Post-depositional processes of elemental enrichment inside dark nodular masses of an ancient aeolian dune from A Coruña, Northwest Spain

This paper focuses on a residual ancient aeolian climbing dune from Punta Penaboa (A Coruña, Northwest Spain) showing evidence of post-depositional weathering, particularly the presence of dark brown nodular masses. The partitioning of trace elements between nodular masses and host sand during post-depositional weathering of the dune is investigated in this work, with the main objective of studying the elemental enrichment patterns in the dark masses. Data of the concentrations of chemical elements were obtained by instrumental neutron activation analysis (INAA) and complemented by mineralogical and microchemical studies, using X-ray powder diffraction (XRD) and scanning electron microscopy (SEM) / energy dispersive X-ray spectrometry (EDS). The dune was dated by optically stimulated luminescence (OSL) , yielding an age of 300ka B.P.. The dark nodular masses preserved the dune sand structure, without defined concentric layers, suggesting an early stage of formation. They consist mainly of quartz grains cemented by clay materials enriched in the majority of the elements studied, especially in Mn, Co, Ba, Sb, Ce, Tb, Th, As, Zr and Hf. The post-depositional transformations of the dune were most likely influenced by migration of chemical compounds from the surrounding slope deposits and granitic rocks, as well as microbial activity that promoted metals concentration in the solutions percolating through the pore network of the dune. Seasonal changes in the redox potential were required to produce the accumulation of Mn and other trace elements in the dune pore network and to promote the fractionation between Ce4+ and trivalent rare earth elements that was observed in the geochemical patterns

Sulfadiazine, sulfamethazine and sulfachloropyridazine removal using three different porous materials: Pine bark, “oak ash” and mussel shell

This work focuses on studying the efficacy of three different by-products to adsorb three antibiotics (sulfadiazine, SDZ; sulfamethazine, SMT; sulfachloropyridazine, SCP). These antibiotics can be considered pollutants of the environment when they reach water, as well as in cases where they are spread on soils through irrigation or contained in sewage sludge or livestock manure. In this study, batch-type adsorption/desorption experiments were performed for each of the three sulfonamides, adding 7 different concentrations of the antibiotics, going from 1 to 50 μmol L−1, and with contact time of 24 h. The results indicate that pine bark is the most efficient bioadsorbent among those studied, as it adsorbs up to 95% of the antibiotics added, while desorption is always less than 11%. However, for “oak ash” and mussel shell the adsorption is always lower than 45 and 15%, respectively, and desorption is high, reaching up to 49% from “oak ash” and up to 81% from mussel shell. Adsorption data showed good fitting to the Linear and Freundlich models, with R2 values between 0.98 and 1.00 in both cases. Kd and KF adsorption parameters showed similar values for the same sorbent materials but were much higher for pine bark than for the other two bioadsorbents. The Freundlich's n parameter showed values in the range 0.81–1.28. The highest KF values (and therefore the highest adsorption capacities) were obtained for the antibiotic SCP in pine bark. Pine bark showed the highest capacity to adsorb each of the antibiotics, increasing as a function of the concentration added. When the concentration of sulfonamide added was 50 μM, the amounts adsorbed were 780 μmol kg−1 for SDZ, 890 μmol kg−1 for SMT, and 870 μmol kg−1 for SCP. “Oak ash” and mussel shell have low adsorption capacity for all three sulfonamides, showing values always lower than 150 μmol kg−1 (oak ash) and 20 μmol kg−1 (mussel shell) when a concentration of 50 μmol L−1 of antibiotic is added. The results of this study could aid to make an appropriate management of the by-products studied, in order to facilitate their valorization and recycling in the treatment of environmental compartments polluted with sulfonamide antibiotics.Agencia Estatal de Investigación | Ref. RTI2018-099574-B-C21Agencia Estatal de Investigación | Ref. RTI2018-099574-B-C2

Aluminium fractionation and speciation in bulk and rhizosphere of a grass soil amended with mussel shells or lime

Acid soils have a high proportion of Al in the exchange complex and are usually amended with lime to reduce the toxic effect of the free Al (Al 3+). To this purpose, in some places like Galicia (NW Spain), there is a high production of wastes such as mussel shells that may substitute the lime. The aim of this work was to study the effect of different amending products derived from mussel shells on the Al chemistry in both bulk and rhizosphere, and on pasture production. The experiments were conducted on plots of an acid soil cultivated with grasses (Dactylis glomerata L., Trifolium repens L. and Lolium perenne L.). Each plot received its own treatment consisting of 1) commercial lime, 2) mussel shells dried and ground till 0-2mm (MDF), 3) mussel shells dried and ground till 2-4mm (MDC), 4) mussel shells heated (550°) and ground till <63μm (MHF), or 5) mussel shells heated (550°C) and ground till 0-2mm (MHC); one plot acted as control and was not treated. Each plot was replicated four times. The soil samples were collected after 16months and submitted to a general characterization. The Al was extracted from the soil by different solutions: ammonium oxalate (Alo=non-crystalline Al), sodium pyrophosphate (Alp=organically bound Al), copper chloride (Alcu=organo-Al complexes of low to medium stability) and ammonium chloride (exchangeable Al); the difference Alp-cu estimated the organo-Al complexes of high stability. From the soil water extracts, the Al was fractionated into acid-soluble (Al-polymers, colloids and organic complexes), non-labile Al (organic monomers) and labile Al (inorganic monomers, namely the species Al 3+, Al-OH, Al-F and Al-SO 4). For each plot, the production of the total dry matter and of that produced by the sown species, were also determined. With respect to the control, all the amending treatments increased the pH in the rhizosphere (5.11 in the control plots, 5.48-5.89 in the amended plots), which showed pH values higher than the bulk (5.13-5.60 in the amended bulk soil; 5.48-5.89 in the amended rhizosphere). Also the contents of C and N were higher in the rhizosphere than in the bulk, without difference among treatments. Concerning with Al chemistry, all the mussel shells derived products had effects similar to those of the commercial lime, with no difference among them. With respect to the control, in the soil solid phase all the treatments induced an increase in the formation of hydroxyl-aluminium complexes in the bulk (Alo: 3500mgkg -1 in the control, 3700-5500mgkg -1 in the amended plots) and organo-Al complexes of high stability in the rhizosphere (Alp-cu: 3563mgkg -1 in the control, 3550-5000mgkg -1 in the amended plots). The exchangeable Al diminished with all treatments, more in the rhizosphere (1.36cmol(+) kg -1 in the control, 0.24-0.47cmol(+) kg -1 in the amended plots) than in the bulk (2.83cmol(+) kg -1 in the control, 0.46-1.23cmol(+) kg -1 in the amended plots). Concerning the water extracts, the treatments induced an increase of organic complexes (polymers and monomers), more pronounced in the rhizosphere (non-labile Al: 0.17μmolL -1 in the control, 10.7-35.7μmolL -1 in the amended plots) than in the bulk (non-labile Al: 0.25μmolL -1 in the control, 0.25-3.57μmolL -1 in the amended plots). Further, in the treated plots the labile Al was dominated by Al-OH complexes, which are considered toxic but a lower level than the Al 3+ and abounded in the control. The production of dry matter due to the sown species was about double in the plots treated with CL and MHF with respect to the control. We conclude that the products derived from mussel shells can substitute the commercial lime in the amending of acid soils, so increasing the value of the shells and limiting the environmental problems derived by their disposal