Self-Diffusion versus Intentional Doping: Beneficial and Damaging Impact on Hematite Photoanode Interfaces.

The comprehension of side effects caused by high-temperature thermal treatments in the design of (photo)electrodes is essential to achieve efficient and cost-effective devices for solar water splitting. This investigation explores the beneficial and damaging impacts of thermal treatments in the (photo)electrode design, unraveling the impact of self-diffusion and its consequences. The industrial-friendly polymeric precursor synthesis (PPS) method, which is known for its easy technological application, was chosen as the fabrication technique for hematite photoabsorbers. For substrate evaluation, two types of conductive glass substrates, aluminum borosilicate and quartz, both coated with fluorine-doped tin oxide (ABS/FTO and QTZ/FTO, respectively), were subjected to thermal treatments following the PPS protocol. Optical and structural analyses showed no significant alterations in substrate properties, whereas X-ray photoelectron spectroscopy (XPS) revealed the migration of silicon and calcium ions from the glass component to the FTO surface. This diffusion can be further mitigated by an oxide buffer layer. To track the potential ion diffusion on the photoabsorber surface and assess its effect on the photoelectrode performance, hematite was selected as the model material and deposited onto the glass substrates. From all the ions that could possibly migrate, only Si4+ and Ca2+ originating from the glass component, as well as Sn4+ from the fluorine-doped tin oxide (FTO), were detected on the surface of the hematite photoabsorber. Interestingly, the so-called "self-diffusion" of these ions did not result in any beneficial effect on the hematite photoelectrochemical response. Instead, intentional modifications showed more substantial impacts on the photoelectrochemical efficiency compared to unintentional self-diffusion. Therefore, "self-diffusion", which can unintentionally dope the hematite, is not sufficient to significantly impact the final photocurrent. These findings emphasize the importance of understanding the true effect of thermal treatments on the photoelectrode properties to unlock their full potential in photoelectrochemical applications.

Solar heterogeneous photo-Fenton for complete inactivation of Escherichia coli and Salmonella typhimurium in secondary-treated wastewater effluent.

In this work, complete elimination of Escherichia coli and Salmonella typhimurium was achieved in 120 min using a heterogeneous photo-Fenton process under sunlight at pH 6.5 in distilled water. A face-centered composite central design 22 with one categoric factor and three replicates at the central point was used to evaluate the effect of iron (III) oxide concentration (0.8-3.4 mg L-1), H2O2 (2-10 mg L-1), and the type of iron oxide phase (maghemite and hematite) on the inactivation of both bacteria. The results showed that the amount of catalyst, H2O2 concentration and their interaction were significant factors (p < 0.05) in the elimination of the microorganisms. Thus, under the best conditions (3.4 mg L-1 of iron (III) oxide and 10 mg L-1 of H2O2) in the experimental ranges, complete inactivation of E. coli and S. typhimurium was achieved (6-log reduction) in 120 min using the photo-Fenton treatment with both iron-oxide phases. Furthermore, the photocatalytic elimination of both bacteria by the photo-Fenton process using hematite and maghemite in secondary-treated wastewater effluent was performed obtaining slower inactivation rates (1.2-5.9 times) than in distilled water due to the matrix effect of the effluent from a wastewater treatment plant. Nevertheless, the process continued to be effective in the effluent, achieving complete bacterial elimination in 150 min using the hematite phase. Additionally, the SEM images of the bacterial cells showed that the heterogeneous photo-Fenton treatment generated permanent and irreversible cell damage, resulting in complete cell death.

Experimental and Simulation Studies on Hematite Interaction with Na-Metasilicate Pentahydrate.

Iron ore is a fundamental pillar in construction globally, however, its process is highly polluting and deposits are becoming less concentrated, making reusing or reprocessing its sources a sustainable solution to the current industry. A rheological analysis was performed to understand the effect of sodium metasilicate on the flow curves of concentrated pulps. The study was carried out in an Anton Paar MCR 102 rheometer, showing that, in a wide range of dosages, the reagent can reduce the yield stress of the slurries, which would result in lower energy costs for transporting the pulps by pumping. To understand the behavior observed experimentally, computational simulation has been used by means of quantum calculations to represent the metasilicate molecule and the molecular dynamics to study the adsorption of metasilicate on the hematite surface. It has been possible to obtain that the adsorption is stable on the surface of hematite, where increasing the concentration of metasilicate increases its adsorption on the surface. The adsorption could be modeled by the Slips model where there is a delay in adsorption at low concentrations and then a saturated value is reached. It was found that metasilicate requires the presence of sodium ions to be adsorbed on the surface by means of a cation bridge-type interaction. It is also possible to identify that it is absorbed by means of hydrogen bridges, but to a lesser extent than the cation bridge. Finally, it is observed that the presence of metasilicate adsorbed on the surface modifies the net surface charge, increasing it and, thus, generating the effect of dispersion of hematite particles which experimentally is observed as a decrease in rheology.

CVD Growth of Hematite Thin Films for Photoelectrochemical Water Splitting: Effect of Precursor-Substrate Distance on Their Final Properties.

The development of photoelectrode materials for efficient water splitting using solar energy is a crucial research topic for green hydrogen production. These materials need to be abundant, fabricated on a large scale, and at low cost. In this context, hematite is a promising material that has been widely studied. However, it is a huge challenge to achieve high-efficiency performance as a photoelectrode in water splitting. This paper reports a study of chemical vapor deposition (CVD) growth of hematite nanocrystalline thin films on fluorine-doped tin oxide as a photoanode for photoelectrochemical water splitting, with a particular focus on the effect of the precursor-substrate distance in the CVD system. A full morphological, structural, and optical characterization of hematite nanocrystalline thin films was performed, revealing that no change occurred in the structure of the films as a function of the previously mentioned distance. However, it was found that the thickness of the hematite film, which is a critical parameter in the photoelectrochemical performance, linearly depends on the precursor-substrate distance; however, the electrochemical response exhibits a nonmonotonic behavior. A maximum photocurrent value close to 2.5 mA/cm2 was obtained for a film with a thickness of around 220 nm under solar irradiation.

Hollow Iron Oxide Nanospheres Obtained through a Combination of Atomic Layer Deposition and Electrospraying Technologies.

In the present study, we report on the successful synthesis of hollow iron oxide nanospheres. The hollow Fe3O4 nanospheres were synthesized following a four-step procedure: electrospraying spherical PVP particles, coating these particles with alumina (Al2O3) and hematite (Fe2O3) through atomic layer deposition and, finally, a thermal reduction process to degrade the polymer (PVP) and convert hematite (Fe2O3) into magnetite (Fe3O4). A structural analysis using X-ray diffraction (XRD) confirmed the effectiveness of the thermal reduction process. A morphological analysis confirmed that the four-step procedure allowed for the obtainment of hollow iron oxide nanospheres, even though the reduction process caused a contraction in the diameter of the particles of almost 300 nm, but did not affect the thickness of the walls of the hollow spheres that remained at approximately 15 nm. Magnetic properties of the hollow iron oxide nanospheres enable their use in applications where the agglomeration of magnetic nanostructures in liquid media is commonly not allowed, such as in drug encapsulation and delivery.

The Influence of Magnetic Field and Nanoparticle Concentration on the Thin Film Colloidal Deposition Process of Magnetic Nanoparticles: The Search for High-Efficiency Hematite Photoanodes.

Hematite is considered a promising photoanode material for photoelectrochemical water splitting, and the literature has shown that the photoanode production process has an impact on the final efficiency of hydrogen generation. Among the methods used to process hematite photoanode, we can highlight the thin films from the colloidal deposition process of magnetic nanoparticles. This technique leads to the production of high-performance hematite photoanode. However, little is known about the influence of the magnetic field and heat treatment parameters on the final properties of hematite photoanodes. Here, we will evaluate those processing parameters in the morphology and photoelectrochemical properties of nanostructured hematite anodes. The analysis of thickness demonstrated a relationship between the magnetic field and nanoparticles concentration utilized to prepare the thin films, showing that the higher magnetic fields decrease the thickness. The Jabs results corroborate to influence the magnetic field since the use of a higher magnetic field decreases the deposited material amount, consequently decreasing the absorption of the thin films. The PEC measurements showed that at higher concentrations, the use of higher magnetic fields increases the JPH values, and lower magnetic fields cause a decrease in JPH when using the higher nanoparticle concentrations.

Comparison of Different Synthetic Routes of Hybrid Hematite-TiO2 Nanotubes-Based Electrodes.

Nowadays, green hydrogen is an important niche of interest in which the search for a suitable composite material is indispensable. In this sense, titanium oxide nanotubes (TiO2 nanotube, TNTs) were prepared from double anodic oxidation of Ti foil in ethylene glycol electrolyte. The morphology of the nanotubes was characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD). Once characterized, nanotubes were used as templates for the deposition of hematite. The use of three synthetic procedures was assayed: Chemical Vapor Deposition (CVD), Successive Ionic Layer Adsorption and Reaction (SILAR), and electrochemical synthesis. In the first case, CVD, the deposition of hematite onto TiO2 yielded an uncovered substrate with the oxide and a negative shift of the flat band potential. On the other hand, the SILAR method yielded a considerable amount of hematite on the surface of nanotubes, leading to an obstruction of the tubes in most cases. Finally, with the electrochemical synthesis, the composite material obtained showed great control of the deposition, including the inner surface of the TNT. In addition, the impedance characterization showed a negative shift, indicating the changes of the interface electrode-electrolyte due to the modification with hematite. Finally, the screening of the methods showed the electrochemical synthesis as the best protocol for the desired material.

New sol-gel-derived magnetic bioactive glass-ceramics containing superparamagnetic hematite nanocrystals for hyperthermia application.

Although the three main phases of iron oxide - hematite, maghemite, and magnetite - exhibit superparamagnetic properties at the nanoscale, only maghemite and magnetite phases have been explored in magnetic bioactive glass-ceramics aimed at applications in cancer treatment by hyperthermia. In this work, it is reported for the first time the superparamagnetic properties of hematite nanocrystals grown in a 58S bioactive glass matrix derived from sol-gel synthesis. The glass-ceramics are based on the (100-x)(58SiO2-33CaO-9P2O5)-xFe2O3 system (x = 10, 20 and 30 wt%). A thermal treatment leads to the growth of hematite (α-Fe2O3) nanocrystals, conferring superparamagnetic properties to the glass-ceramics, which is enough to produce heat under an external alternating magnetic field. Besides, the crystallization does not inhibit materials bioactivity, evidenced by the formation of calcium phosphate onto the glass-ceramic surface upon soaking in simulated body fluid. Moreover, their cytotoxicity is similar to other magnetic bioactive glass-ceramics reported in the literature. Finally, these results suggest that hematite nanocrystals' superparamagnetic properties may be explored in multifunctional glass-ceramics applied in bone cancer treatment by hyperthermia allied to bone regeneration.

Silver Enhances Hematite Nanoparticles Based Ethanol Sensor Response and Selectivity at Room Temperature.

Gas sensors are fundamental for continuous online monitoring of volatile organic compounds. Gas sensors based on semiconductor materials have demonstrated to be highly competitive, but are generally made of expensive materials and operate at high temperatures, which are drawbacks of these technologies. Herein is described a novel ethanol sensor for room temperature (25 °C) measurements based on hematite (α­Fe2O3)/silver nanoparticles. The AgNPs were shown to increase the oxide semiconductor charge carrier density, but especially to enhance the ethanol adsorption rate boosting the selectivity and sensitivity, thus allowing quantification of ethanol vapor in 2-35 mg L-1 range with an excellent linear relationship. In addition, the α-Fe2O3/Ag 3.0 wt% nanocomposite is cheap, and easy to make and process, imparting high perspectives for real applications in breath analyzers and/or sensors in food and beverage industries. This work contributes to the advance of gas sensing at ambient temperature as a competitive alternative for quantification of conventional volatile organic compounds.

On the effects of iron ore tailings micro/nanoparticles in embryonic and larval zebrafish (Danio rerio).

Iron ore tailings (IOT) represent a major problem in the mining industry worldwide due to large volumes of waste disposed in mine sites. IOT are exposed to the environment and subjected to wind and water dispersion, even under non-catastrophic scenarios as dam collapses, and the effects of these particles to the biota are still mostly unknown. This work aimed to prepare and to characterize a suspension containing the finest (micro/nano range) particles of IOT and to evaluate its effects on development and behavior of zebrafish (Danio rerio), at both embryonic and larval stages. IOT suspension comprised 37 mg L-1 of a multi-mineral material mainly composed by hematite and quartz, in a size-range of 33-1400 nm. Regarding in vivo toxicological assays, no robust alterations were recorded in functional, morphological and behavioral end-points analyzed, although a significant adhesion of IOT particles on zebrafish chorion was observed, without a prejudice of embryo hatching. Under applied conditions, iron ore particles did not present harmful effects to the initial stages of zebrafish development, and the particle size range and potential interactions with SiO2 content might be behind such effect.

Synthesis of Oxide Iron Nanoparticles Using Laser Ablation for Possible Hyperthermia Applications.

In this work, iron oxide nanoparticles produced using the laser ablation technique were studied in order to determine the characteristics of these nanoparticles as a function of the laser energy for the possible application in magnetic hyperthermia. Nanoparticles were obtained by varying the power of the laser considering values of 90, 173, 279 and 370 mJ. The morphology of these nanoparticles was determined using the dynamic light scattering (DLS) and scattering transmission electron microscopy (STEM) techniques, confirming that the size of the particles was in the order of nanometers. A great influence of the laser power on the particle size was also observed, caused by the competition between the energy and the temperature. The composition was determined by X-ray diffraction and Raman spectroscopy, showing the presence of magnetite, maghemite and hematite. The hyperthermia measurements showed that the temperature rise of the iron oxide nanoparticles was not greatly influenced by the energy change, the heating capacity of magnetic NPs is quantified by the specific absorption rate (SAR), that tends to decrease with increasing energy, which indicates a dependence of these values on the nanoparticles concentration.

Data on phase and chemical compositions of black sands from "El Ostional" beach situated in Mompiche, Ecuador.

Data revealing the phase and chemical compositions of natural black sands from "El Ostional" beach, located in the northern Ecuadorian Pacific coast have been presented. The samples were collected from six points over the shore area of approximately 500 × 40 m2. The data on crystalline phases (iron titanium oxide, orthoclase feldspar and zircon) were determined by X-ray powder diffraction (XRPD), while semi-quantitative chemical analyses of major (Fe and Ti) and trace elements were obtained by X-ray fluorescence spectroscopy (XRF). The phase composition was verified by scanning electron microscopy (SEM), using backscattered electron (BSE) mode and energy dispersive spectroscopy (EDS). These comprehensive data are a contribution to valorize ilmenite-hematite solid solutions from natural resources towards the identification of novel technological applications.

Data on study of hematite nanoparticles obtained from Iron(III) oxide by the Pechini method.

This article presents the data on α-Fe2O3 nanoparticles synthesized via Pechini method using iron(III) oxide precursor from steel industry. It is important to highlight the added value that is given to an industrial waste. The samples were characterized by thermal analysis (DTA, TG), X-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FTIR). The TG showed three mass changes, whereas DTA resulted in three anomalies. X-ray diffraction pattern of the samples disclosed rhombohedral structure characteristic of the nanocrystalline α-Fe2O3 phase. The crystallite size was estimated for each thermal treatment. Fourier transform infrared spectroscopy confirms the phase purity of prepared nanoparticles. A detailed study on the local structure of the samples was carry out in the region of 800 and 400 cm-1, where the associated bands of Fe-O bonds are presents. The data have not been reported nor discussed for now.

Arsenite removal from contaminated water by precipitation of aluminum, ferrous and ferric (hydr)oxides.

Several methods to remove arsenic from water have been considered, including co-precipitation with Fe and Al (hydr)oxides. Such compounds are considered very effective to remove As from contaminated water due to strong bindings between them. Three Fe:Al molar ratios (100:0, 80:20, and 60:40) were used to synthesize aluminum, ferrous, and ferric (hydr)oxides by precipitation in water highly contaminated with arsenite (50 and 500 mg L-1). The method was very efficient for all treatments (> 93%) at the beginning of the incubation period, excepted the one with 60:40 Fe(II):Al molar ratio at the higher As concentration (500 mg L-1) in which gibbsite was identified in precipitated phases. In spite of the high efficiency, however, the threshold for drinking water was not attained, mainly to the higher As concentration, even 84 days after precipitation. At this high concentration of arsenite, even the required threshold for effluent discharge was not attained in some treatments. The sludge resulting from treatments with higher As concentration were considered hazardous according to results from leaching test and corroborated by BCR extractions. Arsenic associated with Al and adsorbed phases were also assessed by extractions with NH4F and KH2PO4, respectively. In general, the presence of Al increased the efficiency as well as the stability of the sludge resulting from Fe (II) treatments, but did not affect Fe (III) treatments, which were more efficient for As removal.

Pedogenic iron oxides in soils of the Acre State, Brazil / Óxidos de ferro pedogênicos em solos do estado do Acre, Brasil

ABSTRACT: Iron oxides are environmental indicators and influence on physical and chemical behavior of soils. This research aimed to identify and characterize pedogenic iron oxides in soils of the Acre state, Brazil. The soils developed from sedimentary rocks of the Solimões Formation. Twenty one samples of subsurface horizons were collected from ten soil profiles. Soil samples were analyzed by x-ray diffractometry associated to selective chemical dissolutions. Fe contents in the clay minerals (Fes), in the pedogenic iron oxides (Fed) and in the poorly crystalline oxides (Feo) were determined. The Al3+-substitution and the mean crystal diameter of goethite and hematite were estimated. Soils presented low contents of Fes and Fed. The Fed/Fes ratio indicated soils in the intermediate stage of weathering, with dominance of goethite, hematite and maghemite. This condition of weathering was confirmed by the higher frequency of goethites and hematite with intermediate Al3+-substitution. Goethites have isodimensional forms and hematite have flat plaques forms.

RESUMO: Os óxidos de ferro são indicadores ambientais e influenciam o comportamento físico e químico dos solos. Este trabalho objetivou identificar e caracterizar os óxidos de ferro pedogênicos de solos do estado do Acre, desenvolvidos de rochas sedimentares da Formação Solimões. Vinte e uma amostras de horizontes subsuperficiais de dez perfis de solos foram analisadas por difratometria de raios x associada a dissoluções químicas seletivas. Os teores de Fe total (Fes), dos óxidos de Fe pedogênicos (Fed) e de baixa cristalinidade (Feo) foram determinados; e a Al3+-substituição e o diâmetro médio cristalino da goethita e da hematita foram estimados. Em geral, os solos apresentaram baixos teores de Fes e de Fed. A relação Fed/Fes indicou solos em estágio de intemperização intermediário, com dominância dos óxidos de Fe goethita, hematita e maghemita. Essa condição de intemperismo foi reforçada pela maior frequência de goethitas e hematitas com intermediária Al3+-substituição. As goethitas possuem formas isodimencionais e as hematitas ocorrem como placas achatadas.

Sunlight-driven water splitting using hematite nanorod photoelectrodes

ABSTRACT The efficiency of nanostructures for photoelectrochemical water-splitting is fundamentally governed by the capability of the surface to sustain the reaction without electron trapping or recombination by photogenerated holes. This brief review will summarize the latest progress on hematite, designed with columnar morphology via chemical synthesis, for photoelectrochemical cell application. The columnar morphology efficiently minimizes the number of defects, grain boundaries, and surface traps normally present on the planar morphology. The major drawback related to hole diffusion through the solid/liquid interface was addressed by using high annealing temperature combined with dopant addition. A critical view and depth of understanding of these two parameters were discussed focusing on the molecular oxygen evolution mechanism from the sunlight-driven water oxidation reaction.

Pedogenic iron oxides in soils of the Acre State, Brazil

ABSTRACT: Iron oxides are environmental indicators and influence on physical and chemical behavior of soils. This research aimed to identify and characterize pedogenic iron oxides in soils of the Acre state, Brazil. The soils developed from sedimentary rocks of the Solimões Formation. Twenty one samples of subsurface horizons were collected from ten soil profiles. Soil samples were analyzed by x-ray diffractometry associated to selective chemical dissolutions. Fe contents in the clay minerals (Fes), in the pedogenic iron oxides (Fed) and in the poorly crystalline oxides (Feo) were determined. The Al3+-substitution and the mean crystal diameter of goethite and hematite were estimated. Soils presented low contents of Fes and Fed. The Fed/Fes ratio indicated soils in the intermediate stage of weathering, with dominance of goethite, hematite and maghemite. This condition of weathering was confirmed by the higher frequency of goethites and hematite with intermediate Al3+-substitution. Goethites have isodimensional forms and hematite have flat plaques forms.

RESUMO: Os óxidos de ferro são indicadores ambientais e influenciam o comportamento físico e químico dos solos. Este trabalho objetivou identificar e caracterizar os óxidos de ferro pedogênicos de solos do estado do Acre, desenvolvidos de rochas sedimentares da Formação Solimões. Vinte e uma amostras de horizontes subsuperficiais de dez perfis de solos foram analisadas por difratometria de raios x associada a dissoluções químicas seletivas. Os teores de Fe total (Fes), dos óxidos de Fe pedogênicos (Fed) e de baixa cristalinidade (Feo) foram determinados; e a Al3+-substituição e o diâmetro médio cristalino da goethita e da hematita foram estimados. Em geral, os solos apresentaram baixos teores de Fes e de Fed. A relação Fed/Fes indicou solos em estágio de intemperização intermediário, com dominância dos óxidos de Fe goethita, hematita e maghemita. Essa condição de intemperismo foi reforçada pela maior frequência de goethitas e hematitas com intermediária Al3+-substituição. As goethitas possuem formas isodimencionais e as hematitas ocorrem como placas achatadas.

Pedogenic iron oxides in soils of the Acre State, Brazil / Óxidos de ferro pedogênicos em solos do estado do Acre, Brasil

Os óxidos de ferro são indicadores ambientais e influenciam o comportamento físico e químico dos solos. Este trabalho objetivou identificar e caracterizar os óxidos de ferro pedogênicos de solos do estado do Acre, desenvolvidos de rochas sedimentares da Formação Solimões. Vinte e uma amostras de horizontes subsuperficiais de dez perfis de solos foram analisadas por difratometria de raios x associada a dissoluções químicas seletivas. Os teores de Fe total (Fes), dos óxidos de Fe pedogênicos (Fed) e de baixa cristalinidade (Feo) foram determinados; e a Al3+-substituição e o diâmetro médio cristalino da goethita e da hematita foram estimados. Em geral, os solos apresentaram baixos teores de Fes e de Fed. A relação Fed/Fes indicou solos em estágio de intemperização intermediário, com dominância dos óxidos de Fe goethita, hematita e maghemita. Essa condição de intemperismo foi reforçada pela maior frequência de goethitas e hematitas com intermediária Al3+-substituição. As goethitas possuem formas isodimencionais e as hematitas ocorrem como placas achatadas.(AU)

Iron oxides are environmental indicators and influence on physical and chemical behavior of soils. This research aimed to identify and characterize pedogenic iron oxides in soils of the Acre state, Brazil. The soils developed from sedimentary rocks of the Solimões Formation. Twenty one samples of subsurface horizons were collected from ten soil profiles. Soil samples were analyzed by x-ray diffractometry associated to selective chemical dissolutions. Fe contents in the clay minerals (Fes), in the pedogenic iron oxides (Fed) and in the poorly crystalline oxides (Feo) were determined. The Al3+-substitution and the mean crystal diameter of goethite and hematite were estimated. Soils presented low contents of Fes and Fed. The Fed/Fes ratio indicated soils in the intermediate stage of weathering, with dominance of goethite, hematite and maghemite. This condition of weathering was confirmed by the higher frequency of goethites and hematite with intermediate Al3+-substitution. Goethites have isodimensional forms and hematite have flat plaques forms.(AU)

Adsorption of As(V) inside the pores of porous hematite in water.

As(V) adsorption inside the pores of porous hematite in water has been studied in this work. This study was performed on nonporous hematite and porous hematite prepared from the thermal decomposition of goethite and siderite through the measurements of adsorption isotherm, SEM-EDX, XRD and BET. The results demonstrated that the As(V) adsorption was difficult to be realized inside pores if they were too small. This observation might be due to that the pore entrances were blocked by the adsorbed ions and thus the inside surfaces became invalid for the adsorption. Only if the pore size is large enough, the effective surface area inside pores would be close to that on non-porous hematite for As(V) adsorption. In addition, it was found that siderite is better than goethite for preparing porous hematite with thermal decomposition as adsorbent for arsenic removal.

Field-scale spatial correlation between contents of iron oxides and CO2 emission in an Oxisol cultivated with sugarcane

Soil CO2 emission (FCO2) is one of the main sources of carbon release into the atmosphere. Moreover, FCO2 is related to soil attributes governing the transfer of gases from soil to the atmosphere. This study aimed firstly to describe the spatial variability of hematite (Hm), goethite (Gt), iron extracted with sodium dithionite-citrate-bicarbonate (Fed) contents, soil CO2 emission (FCO2) and free-water porosity (FWP) and secondly, to develop statistical models to predict the above mentioned factors in an Oxisol cultivated under manual harvesting of sugarcane (Saccharumspp.) in southeastern Brazil. The study was conducted on an irregular 50 m × 50 m grid containing 89 points, each 0.5-10 m apart. The 0-0.1 m soil layer at each sampling point was used to assess soil FCO2, moisture and total pore volume. The results were subjected to descriptive statistical and geostatistical analyses using auto- and cross-semivariograms. All soil attributes exhibited a spatial dependence structure and the experimental semivariograms fitted spherical and exponential models. The Gt content was the individual attribute that exhibited the highest linear and spatial correlation, especially with FCO2. We were able to use diffuse reflectance spectroscopy to map large areas, which allows for easy identification and estimation of soil attributes such as FCO2 and FWP. Geostatistical techniques faciltate the interpretation of spatial relationships between soil respiration and the examined properties.(AU)