Pyrolysis temperature and biochar redox activity on arsenic availability and speciation in a sediment.

Biochar is widely used for water and soil remediation in part because of its local availability and low production cost. However, its effectiveness depends on physicochemical properties related to its feedstock and pyrolysis temperature, as well as the environmental conditions of its use site. Furthermore, biochar is susceptible to natural aging caused by changes in soil or sediment moisture, which can alter its redox properties and interactions with contaminants such as arsenic (As). In this study, we investigated the effect of pyrolysis temperature and biochar application on the release and transformations of As in contaminated sediments subjected to redox fluctuations. Biochar application and pyrolysis temperature played an important role in As species availability, As methylation, and dissolved organic carbon concentration. Furthermore, successive flooding cycles that induced reductive conditions in sediments increased the As content in the solution by up to seven times. In the solid phase, the application of biochar and the flooding cycle altered the spatial distribution and speciation of carbon, iron (Fe) and As. In general, the application of biochar decreased the reduction of Fe(III) and As(V) after the first cycle of flooding. Our results demonstrate that the flooding cycle plays an important role in the reoxidation of biochar to the point of enhancing the immobilization of As.

The role of dissolved pyrogenic carbon from biochar in the sorption of As(V) in biogenic iron (oxyhydr)oxides.

Water contamination by arsenic (As) affects millions of people around the world, making techniques to immobilize or remove this contaminant a pressing societal need. Biochar and iron (oxyhydr)oxides [in particular, biogenic iron (oxyhydr)oxides (BIOS)] offer the possibility of stabilizing As in remediation systems. However, little is known about the potential antagonism in As sorption generated by the dissolved organic carbon (DOC) from biochar, or whether DOC affects how As(V) interacts with BIOS. For this reason, our objectives were to evaluate the i) As(V) sorption potential in BIOS when there is presence of DOC from pyrolyzed biochars at different temperatures; and ii) identify whether the presence of DOC alters the surface complexes formed by As(V) sorbed in the BIOS. We conducted As(V) sorption experiments with BIOS at circumneutral pH conditions and in the presence of DOC from sugarcane (Saccharum officinarum) straw biochar at pyrolyzed 350 (BC350) and 750 °C (BC750). The As(V) content was quantified by inductively coupled plasma mass spectrometry, and the BIOS structure and As(V) sorption mechanisms were investigated by X-ray absorption spectroscopy. In addition, the organic moieties comprising the DOC from biochars were investigated by attenuated total reflectance Fourier transform infrared spectroscopy. The addition of DOC did not change the biomineral structure or As(V) oxidation state. The presence of DOC, however, reduced by 25 % the sorption of As(V), with BC350 being responsible for the greatest reduction in As(V) sorption capacity. Structural modeling revealed As(V) predominantly formed binuclear bidentate surface complexes on BIOS. The presence of DOC did not change the binding mechanism of As(V) in BIOS, suggesting that the reduction of As(V) sorption to BIOS was due to site blocking. Our results bring insights into the fate of As(V) in surface waters and provide a basis for understanding the competitive sorption of As(V) in environments with biochar application.

Biochar aging: Impact of pyrolysis temperature on sediment carbon pools and the availability of arsenic and lead.

Arsenic (As) and lead (Pb) are potentially toxic elements capable of developing several diseases in human beings such as cancer. Several adsorbent materials, including biochars, have been adopted as alternative measures designed to reduce the availability of As and Pb in water. The retention capacity of potentially toxic elements in biochars varies according to time, feedstock, and the pyrolysis temperature to produce the biochar. Our objectives in this study were to evaluate i) the aging effect of sugarcane straw pyrolyzed biochars at 350 (BC350), 550 (BC550), and 750 °C (BC750) and their ability to immobilize As and Pb; and ii) how the pyrolysis temperature and biochar aging alter the carbon content and quality of the solution and sediment. Biochars were applied at 5% (w/w), and their aging together with As and Pb immobilization effects were evaluated every 45 days over a total period of 180 days. The results were obtained using visible ultraviolet spectroscopy and diffuse reflectance infrared Fourier transform spectroscopy combined with physical fractionation of organic matter and multivariate statistics. The groups formed in the Principal Component Analysis indicated that the change in the availability of As and Pb was related to the aging of the biochar and the temporal changes in the content and quality of organic carbon in the sediment and solution. The pyrolysis temperature was a key factor in the (im)mobilization capacity of As and Pb during the aging of the biochar. The increase in polysaccharides and organic matter associated with the particulate fraction can enhance the release of As in solution (24%). Increasing the fraction of organic matter associated with minerals reduced the availability of Pb by 58%. These findings may provide new insights into understanding the dynamics of organic matter and its role in the immobilization of As and Pb during biochar aging.

Pedotransfer functions of potentially toxic elements in tropical soils cultivated with vegetable crops.

The anthropogenic input of potentially toxic elements (PTEs) from industry, agrochemicals, etc., into the environment are of great concern. Models derived from pedotransfer functions can provide estimates of the levels of PTEs based on soil attributes. Based on the importance of these models in studies in contaminated areas, we assessed the concentrations of the reactive contents of Ba, Cu, Cr, Ni, Pb, and Zn in soils cultivated with vegetable crops in the state of São Paulo, Brazil. We also evaluated the influence of chemical and physical soil attributes on their reactivity and availability. The reactive contents of PTEs represent the fraction of PTEs easily sorbed at the adsorptions sites of organic matter, iron hydroxides, or clay. This fraction can supply information about the PTE content that is more or less readily released into the soil solution. The reactive and available fraction was extracted with 0.43 M HNO3 and 0.01 M CaCl2, respectively. The proportion of reactivity of metal pools decreased in the order of Ba>Zn > Cu > Pb > Ni > Cr. The empirical models were able to predict the relationship between the reactive fractions, the pseudototal content, and the soil attributes. The available concentrations of Cr, Cu, Ni, and Pb in the soils were lower than the limit of quantification, while 3% of the Ba content and 1% of the Zn content were available in the soil solution in relation to their pseudototal content, suggesting low mobility of these elements in the soil.

Availability and zinc accumulation in forage grasses grown in contaminated soil.

Zinc is an important micronutrient to plant growth, but when present in large quantities it can become a toxic element to plants. This study was aimed to evaluate the growth, concentration, accumulation and availability of Zn to forage grasses (Megathyrsus maximus cvs. Aruana and Tanzania, Urochloa brizantha cvs. Xaraés and Marandu and Urochloa decumbens cv. Basilisk) cultivated in Zn contaminated soils. The experiments were conducted under greenhouse conditions over a 90-day evaluation period, and Zn rates were 0, 100, 300 and 900 mg kg-1 of soil. The Zn rates in soil caused growth reduction in all evaluated forage grasses. The cultivar Aruana was generally more tolerant to Zn, while the Marandu was generally more susceptible to the addition of Zn. The cultivar Aruana proved to be superior to others due to its higher growth and higher critical level toxicity of Zn. None of the forage grasses evaluated can be considered a Zn hyperaccumulator. The extraction order was DTPA at pH 7.3 < Mehlich-1 < USEPA 3051 < USEPA 3052 in the soil independent of forage grasses cultivation. The USEPA 3051 extractor was similar to Mehlich-1 in predicting the availability of Zn in soil.

Soil-plant transfer models for metals to improve soil screening value guidelines valid for São Paulo, Brazil.

In Brazil, there is a lack of combined soil-plant data attempting to explain the influence of specific climate, soil conditions, and crop management on heavy metal uptake and accumulation by plants. As a consequence, soil-plant relationships to be used in risk assessments or for derivation of soil screening values are not available. Our objective in this study was to develop empirical soil-plant models for Cd, Cu, Pb, Ni, and Zn, in order to derive appropriate soil screening values representative of humid tropical regions such as the state of São Paulo (SP), Brazil. Soil and plant samples from 25 vegetable species in the production areas of SP were collected. The concentrations of metals found in these soil samples were relatively low. Therefore, data from temperate regions were included in our study. The soil-plant relations derived had a good performance for SP conditions for 8 out of 10 combinations of metal and vegetable species. The bioconcentration factor (BCF) values for Cd, Cu, Ni, Pb, and Zn in lettuce and for Cd, Cu, Pb, and Zn in carrot were determined under three exposure scenarios at pH 5 and 6. The application of soil-plant models and the BCFs proposed in this study can be an important tool to derive national soil quality criteria. However, this methodological approach includes data assessed under different climatic conditions and soil types and need to be carefully considered.

Temporal Changes in Cadmium Speciation in Brazilian Soils Evaluated Using Cd LIII-Edge XANES and Chemical Fractionation.

Chemical speciation of soil cadmium (Cd) dictates its mobility and potential toxicity in the environment. Our objective was to compare temporal changes in speciation of Cd(II) reacted with samples from six Brazilian soils having varying Cd(II) sorption capacities. Cadmium L-edge X-ray absorption near edge structure (XANES) analysis showed there were short-term changes in speciation after reaction with 4.45 mmol Cd kg for 0.5 and 6 h. Chemical fractionation evaluated changes in Cd extractability after reaction with 89 µmol Cd kg for up to 4 mo. The XANES spectral fits suggested that Cd(II) bound with organic matter was a dominant species in all samples, along with Cd(II) bound with iron and aluminum oxides or montmorillonite. In several samples, CdCl apparently precipitated from aqueous Cd(II) during drying. The XANES spectral fits typically showed <25% change in speciation between 0.5 and 6 h of reaction, and chemical fractionation showed significant ( < 0.05) temporal changes in Cd extractability over time in two samples. Our results suggest that Cd(II) discharged into these soils, such as that occurring as a release into the environment, would bind with soil organic matter and oxide minerals or remain dissolved, with little change in speciation in the months following release.

Availability and toxicity of cadmium to forage grasses grown in contaminated soil.

It is important to know the mechanisms for forage development, especially those related to the tolerance of potentially toxic elements, when considering their use in phytoremediation in heavy metal contaminated areas. In this study, we evaluated plant growth, concentration, and the availability of cadmium (Cd) for forage grasses (Panicum maximum Jacq. cv. Aruana and cv. Tanzânia; Brachiaria decumbens cv. Basilisk; Brachiaria brizantha cv. Xaraés and cv. Marandu) cultivated in Cd contaminated soils. The experiments were performed under greenhouse conditions over a 90-day evaluation period, and the Cd rates were 2, 4, and 12 mg/kg of soil. The relative growth rate of the forage grasses decreased as Cd rates increased, and the following descending order of susceptibility was observed: Marandu > Xaraés > Aruana > Tanzânia > Basilisk, with regard to phytotoxicity in these plants. The forage Cd concentration increased in line with increases in the Cd rates. Cd contents extracted by Mehlich-1 and by diethylenetriaminepentaacetic acid presented high positive correlation with forage relative growth. The forage plants did not block Cd entry into the food chain because they were not capable of limiting Cd absorption.

Effect of Soil Water Content on the Distribution of Diuron into Organomineral Aggregates of Highly Weathered Tropical Soils.

We evaluated the effects of soil water content on the retention of diuron and its residual distribution into organomineral aggregates in four Brazilian oxisols. (14)C-Diuron was incubated for days at 25, 50, and 75% of maximum water-holding capacity for each soil. After 42 days, the physical fractionation method was used to obtain >150, 53-150, 20-53, 2-20, and <2 µm aggregate sizes. Diuron retention increased with increasing soil water content for all soils. At lower soil water content, diuron's retention was higher in the sandier soil. It was mostly retained in the fine (<20 µm) aggregates of sandier soil, and for clayed soils, retention was higher in the coarse aggregates (>53 µm). The sorption coefficients (Kd and Koc) generated by batch studies should be carefully used because they do not provide information about aggregation and diffusion effects on pesticides soil sorption.

Runoff and leachate losses of phosphorus in a sandy Spodosol amended with biosolids.

Florida Spodosols are sandy, inherently low in Fe- and Al-based minerals, and sorb phosphorus (P) poorly. We evaluated runoff and leachate P losses from a typical Florida Spodosol amended with biosolids and triple superphosphate (TSP). Phosphorus losses were evaluated with traditional indoor rainfall simulations but used a double-deck box arrangement that allowed leaching and runoff to be determined simultaneously. Biosolids (Lakeland, OCUD, Milorganite, and Disney) represented contrasting values of total P, percent water-extractable P (PWEP), and percentage of solids. All P sources were surface applied at 224 kg P ha(-1), representing a soil P rate typical of N-based biosolids application. All biosolids-P sources lost less P than TSP, and leachate-P losses generally dominated. For Lakeland-amended soil, bioavailable P (BAP) was mainly lost by runoff (81% of total BAP losses). This behavior was due to surface sealing and drying after application of the slurry (31 g kg(-1) solids) material. For all other P sources, BAP losses in leachate were much greater than in runoff, representing 94% of total BAP losses for TSP, 80% for Milorganite, 72% for Disney, and 69% for OCUD treatments. Phosphorus leaching can be extreme and represents a great concern in many coarse-textured Florida Spodosols and other coastal plain soils with low P-sorption capacities. The PWEP values of P sources were significantly correlated with total P and BAP losses in runoff and leachate. The PWEP of a source can serve as a good indicator of potential P loss when amended to sandy soils with low P-retention capacities.

Soil pH on mobility of imazaquin in oxisols with positive balance of charges.

The influence of soil pH on the leaching potential of the ionizable herbicide imazaquin was assessed on the profile of two highly weathered soils having a net positive charge in the B horizon, in contrast to a soil having a net negative charge in the whole profile, using packed soil column experiments. Imazaquin leached to a large extent and faster at Kd values lower than 1.0 L kg(-1), a much more lenient limit than usually proposed for pesticides in the literature (Kd < 5.0 L kg(-1)). The amount of imazaquin leached increased with soil pH. As the soil pH increased, the percentage of imazaquin in the anionic forms, the negative surface potential of the soils, as well as imazaquin water solubility also increased, thus reducing sorption because of repulsive electrostatic forces (hydrophilic interactions). For all surface samples (0-0.2 m), imazaquin did not leach at soil pH values lower than pKa (3.8) and more than 80% of the applied amount was leached at pH values higher than 5.5. For subsurface samples from the acric soils, imazaquin only began to leach at soil pH values > zero point of salt effects (ZPSE > 5.7). In conclusion, the use of surface K(oc) values to predict the amount of imazaquin leached within soil profiles having a positive balance of charges may greatly overestimate its actual leaching potential.

Sorption of imazaquin in soils with positive balance of charges.

The herbicide imazaquin has both an acid and a basic ionizable groups, and its sorption depends upon the pH, the electric potential (psi0), and the oxide and the organic carbon (OC) contents of the soil. Sorption and extraction experiments using 14C-imazaquin were performed in surface and subsurface samples of two acric oxisols (an anionic "rhodic" acrudox and an anionic "xanthic" acrudox) and one non-acric alfisol (a rhodic kandiudalf), treated at four different pH values. Imazaquin showed low to moderate sorption to the soils. Sorption decreased and aqueous extraction increased as pH increased. Up to pH 5.8, sorption was higher in subsurface than in surface layers of the acric soils, due to the positive balance of charges resulted from the high Fe and Al oxide and the low OC contents. It favored electrostatic interactions with anionic molecules of imazaquin. For the subsurface samples of these highly weathered soils, where psi0 was positive and OC was low, it was not possible to predict sorption just by considering imazaquin speciation and its hydrophobic partition to the organic domains of the soil. Moreover, if Koc measured for thesurface samples were assumed to represent the whole profile in predictive models for leaching potential, then it would result in underestimation of sorption potential in subsurface, and consequently result in overestimation of the leaching potential.