Potentially toxic elements in iron mine tailings: Effects of reducing soil pH on available concentrations of toxic elements.

Tailings from iron mining are characterized by high concentrations of iron and manganese oxides, as well as high pH values. With these characteristics, most of the potentially toxic elements (PTE) contained in the tailings are somewhat unavailable. The aim of the present study was to evaluate how a reduction in the pH of iron mine tailings may affect PTE availabilities. The tailings were collected on the banks of the Gualaxo do Norte River (Mariana, MG, Brazil), one of the main areas impacted by the rupture of the Fundão Dam (Barragem de Fundão). A completely randomized experimental design was used, including five pH values (6.4, 5.4, 4.3, 3.7, and 3.4) and five replications. The concentrations of the PTE (Ba, Cr, Cd, Co, Cu, Fe, Mn, Pb, Ni, and Zn) were determined after extraction following different methodologies: USEPA 3051A, DTPA, Mehlich-1, Mehlich-3, and distilled water. A comparison of the available concentrations of the elements in the tailings with those in a soil not impacted by tailings shows that Cr, Cd, Cu, Fe, Mn, Ni, Ba, and Co were higher in the soil impacted by the tailings. The different methods used for evaluating the availability of PTE in the tailings at various pH exhibited the following decreasing order in relation to the quantity extracted: Mehlich-3 > Mehlich-1 > DTPA > distilled water. However, regarding sensitivity to change in pH, the order was DTPA > water > Mehlich-1 > Mehlich-3. The increases in the concentrations of PTE due to the reduction in the pH of the tailings did not lead to concentrations that exceed the limits of Brazilian regulations. The DTPA extractant exhibited higher coefficients of correlation between the PTE concentrations and the pH of the tailings, proving to be suitable for use in areas affected by the deposition of iron mine tailings.

Industrial saline wastewater in a corn-soybean rotation to enhance crop yield without compromising soil health in a subtropical soil.

The production of industrial waste has increased in the last decades along with world population. Wastes are used in agriculture as fertilizers and soil amendments depending on their composition, dynamics in soil and effects on plant growth. The aim of this study was to assess the effect of industrial saline wastewater from heparin production on soil chemistry and plant yield in a subtropical soil in Brazil. Five rates of industrial saline wastewater (0, 10, 20, 40 and 60 m3 ha-1 year-1) were applied as fertilizer in a corn -soybean rotation on an Oxisol with limited nutrient availability. Five soils sampling were done: before and after the first application of the industrial wastewater (2017, corn), before and after the second application of wastewater (2018, soybean) and two years after the first application (2019). Soil K, Ca, Mg, Na content and CEC increased immediately after the application of wastewater but they returned to former values with time due to plant uptake and lixiviation. Wastewater application significantly increased corn (all rates) and soybean (only with the highest rate) yields around 103-250% and 50%, respectively, in comparison with no wastewater application. However, the highest rate temporally increased soil Na content and electrical conductivity (up to 650 and 800%, respectively). Although nutrient uptake, chlorophyll content and corn and soybean yields were enhanced, the use of high rates of industrial saline wastewater could cause soil salinization (mainly in locations with low rainfall), affecting soil chemistry and physical parameters due to clay dispersion, and pollution or water bodies.

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.

Sediment pollution in margins of the Lake Guaíba, Southern Brazil.

Sediments are formed by deposition of organic and inorganic particles on depth of water bodies, being an important role in aquatic ecosystems, including destination and potential source of essential nutrients and heavy metals, which may be toxic for living organisms. The Lake Guaíba supplies water for approximately two million people and it is located in the metropolitan region of Porto Alegre, Rio Grande do Sul State, Brazil. Thus, the aim of this study was to evaluate the sediment pollution in the margins of Lake Guaíba in the vicinity of Porto Alegre city. Surface sediment was sampled in 12 sites to assess the concentration of several elements (C, N, P, Fe, Al, Ca, Mg, Na, K, Mn, Ba, Zn, V, Pb, Cu, Cr, Ni, Cd, Mo, and Se) and the mineralogical composition. Sediment in margins of Lake Guaíba presented predominantly (> 95%) sandy fraction in all samples, but with significant differences between evaluated sites. Sediments in the margins of Lake Guaíba showed indications of punctual water pollution with Pb, Cu, Cr, Ni, TOC, TKN, and P, mainly derived from urban streams that flow into the lake. In order to solve these environmental liabilities, public actions should not focus only on Guaíba, but also in the streams that flow into the lake.

Óxidos de ferro e área superficial de Latossolo subtropical sob campo e floresta nativa / Iron oxides and specific surface area of the subtropical Oxisol under native pasture and forest

As condições climáticas atuais indicam avanço da vegetação de floresta sobre os campos na região dos Campos de Cima da Serra no Rio Grande do Sul. Essa mudança na vegetação altera o conteúdo de matéria orgânica e a umidade do solo. Este estudo objetivou avaliar os óxidos de ferro pedogênicos em um Latossolo sob campo e floresta nativa e relacionar os mesmos com os teores de carbono orgânico e a área superficial específica do solo. Os teores de carbono orgânico são maiores no solo sob floresta e, possivelmente, influenciaram processos dissolutivos de óxidos de ferro cristalinos e a neoformação de tipos metaestáveis de baixa cristalinidade. O incremento de C orgânico no solo sob floresta elevou expressivamente a área superficial específica do solo, mascarando o efeito geralmente positivo dos óxidos de Fe sobre essa característica física.

The current weather conditions indicate a substitution of grassland by forest vegetation in the Campos de Cima da Serra in Rio Grande do Sul, Brazil. This change in vegetation changes the contents of soil organic matter and soil moisture. This study aimed to evaluate the pedogenetic iron oxides in an Oxisol under native forest and grassland and its relationship with soil total organic carbon content and soil specific surface area. Replacing grassland with native forest resulted in an accumulation of soil organic carbon and possibly influenced dissolutive processes of crystalline iron oxides types and neoformation of metastable types of low crystallinity. In native forest soil, the increase of total organic carbon increased the soil specific surface area, masking the positive effect of iron oxides on this physical characteristic.

Caracterização e classificação de solos graníticos em topossequência na região Sul do Brasil / Soil characterization and classification of granitic soils in toposequence in Southern Brazil

Na região sul do Brasil, foi verificada a ocorrência de forte gradiente textural em solos localizados em áreas de morros graníticos. O presente estudo teve como objetivo avaliar os processos pedogenéticos envolvidos na formação de solos em topossequência de granito em Porto Alegre (RS). Foram descritos e amostrados morfológica, química, física e mineralogicamente quatro perfis de solos localizados em diferentes segmentos da paisagem. Os perfis de solos do topo, encosta superior e sopé da topossequência apresentaram gradiente textural expressivo, e a relação argila fina:argila total aumentou nos horizontes subsuperficias (Bt), indicando transporte da fração mais fina. O índice de uniformidade inferior a 0,6 sugeriu que os solos não apresentaram indícios de descontinuidade litológica. O índice Ki, a relação Fe2O3d/Fe2O3s e a presença de feldspato e minerais 2:1 e 2:1:1, constatadas pela difração de raios-x indicaram grau de intemperismo intermediário. A difração por raios x também mostrou aumento do argilomineral caulinita em profundidade. Na encosta inferior, o perfil de solo não apresentou horizonte B pedogenético. Os resultados são indicativos da ocorrência da lessivagem como o principal processo pedogenético atuante, apesar das características indicativas de estádio de intemperismo pouco avançado.

In Brazil's South region, it had been verified high textural change in soils of granitic hilly areas. This study had the objective to evaluate pedogenetic processes involved in a granite toposequence in Porto Alegre city, Brazil. Soil profiles were described and analyzed in morphological, physical, chemical and mineralogical issues. Soil profiles at summit, upper slope and foot slope showed expressive textural change and the relationship fine clay:total clay increased in subsurface horizons (Bt), indicating finer fraction translocation. Uniformity index lower than 0,6 showed absence of lithologic discontinuity. Ki index, Fe2O3(d)/Fe2O3(s) relationship and presence of feldspar, 2:1 and 2:1:1 minerals, detected in X-Ray diffraction analysis, indicated intermediate weathering degree. X-Ray diffraction also indicates higher caulinite content in subsurface. At down slope position, soil profile didn't show the presence of B pedogenetic horizon. Results indicated lessivage as the main pedogenetic process, associated with the presence of some characteristics, which shows low advanced pedogenetic development in these profiles.

Atributos químicos e área superficial específica em Latossolo subtropical de altitude sob usos e manejos distintos / Chemical attributes and specific surface area in highland subtropical Oxisol under different use and managements

A interferência antrópica tem modificado a condição original do solo nos Campos de Cima da Serra. O estudo avaliou atributos químicos e físicos de um Latossolo sob campo nativo (CN), campo nativo manejado com queima (CNq), mata nativa (MN), florestamento de pinus (FP) e lavoura em sistema plantio convencional (LA), nas camadas de 0,00-0,025, 0,025-0,05, 0,05-0,10, 0,10-0,20, 0,20-0,30m. A mineralogia foi avaliada por difratometria de raios X. Foram avaliados o C orgânico total (COT), pH (H2O); Ca, Mg, K, Na e Al trocáveis; H+Al e P; e calculou-se a soma de bases, a capacidade de troca de cátions, a saturação por bases e por Al. Estimou-se a área superficial específica (ASE) e a capacidade máxima de adsorção de fósforo (CMAP). O solo apresentou mineralogia caulinítica e oxídica. No CN, o COT variou entre 15,3 e 56,4g kg-1, o pH foi ≤4,8, a CTC foi alta (18

The original landscape of Campos de Cima da Serra region has changed by anthropogenic interference. The study aimed to evaluate soil chemical and physical attributes of an Oxisol under natural grassland (CN), burned natural grassland (CNq), natural forest (MN), pine afforestation (PF) and annual crops in conventional tillage system (LA), in the 0.00-0.025, 0.025-0.05, 0.05-0.10, 0.10-0.20, 0.20-0.30m layers. The mineralogy was evaluated by X-ray diffraction. It was evaluated the total organic carbon (TOC); pH (H2O); exchangeable Ca, Mg, K, Na and Al; H+Al and P contents; and calculated bases sum (S), cation exchange capacity (CEC) and bases and Al saturation on CEC. It was estimated soil specific surface area (SSA) and maximum phosphorus adsorption capacity (MPAC). The soil showed kaolinitic and oxidic mineralogy. In the CN soil TOC content ranged between 15.3 and 56.4g kg-1, pH values ≤4.8; CEC was high (18

Substâncias húmicas em Latossolo subtropical de altitude sob usos e manejos distintos / Humic substances in highland subtropical Oxisol under different use and managements

A interferência antrópica no solo tem modificado a formação original nos Campos de Cima da Serra. O estudo objetivou avaliar a distribuição das substâncias húmicas em um Latossolo sob campo nativo (CN), campo nativo queimado (CNq), mata nativa (MN), florestamento de pinus (FP) e lavoura (LA). Os teores de C orgânico total (COT) e de C em compartimentos químicos da matéria orgânica do solo (MOS) foram determinados. Os usos e manejos adotados no solo afetaram os teores de COT e do C nos compartimentos da MOS. Com relação ao ambiente CN, a MN aumentou o teor de COT, o qual se manteve equivalente no manejo com queima e foi reduzido pelos usos do solo com LA e FP. As alterações de uso e manejo do solo tenderam a reduzir o C nas frações húmicas e modificaram a distribuição das frações ácidos húmicos e fúlvicos.

The anthropic interference have changed the original soil condition in Campos de Cima da Serra region, Brazil. This study aimed to evaluate the distribution of humic substances in an Oxisol under native pasture (CN), native burned pasture (CNq), native forest (MN), pine afforestation (FP) and annual crops (LA). The levels of total organic carbon (TOC) and C compartments of chemical soil organic matter (SOM) were determined. The use and management adopted affected the levels of TOC and C in the chemical compartments of the SOM. In comparison to CN, the MN increased the amounts of TOC, which remained unchanged in the CNq and was reduced by land uses with LA and FP. Changes in land use and management tended to reduce the C in humic fractions and modified the humic and fulvic acids distribution.

Atributos físicos e químicos de agregados pedogênicos e de coprólitos de minhocas em diferentes classes de solos da Paraíba / Physical and chemical attributes of pedogenic aggregates and earthworm casts in different soil classes of Paraíba

A estrutura do solo é constituída de agregados pedogênicos e biogênicos, formados respectivamente pela hierarquização de agregados e pela ação da macrofauna, sobretudo a das minhocas. Neste estudo, objetivou-se a comparação entre agregados do solo (pedogênicos) e coprólitos de minhocas (biogênicos) de diferentes tamanhos e classes de solos. As coletas de amostras indeformadas de solos e coprólitos de minhocas (Pontoscolex corethrurus Muller, 1857) foram realizadas em quatro solos de classes diferentes do Estado da Paraíba (Latossolo Amarelo, Argissolo Vermelho Amarelo, Luvissolo Crômico e Nitossolo Vermelho). As caracterizações físicas e químicas de agregados e coprólitos foram realizadas após secagem à sombra e separação em três classes de diâmetros (20,0 - 9,52; 9,52 - 6,35 e 6,35 - 4,76 mm). A granulometria mostrou ser similar para cada tipo de agregado (pedogênico e biogênico), independentemente do tamanho dos agregados. Em geral, os coprólitos apresentaram maiores proporções de argila, silte e areia fina e menor proporção da fração areia grossa, maior estabilidade e maiores teores de carbono orgânico e cátions trocáveis, comparativamente aos agregados pedogênicos. Os resultados refletem um processo genético peculiar e sugerem a importância dos agregados biogênicos como indicadores da qualidade do solo.

The soil structure is composed by pedogenic and biogenic aggregates, formed respectively by aggregate hierarchy and macrofauna activity, especially by earthworms. The objective of this study was to compare soil aggregates and earthworm casts with different aggregate-size classes and soil classes. The sampling of undisturbed soil and earthworm casts (Pontoscolex corethrurus, Muller, 1857) was made in four soils of different classes in the State of Paraíba (Oxisol, Ultisol, Alfisol and Nitisol). The chemical and physical evaluations of aggregates and earthworm casts were determined after dry and split into three aggregate-size classes (20.0 to 9.52, 9.52 to 6.35 and 6.35 to 4.76 mm). The particle-size distribution was similar to aggregates and earthworm casts, independent of aggregate-size classes. Earthworm casts had higher proportions of clay, silt and fine sand, lower coarse sand, higher physical stability and more organic carbon and cations contents than the pedogenic aggregates. These results show a peculiar genetic process that makes biogenic aggregates an important indicator of soil quality.

Atributos químicos relacionados ao processo de sulfurização em solos construídos após mineração de carvão / Chemical attributes of constructed soils after surface coal mining related to sulphurization process

A mineração de carvão a céu aberto envolve a remoção superficial do solo e de camadas geológicas, os quais devem ser repostos visando à reabilitação das áreas mineradas. Essa obra expõe o carvão às condições oxidativas do ar e altera as características originais do solo e da paisagem. Como consequência, o processo de sulfurização pode ser ativado nos solos construídos em razão da oxidação da pirita, condicionando alterações químicas e mineralógicas. Nesse contexto, o estudo objetivou avaliar a evolução temporal de solos construídos há 24 (SA-24) e dois (SA-2) anos, em duas áreas mineradas e reconstruídas no Município de Minas do Leão, Rio Grande do Sul (RS), tendo como base atributos químicos relacionados com o processo de sulfurização. Para tanto, foram determinados o pH, a condutividade elétrica (CE), os teores de bases (SB) e de alumínio (Al3+) trocáveis, a acidez potencial (H+Al), os teores totais de Al, Fe e Si e o teor de sulfato solúvel (S-SO4(2-)) e calculadas a capacidade de troca de cátions (CTC), a saturação por bases (V) e a saturação por alumínio (m). Os resultados indicaram a atuação do processo de sulfurização nos solos construídos de ambas as áreas reabilitadas. A CE e os teores de S-SO4(2-) foram maiores na SA-2, indicando um estádio de sulfurização mais ativo nos solos dessa área. Na SA-24, a menor CE e os menores teores de S-SO4(2-), de SB e V, bem como a maior saturação por Al e teores de H+Al, sugerem a proximidade do estádio de pós-sulfurização. Elementos como Al e P concentraram-se relativamente nos solos construídos mais antigos. Os solos em ambas as áreas apresentam limitações químicas para o desenvolvimento de vegetação, influindo negativamente para a recuperação das áreas.

Coal stripmining involves the removal of upper soil and geological layers, which must be relocated in a similar way that in the original profile when reconstructing the landscape. As this process changes soil and landscape characteristics, pirite may oxide and change soil chemical and mineralogical characteristics. In this context, the study aimed to evaluate the temporal evolution of soils reconstructed 2 (SA-2) and 24 (SA-24) year ago, in Boa Vista Coal Mining, in Minas do Leão, Rio Grande do Sul, Brazil. Soil characteristics measured were pH, electrical conductivity (EC), bases and aluminium content, potential acidity (H+Al), and contents of Al, Fe, Si, and soluble sulphate. Calculations accounted for cation exchange capacity, base saturation and aluminum saturation. Results indicated occurrence of oxidation processes in both reconstructed areas. Electrical condutivity and soluble phosphate contents were higher in SA-2, indicating a more active sulphurization stage in these soils. In soils of area SA-24, lower EC and smaller contents of soluble sulphate, lower base saturation, as well as higher aluminum saturation and H+Al suggest a more advanced sulphurization process compared to SA-2. Aluminum and P concentrated in older soil profiles. Soils in both areas have chemical limitations for plant growth with adversely affects to recuperation of the area.