Remediation of contaminated soil with heavy metal using triple superphosphate, red mud and zeolites

Devido à persistência de metais pesados em solos, a contaminação por estes elementos é considerada permanente resultando no impacto agravante da degradação das propriedades químicas e biológicas do solo. As técnicas de estabilização para remediação de solos contaminados com metais pesados têm se destacado como uma opção eficaz, além de resultar num custo/benefício mais acessível quando comparado aos métodos de descontaminação tradicionais. Quando associada à fitoestabilização, constitui uma das técnicas mais promissoras, pois além de promover a reabilitação da área impactada, diminui os riscos ambientais, na medida em que protege o solo da erosão hídrica e reduz a lixiviação dos contaminantes. O conhecimento da distribuição dos metais nas frações do solo é essencial à predição do comportamento geoquímico destes no ambiente e, permite ainda avaliar a eficiência dos procedimentos remediadores e sua longevidade. Cd, Pb, Cu, Ni e Zn são de grande interesse na regulamentação por agências governamentais, visto que em concentrações elevadas em águas, solos e ar representam riscos à saúde humana. Neste contexto, o presente trabalho avaliou o potencial de imobilização de superfosfato triplo, lama vermelha e zeólitas para um solo contaminado com resíduo industrial rico em Cd, Pb, Cu, Ni e Zn, por meio de ensaio de incubação em vasos. Posteriormente, a capacidade de promover o crescimento vegetal em cada tratamento foi avaliada através de ensaios com milho (Zea mays), em vasos, e pelo método de Neubauer, em placas de Petri, utilizando o arroz (Oryza sativa). O comportamento e distribuição dos metais foram avaliados pelo método de extração seqüencial de Tessier. De maneira geral, todos os remediadores reduziram os teores disponíveis dos metais no solo, com variações sobre as doses e os elementos. O superfosfato triplo reduziu, principalmente, a disponibilidade de Pb, Cu e Zn. Zeólitas e lama vermelha apresentaram maior redução sobre os teores disponíveis de Cd e Ni. O superfosfato triplo promoveu redução de pH e, no sentido oposto, a lama vermelha elevou o pH do solo. Os dados de extração seqüencial apontaram o deslocamento dos metais para a fração oxi-hidróxidos de ferro e manganês, após os tratamentos. O superfosfato triplo foi o tratamento que mais promoveu o crescimento vegetal e produção de matéria seca.Due to the heavy metal persistence in soils, the contamination by these elements is considered permanent and might result in great impact causing a degradation of the chemical and biological properties of the soil. Stabilization techniques have been used as an efficient tool for the remediation of soils that are contaminated by heavy metals, and they show also a cost/benefice relationship more accessible when compared with the traditional methods of decontamination. The association of stabilization and phytostabilization constitute a prominent technique because decrease the environmental risk besides recovering and rehabilitating the impacted area, protecting the soil from water erosion and leaching of the contaminants. The knowledge of the heavy metal distribution in the soil fractions is essential to the prediction of the geochemical behavior these metals in the environmental and allows also evaluate the efficacy of the remediation procedures and their longevity. Cd, Pb, Cu, Ni and Zn are of great interest to the regulamentation by the governmental agencies because if they are found in high concentration in water, soils and air they represent risk to the human health. In this context, this work evaluated the potential of the immobilization for triple superphosphate, red mud and zeolites in a contaminated soil with industrial residues rich in Cd, Pb, Cu, Ni and Zn, by using vase soil incubation experiment. Later, it was evaluated the capacity to promote the vegetal growth in each treatment through corn (Zea mays) experiment in vases and also by Neubauer method in Petri plates, using rice (Oryza sativa). The behavior and distribution of heavy metals were evaluated by the sequential extraction of Tessier. In general, all remediates reduced the available concentration of the heavy metals in the soil, varying with doses and the elements. The triple superphosphate reduced mainly the availability of Pb, Cu and Zn. Zeolites and red mud presented higher reduction in the available concentration of Cd and Ni. The triple superphosphate promoted pH reduction and in an opposite way the red mud increased the soil pH. The sequential data extraction showed the heavy metals moving to the iron and manganese oxi-hydroxide fractions after the treatments. The triple superphosphate was the treatment that has promoted higher vegetal growth

Geochemical behavior of mercury (Hg) in mangroves soils from São Paulo State

Os ecossistemas costeiros do litoral do Estado de São Paulo apresentam-se ambientalmente degradados, em conseqüência da concentração populacional e instalação de pólos industriais e petroquímicos. O lançamento de rejeitos urbanos, industriais e portuários nos corpos dágua resulta no aporte indiscriminado de poluentes nos ambientes estuarinos. O metal pesado mercúrio (Hg) constitui um dos poluentes de maior risco para o equilíbrio ecológico e saúde humana, justificado pela elevada toxicidade e potencial de bioacumulação e biomagnificação através da cadeia alimentar. O presente trabalho teve por objetivos: (a) determinar o conteúdo de Hg total em solos de manguezais da Baixada Santista (rio Cascalho, Mariana, Crumahú, Irirí e Canal da Cosipa) e Ilha do Cardoso; (b) verificar a influência do preparo de amostras na determinação de Hg em solos estuarinos; (c) analisar parâmetros químicos relacionados à geoquímica do Hg; (d) avaliar a distribuição do conteúdo total de Hg nas frações mais relevantes em solos de manguezais por meio de extração seqüencial. Foi determinado um enriquecimento de Hg nas camadas superficiais dos solos da Baixada Santista e Ilha do Cardoso, porém não foi verificado um padrão uniforme de distribuição das concentrações de Hg total nos perfis amostrados. O manguezal do rio Cascalho e Canal da COSIPA apresentaram elevados teores de Hg (5,65 mg.kg-1 e 1,64 mg.kg-1, respectivamente), caracterizando áreas altamente poluídas. Em uma nova amostragem nos manguezais do rio Cubatão, próximo ao rio Cascalho, os teores de Hg total permaneceram em concentrações superiores ao valor de alerta estabelecido pela CETESB. Em função da variabilidade dos resultados, a influência do preparo de amostras desta natureza foi analisada comparando-se teores totais em amostras úmidas, sem tratamentos prévios de secagem e moagem; secas pelo processo de liofilização, sem posterior moagem; amostras submetidas aos pré-tratamentos de secagem em estufa a 25°C e moagem; amostras submetidas aos pré-tratamentos de secagem em estufa a 180°C e moagem. Uma vez que a umidade em cada sub-amostra pode diferir, a determinação do conteúdo de Hg total na amostra úmida pode ser a causa primária da variabilidade entre os resultados, somada à distribuição desuniforme de raízes e matéria orgânica, e variações texturais. A utilização de amostras secas pelo processo de liofilização e posteriormente moídas pode contribuir para a precisão analítica dos resultados gerados da extração de Hg, em solos de ambientes estuarinos. Com base nos resultados de Eh e pH foi verificado que a quase totalidade das amostras se situam no campo de estabilidade do Hg elementar e em menor proporção no campo de estabilidade do HgS, favorecendo a formação de Hg elementar e o processo de piritização. De acordo com a extração seqüencial, o Hg encontra-se associado principalmente à fração pirítica, enquanto que nas frações mais reativas dos solos, foram determinadas menores concentrações de Hg (frações trocável e solúvel, carbonatos, ferridrita e lepidocrocita), e concentrações ainda relativamente inferiores na fração correspondente às formas cristalinas de ferro, em todas as amostras.Coastal ecosystems at São Paulo State show a condition of environmental degradation, due to high density of population and presence of industrial and petrochemical poles. The disposal of urban, industrial and harbor wastes into water bodies result in indiscriminate accumulation of pollutants in estuarines soils. Mercury (Hg) constitutes one of the most dangerous pollutants for the ecological balance and human health, because of its high toxicity and potential for bioaccumulation and biomagnification through the food chain. The current study aimed to: (a) determine total content of Hg in mangroves soils from Baixada Santista region (Cascalho, Mariana, Crumahú and Irirí rivers and COSIPA Channel) and Cardoso Island; (b) verify the effects of sample pre-treatments to determine Hg in mangrove soils; (c) analyze chemical parameters related to the geochemistry of Hg; (d) evaluate the distribution of total Hg in the most relevant fractions of mangroves soils using sequential extraction technique. An enrichment in total Hg was observed in the superficial layers of Baixada Santista and Cardoso Island soils, although there was no regular pattern of total Hg distribution at the studied profiles. Mangroves soils from Cascalho River and COSIPA Channel showed high Hg concentrations (5,65 mg.kg-1 e 1,64 mg.kg-1, respectively), characterizing highly polluted areas. Soil samples from Cubatão River, close to Cascalho River, showed total Hg values greater than the alert level established by CETESB. Due to the great data variability the effects of sample pre-treatment were analyzed by comparing the total Hg contents in fresh samples without previous drying and grinding treatments with samples dried by liofilization without later grinding; samples submitted to pre-drying treatments at 25°C and grinding, samples submitted to pre-drying treatments at 180°C and grinding. Since water content may vary from one sample to another, the establishment of total Hg content in fresh samples can be the main cause of results variability, in addition to the non-uniform distribution of root, organic matter and textural variations. The use of liofilized and ground samples may contribute to the analytical precision. Regarding Hg geochemistry, data obtained from Eh-pH correlation evidence that most samples are located in the elemental Hg stability field and, in a smaller proportion, in the HgS stability field, favoring elemental Hg formation and pyritization process. Sequential extraction data show that Hg is mainly associated to the pyritic fraction, followed by the most reactive fractions (soluble, exchangeable, carbonates, ferrihydrite and lepdocrocite fractions), and the fraction corresponding to crystalline iron oxides

Chromium in soil organic matter and cowpea after four consecutive annual applications of composted tannery sludge

Tannery sludge contains high concentrations of inorganic elements, such as chromium (Cr), which may lead to environmental pollution and affect human health The behavior of Cr in organic matter fractions and in the growth of cowpea (Vigna unguiculata L.) was studied in a sandy soil after four consecutive annual applications of composted tannery sludge (CTS). Over a four-year period, CTS was applied on permanent plots (2 x 5 m) and incorporated in the soil (0-20 cm) at the rates of 0, 2.5, 5.0, 10.0, and 20.0 Mg ha(-1) (dry weight basis). These treatments were replicated four times in a randomized block design. In the fourth year, cowpea was planted and grown for 50 days, at which time we analyzed the Cr concentrations in the soil, in the fulvic acid, humic acid, and humin fractions, and in the leaves, pods, and grains of cowpea. Composted tannery sludge led to an increase in Cr concentration in the soil. Among the humic substances, the highest Cr concentration was found in humin. The application rates of CTS significantly increased Cr concentration in leaves and grains.O lodo de curtume compostado contém elevadas concentrações de elementos inorgânicos, como o crômio (Cr), que podem levar à poluição ambiental e influenciar na saúde humana. O comportamento envolvendo o Cr nas frações da matéria orgânica e no crescimento do feijão-caupi (Vigna unguiculata L.) foi estudado em solo arenoso, após quatro anos de aplicações anuais consecutivas de lodo de curtume compostado (LCC). Durante quatro anos, o LCC foi aplicado em parcelas permanentes (2 × 5 m) e incorporado no solo (0-20 cm), nas doses de 0; 2,5; 5,0; 10,0 e 20,0 Mg ha-1 (base seca). Esses tratamentos foram repetidos quatro vezes em blocos ao acaso. No quarto ano, o feijão-caupi foi semeado e cresceu por 50 dias, quando se analisaram as concentrações de Cr no solo, nas frações ácidos fúlvicos, ácidos húmicos e humina, nas folhas, nas vagens e nos grãos do feijão-caupi. O LCC promoveu aumento na concentração de Cr no solo. Entre as substâncias húmicas, a maior concentração de Cr foi encontrada na humina. As doses de LCC elevaram o teor de Cr nas folhas e grãos.Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq

Availability and spatial variability of copper, iron, manganese and zinc in soils of the State of Ceará, Brazil

ABSTRACT The aim of the present work was to: (i) determine and map the micronutrient content (copper - Cu, iron - Fe, manganese - Mn and zinc - Zn) in soils of the State of Ceará; (ii) evaluate soil attributes related to micronutrient availability; and (iii) evaluate, by ordinary kriging, the spatial dependence of the micronutrient content. The study area is located in the central region of Ceará, in the basin of the River Banabuiú. Soil samples were collected in the surface and subsurface layers to determine the chemical attributes, granulometry, and micronutrient content, extracted with Mehlich-1 solution. The sites of the principal types of soil in the region were spatialised and the results submitted to descriptive analysis and Pearson correlation analysis. The semivariograms with the best fit were tested using the ordinary kriging method, and the maps of spatial variability were prepared. The highest values for the mean, maximum and minimum levels of Cu and Fe are found in the subsurface layers, while for Mn and Zn, they are found in the surface layers. In the surface layers, the majority of soils present Fe, Mn and Zn in levels suitable for agricultural production, while the levels of Cu are classified as medium to low. The micronutrients showed a significant positive correlation, especially with the soil attributes and with each other. Cu, Fe, Mn and Zn are classified as having medium to strong spatial dependence in the surface and subsurface layers

Availability and spatial variability of copper, iron, manganese and zinc in soils of the State of Ceará, Brazil

<div><p>ABSTRACT The aim of the present work was to: (i) determine and map the micronutrient content (copper - Cu, iron - Fe, manganese - Mn and zinc - Zn) in soils of the State of Ceará; (ii) evaluate soil attributes related to micronutrient availability; and (iii) evaluate, by ordinary kriging, the spatial dependence of the micronutrient content. The study area is located in the central region of Ceará, in the basin of the River Banabuiú. Soil samples were collected in the surface and subsurface layers to determine the chemical attributes, granulometry, and micronutrient content, extracted with Mehlich-1 solution. The sites of the principal types of soil in the region were spatialised and the results submitted to descriptive analysis and Pearson correlation analysis. The semivariograms with the best fit were tested using the ordinary kriging method, and the maps of spatial variability were prepared. The highest values for the mean, maximum and minimum levels of Cu and Fe are found in the subsurface layers, while for Mn and Zn, they are found in the surface layers. In the surface layers, the majority of soils present Fe, Mn and Zn in levels suitable for agricultural production, while the levels of Cu are classified as medium to low. The micronutrients showed a significant positive correlation, especially with the soil attributes and with each other. Cu, Fe, Mn and Zn are classified as having medium to strong spatial dependence in the surface and subsurface layers.</p></div

Chromium, Cadmium, Nickel, and Lead in a Tropical Soil after 3 Years of Consecutive Applications of Composted Tannery Sludge

Agricultural use of tannery sludge (TS) may increase risks to soils. Thus, composting is recognized as one of the most suitable alternatives for TS recycling. Field experiments were carried out to evaluate the effects of composted tannery sludge (CTS) on chromium (Cr), cadmium (Cd), nickel (Ni), and lead (Pb) accumulation in soil after 3 years. Soil samples were collected 60 days after CTS application. After 3 years, The CTS increased Cr and Ni content, while Cd and Pb contents decreased. The third year, Cr contents showed linear increases as CTS rates were applied. The application of CTS, after 3 years, in the 2.5, 5, and 10 Mg ha(-1) increased Cr significantly (140.7%, 159.7%, and 19%, respectively) and Ni (32%, 53%, and 43.8%, respectively) contents in the soil surface layer. This means that consecutive amendments of CTS increase Cr contents in the soil and plants

Soil microbial properties after 5 years of consecutive amendment with composted tannery sludge

Composting has been recognised an alternative method to tannery sludge recycling and afterwards to be used in agriculture. As the tannery sludge contains salts and chromium, the application of composted tannery sludge (CTS) should be performed carefully to minimise negative effects on soil microbial properties. Therefore, this study evaluated the effects of 5-year repeated CTS amendment on soil microbial biomass (SMB) and enzyme activities in a tropical soil. CTS was applied during 5 years at 0, 2.5, 5, 10 and 20 Mg ha(-1), and at the fifth year, the microbial biomass C (MBC) and N (MBN), basal and substrate-induced respiration (SIR), metabolic quotient (qCO(2)) and dehydrogenase (DHA) and fluorescein diacetate (FDA) hydrolysis were determined in the soil samples. Soil MBC and MBN showed the highest values with the amendment of 5 Mg ha(-1) CTS. Soil respiration increased with the increase in CTS rates, while SIR showed the highest values with the amendment of 0, 2.5 and 5 Mg ha(-1) CTS. DHA activity showed the highest values with the amendment up to 2.5 Mg ha(-1), while FDA hydrolysis increased up to the rate of 5 Mg ha(-1) CTS. The results show that after 5 years of permanent amendment of CTS, soils amended with 2.5 Mg ha(-1) have SMB and enzymatic activities similar to those in unamended soil.Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES