Surface Complexation Modeling in Variable Charge Soils: Charge Characterization by Potentiometric Titration

ABSTRACT Intrinsic equilibrium constants of 17 representative Brazilian Oxisols were estimated from potentiometric titration measuring the adsorption of H+ and OH− on amphoteric surfaces in suspensions of varying ionic strength. Equilibrium constants were fitted to two surface complexation models: diffuse layer and constant capacitance. The former was fitted by calculating total site concentration from curve fitting estimates and pH-extrapolation of the intrinsic equilibrium constants to the PZNPC (hand calculation), considering one and two reactive sites, and by the FITEQL software. The latter was fitted only by FITEQL, with one reactive site. Soil chemical and physical properties were correlated to the intrinsic equilibrium constants. Both surface complexation models satisfactorily fit our experimental data, but for results at low ionic strength, optimization did not converge in FITEQL. Data were incorporated in Visual MINTEQ and they provide a modeling system that can predict protonation-dissociation reactions in the soil surface under changing environmental conditions.

Surface Complexation Modeling in Variable Charge Soils: Prediction of Cadmium Adsorption

ABSTRACT Intrinsic equilibrium constants for 22 representative Brazilian Oxisols were estimated from a cadmium adsorption experiment. Equilibrium constants were fitted to two surface complexation models: diffuse layer and constant capacitance. Intrinsic equilibrium constants were optimized by FITEQL and by hand calculation using Visual MINTEQ in sweep mode, and Excel spreadsheets. Data from both models were incorporated into Visual MINTEQ. Constants estimated by FITEQL and incorporated in Visual MINTEQ software failed to predict observed data accurately. However, FITEQL raw output data rendered good results when predicted values were directly compared with observed values, instead of incorporating the estimated constants into Visual MINTEQ. Intrinsic equilibrium constants optimized by hand calculation and incorporated in Visual MINTEQ reliably predicted Cd adsorption reactions on soil surfaces under changing environmental conditions.

Electrical Conductivity and Chemical Composition of Soil Solution: Comparison of Solution Samplers in Tropical Soils

ABSTRACT Soil solution samplers may have the same working principle, but they differ in relation to chemical and physical characteristics, cost and handling, and these aspects exert influence on the chemical composition of the soil solution obtained. This study was carried out to evaluate, over time, the chemical composition of solutions extracted by Suolo Acqua, with the hydrophilic membrane (HM) as a standard, using soils with contrasting characteristics, and to determine the relationship between electrical conductivity (EC) and concentration of ions and pH of soil solution samples. This study was carried out under laboratory conditions, using three soils samples with different clay and organic matter (OM) contents. Soil solution contents of F−, Cl−, NO−3, Br−, SO42−, Na+, NH4+, K+, Mg2+, Ca2+, were analyzed, as well as inorganic, organic, and total C contents, pH, and EC, in four successive sampling times. Soil solution chemical composition extracted by the Suolo Acqua sampler is similar to that collected by the HM, but the Suolo Acqua extracted more Na+ and soluble organic C than the HM solution. Solution EC, cation and anion concentrations, and soluble C levels are higher in the soil with greater clay and OM contents (Latossolo and Cambissolo in this case). Soil solution composition varied over time, with considerable changes in pH, EC, and nutrient concentrations, especially associated with soil OM. Thus, single and isolated sampling of the soil solution must be avoided, otherwise composition of the soil solution may not be correctly evaluated. Soil solution EC was regulated by pH, as well as the sum of cation and anion concentrations, and the C contents determined in the soil liquid phase.

Background and Reference Values of Metals in Soils from Paraíba State, Brazil

ABSTRACT Soil contamination by heavy metals threatens ecosystems and human health. Environmental monitoring bodies need reference values for these contaminants to assess the impacts of anthropogenic activities on soil contamination. Quality reference values (QRVs) reflect the natural concentrations of heavy metals in soils without anthropic interference and must be regionally established. The aim of this study was to determine the natural concentrations and quality reference values for the metals Ag, Ba, Cd, Co, Cu, Cr, Mo, Ni, Pb, Sb and Zn in soils of Paraíba state, Brazil. Soil samples were collected from 94 locations across the state in areas of native vegetation or with minimal anthropic interference. The quality reference values (QRVs) were (mg kg-1): Ag (<0.53), Ba (117.41), Cd (0.08), Co (13.14), Cu (20.82), Cr (48.35), Mo (0.43), Ni (14.44), Sb (0.61), Pb (14.62) and Zn (33.65). Principal component analysis grouped the metals Cd, Cr, Cu, Ni, Pb and Sb (PC1); Ag (PC2); and Ba, Co, Fe, Mn and Zn (PC3). These values were made official by Paraíba state through Normativa Resolution 3602/2014.

Behavior of Eucalyptus urophylla and Eucalyptus citriodora Seedlings Grown in Soil Contaminated by Arsenate

ABSTRACT Persistent areas of tailings and deposits from coal and gold mining may present high levels of arsenic (As), mainly in the arsenate form, endangering the environment and human health. The establishment of vegetation cover is a key step to reclaiming these environments. Thus, this study aimed to evaluate the potential of Eucalyptus urophylla and E. citriodora seedlings for use in phytoremediation programs of arsenate-contaminated areas. Soil samples were incubated at increasing rates (0, 50, 100, 200 and 400 mg dm-3) of arsenic (arsenate form, using Na2HAsO4) for 15 days. The seedlings were produced in a substrate (vermiculite + sawdust) and were transplanted to the pots with soil three months after seed germination. The values of plant height and diameter were taken during transplanting and 30, 60 and 90 days after transplanting. In the last evaluation, the total leaf area and biomass of shoots and roots were also determined. The values of available As in soil which caused a 50 % dry matter reduction (TS50%), the As translocation index (TI) from the roots to the shoot of the plants, and its bioconcentration factor (BF) were also calculated. Higher levels of arsenate in the soil significantly reduced the dry matter production of roots and shoots and the height of both species, most notably in E. urophylla plants. The highest levels of As were found in the root, with higher values for E. citriodora (ranging from 253.86 to 400 mg dm-3). The TI and BF were also reduced with As doses, but the values found in E. citriodora were significantly higher than in E. urophylla. E. citriodora plants presented a higher capacity to tolerate As and translocate it to the shoot than E. urophylla. Although these species cannot be considered as hyperaccumulators of As, E. citriodora presented the potential to be used in phytoremediation programs in arsenate-contaminated areas due to the long-term growth period of this species.

PERSISTENCE OF ATRAZINE, METRIBUZIN AND SIMAZINE HERBICIDES IN TWO SOILS

An oat bioassay was conducted in pots under greenhouse conditions to determine the persistence of atrazine, metribuzin and simazine herbicides in soils of the southeast of Buenos Aires Province, Argentina. Atrazine rates of 0, 0.58, 1.16 and 2.32 mug g-1 of active ingredient (a.i.), metribuzin rates of 0, 0.14, 0.28 and 0.56 mug g-1 of a.i., and simazine rates of 0, 0.72, 1.45 and 2.9 mug g-1 of a.i. dry soil weight were applied to pots containing soils from Balcarce and San Cayetano sites. Organic matter (OM) content and pH of Balcarce soil were 5.5% and 5.8%, while for San Cayetano soil were 2.9% and 6.7%, respectively. Relative dry weight (RDW) of oat shoots was calculated as percentage of control. Considering a 20% RDW reduction of oat shoots, persistences of recommended rates for the region were: atrazine (1.16 mug g-1 of a.i.), 78 and 130 days after treatment (DAT) for Balcarce and San Cayetano soil, respectively; metribuzin (0.28 mug-1 of a.i.), 63 and 77 DAT for Balcarce and San Cayetano soil, respectively; simazine (1.45 mug g-1 of a.i.), 81 and 156 DAT for Balcarce and San Cayetano soil, respectively. Results show that persistence of atrazine, metribuzin and simazine in soil increased with high rates, low OM content and high pH.

Boron adsorption in soils from the State of São Paulo, Brazil

Boron adsorption was studied in five representative soils (Rhodic Hapludox, Arenic Paleudalf and three Typic Hapludox) from the State of São Paulo, Brazil. Adsorption was higher in the clayey Oxisols, followed by the Alfisol and the coarser Oxisols. Calcium carbonate promoted an increase in the amount of adsorbed boron in all soils, with the most pronounced effect in the coarser-textured Oxisols. High correlation coefficients were found between adsorbed boron and clay and amorphous aluminum oxide contents and specific surface area (r = 0.79, 0.76 and 0.73, respectively, p < 0.01). Clay content, free aluminum oxide, and hot CaCl2 (0.01 mol L-1)-extracted boron explained 93% of the variation of adsorbed boron. Langmuir and Freundlich isotherms fitted well to the adsorbed data, and highest values for maximum boron adsorption were found in clayey soils, which were significantly correlated with contents of total, free and amorphous iron and aluminum oxides, as well with the physical attributes. Ninety four percent of the variation in the maximum adsorption could be related to the free iron content.

Enhanced degradation of metalaxyl in agricultural soils of São Paulo State, Brazil

This work investigated the effect of repeated applications on enhanced degradation of metalaxyl in two different agricultural soils used for cultivation of orange and lemon from Casa Branca and Itapetininga districts of São Paulo State, Brazil. Soil samples were collected from areas repeatedly treated with commercial ridomil 50GR for six successive years, and from other areas never exposed to this fungicide. At the laboratory, soil samples received a 14C-metalaxyl solution and its degradation was studied through radiometric techniques to measure biomineralization and recovery of extractable- and soil-bound products. Enhanced degradation was verified only in one soil, although partial degradation and mineralization of the fungicide were detected in both soils. The different rates and patterns of metalaxyl degradation in the soils were probably due to their different physical, chemical, and biological characteristics.

Characterization and discrimination of soils by their reflected electromagnetic energy

The objective of this work was to verify if reflected energy of soils can characterize and discriminate them. A spectroradiometer (Spectral reflectance between: 400-2,500 nm) was utilized in laboratory. The soils evaluated are located in Bauru region, SP, Brazil, and are classified as Typic Argiudoll (TR), Typic Eutrorthox (LR), Typic Argiudoll (PE), Typic Haplortox (LE), Typic Paleudalf (PV) and Typic Quartzipsamment (AQ). They were characterized by their spectral reflectance as for descriptive conventional methods (Brazilian and International) according to the types of spectral curves. A method for the spectral descriptive evaluation of soils was established. It was possible to characterize and discriminate the soils by their spectral reflectance, with exception for LR and TR. The spectral differences were better identified by the general shape of spectral curves, by the intensity of band absorption and angle tendencies. These characteristics were mainly influenced by organic matter, iron, granulometry and mineralogy constituents. A reduction of iron and clay contents, which influenced higher reflectance intensity and shape variations, occurred on the soils LR/TR, PE, LE, PV and AQ, on that sequence. Soils of the same group with different clay textures could be discriminated. The conventional descriptive evaluation of spectral curves was less efficient on discriminating soils. Simulated orbital data discriminated soils mainly by bands 5 and 7.

Adsorption of glyphosate in chilean soils and its relationship with unoccupied phosphate binding sites

The objective of this work was to investigate glyphosate adsorption by soils and its relationship with unoccupied binding sites for phosphate adsorption. Soil samples of three Chilean soils series - Valdivia (Andisol), Clarillo (Inceptisol) and Chicureo (Vertisol) - were incubated with different herbicide concentrations. Glyphosate remaining in solution was determined by adjusting a HPLC method with a UV detector. Experimental maximum adsorption capacity were 15,000, 14,300 and 4,700 mg g¹ for Valdivia, Clarillo, and Chicureo soils, respectively. Linear, Freundlich, and Langmuir models were used to describe glyphosate adsorption. Isotherms describing glyphosate adsorption differed among soils. Maximum adjusted adsorption capacity with the Langmuir model was 231,884, 17,874 and 5,670 mg g-1 for Valdivia, Clarillo, and Chicureo soils, respectively. Glyphosate adsorption on the Valdivia soil showed a linear behavior at the range of concentrations used and none of the adjusted models became asymptotic. The high glyphosate adsorption capacity of the Valdivia soil was probably a result of its high exchangeable Al, extractable Fe, and alophan and imogolite clay type. Adsorption was very much related to phosphate dynamics in the Valdivia soil, which showed the larger unoccupied phosphate binding sites. However relationship between unoccupied phosphate binding sites and glyphosate adsorption in the other two soils (Clarillo and Chicureo) was not clear.

Remaining phosphorus and sodium fluoride pH in soils with different clay contents and clay mineralogies

The remaining phosphorus (Prem) has been used for estimating the phosphorus buffer capacity (PBC) of soils of some Brazilian regions. Furthermore, the remaining phosphorus can also be used for estimating P, S and Zn soil critical levels determined with PBC-sensible extractants and for defining P and S levels to be used not only in P and S adsorption studies but also for the establishment of P and S response curves. The objective of this work was to evaluate the effects of soil clay content and clay mineralogy on Prem and its relationship with pH values measured in saturated NaF solution (pH NaF). Ammonium-oxalate-extractable aluminum exerts the major impacts on both Prem and pH NaF, which, in turn, are less dependent on soil clay content. Although Prem and pH NaF have consistent correlation, the former has a soil-PBC discriminatory capacity much greater than pH NaF.

Rhizobium strains competitiveness on bean nodulation in Cerrado soils

The objective of this work was to identify the most competitive and effective Rhizobium strains in order to increase common bean yield by nitrogen fixation as alternative or complementation to the nitrogen fertilization. Competitiveness tests were lead in axenic conditions, in Cerrado soil pots and in three field experiments, with native Rhizobium strains that were previously identified, according to their effectiveness and genetic variability. The identification of strains in nodules was performed using serological tests (axenic conditions) - agglutination and enzyme linked immunosorbent (Elisa) assays - and random amplified polymorfic DNA (RAPD) (Cerrado soil). Plant yield was determined using the dry weight (greenhouse conditions), total N and grain yield (field experiments). Among the analyzed Rhizobium strains, native strain SLA 2.2 and commercial strain CIAT 899 were the dominant nodules in plants of the most productive plots, presenting yield productivity similar or higher to those obtained in treatments where 20 kg ha-1 of N were applied.

Numerical procedure for estimating temperature in solarized soils

The objective of this work was to develop a simplified numerical procedure for the estimation of accumulated monthly hours of solarized soil temperatures. The proposed model requires monthly means of daily solar radiation and maximum air temperature as input data, and a daily pattern of temperature variation assumed to be sine-shaped. The procedure was verified using observations made during the years 1992 and 1993 in Jaguariúna, SP. The proposed procedure can predict monthly temperature hours at 10 cm depth in the solarized soil, with acceptable accuracy, in the region for which it was developed.

Zinc adsorption in highly weathered soils

The objective of this work was to assess the effects of pH and ionic strength upon zinc adsorption, in three highly weathered variable charge soils. Adsorption isotherms were elaborated from batch adsorption experiments, with increasing Zn concentrations (0-80 mg L-1), and adsorption envelopes were constructed through soil samples reactions with 0.01, 0.1 and 1 mol L-1 Ca(NO3)2 solutions containing 5 mg L-1 of Zn, with an increasing pH value from 3 to 8. Driving force of reaction was quantified by Gibbs free energy and separation factor. Isotherms were C-, H- and L-type and experimental results were fitted to nonlinear Langmuir model. Maximum adsorption ranged from 59-810 mg kg-1, and Zn affinity was greater in subsoil (0.13-0.81 L kg-1) than in the topsoil samples (0.01-0.34 L kg-1). Zinc adsorption was favorable and spontaneous, and showed sharply increase (20-90%) in the 4-6 pH range. No effect of ionic strength was observed at pH values below 5, because specific adsorption mechanisms predominated in the 3-5 pH range. Above pH 5, and in subsoil samples, Zn was adsorbed by electrostatic mechanisms, since ionic strength effect was observed. Despite depth and ionic strength effects, Zn adsorption depends mainly on the pH.

State of the science and the way forward for the ecotoxicological assessment of contaminated land

Over the past two decades, soil ecotoxicologists have made strides in utilizing the basic concepts and advancements in soil zoology and ecology. They have applied the existing tools, and developed new ones to investigate how chemical contamination can affect soil ecosystems, including the degradation or destruction of soil quality and habitats or the diminishment of belowground biodiversity. Soil ecotoxicologists are applying a suite of standard protocols, originally developed as laboratory tests with single chemicals (e.g., pesticides), and further enhancing both the approaches and protocols for the assessment of contaminated lands. However, ecological relevance of some approaches remains unresolved. The authors discuss the main challenges for a coherent ecotoxicological assessment of soil ecosystems amid contaminated lands, and provide recommendations on how to integrate the effects of physical and chemical soil properties, the variations in the diversity of soil invertebrates, and the interactions among organisms of various trophic levels. The review examines new international approaches and test methods using examples from three continents (in particular research conducted in Brazil), and provides recommendations for improving ecological relevance of ecotoxicological investigations of contaminated lands.