CATENA, 136, 2016, 30–43

http://dx.doi.org/10.1016/j.catena.2015.03.005

This study aims at extensively defining serpentinite quarry soils and analysing their content and distribution of heavy metals using chemical sequential extraction. The association with the different geochemical phases of the soil was verified using TOF-SIMS and SEM-EDS techniques. Seven soils were chosen in two serpentinite quarries located in Moeche (M) and Silleda (C) (Galicia, northwest of Spain). The selected areas for soil sampling were: dump sites (M1, M2 and C1), rock extraction sites (M3, C2), and quarry boundaries (M4 and C3). The total soil concentration of Co, Cr, Ni, and V varied from 1472 to 7132, 1499 to 4309, 76 to 373, and 21 to 140 mg kg− 1, respectively. In all cases they exceed the maximum limit permitted in soils. After chemical sequential extraction it was found that the high content of Co, Cr, Ni, and V is associated with the residual fraction of the soils. In addition, Fe and Mn oxides have a high capacity for Co fixation, whereas Cr, Ni, and V are mainly associated with magnesium silicates. The fractions related to organic matter and the soluble or available forms are, respectively low and very low, not exceeding 2.5% in any of the soils. This association of the metals with magnesium silicates and Fe oxides, and the low content of metals bound to organic matter were identified by using the TOF-SIMS and SEM-EDS techniques. Both techniques confirmed and verified the results obtained during the chemical sequential extraction by checking the interaction of heavy metals with the different components of the soil.

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

Environmental Science and Pollution Research

DOI: 10.1007/s11356-016-7108-0

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.

Cr(VI) sorption/desorption on pine sawdust and oak wood ash

International Journal of Environmental Research and Public Health

DOI: 10.3390/ijerph120808849

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.

Cr(VI) sorption/desorption on untreated and mussel-shell-treated soil materials: fractionation and effects of pH and chromium concentration

Solid Earth, 6, 373–382, 2015

doi 10.5194/se-6-373-2015

We used batch-type experiments to study Cr(VI) sorption/desorption on granitic material, forest soil, pyritic material, mussel shell, and on forest soil and granitic material amended with 12 t ha−1 (1.2 kg m−2) shell, considering the effects of varying Cr(VI) concentration and pH. Sequential extractions were carried out to fractionate adsorbed Cr(VI) and to determine the stability of Cr(VI) retention. The pyritic material had the highest Cr(VI) retention capacity, whereas the granitic material showed the lowest retention potential. When high Cr concentrations were added, some saturation of the adsorbent surfaces became apparent, but Cr release remained low. The highest Cr retention was achieved at a very acid pH value, with release progressively increasing as a function of increasing pH. The amendment with 12 t ha−1 mussel shell did not cause marked changes in Cr(VI) re- tention. Sorption data were satisfactory adjusted to the Fre- undlich model. Regarding Cr(VI) fractionation, the soluble fraction (weakly bound) was dominant in mussel shell and in the unamended and amended granitic material, whereas more stable fractions dominated in the pyritic material (resid- ual fraction) and in the forest soil (oxidizable fraction). In conclusion, the pyritic material presented the highest Cr(VI) retention capacity, while the retention was low and weak on the granitic material; mussel shell was not characterized by a marked Cr(VI) retention potential, and it did not cause re- markable increase in Cr(VI) retention when used to amend the granitic material or the forest soil.