F. Macías

Chemical and structural properties of carbonaceous products obtained by pyrolysis and hydrothermal carbonisation of corn stover

The main properties of chars produced from corn stover, either by pyrolysis at 550°C (to produce biochar) or by hydrothermal carbonisation (to produce hydrochar), were studied. Carbonaceous materials were characterised by: SEM imaging, solid-state 13C NMR, FT-IR, Raman spectroscopy, and XPS. The following parameters were determined: elemental composition, cation exchange capacity, acid groups contents, BET, and yield. The hydrochar had a low ash content and low pH (4.7); recovery of C was high (57%), although only about half of the C was aromatic. Atomic O/C and H/C ratios in the hydrochar were higher than in the biochar. The same pattern was observed for the estimated concentration of carboxylic functional groups (0.07 compared with 0.04 mol/kg). The biochar had higher ash content than the hydrochar, and also higher pH (~10) (lime equivalence ~40 kg CaCO3/t). The C recovery (46%) was lower than in the hydrochar, although most of the C recovered was aromatic. Both chars could be used as soil amendments, for very different requirements. Soil responses and the residence times of the chars (especially the hydrochar) must be studied in detail to pursue long-term C sequestration.

Simulated geochemical weathering of a mineral ash-rich biochar in a modified Soxhlet reactor.

Although there are many studies on the characterization of C in biochar and its C sequestration potential, there is little knowledge on the mineral fraction in biochar and its weathering. The latter, however, can have powerful implications on nutrient availability. In the present study, a modified Soxhlet reactor was used to simulate the long-term geochemical weathering of an ash-rich biochar produced from sewage sludge of a non-industrial area in New Zealand. The weathering process took place during a period of 300 h, with and without the addition of humic acid (1.00 g added to 20.00 g of biochar), and the treatments were referred to as treatment BC-HA and BC-B, respectively. Both the leaching kinetics and the transformations within the solid phase were studied. The results revealed that substantial amounts of K (8.5-10.2%) and S (20.2-28.3%) were recovered in the weathering solutions. Noticeable Ca (17.9-20.7%) and P (15.4%) in the solid were released but only a few were recovered in the weathering solutions because of the precipitation. The presence of humic acids increased this dissolution and thus the availability of K, S, Ca, Mg and P, but induced N immobilization. Nitrogen availability was already very low (<1.0% of the total N) due to the probable recalcitrant heterocyclic N structure. The pH of the biochar samples dropped from 8.4 to 7.5; this was mainly attributed to loss of base cations through leaching and probable carbonation of the system. The XPS spectra evidenced the oxidation of C in biochar during the weathering process with the formation of carbonyl and carboxylic functional groups. The results obtained in this study showed some promise for the positive use of modified Soxhlet extractor in simulating the geochemical weathering in ash-rich biochars and providing a better understanding on the kinetics of nutrient release. This will be key information in assessing the added value of biochars as soil amendments.

Variation with depth and season in metal sulfides in salt marsh soils

Seasonal monitoring of metal sulfides was carried out in four soils ofthe Ría de Ortigueira salt marshes. Soils from the high salt marsh (withsuboxic redox conditions at the surface), had low concentrations of ironsulfides (AVS and pyrite fraction) and thus a low degree of trace metalpyritization (DTMP) in surface layers (0–10 cm), butconcentrations of metals associated with the pyrite fraction increasedconsiderably at depth (27.5 cm). In the low salt marsh soils (withanoxic conditions at the surface) maximum concentrations of metal sulfides werefound in the surface layers of soils colonized by Spartinamaritima. These results are explained by the double effectexerted by roots in strongly reduced soils. On the one hand, they stimulate theactivity of sulfate-reducing bacteria and on the other, they favour the partialoxidation of the soil, thus generating polysulfides with which Fe2+immediately precipitates as pyrite, whereas in the deepest, permanently anoxiclayers, pyrite must be formed in a reaction in which FeS is an intermediate, asfollows: FeS + H2S→ FeS2 + H2.Concentrations of metal sulfides also varied greatly with the season, with twopatterns being distinguished. In soils colonized by S.maritima in both high and low salt marshes, the lowestconcentrations were found in summer. At this time of the year there is a netloss of metal sulfides throughout the profile, presumably due to physiologicalactivity of plants (evapotranspiration and release of oxygen from roots). Incontrast, maximum concentrations of AVS and pyritic metals were found in thesummer in the low salt marsh soils not colonized by vascular plants (creekbottom). In this case, the higher temperatures increased the activity ofsulfur-reducing bacteria leading to synthesis and accumulation of metalsulfidesin the soil.

Leaching of potential hazardous elements of coal cleaning rejects

The geochemical characteristics of coal cleaning rejects (CCR) in Santa Catarina State, Brazil, were investigated. Around 3.5 million ton/ year of coal waste are dumped in Santa Catarina State. Coal beneficiation by froth flotation results in large amounts of CCR composed of coaly and mineral matter, the latter characterised by the occurrence of sulphide minerals and a broad array of leachable elements. The total and leachable contents of more than 60 elements were analysed. Atmospheric exposure promotes sulphide oxidation that releases substantial sulphate loads as well as Ca2 + , K + , Mg2 + , Cl −  and Al3 + . The metals with the most severe discharges were Zn, Cu, Mn, Co, Ni and Cd. Most trace pollutants in the CCR displayed a marked pH-dependent solubility, being immobile in near-neutral samples. The results highlight the complex interactions among mineral matter solubility, pH and the leaching of potentially hazardous elements.

Spatial variation in pyritization of trace metals in salt-marsh soils

In the present study, the pyritization of trace metals was studied in 12soils from 3 salt marshes in the Ría of Ortigueira (NW Spain). Theconcentrations of trace metals in the pyrite fraction were related tophysicochemical conditions, physiographical position in the salt marsh, and thepresence or absence and type of vegetation. Redox conditions in soils from thelow-salt marsh and from the creek bottom were strongly reducing throughout theprofile, and there were higher concentrations of Fe and some trace metals (Cuand Mn) in the pyrite fraction (soluble in HNO3) than in thereactivefraction (soluble in 1N HCl). In contrast, the trace-metal content in pyritefraction in the surface layers of the high-salt marsh was low. In some of thesoils, there was a significant increase in the pyrite content below 25cm, and levels of Fe, Mn and Cu incorporated into this fractionwere similar to those in the reactive fraction. The degree of pyritizationvaried greatly among metals in the order: Cu∼Fe-1NHCl>dithionite-Fe>Ni∼Mn>>Zn>Cr, although when we consideredonly the amorphous forms (ascorbate-Fe) as reactive-Fe, the order was:ascorbate-Fe>>Cu>Ni∼Mn>>Zn>Cr. These differences appearedto be a consequence of the different geochemical behaviour of each metal(mainlyin terms of the thermodynamic stability of sulfides and reaction kinetics),except for Zn. The low concentrations of Zn obtained may have been due to thesolubility of ZnS in 1N HCl, which meant that it was extracted with thereactivefraction. Finally, we observed a direct relationship between DOP and DTMP,whichwas independent of the geochemical behaviour of each metal and of itsconcentration in the soil. Thus, the strong correlation between pyrite-Fe andthe metals associated with this fraction appears to indicate that these metalscoprecipitate with pyrite rather than form metal sulfides.

Coal cleaning residues and Fe-minerals implications

In the present investigation, a study was undertaken to understand the origin of Fe-minerals presents in Brazilian coal mining and to understand the environmental implication and the chemical heterogeneity in the study area. Coal cleaning residue samples rich in clays, quartz, sulphides, carbonates, sulphates, etc. were sampled from Lauro Muller, Urussanga, Treviso, Siderópolis, and Criciúma cities in the Santa Catarina State and a total of 19 samples were collected and Mössbauer, XRD, SEM/EDX, and TEM analyses were conducted on the samples. The major Fe-minerals identified are represented by the major minerals chlorite, hematite, illite, and pyrite, while the minor minerals include, ankerite, chalcopyrite, goethite, hematite, jarosite, maghemite, magnetie, marcasite, melanterite, natrojarosite, oligonite, pyrrhotite, rozenite, schwertmannite, siderite, and sideronatrile. Pyrite is relatively abundant in some cases, making up to around 10% of the mineral matter in several samples. The sulphates minerals such as jarosite and others, probably represent oxidation products of pyrite, developed during exposure or storage.

Phytotoxicity of hexachlorocyclohexane: effect on germination and early growth of different plant species.

The aim of the present study was to select candidate plant species for phytoremediation of soils contaminated with hexachlorocyclohexane (HCH). For this purpose, an experiment was carried out under controlled conditions of germination and growth, with nine plant species of economic and/or agricultural interest, in a soil contaminated with a heterogeneous mixture (at eight different levels of contamination) of the main HCH isomers (alpha-, beta-, gamma- and delta-HCH). The results revealed differences in the plant responses to the control soil and the soils containing HCH. Germination was not as strongly affected as other parameters such as the rate of germination and seedling vigour. In general, all of the species displayed signs of stress in response to the presence of HCH, although to different degrees. Some of the species used in the experiment (Hordeum vulgare L., Brassica sp., Phaseoulus vulgaris L.) were capable of mitigating the negative effects of HCH, and displayed a certain degree of resistance, as their biomass production was not greatly affected by the contaminant. These (tolerant) plants therefore appear to be ideal for phytoremediation purposes.

Heavy metal geochemistry of saltmarsh soils from the Rı́a of Ortigueira (mafic and ultramafic areas, NW Iberian Peninsula)

Concentrations of Fe, Mn, Ni, Cu, Cr and Zn in their total, silicate, organic, reactive and pyrite fractions were determined in soils collected from the Ortigueira saltmarshes (Esteiro, Ladrido and Mera, NW Iberian Peninsula), from sediments of the Landoi and Esteiro Rivers, and from sludge generated by a nearby dunite mine. The Esteiro saltmarsh presented clear enrichments of the four metals studied (first 10 cm), especially of Ni and Cr, whose concentrations were among the highest. It is proposed that the elevated Cr and Ni levels found in the Esteiro saltmarsh were derived from recent contributions of the mine, which are partially discharged into the Landoi River. Total Cu and Zn concentrations were lower than the corresponding ones for Cr and Ni. Under suboxic conditions, Ni, Cr, Cu and Zn were mainly associated with the reactive fraction. Under anoxic conditions, Cu and Ni were associated mainly with the pyrite phase. Pyritic Zn and Cr concentrations were relatively low and similar in all three saltmarshes; however, where anoxic-sulfidic conditions prevailed these two metals were mainly associated with the reactive and organic fractions.

Spatial and seasonal variation in heavy metals in interstitial water of salt marsh soils

The composition of interstitial water collected from a salt marsh in NW Spain showed clear seasonal and spatial variations associated with redox cycles of Fe and S. In the summer, salinity increased in all soils as a consequence of the increase in evapotranspiration. The pH and concentrations of heavy metals also differed with season, but not all environments showed the same variations. Soils not colonized by plants had the highest pH and lowest heavy metal concentrations in the summer. These results support the idea that higher temperatures lead to an increase in the activity of sulfate-reducing bacteria, which in turn leads to an increase in alkalinity and concentration of sulfides in the water. Trace metals tend to precipitate with sulfides under these conditions and are removed from the interstitial water. In contrast, in the soils colonized by Spartina maritima, the oxidation of metal sulfides during the summer led to a decrease in pH and an increase in the metal concentrations in the interstitial water. The results obtained concur with those found for seasonal variations in metal sulfides in soils from the same salt marsh.

Producing biochars with enhanced surface activity through alkaline pretreatment of feedstocks

Surface-activated biochars not only represent a useful carbon sink, but can also act as useful filtering materials to extract plant nutrients (e.g. NH4 + ) from wastes (e.g. animal or municipal waste streams) and added thereafter to soils. Biochars produced by low-temperature pyrolysis of fibrous debarking waste from pine (PI) and eucalyptus (EU) were pre- treated with either diluted (L) or undiluted (S) alkaline tannery waste (L-PI, S-PI, L-EU, S-EU). Biochars produced from untreated feedstock were used as controls. Samples were characterised by FT-IR, solid-state CP MAS 13 C NMR, XPS, SEM microphotographs, and BET specific surface area. Elemental composition, carbon recovery, yield, surface charge, and NH4 + sorption/desorption properties were also studied. Carbon recovery was lower in biochars prepared from L-EU and S-EU (43 and 42%, respectively) than in control EU (45%) but these biochars showed greater changes in their chemical characteristics than those made from L-PI and S-PI, which showed minimal decrease in recovered carbon. The specific surface area of the biochars decreased with treatments, although acidic surface groups increased. In subsequent sorption experiments, treated biochars retained more NH4 + from a 40mg N/L waste stream (e.g. 61% retention in control EU and 83% in S-EU). Desorption was low, especially in treated biochars relative to untreated biochars (0.1-2% v. 14-27%). The results suggest that surface activated biochars can be obtained with negligible impairment to the carbon recovered.