New Trends in Biochar Pyrolysis and Modification Strategies: Feedstock, Pyrolysis Conditions, Sustainability Concerns and Implications for Soil Amendment

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Temporal effect of MgO reactivity on the stabilization of lead contaminated soil

Elevated soil lead (Pb) concentrations are a global concern owing to the toxic effects of this heavy metal. Solidification/stabilization (S/S) of soils using reagents like Portland cement (PC) is a common approach for the remediation of Pb contaminated sites. However, it has been reported that under long-term field conditions, the performance of PC treatments can diminish significantly. Therefore, novel reagents that provide longer-term stabilization performance are needed. In this study, four magnesium oxide (MgO) products of different reactivity values were applied (5 wt%) to a Pb contaminated clayey soil. The short-term (1–49 days) and long-term (25–100 years) temporal stabilization effects were investigated by laboratory incubation and accelerated ageing methods, respectively. The concentration of Pb in Toxicity Characterization Leaching Procure (TCLP) leachate was ~14 mg/L for the untreated soil; ~1.8 times higher than the TCLP regulatory level (5 mg/L). Only one day after treatment with MgO, the leachate concentration was reduced to below the regulatory level (a reduction of 69.4%–83.2%), regardless of the MgO type applied. However, in the long-term accelerated ageing experiments, only treatments using the most reactive MgO type could provide leachate concentrations that were consistently below the TCLP threshold throughout the 100 years of simulated ageing. The soil treated with the MgO of lowest reactivity was the first to exceed the regulatory level, at simulated year 75. It is thus demonstrated that MgO reactivity has a significant effect on its long-term effectiveness for contaminated soil stabilization. This is attributed to differences in their specific surface area and readiness to carbonate, which may facilitate the immobilization of Pb in the long term. It is also noteworthy that compared to PC, reactive MgO is more environmentally friendly owing to lower energy consumption and reduced CO2 emissions during its manufacture

Redox-induced mobilization of Ag, Sb, Sn, and Tl in the dissolved, colloidal and solid phase of a biochar-treated and un-treated mining soil

The aim of this work was to study the redox-induced mobilization of Ag, Sb, Sn, and Tl in the dissolved, colloidal, and sediment phase of a mining soil treated and untreated with biochar as affected by the redox potential (E-H)-dependent changes of soil pH, dissolved organic carbon, Fe, Mn and S. The experiment was conducted stepwise at two E-H cycles (+200 mV -> -30 mV -> +333 mV -> 0 mV) using biogeochemical microcosm. Silver was abundant in the colloidal fraction in both cycles, indicating that Ag might be associated with colloids under different redox conditions. Antimony, Sn and Tl were abundant in the colloidal fraction in the first cycle and in the dissolved fraction in the second cycle, which indicates that they are retained by colloids under oxic acidic conditions and released under reducing alkaline conditions. Release of dissolved Sb, Sn, and Tl was governed positively by pH, Fe, S, and dissolved aromatic compounds. Biochar mitigated Ag release, but promoted Sb, Sn, and Tl mobilization, which might be due to the wider range of E-H (-12 to +333) and pH (4.9-8.1) in the biochar treated soil than the un-treated soil (E-H = -30 to +218; pH = 5.9-8.6). Also, the biochar surface functional groups may act as electron donors for the Sb, Sn, and Tl reduction reactions, and thus biochar may play an important role in reducing Tl3+ to Tl+, Sb5+ to Sb3+, and Sn4+ to Sn2+, which increase their solubility under reducing conditions as compared to oxic conditions. Thallium and Sb exhibit higher potential mobility in the solid phase than Sn and Ag. Biochar increased the potential mobility of Sb, Sn, and Tl under oxic acidic conditions. The results improve our understanding of the redox-driven mobilization of these contaminants in soils

Differential impact of two risk communications on antipsychotic prescribing to people with dementia in Scotland: segmented regression time series analysis 2001-2011

The two risk communications were associated with reductions in antipsychotic use, in ways which were compatible with marked differences in their content and dissemination. Further research is needed to ensure that the content and dissemination of regulatory risk communications is optimal, and to track their impact on intended and unintended outcomes. Although rates are falling, antipsychotic prescribing in dementia in Scotland remains unacceptably hig

Relative Reactivity of Biogenic and Chemogenic Uraninite and Biogenic Non-Crystalline U(IV)

Aqueous chemical extractions and X-ray absorption spectroscopy (XAS) analyses were conducted to investigate the reactivity of chemogenic uraninite, nanoparticulate biogenic uraninite, and biogenic monomeric U(IV) species. The analyses were conducted in systems containing a total U concentration that ranged from 1.48 to 2.10 mM. Less than 0.02% of the total U was released to solution in extractions that targeted water-soluble and ion exchangeable fractions. Less than 5% of the total U was solubilized via complexation with a 0.1 M solution of NaF. Greater than 90% of the total U was extracted from biogenic uraninite and monomeric U(IV) after 6 h of reaction in an oxidizing solution of 50 mM K2S2O8. Additional oxidation experiments with lower concentrations (2 mM and 10 mM) of K2S2O8 and 8.2 L-1 dissolved oxygen suggested that monomeric U(IV) species are more labile than biogenic uraninite; chemogenic uraninite was much less susceptible to oxidation than either form of biogenic U(IV). These results suggest that noncrystalline forms of U(IV) may be more labile than uraninite in subsurface environments. This work helps fill critical gaps in our understanding of the behavior of solid-associated U(IV) species in bioremediated sites and natural uranium ore deposits

Biogeochemical controls on the product of microbial U(VI) reduction

Biologically mediated immobilization of radio-nuclides in the subsurface is a promising strategy for the remediation of uranium-contaminated sites. During this process, soluble U(VI) is reduced by indigenous microorganisms to sparingly soluble U(TV). The crystalline U(IV) phase uraninite, or UO2, is the preferable end-product of bioremediation due to its relatively high stability and low solubility in comparison to biomass-associated nonuraninite U(IV) species that have been reported in laboratory and under field conditions. The goal of this study was to delineate the geochemical conditions that promote the formation of nonuraninite U(IV) versus uraninite and to decipher the mechanisms of its preferential formation. U(IV) products were prepared under varying geochemical conditions and characterized with X-ray absorption spectroscopy (XAS), scanning transmission X-ray microscopy (STXM), and various wet chemical methods. We report an increasing fraction of nonuraninite U(IV) species with decreasing initial U concentration. Additionally, the presence of several common groundwater solutes (sulfate, silicate, and phosphate) promote the formation of nonuraninite U(IV). Our experiments revealed that the presence of those solutes promotes the formation of bacterial extracellular polymeric substances (EPS) and increases bacterial viability, suggesting that the formation of nonuraninite U(IV) is due to a biological response to solute presence during U(VI) reduction. The results obtained from this laboratory-scale research provide insight into biogeochemical controls on the product(s) of uranium reduction during bioremediation of the subsurface

Effects of excessive impregnation, magnesium content, and pyrolysis temperature on MgO-coated watermelon rind biochar and its lead removal capacity

MgO-coated watermelon rind biochar (MWRB) is a potentially highly-effective waste-derived material in environmental applications. This research aims to provide valuable insights into the optimization of the production of MWRB for superior environmental performance. It was found that the Mg content of the MWRB could be easily controlled by adjusting the Mg/feedstock mass ratio during excessive impregnation. The BET surface area was found to first increase and then decrease as the Mg content of the MWRB (produced at 600 °C) increased from 1.52% to 10.1%, with an optimal surface area of 293 m2/g observed at 2.51%. Similarly, an optimum pyrolysis temperature of 600 °C was observed in the range of 400–800 °C for a maximum surface area of the MWRB at a fixed Mg/feedstock ratio of 0.48% (resulting in MWRBs with Mg contents of 1.89–2.51%). The Pb removal capacity of the MWRB (produced at 600 °C) increased with increasing Mg content, with a greatest Pb removal capacity of 558 mg/g found for the MWRB with the highest Mg content (10.1%), an improvement of 208% over the 181 mg/g Pb removal capacity of unmodified WRB produced at 600 °C. The Pb removal capacity of the MWRB (produced with 1.89–2.51% Mg) was also discovered to increase from 81.7 mg/g (at 400 °C) to 742 mg/g (at 700 °C), before dropping to 368 mg/g at 800 °C. These findings suggest that the MWRB can be more efficiently utilized in soil and water remediation by optimizing its synthesis conditions

The product of microbial uranium reduction includes multiple species with U(IV)-phosphate coordination

Until recently, the reduction of U(VI) to U(IV) during bioremediation was assumed to produce solely the sparingly soluble mineral uraninite, UO2(s). However, results from several laboratories reveal other species of U(IV) characterized by the absence of an EXAFS U-U pair correlation (referred to here as noncrystalline U(IV)). Because it lacks the crystalline structure of uraninite, this species is likely to be more labile and susceptible to reoxidation. In the case of single species cultures, analyses of U extended X-ray fine structure (EXAFS) spectra have previously suggested U(IV) coordination to carboxyl, phosphoryl or carbonate groups. In spite of this evidence, little is understood about the species that make up noncrystalline U(IV), their structural chemistry and the nature of the U(IV)-ligand interactions. Here, we use infrared spectroscopy (IR), uranium L-III-edge X-ray absorption spectroscopy (XAS), and phosphorus K-edge XAS analyses to constrain the binding environments of phosphate and uranium associated with Shewanella oneidensis MR-1 bacterial cells. Systems tested as a function of pH included: cells under metal-reducing conditions without uranium, cells under reducing conditions that produced primarily uraninite, and cells under reducing conditions that produced primarily biomass-associated noncrystalline U(IV). P X-ray absorption near-edge structure (XANES) results provided clear and direct evidence of U(IV) coordination to phosphate. Infrared (IR) spectroscopy revealed a pronounced perturbation of phosphate functional groups in the presence of uranium. Analysis of these data provides evidence that U(IV) is coordinated to a range of phosphate species, including monomers and polymerized networks. U EXAFS analyses and a chemical extraction measurements support these conclusions. The results of this study provide new insights into the binding mechanisms of biomass-associated U(IV) species which in turn sheds light on the mechanisms of biological U(VI) reduction. (C) 2014 Elsevier Ltd. All rights reserved

Comparison of nickel adsorption on biochars produced from mixed softwood and Miscanthus straw.

In order to understand the influence of feedstock type on biochar adsorption of heavy metals, the adsorption characteristics of nickel (Ni2+), copper (Cu2+) and lead (Pb2+) onto biochars derived from mixed softwood and Miscanthus straw were compared. The biochars were produced from mixed softwood pellets (SWP) and Miscanthus straw pellets (MSP), at both 550 and 700 °C for each material, using a standardised production procedure recommended by the UK Biochar Research Centre. Kinetics analyses show that the adsorption of Ni2+ to all four biochars reached equilibrium within 5 min. The degree of Ni2+ removal for all four biochars remained nearly constant within initial pH values of 3-8, because the equilibrium pH values within this range were similar due to the buffering effect of the biochars. A sharp increase of Ni2+ removal percentage for all biochars at initial solution pH 8-10 was observed as the equilibrium pH also increased. MSP derived biochars generally had higher maximum adsorption capacities (Qmax) for the three tested metals as compared with those from SWP, which was likely due to their higher degree of carbonisation during production. This study shows that feedstock type is a primary factor affecting the adsorption capacities of the tested biochars for heavy metals

Hydrometallurgical processes for heavy metals recovery from industrial sludges

Hydrometallurgical approaches have been successfully employed for metal separation and recovery from various types of waste materials. Therefore, hydrometallurgy is a promising technology for metal recovery and the removal of potentially toxic heavy metals found in industrial sludge. However, a comprehensive review that focuses on the heavy metal recovery from industrial sludge using hydrometallurgical approaches has not been conducted in the recent past. The present review discusses the capacity of hydrometallurgical techniques in recovering heavy metals sourced from different types of industrial sludges, highlighting recent scientific findings. Hydrometallurgical approaches primarily consist of three process stages: metal dissolution, concentration and purification, and metal recovery. The chemical characteristics of industrial sludge, including the type, concentration and speciation of heavy metals, directly impact selection of the best recovery method. Solvent extraction, ion-exchange, and adsorption are the major techniques employed in concentration and purification, whereas electrodeposition and precipitation are the main methods used in metals recovery. Future research should focus on the development of more efficient and environmentally-friendly methods for metal dissolution from industrial sludges contaminated with multiple metals, while increasing selectivity and energy use efficiency in the concentration and purification, and recovery steps