VIS-NIR SPECTROMETRY, SOIL PHOSPHATE EXTRACTION METHODS AND INTERACTIONS OF SOIL ATTRIBUTES

The objective of this study was to evaluate the relationships between the spectra in the Vis-NIR range and the soil P concentrations obtained from the PM and Prem extraction methods as well as the effects of these relationships on the construction of models predicting P concentration in Oxisols. Soil samples' spectra and their PM and Prem extraction solutions were determined for the Vis-NIR region between 400 and 2500 nm. Mineralogy and/or organic matter content act as primary attributes allowing correlation of these soil phosphorus fractions with the spectra, mainly at wavelengths between 450-550, 900-1100 nm, near 1400 nm and between 2200-2300 nm. However, the regression models generated were not suitable for quantitative phosphate analysis. Solubilization of organic matter and reactions during the PM extraction process hindered correlations between the spectra and these P soil fractions. For Prem,, the presence of Ca in the extractant and preferential adsorption by gibbsite and iron oxides, particularly goethite, obscured correlations with the spectra.

Environmental behavior of soils and mixtures of soil-whitewash mud

The present study sought to observe the behavior of soils in natural state and in mixtures, in different ratios, with the industrial solid residue called whitewash mud. The work was conducted with samples of typical soils from the region of Alagoinhas, Bahia-Brazil. Wet chemical analysis and atomic absorption spectrophotometry were used in order to obtain the classification of the industrial solid residue. Solubilization and leaching tests were performed and X-ray diffraction and electron microscopy techniques were carried out. The results showed that the whitewash mud was classified as non-inert, but with great capacity of heavy metal retention largely owed to the kaolinite and goethite presence in the clay fraction of the soils, making it difficult to have heavy metals readily available for exchange.

Development of pure and doped gamma ferric oxide

Optimum conditions and experimental details for the formation of v-Fe203 from goethite have been worked out. In another method, a cheap complexing medium of starch was employed for precipitating acicular ferrous oxalate, which on decomposition in nitrogen and subsequent oxidation yielded acicular y-Fe203. On the basis of thermal decomposition in dry and moist nitrogen, DTA, XRD, GC and thermodynamic arguments, the mechanism of decomposition was elucidated. New materials obtained by doping ~'-Fe203 with 1-16 atomic percent magnesium, cobalt, nickel and copper, were synthesised and characterized

A preliminary investigation into the use of ochre as a remedial amendment in arsenic-contaminated soils

Ochre is an unwanted waste product that accumulates in wetlands and streams draining abandoned coal and metal mines. A potential commercial use for ochre is to remediate As contaminated soil. Arsenic contaminated soil (605 mg kg(-1)) was mixed with different ochres (A, B and C) in a mass ratio of 1:1 and shaken in 20 mL of deionised water. After 72 h As concentration in solution was ca. 500 mu g kg(-1) in the control and 1-2.5 mu g kg(-1) in the ochre treated experiments. In a second experiment soil:ochre mixtures of 0.05-1:1 were shaken in 20 mL of deionised water for 24 h. For Ochres A and C, as Solution concentration was reduced to ca. 1 mu gkg(-1) by 0.2-1:1 ochre:soil mixtures. For Ochre B, as concentration only reached ca. 1 mu g kg(-1) in the 1:1 ochre:soil inix. Sorption of As was best modelled by a Freundlich isotherm using As sorption per mass of goethite in the ochre (log K= 1.64, n = 0.79, R-2 = 0.76, p <= 0.001). Efficiency of ochre in removing As from solution increased with increasing total Fe, goethite, citrate dithionite extractable Fe and surface area. (c) 2005 Elsevier Ltd. All rights reserved.

Analysis of red and yellow ochre samples from Clearwell Caves and Catalhoyuk by vibrational spectroscopy and other techniques

Ochre samples excavated from the neolithic site at Qatalhoyuk, Turkey have been compared with "native" ochres from Clearwell Caves, UK using infrared spectroscopy backed up by Raman spectroscopy, scanning electron microscopy (with energy-dispersive X-rays (EDX) analysis), powder X-ray diffraction, diffuse reflection UV-Vis and atomic absorption spectroscopies. For the Clearwell Caves ochres, which range in colour from yellow-orange to red-brown, it is shown that the colour is related to the nature of the chromophore present and not to any differences in particle size. The darker red ochres contain predominantly haematite while the yellow ochre contains only goethite. The ochres from Qatalhoyuk contain only about one-twentieth of the levels of iron found in the Clearwell Caves ochres. The iron oxide pigment (haematite in all cases studied here) has been mixed with a soft lime plaster which also contains calcite and silicate (clay) minerals. (C) 2003 Elsevier B.V. All rights reserved.

The development and contribution of surface charge by crop residues in two Malawian acid soils

The effects of maize and soya bean residues on the pH and charge of a loamy sand (Kawalazi) and a sandy clay loam (Naming'omba) from Malawi were measured to determine both the indirect effect of the residues on soil charge through the changes in pH, and the direct contribution of charge carried on the residue surfaces. The soils had pH values (10 mM CaCl2) of 4.3 and 5.0 and organic matter contents were 1.4% and 2.7%, respectively. The clay fractions were dominated by kaolinite and goethite, and mica was present in both samples. The soils were incubated for 28 days with maize (Zea mays) and soya bean (Glycine max) residues. The maximum addition of residue (12.0%) in the Kawalazi and Naming'omba soils increased the pH from 4.3 and 5.0 to 4.8 and 5.3 (maize) and to 9.0 and 8.8 (soya bean), respectively. Negative charge increased from 2.1 and 4.7 cmol(c) kg(-1) to 3.8 and 7.5 (maize) and to 5.3 and 9.3 cmol(c) kg(-1) (soya bean). Positive charge increased from 0.72 and 0.62 to 0.87 and 0.85 cmol(c) kg(-1) (maize) and to 0.75 and 0.68 (soya bean). The charge contribution by the residues was calculated by difference between the charge on a sample incubated with residue and the charge on a soil without residue limed to the same pH value. Up to 100 cmolc negative charge and 10 cmol(c) of positive charge per kg of residue were directly contributed to the soil-residue mixture, the amounts depending on the type of residue, the extent to which the residue was decomposed in the soil and the pH of the mixture. The Anderson and Sposito method [Soil Sci. Soc. Am. J. 55 (1991) 1569] was used to partition the permanent negative charge (holding Cs+) from variable negative charge (holding Li+). In the pH range 3.7-6.5 the maize residue contributed between 3 and 26 cmol(c) of variable charge per kg of residue in the Kawalazi soil and between 6 and 25 cmol(c) per kg of residue in the Naming'omba soil. For soya bean the values were between I and 28 and between 4 and 68 cmolc per kg of residue, respectively. At a given pH value, the charge tended to increase with time of incubation and for a given addition of residue, pH decreased during incubation. Addition of residues contributed no permanent negative charge and the charge on the soil measured by Cs adsorption was independent of pH change caused by the residue showing that the method is valid for soil-residue mixtures. With time there was a decrease in the amount of permanent charge probably due to masking as humic material become adsorbed on mineral surfaces. (C) 2003 Elsevier Science B.V. All rights reserved.

Mineral and geochemical characterization of a leptic aluandic soil and a thapto aluandic-ferralsol developed on trachytes in Mount Bambouto (Cameroon volcanic line)

Mineral and geochemical investigations were carried out on soil samples and fresh rock (trachytes) from two selected soil profiles (TM profile on leptic aluandic soils and TL profile on thapto aluandic-ferralsols) from Mount Bambouto to better understand geochemical processes and mineral paragenesis involved in the development of soils in this environment. In TM profile, the hydrated halloysites and goethite occur in the weathered saprolite boulders of BC horizon while dehydrated halloysite, gibbsite and goethite dominate the soils matrices of BC and A horizons. In TL profile, the dehydrated halloysites and goethite are the most abundant secondary minerals in the weathered saprolites of C and BC horizons while gibbsite, hematite and kaolinite occur in the soil matrices of BC, B and A horizons. The highest gibbsite content is in the platy nodules of B horizon. In both soil profiles, organo-metal complexes (most likely of AI and Fe) are present in the surface A horizon. Geochemically, between the fresh rock and the weathered saprolites in both soils, SiO2, K2O, CaO, Na2O and MgO contents decrease strongly while Fe2O3 and Al2O3 tend to accumulate. The molar ratio of SiO2/Al2O3 (Ki) and the sum of Ca, Mg, K and Na ions (TRB) also decreases abruptly between fresh rocks and the weathered saprolites, but increases significantly at the soil surface. The TM profile shows intense Al enrichment whereas the TL profile highlights enrichment in both AI and Fe as the weathering progresses upwards. Both soil profiles are enriched in Ni, Cu, Ba and Co and depleted in U, Th, Ta, Hf, Y, Sr, Pb, Zr and Zn relative to fresh rock. They also show a relatively low fractionation of the rare earth elements (REE: La, Nd, Sm, Eu, Tb, Yb and Lu), except for Ce which tends to be enriched in soils compared to CI chondrite. All these results give evidence of intense hydrolysis at soil deep in Mount Bambouto resulting in the formation of halloysite which progressively transforms into gibbsite and/or dehydrated halloysite. At the soil surface, the prominent pedogenetic process refers to andosolization with formation of organo-metal complexes. In TL profile, the presence of kaolinite in soil matrices BC and B horizons is consistent with ferralitization at soil deep. In conclusion, soil forming processes in Mount Bambouto are strongly influenced by local climate: (i) in the upper mountain (>2000 m), the fresh, misty and humid climate favors andosolization; whereas (ii) in the middle lands (1700-2000 m) with a relatively dry climate, both andosolization at the soil surface and ferralitization at soil deep act together. (C) 2009 Elsevier B.V. All rights reserved.

Using aircraft measurements to determine the refractive index of Saharan dust during the DODO Experiments

Much uncertainty in the value of the imaginary part of the refractive index of mineral dust contributes to uncertainty in the radiative effect of mineral dust in the atmosphere. A synthesis of optical, chemical and physical in-situ aircraft measurements from the DODO experiments during February and August 2006 are used to calculate the refractive index mineral dust encountered over West Africa. Radiative transfer modeling and measurements of broadband shortwave irradiance at a range of altitudes are used to test and validate these calculations for a specific dust event on 23 August 2006 over Mauritania. Two techniques are used to determine the refractive index: firstly a method combining measurements of scattering, absorption, size distributions and Mie code simulations, and secondly a method using composition measured on filter samples to apportion the content of internally mixed quartz, calcite and iron oxide-clay aggregates, where the iron oxide is represented by either hematite or goethite and clay by either illite or kaolinite. The imaginary part of the refractive index at 550 nm (ni550) is found to range between 0.0001 i to 0.0046 i, and where filter samples are available, agreement between methods is found depending on mineral combination assumed. The refractive indices are also found to agree well with AERONET data where comparisons are possible. ni550 is found to vary with dust source, which is investigated with the NAME model for each case. The relationship between both size distribution and ni550 on the accumulation mode single scattering albedo at 550 nm (ω0550) are examined and size distribution is found to have no correlation to ω0550, while ni550 shows a strong linear relationship with ω0550. Radiative transfer modeling was performed with different models (Mie-derived refractive indices, but also filter sampling composition assuming both internal and external mixing). Our calculations indicate that Mie-derived values of ni550 and the externally mixed dust where the iron oxide-clay aggregate corresponds to the goethite-kaolinite combination result in the best agreement with irradiance measurements. The radiative effect of the dust is found to be very sensitive to the mineral combination (and hence refractive index) assumed, and to whether the dust is assumed to be internally or externally mixed.

Analysis of red and yellow ochre samples from Clearwell Caves and Catalhoyuk by vibrational spectroscopy and other techniques

Ochre samples excavated from the neolithic site at Qatalhoyuk, Turkey have been compared with "native" ochres from Clearwell Caves, UK using infrared spectroscopy backed up by Raman spectroscopy, scanning electron microscopy (with energy-dispersive X-rays (EDX) analysis), powder X-ray diffraction, diffuse reflection UV-Vis and atomic absorption spectroscopies. For the Clearwell Caves ochres, which range in colour from yellow-orange to red-brown, it is shown that the colour is related to the nature of the chromophore present and not to any differences in particle size. The darker red ochres contain predominantly haematite while the yellow ochre contains only goethite. The ochres from Qatalhoyuk contain only about one-twentieth of the levels of iron found in the Clearwell Caves ochres. The iron oxide pigment (haematite in all cases studied here) has been mixed with a soft lime plaster which also contains calcite and silicate (clay) minerals. (C) 2003 Elsevier B.V. All rights reserved.

A high resolution late Holocene palaeo environmental record from the central Adriatic Sea

A multi-proxy study of a Holocene sediment core (RF 93-30) from the western flank of the central Adriatic, in 77 m of water, reveals a sequence of changes in terrestrial vegetation, terrigenous sediment input and benthic fauna, as well as evidence for variations in sea surface temperature spanning most of the last 7000 yr. The chronology of sedimentation is based on several lines of evidence, including AMS 14C dates of foraminifera extracted from the core, palaeomagnetic secular variation, pollen indicators and dated tephra. The temporal resolution increases towards the surface and, for some of the properties measured, is sub-decadal for the last few centuries. The main changes recorded in vegetation, sedimentation and benthic foraminiferal assemblages appear to be directly related to human activity in the sediment source area, which includes the Po valley and the eastern flanks of the central and northern Appenines. The most striking episodes of deforestation and expanding human impact begin around 3600 BP (Late Bronze Age) and 700 BP (Medieval) and each leads to an acceleration in mass sedimentation and an increase in the proportion of terrigenous material, reflecting the response of surface processes to widespread forest clearance and cultivation. Although human impact appears to be the proximal cause of these changes, climatic effects may also have been important. During these periods, signs of stress are detectable in the benthic foram morphotype assemblages. Between these two periods of increased terrigeneous sedimentation there is smaller peak in sedimentation rate around 2400BP which is not associated with evidence for deforestation, shifts in the balance between terrigenous and authigenic sedimentation, or changes in benthic foraminifera. The mineral magnetic record provides a sensitive indicator of changing sediment sources: during forested periods of reduced terrigenous input it is dominated by authigenic bacterial magnetite, whereas during periods of increased erosion, anti-ferromagetic minerals (haematite and/or goethite) become more important, as well as both paramagnetic minerals and super-paramagnetic magnetite. Analysis of the alkenone, U37k′, record provides an indication of possible changes in sea surface temperature during the period, but it is premature to place too much reliance on these inferred changes until the indirect effects of past changes in the depth of the halocline and in circulation have been more fully evaluated. The combination of methods used and the results obtained illustrate the potential value of such high resolution near-shore marine sedimentary sequences for recording wide-scale human impact, documenting the effects of this on marine sedimentation and fauna and, potentially, disentangling evidence for human activities from that for past changes in climate.

A new data set of soil mineralogy for dust-cycle modeling

The mineralogy of airborne dust affects the impact of dust particles on direct and indirect radiative forcing, on atmospheric chemistry and on biogeochemical cycling. It is determined partly by the mineralogy of the dust-source regions and partly by size-dependent fractionation during erosion and transport. Here we present a data set that characterizes the clay and silt-sized fractions of global soil units in terms of the abundance of 12 minerals that are important for dust–climate interactions: quartz, feldspars, illite, smectite, kaolinite, chlorite, vermiculite, mica, calcite, gypsum, hematite and goethite. The basic mineralogical information is derived from the literature, and is then expanded following explicit rules, in order to characterize as many soil units as possible. We present three alternative realizations of the mineralogical maps, taking the uncertainties in the mineralogical data into account. We examine the implications of the new database for calculations of the single scattering albedo of airborne dust and thus for dust radiative forcing.

Adsorption of Pb(2+), Cu(2+) and Cd(2+) in FDU-1 silica and FDU-1 silica modified with humic acid

Ordered mesoporous silica with cubic structure, type FDU-1, was synthesized under strong acid media using B-50-6600 poly(ethylene oxide)-poly(butilene oxide)-poly(ethylene oxide) triblock copolymer (EO(39)BO(47)EO(39)) and tetraethyl orthosilicate (TEOS). Humic acid (HA) was modified to the synthesis process at a concentration of 1.5 mmol per gram of SiO(2). Thermogravimetry, small angle X-ray diffraction, nitrogen adsorption and high resolution transmission electron microscopy were used to characterize the samples. The pristine FDU-1 and FDU-1 with incorporated 1.5 mmol of HA were tested for adsorption of Pb(2+), Cu(2+) and Cd(2+) in aqueous solution. Incorporation of humic acid into the FDU-1 silica afforded an adsorbent with strong affinity for Cd(2+), Cu(2+) and Pb(2+) from single ion solutions. Adsorption of Cu(2+) was significantly enhanced after incorporation of humic acid, a fact that can be explained by the formation of complexes with carboxylic and phenolic groups at low concentrations of the metal cation. The results demonstrated the potential applicability of FDU-1 with incorporated HA in the removal of low concentrations of heavy metal cations from aqueous solution, such as wastewaters, after usual precipitation of metal hydroxides in alkaline medium and proper pH conditioning in the range between 6 and 7. (C) 2007 Elsevier Inc. All rights reserved.

Geochemistry of iron and manganese in soils and sediments of a mangrove system, Island of Pai Matos (Cananeia - SP, Brazil)

Five zones along a transect of 180 m were selected for study on the Island of Pai Matos (Sao Paulo, Brazil). Four of the zones are colonised by vascular plants (Spartina SP, Laguncularia LG, Avicennia AV and Rhizophora RH) and were denominated soils, and the other zone, which lacks vegetation, was denominated sediment (SD). The geochemical conditions differed significantly in soils and sediment and also at different depths. The soils were oxic (Eh > 350 mV) or suboxic (Eh: 350-100 mV) at the surface and anoxic (Eh < 100 mV) at depth, whereas in the sediment anoxic conditions prevailed at all depths, but with a lower concentration of sulphides in the pore water and pyrite in the solid fraction. Under these geochemical conditions Fe is retained in the soils, while the Mn tends to be mobilized and lost. The most abundant form of iron oxyhydroxide was lepidocrocite (mean concentration for all sites and depths, 45 +/- 19 mu mol g(-1)), followed by goethite (30 19 mu mol g(-1))and ferrihydrite (19 +/- 11 mu mol g(-1)),with significant differences among the mean concentrations. There was a significant decrease with depth in all the types of Fe oxyhydroxides measured, particularly the poorly crystalline forms. The pyrite fraction was an important component of the free Fe pool (non-silicate Fe) in all soils as well as in the sediment, especially below 20 cm depth (mean concentration for all sites and depths, 60 +/- 54 mu mol CI). Furthermore, the mean concentration of Fe-pyrite for all sites and depths was higher than that obtained for any of the three Fe oxyhydroxides measured. The Fe-AVS was a minor fraction, indicating that the high concentrations of dissolved Fe in the soils in the upper area of the transect result from the oxidation of Fe sulphides during low tide. Mossbauer spectroscopy also revealed that most of the Fe (III) was associated with silicates, in this case nontronite. The presence of crystals of pyrite associated with phyllosilicates in samples from the upper layer of the soils may indicate that pyritization of this form of Fe(III) is more rapid than usually reported for ocean bed sediments. The sequential extraction of Mn did not reveal any clearly dominant fraction, with the Mn-carbonate fraction being the most prevalent, followed by exchangeable Mn and oxides of Mn, whereas pyrite-Mn and Mn associated with crystalline Fe-oxides were present at significantly lower concentrations. The high concentration of dissolved Mn found in the soils in the lower part of the transect is consistent with the fact that the solubility is determined by the carbonate fraction. Unlike for Fe, in the soils in the higher zone, which are subject to intense drainage during low tide, there was loss of Mn, as reflected by the concentration of total Mn. (C) 2008 Elsevier B.V. All rights reserved.

Rock magnetism in soils of the Pampean plain. Buenos Aires province, Argentina. Linking climate and magnetic behaviour

Results of the study of Argiudolls in two localities (Zarate and Veronica) of the Pampean plain, Argentina, are presented in this contribution. This is a typical area covered by loess. The magnetic studies carried out allowed to determine the presence of detrital magnetite and titanomagnetite, as well as maghemite, pedogenic goethite and superparamagnetic particles (SP). In Veronica soils, a depletion of ferromagnetic minerals is recorded The dominant process in these soils has been the reductive loss of detrital magnetite and titanomagnetite. This is associated with a greater degree of evolution of the soil, which is determined by the concentration and type of detected clays. The higher clay concentration in these soils facilitated reducing conditions and a greater loss of detrital magnetic particles. The loss is reinforced under poor drainage conditions. In the poorly drained soil of Zarate, a concentration of magnetic particles is observed in the Bt horizon, which is associated with an illuviation process. The well drained soil of the same locality shows neoformation of SP particles. These particles would have an ephemeral life until a new wet period in the annual cycle occurs. Although some characteristics of the magnetic signal appear reinforced by the conditions of drainage, this aspect does not seem to be too significant, at least in the Pampean region with low topographic gradients.