ABSTRACT Extensive pastures are commonly converted to sugarcane areas in Brazil. In soils cultivated with sugarcane, tillage and fertilization are management practices commonly carried out. Soil management practices alter the physical and chemical properties increasing or decreasing metal availability. The purpose of this study was to quantify soil metal concentrations during pasture-to-sugarcane conversion correlating these changes with physical and chemical properties. The results showed that the concentration of metals in soil samples occurred according to the following order Fe > Mn > Cr > Zn > Cu > Pb > Cd. Significant increases in soil metal concentrations due the sugarcane cultivation were observed to Cd and Cu. The soil physical and chemical properties presented correlations with soil metal concentrations. There was a strong relationship on inorganic fertilization to change in soil metal concentrations. The principal component analysis (PCA) explained 55.4% of the total data variance, separating factors in two groups that pointed to an influence of fertilization on metal grouping. Inorganic fertilizer application may input 1.06 g·ha–1·year–1 Cd. The Cd concentration ranged from 0.15 to 1.07 mg·kg–1, representing addictions of 9.54 mg·ha–1·year–1 Cd in soil. The metal concentrations observed after five years of pasture-to-sugarcane conversion did not represent environmental risks since the concentrations remained below the Brazilian official determinations.

The Mundaú-Manguaba lagoon estuary complex is the most important ecosystem in the state of Alagoas, and a source of sustenance for a large number of the state’s inhabitants. However, degradation by anthropic sources has been causing impacts on this ecosystem. Understanding the characteristics of the natural organic material of the waters of the mundaú-manguaba lagoon complex is extremely important to understand the interaction dynamics of the contaminants in these lagoons. Thus, the objective of this work was to extract and characterize aquatic humic substances from the Mundau-Manguaba lagoon complex and to evaluate the interaction of this organic material with mercury ions. The profile of the aquatic humic substances of the respective lagoons evidenced the greater influence of aliphatic groups in their structures. The interactions of aquatic humic substances and mercury ions are directly related to the oxygen groups in their structures, corroborated by Principal Component Analysis. Thus, understanding the water and organic matter characteristics present in the Mundaú-Manguaba estuarine lagoon complex is fundamental for establishing strategies, seeking the preservation of this ecosystem and remediation of environmental contamination.

In rivers, sediments act as sinks for retaining contaminants. This study evaluated the influence of sediment humic substances (HS) on the bioavailability of metals. The levels of metals in sediments and HS indicated that most are complexed with HS. Characterization of HS showed a high degree of humification. The complexation capacity of HS for metals established the affinity order:Pb2+<Cd2+<Co2+<Ni2+<Cu2+<Zn2+<Mn2+<Fe2+. Chemometric analysis demonstrated a correlation between the structural characteristics of HS and complexation capacity of metals.

This study used chemometric tools and a Geographic Information System (GIS) to determine the influence of organic matter and anthropogenic activity on the distribution of metal species between two major communities of the Middle Negro River Basin-AM. Higher concentrations of metal species were determined in flooded regions. The chemometric analysis showed the affinity of organic matter for potentially toxic metals, indicating its selectivity. GIS spatial analysis has shown that proximity to urban areas is a variable that is likely to influence the pattern of concentration of organic matter, and consequently the distribution of metal species between flooded and non-flooded areas.

The knowledge of the structure characteristic of the Organic Matter is important for the understanding of the natural process. In this context aquatic humic substances (principal fraction) were isolated from water sample collected from the two distinct rivers, using procedure recommended for International Humic Substances Society and characterized by elemental analysis, electron paramagnetic resonance and nuclear magnetic resonance (13C NMR). The results were interpreted using principal component analysis (PCA) and the statistical analyses showed different in the structural characteristics of the aquatic humic substances studied.

The region of Aracá River (Middle and Upper Rio Negro-AM) has peculiar characteristics, having soils with atypical profile and high organic matter contents in great deep. The levels of aluminum and iron in the soil samples increased as a function of depth and concentrations of mercury ranged from 0.097 to 0.964 µg g-1. Statistical analysis showed the degree of similarity between soil samples collected. The highest concentrations of mercury in soil samples are directly related to soil higher content of organic matter, directly influencing the fate and bioavailability of mercury species to the environment.

Neste trabalho substâncias húmicas (SH) extraídas de solos não alagáveis (Araçá) e alagáveis (Iara) foram caracterizadas com cálculos de estabilidade e energias de ativação associadas com a desidratação e decomposição térmica de SH utilizando TGA and DTA, ressonância paramagnética eletrônica (EPR) e razões atômicas C/H, C/N e C/O. Para SH extraídas de solos alagáveis, existe evidências da influência da umidade sobre o processo de humificação da matéria orgânica. Observações do comportamento térmico, com análise elementar, indicaram a presença de fósseis de carbono orgânico nas partículas de argila, o que só decompõe acima de 800 ºC. Essa característica pode explicar as diferentes estabilidades térmicas e energias de ativação requeridas na pirólise para amostra Iara comparada a amostra Araçá.

In this work humic substances (HS) extracted from non-flooded (Araçá) and flooded (Iara) soils were characterized through the calculation of stability and activation energies associated with the dehydration and thermal decomposition of HS using TGA and DTA, electronic paramagnetic resonance and C/H, C/N and C/O atomic ratios. For HS extracted from flooded soils, there was evidence for the influence of humidity on the organic matter humification process. Observations of thermal behaviour, with elemental analysis, indicated the presence of fossilized organic carbon within clay particles, which only decomposed above 800 ºC. This characteristic could explain the different thermal stability and pyrolysis activation energies for Iara HS compared to Araçá HS.

The work reported here involved the characterization of sludges produced at water treatment plants in Jaboticabal-SP using FeCl3 as flocculant, and in Taquaritinga-SP and Manaus-AM using Al2(SO4)3 as flocculant. An evaluation was also made of the interaction of organic matter extracted from the sludges with different metal species. The results indicated that all the sludges produced at water treatment plants have an important agricultural potential and that their use depends on the characteristics of the raw water and the type of flocculant employed in conventional treatment. The humic substances extracted from the sludges showed different affinities for metal species, favoring eventual exchanges between potentially toxic metals and macro- and micronutrients. An alternative for the use of sludge in agriculture is to pretreat it to remove potentially toxic metals and enrich it with micro- and macronutrients that can be released to the plant.

Samples of soil, water and sediment were collected and analyzed in order to evaluate chromium contamination due to deposition of tannery residues onto soils under different management regimes. The results showed that soils used for sugar cane cultivation were not adversely impacted. However, in the case of mango plantations, variable concentrations of chromium were measured in the soil profile, with 22.2% of values being higher than permitted legal limits, and 38.9% being at levels requiring remediation. Concentrations of bioavailable chromium were lower than the detection limit of the method (0.01 mg of chromium kg-1 of soil), indicating that all of the chromium present in the samples was either complexed or in an insoluble form. Chromium concentrations measured in samples of water and sediments were indicative of low mobility of the metal in soils. The main cause of differences found between soil samples obtained from different cultivations was the type of soil management.

Soils play an important role in the biogeochemical cycle of mercury as a sink for and source of this metallic species to atmospheric and hydrological compartments. In the study reported here, various types of soil were evaluated to ascertain the influence of parameters such as pH, organic matter content, Fe, Al, sand, silt, clay, C/H, C/N, C/O atomic ratios, and cation exchange capacity on the distribution of Hg in Amazonia's mid-Negro River basin. The data obtained were interpreted by multivariate exploratory analyses (hierarchical cluster analysis and principal component analysis), which indicated that organic matter plays an important role in mercury uptake in the various soils studied. The soils in floodable areas were found to contain 1.5 to 2.8-fold higher Hg concentrations than those in non-floodable areas. Since these soils are flooded almost year-round, they are less available to participate in redox processes at the soil/atmosphere interface. Hence, floodable areas, which comprise humic-rich soils, accumulate more mercury than non-floodable soils, thus playing an important role in the biogeochemical cycle of Hg in Amazonia's mid-Negro River basin.

A capacidade de complexação de substâncias húmicas extraídas de amostras de turfa coletadas na região do Rio Mogi em Ribeirão Preto, SP, Brasil, foi determinada utilizando Al(III), Pb(II), Cr(VI) e Cd(II). A seguinte ordem de afinidade foi observada: Cr(VI)< Cd(II)<Pb(II)<Al(III). O teste toxicológico LD50 mostrou que as substâncias húmicas não são tóxicas até a concentração máxima de 512 mg kg-1. Esses resultados reforçam a possibilidade do uso das substâncias húmicas como agente desintoxicante de metais.

The complexation capacity of humic substances extracted from peat samples taken from the Mogi River in Ribeirao Preto, SP, Brazil, was determined using metal ions (Al(III), Pb(II), Cr(VI) and Cd(II)), yielding the following order of affinity: Cr(VI)< Cd(II)<Pb(II)<Al(III). An oral LD50 test showed that these humic substances are nontoxic up to a maximum concentration of 512 mg kg-1. These findings reinforce the possibility of using humic substances as a metal detoxicant.

Amostras de turfa (SAO e ITA) coletadas no Estado de Sergipe, Brasil, foram caracterizadas por diferentes técnicas: análise térmica e elementar, infravermelho, espectroscopia de ressonância magnética nuclear de 13C (NMR), microscopia eletrônica de varredura (SEM), microscopia eletrônica de varredura ambiental (ESEM), difratometria de raios X (XRD) e comparadas com outras amostras de turfa (SAP) coletadas no Estado de São Paulo, Brasil. As razões mais baixas O/C, E4/E6 e as curvas de análise térmica diferencial (DTA) da amostra de Santo Amaro (SAO) indicaram que esta possui o mais alto grau de decomposição. Resultados da espectroscopia na região do infravermelho mostraram que as amostras de Itabaiana (ITA) e São Paulo (SAP) apresentam pico predominante a 1086 cm-1 atribuídos a presença de Si-O diferente da amostra de Santo Amaro (SAO). Esta mostrou dois picos intensos a 2920 cm-1 e 2850 cm-1 corroborando com dados de RMN 13C e análise termogravimétrica em que houve maior abundância dos grupos C-alquila. A difratometria de raios X (XRD) da amostra de SAO apresentou características de material amorfo. Entretanto, as amostras de SAP e ITA revelam maior presença de quartzo mineral. A microscopia eletrônica de varredura (SEM) e a microscopia eletrônica de varredura ambiental (ESEM) mostraram que a superfície das amostras de turfa possui grânulos porosos de matéria orgânica. As amostras de turfa de ITA e SAP são semelhantes enquanto a de SAO possui alto teor de matéria orgânica. Apenas a amostra de SAO apresenta características de turfa. Os resultados deste estudo mostraram que as amostras são muito diferentes devido aos teores variáveis de material orgânico e inorgânico.

Peat was taken from the Sergipe State, Brazil and characterized by several techniques: elemental and thermal analyses; Fourier infrared (FTIR) and solid state 13C nuclear magnetic resonance (NMR) spectroscopies; scanning electron microscopy (SEM), environmental scanning electron microscopy (ESEM) and X-ray diffractometry (XRD). Also, the Sergipe State peat samples were compared with other peat sample from later from Sao Paulo State, Brazil. The lowest O/C and E4/E6 ratios and differential thermal analysis (DTA) curves of the Santo Amaro (SAO) sample indicated that this sample had the highest degree of decomposition. FTIR results showed that Itabaiana (ITA) and São Paulo (SAP) samples presented more prominent peak at 1086 cm-1 attributed the presence of Si-O than SAO sample spectra. The SAO sample showed two more intense peaks at 2920 cm-1 and 2850 cm-1. These results were corroborated by 13C NMR and thermal gravimetric (TG) where the relative abundance of the alkyl-C groups was greater in the SAO sample. The X-ray diffractometry (XRD) of SAO sample is characteristic of amorphous matter however, the SAP and ITA samples revealed the large presence of quartz mineral. The scanning electron microscopy (SEM) and environmental scanning electron microscopy (ESEM) showed that the surface of peat samples have porous granules of organic material. The ITA and SAP peat samples are alike while SAO peat sample is richer in organic material. Only the SAO sample has truthful characteristics of peat. The results of this study showed that the samples are very different due to variable inorganic and organic material contents.