Thermal stability of the soil minerals destinezite and diadochite Fe3+2(PO4)(SO4)(OH)·6H2O - implications for soils in bush fires

Thermogravimetry combined with evolved gas mass spectrometry has been used to ascertain the stability of the soil minerals destinezite and diadochite. These two minerals are identical except for their morphology. Diadochite is amorphous whereas destinezite is crystalline. Both minerals are found in soils. It is important to understand the stability of these minerals because soils are subject to bush fires especially in Australia. The thermal analysis patterns of the two minerals are similar but not identical. Subtle differences are observed in the DTG patterns. For destinezite, two DTG peaks are observed at 129 and 182°C attributed to the loss of hydration water, whereas only a broad peak with maximum at 84°C is observed for diadochite. Higher temperature mass losses at 685°C for destinezite and 655°C for diadochite, based upon the ion current curves, are due to sulphate decomposition. This research has shown that at low temperatures the minerals are stable but at high temperatures, as might be experienced in a bush fire, the minerals decompose.

Mapping of adhesion forces on soil minerals in air and water by atomic force spectroscopy (AFS)

The adhesion force between an atomic force microscope (AFM) tip and sample surfaces, mica and quartz substrates, was measured in air and water. The force curves show that the adhesion has a strong dependence on both the surface roughness and the environmental conditions surrounding the sample. The variability of the adhesion force was examined in a series of measurements taken at the same point, as well as at different places on the sample surface. The adhesion maps obtained from the distribution of the measured forces indicated regions contaminated by either organic compounds or adsorbed water. Using simple mathematical expressions we could quantitatively predict the adhesion force behavior in both air and water. The experimental results are in good agreement with theoretical calculations, where the adhesion forces in air and water were mostly associated with capillary and van der Waals forces, respectively. A small long-range repulsive force is also observed in water due to the overlapping electrical double-layers formed on both the tip and sample surfaces.

Use of Sr isotopes as a tool to decipher the soil weathering processes in a tropical river catchment, southwestern India

River water composition (major ion and Sr-87/Sr-86 ratio) was monitored on a monthly basis over a period of three years from a mountainous river (Nethravati River) of southwestern India. The total dissolved solid (TDS) concentration is relatively low (46 mg L-1) with silica being the dominant contributor. The basin is characterised by lower dissolved Sr concentration (avg. 150 nmol L-1), with radiogenic Sr-87/Sr-86 isotopic ratios (avg. 0.72041 at outlet). The composition of Sr and Sr-87/Sr-86 and their correlation with silicate derived cations in the river basin reveal that their dominant source is from the radiogenic silicate rock minerals. Their composition in the stream is controlled by a combination of physical and chemical weathering occurring in the basin. The molar ratio of SiO2/Ca and Sr-87/Sr-86 isotopic ratio show strong seasonal variation in the river water, i.e., low SiO2/Ca ratio with radiogenic isotopes during non-monsoon and higher SiO2/Ca with less radiogenic isotopes during monsoon season. Whereas, the seasonal variation of Rb/Sr ratio in the stream water is not significant suggesting that change in the mineral phase being involved in the weathering reaction could be unlikely for the observed molar SiO2/Ca and Sr-87/Sr-86 isotope variation in river water. Therefore, the shift in the stream water chemical composition could be attributed to contribution of ground water which is in contact with the bedrock (weathering front) during non-monsoon and weathering of secondary soil minerals in the regolith layer during monsoon. The secondary soil mineral weathering leads to limited silicate cation and enhanced silica fluxes in the Nethravati river basin. (C) 2015 Elsevier Ltd. All rights reserved.

The role of calcite and gypsum in the leaching of potassium in a sandy soil

Pulses of potassium (K+) applied to columns of repacked calcium (Ca2+) saturated soil were leached with distilled water or calcium chloride (CaCl2) solutions of various concentrations at a rate of 12 mm h(-1). With increased Ca2+ concentration, the rate of movement of K+ increased, as did the concentration of K+ in the displaced pulse, which was less dispersed. The movement of K+ in calcite-amended soil leached with water was at a similar rate to that of the untreated soil leached with 1 mM CaCl2, and in soil containing gypsum, movement was similar to that leached with 15 mM CaCl2. The Ca2+ concentrations in the leachates were about 0.4 and 15 mM respectively the expected values for the dissolution of the two amendments. Soil containing native K+ was leached with distilled water or CaCl2 solutions. The amount of K+ leached increased as Ca2+ concentration increased, with up to 34% of the exchangeable K+ being removed in five pore volumes of 15 mM CaCl2. Soil amended with calcite and leached with water lost K+ at a rate between that for leaching the unamended soil with 1 mM CaCl2 and that with water. Soil containing gypsum and leached with water lost K+ at a similar rate to unamended soil leached with 15 mM CaCl2. The presence of Ca2+ in irrigation water and of soil minerals able to release Ca2+ are of importance in determining the amounts of K+ leached from soils. The LEACHM model predicted approximately the displacement of K+, and was more accurate with higher concentrations of displacing solution. The shortcomings of this model are its inability to account for rate-controlled processes and the assumption that K+:Ca2+ exchange during leaching can be described using a constant adsorption coefficient. As a result, the pulse is predicted to appear a little earlier and the following edge has less of a tail than chat measured. In practical agriculture, the model will be more useful in soils containing gypsum or leached with saline water than in either calcareous or non-calcareous soils leached with rainwater.

Identification and dissolution behavior of the secondary uranium minerals in the corrosion products of Depleted Uranium (DU) ammunition formed in soils

In der vorliegenden Studie wurden verschiedene Techniken eingesetzt um drei Proben (4, 7, and 8) die aus denrnKorrosionsprodukten von aus dem Kosovo Krieg stammenden Munitionskugeln, bestehend aus abgereichertem Uranrn(Depleted Uranium - DU), zu untersuchen. Als erstes Verfahren wurde die Raman-Spektroskopie eingesetzt. Hierbeirnzeigte sichin den Proben, charakterisiert durch einen Doppelpeak, die Anwesenheit von Schoepitrn(UO2)8O2(OH)12(H2O)12. Der erste und zweite Peakzeigte sich im Spektralbereich von 840,3-842,5 cm-1rnbeziehungsweise 853,6-855,8 cm-1. Diese Werte stimmen mit den Literaturwerten für Raman-Peaks für Schoepitrnüberein. Des Weiteren wurde bei dieser Untersuchungsmethode Becquerelite Ca(UO2)6O4(OH)6(H2O)8 mit einemrnPeak im Bereich zwischen 829 to 836 cm-1 gefunden. Aufgrund des Fehlens des Becquerelitespektrums in derrnSpektralbibliothek wurde eine in der Natur vorkommende Variante analysiert und deren Peak bei 829 cm-1 bestimmt,rnwas mit den Ergebnissen in den Proben korrespondiert. Mittels Röntgenbeugung (X-Ray Diffraction, XRD) zeigtenrnsich in allen Proben ähnliche Spektren. Das lässt darauf schließen, dass das pulverisierte Material in allen Probenrndas gleiche ist. Hierbei zeigte sich eine sehr gute Übereinstimmung mit Schoepit und/oder meta-rnSchoepit(UO2)8O2(OH)12(H2O)10, sowie Becquerelite. Weiterhin war weder Autunit, Sabugalit noch Uranylphosphatrnanwesend, was die Ergebnisse einer anderen Studie, durchgeführt an denselben Proben, wiederlegt. DiernAnwesenheit von P, C oder Ca im Probenmaterial konnte ausgeschlossen werden. Im Falle von Calciumkann diesrnmit der Anwesenheit von Uran erklärt werden, welches aufgrund seines Atomradius bevorzugt in Becquerelite (1:6)rneingebaut wird. Die beiden Hauptpeaks für Uran lagen im Falle von U 4f 7/2 bei 382.0 eV und im Falle von U 4f 5/2rnbei 392 eV. Diese Werte mit den Literaturwerten für Schoepit und meta-Schoepitüberein. Die Ergebnissernelektronenmikroskopischen Untersuchung zeigen U, O, Ca, Ti als dominante Komponenten in allen Messungen.rnElemente wie Si, Al, Fe, S, Na, und C wurden ebenfalls detektiert; allerdings kann nicht ausgeschlossen werden,rndass diese Elemente aus dem Boden in der unmittelbaren Umgebung der Munitionsgeschosse stammen. Gold wurdernebenfalls gemessen, was aber auf die Goldarmierung in den Probenaufbereitungsbehältern zurückgeführt werdenrnkann. Die Elektronenmikroskopie zeigte außerdem einige Stellen in denen elementares Uran und Bodenmineralernsowie sekundäre Uranminerale auftraten. Die Elementübersicht zeigt einen direkten Zusammenhang zwischen U andrnCa und gleichzeitig keine Korrelation zwischen U und Si, oder Mg. Auf der anderen Seite zeigte sich aber einrnZusammenhang zwischen Si und Al da beide Konstituenten von Bodenmineralen darstellen. Eine mit Hilfe derrnElektronenstrahlmikroanalyse durchgeführte quantitative Analyse zeigte den Massenanteil von Uran bei ca. 78 - 80%,rnwas mit den 78,2% and 79,47% für Becquerelite beziehungsweise Schoepit aufgrund ihrer Summenformelrnkorrespondiert. Zusätzlich zeigt sich für Calcium ein Massenanteil von 2% was mit dem Wert in Becquerelite (2.19%)rnrecht gut übereinstimmt. Der Massenanteil von Ti lag in einigen Fällen bei 0,77%, was auf eine noch nicht korrodierternDU-Legierung zurückzuführen ist. Ein Lösungsexperiment wurde weiterhin durchgeführt, wobei eine 0,01 M NaClO4-rnLösung zum Einsatz kam in der die verbliebene Probensubstanz der Korrosionsprodukte gelöst wurde;rnNatriumperchlorate wurde hierbei genutzt um die Ionenstärke bei 0,01 zu halten. Um Verunreinigungen durchrnatmosphärisches CO2 zu vermeiden wurden die im Versuch für die drei Hauptproben genutzten 15 Probenbehälterrnmit Stickstoffgas gespült. Eine Modelkalkulation für den beschriebenen Versuchsaufbau wurde mit Visual MINTEQrnv.3.0 für die mittels vorgenannten Analysemethoden beschriebenen Mineralphasen im pH-Bereich von 6 – 10 imrnFalle von Becquerelite, und Schoepit berechnet. Die modellierten Lösungskurven wurden unter An- und Abwesenheitrnvon atmosphärischem CO2 kalkuliert. Nach dem Ende des Lösungsexperiments (Dauer ca. 6 Monate) zeigten diernKonzentrationen des gelösten Urans, gemessen mittels ICP-OES, gute Übereinstimmung mit den modelliertenrnSchoepit und Becquerelite Kurven. Auf Grund des ähnlichen Löslichkeitverhaltens war es nicht möglich zwichen denrnbeiden Mineralen zu unterscheiden. Schoepit kontrolliert im sauren Bereich die Löslichkeit des Urans, währendrnbecquerelit im basichen am wenigsten gelöst wird. Des Weiteren bleibt festzuhalten, dass ein Anteil an CO2 in diernverschlossenen Probenbehälter eingedrungen ist, was sich mit der Vorhersage der Modeldaten deckt. Die Löslichkeitrnvon Uran in der Lösung als Funktion des pH-Wertes zeigte die niedrigsten Konzentrationen im Falle einer Zunahmerndes pH-Wertes von 5 auf 7 (ungefähr 5,1 x 10-6 mol/l) und einer Zunahme des pH-Wertes auf 8 (ungefähr 1,5 x 10-6rnmol/l bei). Oberhalb dieses Bereichs resultiert jeder weitere Anstieg des pH-Wertes in einer Zunahme gelösten Uransrnin der Lösung. Der ph-Wert der Lösung wie auch deren pCO2-Wert kontrollieren hier die Menge des gelösten Urans.rnAuf der anderen Seite zeigten im Falle von Becquerelite die Ca-Konzentrationen höhere Werte als erwartet, wobeirnwahrscheinlich auf eine Vermischung der Proben mit Bodensubstanz zurückgeführt werden kann. Abschließendrnwurde, unter Berücksichtigung der oben genannten Ergebnisse, eine Fallstudie aus Basrah (Irak) diskutiert, wo inrnzwei militärischen Konflikten Uranmunition in zwei Regionen unter verschiedenen Umweltbedingungen eingesetztrnwurden.

Characterisation of atmospheric deposited particles during a dust storm in urban areas of Eastern Australia

The characteristics of dust particles deposited during the 2009 dust storm in the Gold Coast and Brisbane regions of Australia are discussed in this paper. The study outcomes provide important knowledge in relation to the potential impacts of dust storm related pollution on ecosystem health in the context that the frequency of dust storms is predicted to increase due to anthropogenic desert surface modifications and climate change impacts. The investigated dust storm contributed a large fraction of fine particles to the environment with an increased amount of total suspended solids, compared to dry deposition under ambient conditions. Although the dust storm passed over forested areas, the organic carbon content in the dust was relatively low. The primary metals present in the dust storm deposition were aluminium, iron and manganese, which are common soil minerals in Australia. The dust storm deposition did not contain significant loads of nickel, cadmium, copper and lead, which are commonly present in the urban environment. Furthermore, the comparison between the ambient and dust storm chromium and zinc loads suggested that these metals were contributed to the dust storm by local anthropogenic sources. The potential ecosystem health impacts of the 2009 dust storm include, increased fine solids deposition on ground surfaces resulting in an enhanced capacity to adsorb toxic pollutants as well as increased aluminium, iron and manganese loads. In contrast, the ecosystem health impacts related to organic carbon and other metals from dust storm atmospheric deposition are not considered to be significant.

The effects of high stocking rates on milk production from dryland and irrigated Mediterranean pastures

An experiment using herds of similar to 20 cows (farmlets) assessed the effects of high stocking rates on production and profitability of feeding systems based on dryland and irrigated perennial ryegrass-based pastures in a Mediterranean environment in South Australia over 4 years. A target level of milk production of 7000 L/cow.year was set, based on predicted intakes of 2.7 t DM/cow.year as concentrates, pasture intakes from 1.5 to 2.7 t/cow.year and purchased fodder. In years 1 and 2, up to 1.5 t DM/cow.year of purchased fodder was used and in years 3 and 4 the amounts were increased if necessary to enable levels of milk production per cow to be maintained at target levels. Cows in dryland farmlets calved in March to May inclusive and were stocked at 2.5, 2.9, 3.3, 3.6 and 4.1 cows/ha, while those in irrigated farmlets calved in August to October inclusive and were stocked at 4.1, 5.2, 6.3 and 7.4 cows/ha. In the first 2 years, when inputs of purchased fodder were limited, milk production per cow was reduced with higher stocking rates (P < 0.01), but in years 3 and 4 there were no differences. Mean production was 7149 kg/cow.year in years 1 and 2, and 8162 kg/cow.year in years 3 and 4. Production per hectare was very closely related to stocking rate in all years (P < 0.01), increasing from 18 to 34 t milk/ha.year for dryland farmlets (1300 to 2200 kg milk solids/ha) and from 30 to 60 t milk/ha.year for irrigated farmlets (2200 to 4100 kg milk solids/ha). Almost all of these increases were attributed to the increases in grain and purchased fodder inputs associated with the increases in stocking rate. Net pasture accumulation rates and pasture harvest were generally not altered with stocking rate, though as stocking rate increased there was a change to more of the pasture being grazed and less conserved in both dryland and irrigated farmlets. Total pasture harvest averaged similar to 8 and 14 t DM/ha.year for dryland and irrigated pastures, respectively. An exception was at the highest stocking rate under irrigation, where pugging during winter was associated with a 14% reduction in annual pasture growth. There were several indications that these high stocking rates may not be sustainable without substantial changes in management practice. There were large and positive nutrient balances and associated increases in soil mineral content (P < 0.01), especially for phosphorus and nitrate nitrogen, with both stocking rate and succeeding years. Levels under irrigation were considerably higher (up to 90 and 240 mg/kg of soil for nitrate nitrogen and phosphorus, respectively) than under dryland pastures (60 and 140 mg/kg, respectively). Soil organic carbon levels did not change with stocking rate, indicating a high level of utilisation of forage grown. Weed ingress was also high (to 22% DM) in all treatments and especially in heavily stocked irrigated pastures during winter. It was concluded the higher stocking rates used exceeded those that are feasible for Mediterranean pastures in this environment and upper levels of stocking are suggested to be 2.5 cows/ha for dryland pastures and 5.2 cows/ha for irrigated pastures. To sustain these suggested stocking rates will require further development of management practices to avoid large increases in soil minerals and weed invasion of pastures.

Composition and stability of organic matter fractions in soils under different land use regimes

Soil organic matter (SOM) vitally impacts all soil functions and plays a key role in the global carbon (C) cycle. More than 70% of the terrestric C stocks that participate in the active C cycle are stored in the soil. Therefore, quantitative knowledge of the rates of C incorporation into SOM fractions of different residence time is crucial to understand and predict the sequestration and stabilization of soil organic carbon (SOC). Consequently, there is a need of fractionation procedures that are capable of isolating functionally SOM fractions, i.e. fractions that are defined by their stability. The literature generally refers to three main mechanisms of SOM stabilization: protection of SOM from decomposition by (i) its structural composition, i.e. recalcitrance, (ii) spatial inaccessibility and/or (iii) interaction with soil minerals and metal ions. One of the difficulties in developing fractionation procedures for the isolation of functional SOM fractions is the marked heterogeneity of the soil environment with its various stabilization mechanisms – often several mechanisms operating simultaneously – in soils and soil horizons of different texture and mineralogy. The overall objective of the present thesis was to evaluate present fractionation techniques and to get a better understanding of the factors of SOM sequestration and stabilization. The first part of this study is attended to the structural composition of SOM. Using 13C cross-polarization magic-angle spinning (CPMAS) nuclear magnetic resonance (NMR) spectroscopy, (i) the effect of land use on SOM composition was investigated and (ii) examined whether SOM composition contributes to the different stability of SOM in density and aggregate fractions. The second part of the present work deals with the mineral-associated SOM fraction. The aim was (iii) to evaluate the suitability of chemical fractionation procedures used in the literature for the isolation of stable SOM pools (stepwise hydrolysis, treatments using oxidizing agents like Na2S2O8, H2O2, and NaOCl as well as demineralization of the residue obtained by the NaOCl treatment using HF (NaOCl+HF)) by pool sizes, 13C and 14C data. Further, (iv) the isolated SOM fractions were compared to the inert organic matter (IOM) pool obtained for the investigated soils using the Rothamsted Carbon Model and isotope data in order to see whether the tested chemical fractionation methods produce SOM fractions capable to represent this pool. Besides chemical fractionation, (v) the suitability of thermal oxidation at different temperatures for obtaining stable SOC pools was evaluated. Finally, (vi) the short-term aggregate dynamics and the factors that impact macroaggregate formation and C stabilization were investigated by means of an incubation study using treatments with and without application of 15N labeled maize straw of different degradability (leaves and coarse roots). All treatments were conducted with and without the addition of fungicide. Two study sites with different soil properties and land managements were chosen for these investigations. The first one, located at Rotthalmünster, is a Stagnic Luvisol (silty loam) under different land use regimes. The Ah horizons of a spruce forest and continuous grassland and the Ap and E horizons of two plots with arable crops (continuous maize and wheat cropping) were examined. The soil of the second study site, located at Halle, is a Haplic Phaeozem (loamy sand) where the Ap horizons of two plots with arable crops (continuous maize and rye cropping) were investigated. Both study sites had a C3-/C4-vegetational change on the maize plot for the purpose of tracing the incorporation of the younger, maize-derived C into different SOM fractions and the calculation of apparent C turnover times of these. The Halle site is located near a train station and industrial areas, which caused a contamination with high amounts of fossil C. The investigation of aggregate and density fractions by 13C CPMAS NMR spectroscopy revealed that density fractionation isolated SOM fractions of different composition. The consumption of a considerable part (10–20%) of the easily available O-alkyl-C and the selective preservation of the more recalcitrant alkyl-C when passing from litter to the different particulate organic matter (POM) fractions suggest that density fractionation was able to isolate SOM fractions with different degrees of decomposition. The spectra of the aggregate fractions resembled those of the mineral-associated SOM fraction obtained by density fractionation and no considerable differences were observed between aggregate size classes. Comparison of plant litter, density and aggregate size fractions from soil under different land use showed that the type of land use markedly influenced the composition of SOM. While SOM of the acid forest soil was characterized by a large content (> 50%) of POM, which contained high amounts of spruce-litter derived alkyl-C, the organic matter in the biologically more active grassland and arable soils was dominated by mineral-associated SOM (> 95%). This SOM fraction comprised greater proportions of aryl- and carbonyl-C and is considered to contain a higher amount of microbially-derived organic substances. Land use can alter both, structure and stability of SOM fractions. All applied chemical treatments induced considerable SOC losses (> 70–95% of mineral-associated SOM) in the investigated soils. The proportion of residual C after chemical fractionation was largest in the arable Ap and E horizons and increased with decreasing C content in the initial SOC after stepwise hydrolysis as well as after the oxidative treatments with H2O2 and Na2S2O8. This can be expected for a functional stable pool of SOM, because it is assumed that the more easily available part of SOC is consumed first if C inputs decrease. All chemical treatments led to a preferential loss of the younger, maize-derived SOC, but this was most pronounced after the treatments with Na2S2O8 and H2O2. After all chemical fractionations, the mean 14C ages of SOC were higher than in the mineral-associated SOM fraction for both study sites and increased in the order: NaOCl < NaOCl+HF ≤ stepwise hydrolysis << H2O2 ≈ Na2S2O8. The results suggest that all treatments were capable of isolating a more stable SOM fraction, but the treatments with H2O2 and Na2S2O8 were the most efficient ones. However, none of the chemical fractionation methods was able to fit the IOM pool calculated using the Rothamsted Carbon Model and isotope data. In the evaluation of thermal oxidation for obtaining stable C fractions, SOC losses increased with temperature from 24–48% (200°C) to 100% (500°C). In the Halle maize Ap horizon, losses of the young, maize-derived C were considerably higher than losses of the older C3-derived C, leading to an increase in the apparent C turnover time from 220 years in mineral-associated SOC to 1158 years after thermal oxidation at 300°C. Most likely, the preferential loss of maize-derived C in the Halle soil was caused by the presence of the high amounts of fossil C mentioned above, which make up a relatively large thermally stable C3-C pool in this soil. This agrees with lower overall SOC losses for the Halle Ap horizon compared to the Rotthalmünster Ap horizon. In the Rotthalmünster soil only slightly more maize-derived than C3-derived SOC was removed by thermal oxidation. Apparent C turnover times increased slightly from 58 years in mineral-associated SOC to 77 years after thermal oxidation at 300°C in the Rotthalmünster Ap and from 151 to 247 years in the Rotthalmünster E horizon. This led to the conclusion that thermal oxidation of SOM was not capable of isolating SOM fractions of considerably higher stability. The incubation experiment showed that macroaggregates develop rapidly after the addition of easily available plant residues. Within the first four weeks of incubation, the maximum aggregation was reached in all treatments without addition of fungicide. The formation of water-stable macroaggregates was related to the size of the microbial biomass pool and its activity. Furthermore, fungi were found to be crucial for the development of soil macroaggregates as the formation of water-stable macroaggregates was significantly delayed in the fungicide treated soils. The C concentration in the obtained aggregate fractions decreased with decreasing aggregate size class, which is in line with the aggregate hierarchy postulated by several authors for soils with SOM as the major binding agent. Macroaggregation involved incorporation of large amounts maize-derived organic matter, but macroaggregates did not play the most important role in the stabilization of maize-derived SOM, because of their relatively low amount (less than 10% of the soil mass). Furthermore, the maize-derived organic matter was quickly incorporated into all aggregate size classes. The microaggregate fraction stored the largest quantities of maize-derived C and N – up to 70% of the residual maize-C and -N were stored in this fraction.

Mineralogy of the clay fraction of Alfisols in two slope curvatures: III - spatial variability

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Recruitment limitation constrains local species richness and productivity in dry grassland

Species coexistence and local-scale species richness are limited by the availability of seeds and microsites for germination and establishment. We conducted a seed addition experiment in seminatural grassland at three sites in southern Switzerland and repeated the experiment in two successive years to evaluate various circumstances under which seed limitation and establishment success affect community functioning. A collection of 144000 seeds of 22 meadow species including grasses and forbs of local provenance was gathered, and seeds were individually sown in a density that resembled natural seed rain. The three communities were seed limited. Three years after sowing, single species varied in emergence (0–50%), survival (0–69%), and establishment rates (0–27%). One annual and 13 perennial species reached reproductive stage. Low establishment at one site and reduced growth at another site indicated stronger microsite limitation compared to the third site. Recruitment was influenced by differences in abiotic environmental conditions between sites (water availability, soil minerals) and by within-site differences in biotic interaction (competition). At the least water-limited site, sowing resulted in an increase in phytomass due to establishment of short-lived perennials in the second and third years after sowing. This increase persisted over the following two years due to establishment of longer-lived perennials. After sowing in a wetter year with higher phytomass, however, productivity did not increase, because higher intensity of competition in an early phase of establishment resulted in less vigorous plants later on. Due to the generally favorable weather conditions during this study, sowing year had a small effect on numbers of established individuals over all species. Recruitment limitation can thus constrain local-scale species richness and productivity, either by a lack of seeds or by reduced seedling growth, likely due to competition from the established vegetation.

Dinâmica do fósforo no solo em função da adição de ácidos orgânicos de baixa massa molar

A baixa eficiência da adubação fosfatada em solos altamente intemperizados é devido, entre outros fatores, à adsorção do fósforo (P) à superfície das argilas silicatadas do tipo 1:1 e, principalmente, dos (hidr)óxidos de Fe e de Al. Manejos do solo que induzem a solubilização de formas de P indisponíveis para as plantas têm sido intensamente estudados nos últimos anos. Uma tentativa de aumentar a concentração de P disponível na solução do solo para sua absorção pelas plantas é a mobilização de P por ânions de ácidos orgânicos de baixa massa molar (AOBMM). Ânions derivados de AOBMM exsudados pelas raízes de plantas ou excretados por microrganismos são associados com algumas condições de rizosfera como deficiência de P e fitotoxidez de Al e interagem com o solo de forma a aumentar a biodisponibilidade de P. Dependendo dos atributos do solo, do grau de dissociação, das propriedades e do número de grupos carboxílicos dos ânions orgânicos, o P pode ser mobilizado do solo principalmente devido à dissolução complexométrica de minerais e à adsorção competitiva dos grupos funcionais carboxílicos e fosfato nos sítios de superfície coloidais. A capacidade dos ânions citrato, malato e oxalato em mobilizar P de amostras de um Neossolo Quartzarênico típico (RQ) e de um Latossolo Vermelho ácrico (LVwf) foi avaliada por meio de um estudo de lixiviação de ânions em colunas. Devido a não detecção de P nos efluentes das colunas com LVwf, foi realizado outro estudo em colunas, no qual somente citrato foi lixiviado, mas num volume maior, e as alterações das formas de P nas amostras desse solo induzidas pela lixiviação de citrato foram identificadas por espectroscopia de absorção de raios-X na borda K do fósforo (X-ray absorption near edge structure -XANES - spectroscopy). A capacidade dos ânions de AOBMM em solubilizar P foi mais dependente do teor de P disponível e de outros atributos do solo que do número de grupos funcionais carboxílicos dos ânions orgânicos. Somente o oxalato mobilizou P do RQ, enquanto todos os ânions de AOBMM foram capazes de mobilizar P do LVwf. Quando baixos volumes de solução contendo ânions de AOBMM foram lixiviados no solo, além do aumento do pH, a mobilização de P foi acompanhada pela mobilização de Al no RQ (pH água = 5), e pela mobilização de Ca no LVwf (pH água = 5.6), o que indica solubilização de P pela complexação de Al, Ca, ou Fe, de fosfatos insolúveis, ou pela inibição da precipitação de P com esses metais. Ao lixiviar um volume maior de citrato no LVwf, o P também não foi detectado nos efluentes das colunas, mas houve lixiviação intensa de Al e Fe, bem como mudanças nas proporções de formas de P no solo caracterizadas pelos espectros XANES. Embora tenhamos encontrado indícios da ação dos principais mecanismos de solubilização de P (dissolução complexométrica de minerais e troca de ligantes entre grupos funcionais carboxílicos e P adsorvido ao solo), os ânions de AOBMM mostraram pouco potencial de efetivamente aumentar a biodisponibilidade de P.

Raman spectroscopic study of the minerals diadochite and destinezite Fe3+2(PO4,SO4)2(OH)•6H2O – implications for soil science

The two minerals diadochite and destinezite of formula Fe2(PO4,SO4)2(OH)•6H2O have been characterised by Raman spectroscopy and complimented with infrared spectroscopy. These two minerals are both found in soils and are identical except for their morphology. Diadochite is amorphous whereas destinezite is highly crystalline. The spectra of diadochite are broad and ill-defined, whereas the spectra of destinezite are intense and well defined. Bands are assigned to phosphate and sulphate stretching and bending modes. Two symmetric stretching modes for both the phosphate and sulphate symmetric stretching modes support the concept of non-equivalent phosphate and sulphate units in the mineral structure. Multiple water bending and stretching modes imply that non-equivalent water molecules in the structure exist with different hydrogen bond strengths.

Retrieving clay minerals from stabilised soil compacts

Stabilised soil products such as stabilised soil blocks, rammed earth and stabilised adobe are being used for building construction since the last 6-7 decades. Major advantages of stabilised soil products include low embodied carbon, use of local materials, decentralized production, and easy to adjust the strength, texture, size and shape. Portland cement and lime represent the most commonly used stabilisers for stabilised soil products. The mechanism of strength development in cement and lime stabilised soils is distinctly different. The paper presents results of scientific investigations pertaining to the status of clay minerals in the 28 day cured cement and lime stabilised soil compacts. XRD, SEM imaging, grain size distribution and Atterberg's limits of the ground stabilised soil products and the natural soil were determined. Results reveal that clay minerals can be retrieved from cement stabilised soil products, whereas in lime stabilised soil products clay minerals get consumed in the lime-clay reactions and negligible percentage of clay minerals are left in the stabilised soil compacts. The results of the present investigation clearly demonstrate that cement stabilisation is superior to lime stabilisation in retrieving the clay minerals from the stabilised soil compacts. (C) 2014 Elsevier B.V. All rights reserved.

Raman spectroscopy of some complex arsenate minerals—implications for soil remediation

The application of spectroscopy to the study of contaminants in soils is important. Among the many contaminants is arsenic, which is highly labile and may leach to non-contaminated areas. Minerals of arsenate may form depending upon the availability of specific cations for example calcium and iron. Such minerals include carminite, pharmacosiderite and talmessite. Each of these arsenate minerals can be identified by its characteristic Raman spectrum enabling identification.