Negative impacts of perishable waste biochar to Escherichia coli and exploring potential damage factors.

Agricultural application of pyrolysis­carbonized perishable wastes can target reduction treatment and resource utilization of the wastes. However, potential undesirable impact has rarely been assessed. In this study, the adverse effect of perishable waste biochars (PWB) from different pyrolysis temperatures on Escherichia coli (E. coli) was explored and the potential risk factors were further analyzed. The results showed that PWBs pyrolyzed at 350, 500, and 650 °C inhibited the growth of E. coli, and PWB pyrolyzed at 500 °C showed the most inhibition. The exposure to PWB damaged the antioxidative system, as revealed by the concentration-dependent increasing of intracellular ROS. In addition, the toxicity at the gene level in terms of cell division and growth inhibition, the damage of cell membrane, antioxidant system disturbance, and DNA damage occurred, resulting in loss of the cell rules of morphology and eventual death. According to our results, the inhibitory effect on the growth of E. coli was mainly caused by PWB solids, accounting for >70 %. The membrane disruption and oxidative damage of E. coli by PWB were possibly induced by the direct physical interaction between cell and char particles. The growth of E. coli can be partly influenced by PWB extraction solutions that varied between PWB types, due to the differences in pH, released DOC and the production of extracellular ∙OH. The exploration of these potential hazards could provide new insights into the fate and toxicity of PWB in the environment and help guide the safe and sustainable applications for PWB.

Speciation Evolution of Phosphorus and Sulfur Derived from Sewage Sludge Biochar in Soil: Ageing Effects.

Phosphorus (P) and sulfur (S) are usually involved simultaneously in the immobilization of heavy metals in sewage sludge during pyrolysis, and thus their speciation in sewage sludge-derived biochar (SSB) profoundly affects the recycling of the nutrients and the environmental risks of sewage sludge. Here, we investigated the speciation evolution of P and S in SSB induced by ageing processes in soil using X-ray absorption near edge structure spectroscopy. Results showed that Ca-bound compounds like hydroxyapatite dominated the P forms, while over 60% of S existed as reduced inorganic sulfides in the SSB. The stable Ca-associated P species in SSB tended to be transformed gradually into relatively soluble species during ageing in soil. The speciation composition of S in SSB remained almost unaffected when aged in pot soils, whereas about 33.6% of reduced sulfides were transformed into oxidized species after 1-year ageing in field soils. SSB significantly increased the proportion of sulfides and the contents of available P and S in the amended soil but showed relatively weak effects on the speciation distribution of P in the soil because of their similar compositions. These findings provide insights into biogeochemistry of nutrients and behaviors of heavy metals in SSB after its application to the soil environments.

Rethinking the biotic and abiotic remineralization of complex phosphate molecules in soils and sediments.

Phosphorus (P) is an essential macronutrient for all living organisms. Despite a diversity of P compounds in the environment, orthophosphate is the most bioavailable form of P. Remineralization of complex P molecules (e.g., organic P and phosphoanhydrides) into orthophosphate is traditionally considered to be carried out primarily by enzymes. Natural minerals are recently viewed to be abiotic catalysts (as compared to the organic phosphatases) to facilitate the cleavage of terminal P-O-C/P bonds and remineralization of complex P compounds. However, quantitative comparison between biotic and abiotic remineralization pathways of complex P molecules is still missing, impeding our capability to assess the importance and contribution of abiotic P remineralization in the environment. This study compares the hydrolysis rates of six organic phosphates and three inorganic phosphoanhydrides by representative enzymes (acid and alkaline phosphatases) and natural oxide minerals (hematite, birnessite, and boehmite). The results show that enzymes and minerals have different substrate preferences. Specifically, alkaline phosphatase hydrolyzes phosphate monoesters faster than phosphoanhydrides, whereas acid phosphatase and minerals show higher hydrolysis rates toward phosphoanhydrides than phosphate monoesters. Although the hydrolysis rates by enzymes (~µM hr-1) are orders of magnitude higher than those by minerals (~µM d-1), normalization of the rates by the natural abundance of enzymes and minerals leads to comparable contributions of both processes in soils and sediments. These results highlight the significance of natural minerals in the remineralization of complex P compounds, a process that was traditionally overlooked but with important implications for constraining P biogeochemical cycling in the environment.

Thermochemistry of sulfur during pyrolysis and hydrothermal carbonization of sewage sludges.

Sulfur (S) is an abundant and redox-active element in urban wastewater systems and plays a critical role in both the wastewater and sludge treatment processes. This study comparatively characterized the transformation of S and several closely associated metals (Cu, Zn, and Fe) during pyrolysis (250 to 750 °C) and hydrothermal carbonization (HTC, 150 to 275 °C) treatments of sewage sludge. S, Fe, Zn, and Cu K-edge X-ray absorption spectroscopy was applied to quantitatively evaluate the fate of S and contribution of different S species in regulating metal speciation. During pyrolysis, aliphatic-S and sulfonate were preferentially degraded at low temperature (below 350 °C) and sulfate was thermochemically reduced at temperature above 450 °C, while metal sulfides (up to 27%) and thiophenes (up to 70%) were increasingly formed. Similar to the pyrolysis process, metal sulfides (up to 40% at temperature above 200 °C) and thiophenes were formed during HTC. The degradation of thiols and organic sulfide, as well as sulfate reduction, released sulfide and strongly affected metal speciation. For example, almost all Cu and half of Zn were transformed into Cu-Fe- or Zn-Fe-sulfides during HTC, whereas they were partially desulfidized during pyrolysis. High abundance of reduced S species (S-1 and S-2) in hydrochars may contribute to their strong reductive adsorption of Cr(VI). Results from this work reveal the thermochemical reactions driving the transformations of S and its associated metals during pyrolysis and HTC. The results provide fundamental knowledge for selecting thermochemical sludge treatment techniques for value-added applications of the products.

Copper Speciation Evolution in Swine Manure Induced by Pyrolysis.

Swine manures generally contain high levels of copper (Cu) resulting from its use as a growth promoter in feedstuff. Pyrolysis can further concentrate Cu whereas decrease its available fraction in swine manures. Here we investigated the speciation transformation of Cu and associated elements in swine manures induced by pyrolysis using multiple X-ray absorption spectroscopies. Results showed that over 82% of Cu existed as Cu(I)-S and Cu(I)-thiolate complexes in swine manures, which were transformed into stable Cu(I)2S during pyrolysis at a low temperature of 300 °C and partially oxidized and desulfurized into Cu(II) compounds at a high temperature of 500 °C. The speciation evolution of Cu in swine manures was consistent with the speciation distribution of sulfur in feedstuff and its following changes in swine manures during pyrolysis. About 58% of phosphorus existed as CaHPO4 and struvite in swine manures, which were gradually transformed into stable Ca-bound species such as hydroxyapatite during pyrolysis. The formation of stable phosphate, together with concentrated carbonates, significantly decreased the available Cu in pyrolyzed manures. These findings suggested that the high levels of S and P in feedstuff profoundly affected the speciation of Cu in the swine manures and derived biochars. This study has important implications to our understanding of the behaviors of heavy metals in manure-derived biochars once entering soil environments.

Energy and Nutrient Recovery from Sewage Sludge and Manure via Anaerobic Digestion with Hydrothermal Pretreatment.

Global expectation for sustainability has prompted the transition of practices in wastewater treatment plants toward not only waste management but also energy and nutrient recovery. It has been shown that low-temperature hydrotherm (HT) treatment can enhance downstream biogas production via anaerobic digestion (AD). Yet, because the application of combined HT and AD is still at an early stage, a systematic understanding of the dynamic speciation evolution of important elements is still lacking. This study investigates energy and nutrient recovery from sewage sludge and swine manure via combined HT-AD treatment. Bench-scale investigation was conducted to evaluate biogas production and understand the dynamic evolution of organic carbon (C) and phosphorus (P) speciation. C and P speciations were characterized using complementary chemical and spectroscopic techniques, including 13C nuclear magnetic resonance (NMR) spectroscopy, P X-ray absorption near edge structure (XANES) spectroscopy, and sequential chemical extraction. Results from this study suggest that low-temperature HT pretreatment can achieve enhanced biogas production for sludge compared to the minimal effect on the biogas production from manure. It also provides guidance for P recovery from liquid digestate and solid residue after the AD process.

Polyphosphate Adsorption and Hydrolysis on Aluminum Oxides.

The geochemical behaviors of phosphate-containing species at mineral-water interfaces are of fundamental importance for controlling phosphorus mobility, fate, and bioavailability. This study investigates the sorption and hydrolysis of polyphosphate (a group of important long-chained phosphate molecules) on aluminum oxides in the presence of divalent metal cations (Ca2+, Cu2+, Mg2+, Mn2+, and Zn2+) at pH 6-8. γ-Al2O3 with three particle sizes (5, 35, and 70 nm) was used as an analogue of natural aluminum oxides to investigate the particle size effect. All metal cations enhanced polyphosphate hydrolysis at different levels, with Ca2+ showing the most significant enhancement, and the difference in the enhancement might be due to the intrinsic affinity of metal cations to polyphosphate. In the presence of Ca2+, the hydrolysis rate decreased with increasing mineral particle size. Solid-state 31P nuclear magnetic resonance spectroscopy (NMR) revealed the main surface P species to be amorphous calcium phosphate precipitates, phosphate groups in polyphosphate that formed direct bonds with the mineral surface as inner-sphere complexes, and phosphate groups in polyphosphate that were not directly bonded to the mineral surfaces. Our results reveal the critical roles of mineral-water interface processes and divalent metal cations on controlling polyphosphate speciation and transformation and phosphorus cycling.

Comprehensive Understandings of Rare Earth Element (REE) Speciation in Coal Fly Ashes and Implication for REE Extractability.

In recent years, recovery of rare earth elements (REEs) from coal fly ashes (CFAs) has been considered as a promising resource recovery option. Yet, quantitative information on REE speciation in CFAs and its correlation with REE extractability are not well established. This study systematically investigated the REE speciation-extractability relationship in four representative CFA samples by employing multiple analytical and spectroscopic techniques across the micro to bulk scale and in combination with thermodynamic calculations. A range of REE-bearing phases are identified, such as REE oxides, REE phosphates, apatite, zircon, and REE-bearing glass phase. REEs can occur as discrete particles, as particles encapsulated in the glass phase, or distribute throughout the glass phase. Although certain discrepancies exist on the REE speciation quantified by X-ray adsorption spectroscopy and acid leaching due to intrinsic limitations of each method, both approaches show significant fractions of REE oxides, REE phosphates, apatite, and REE-bearing Fe oxides. This study contributes to an in-depth understanding of the REE speciation-distribution-extractability relationship in CFAs and can help identify uncertainties associated with the quantification of REE speciation. It also provides a general methodology for future studies on REE speciation in complex environmental samples and a knowledge basis for the development of effective REE recovery techniques.

Molecular understanding of dissolved black carbon sorption in soil-water environment.

Dissolved black carbon (DBC) involves in many biogeochemical processes in both terrestrial and aquatic environments. About 26.5 Tg of charcoal- or black carbon-derived DBC was released into aquatic environments annually, accounting to ∼10% of the global riverine flux of dissolved organic carbon (DOC). Yet the sorption behaviors of DBC and their effects on water quality in soil-water environment are poorly understood. Here we examined the molecular composition variations of DOC induced by the sorption of two biochar-derived DBCs (pyrolyzed at 300 °C and 500 °C) on three contrasting soils. The DBCs were adsorbed mainly through competitive displacement of soil surface functional groups and co-sorption with soil indigenous DOC, which varied with soil properties and the aromaticity of the DBCs. Ultrahigh resolution mass spectrometry analysis indicated that compounds with rich oxygen content or unsaturated structures such as tannins and unsaturated aromatics from both DBC and soil DOC, were preferentially adsorbed on the soils in the presence of DBC. In contrast, compounds with high aromatic structures including condensed aromatics and lignins were concentrated in the aquatic phase. Molecular fractionation also occurred to the heteroatomic compounds during the sorption, and the heteroatomic dissolved organic sulphur in the DBCs was easier to be adsorbed relative to dissolved organic nitrogen. Our results suggest that DBC sorption in soil-water environment could have important implications for water quality by altering DOC molecular composition and decreasing DOC molecular diversity at the soil-water interface. This study provides essential information for understanding the behavior of DBC in the environments.

Formation of Zn-Al layered double hydroxides (LDH) during the interaction of ZnO nanoparticles (NPs) with γ-Al2O3.

Zinc and aluminum layered double hydroxides (Zn-Al LDH) are a common group of major Zn species in various Zn-contaminated soil/sediment environments, yet their formation pathways and underlying mechanisms under varied conditions are not well understood. This study investigated the formation of Zn-Al LDHs through the direct interaction of two solid substrates, ZnO nanoparticles (NPs) and a representative Al oxide, γ-Al2O3. Batch experiments and complementary microscopic and spectroscopic analyses were conducted to elucidate the reaction kinetics and mechanisms, as well as the morphologic and structural evolution of the products. Dissolved Zn and Al concentrations decreased significantly in a dual solid system compared to a single solid system. A bulk Zn-Al LDH phase was found to form under a wide pH range (6.5-9.5). Aside from Zn-Al LDH, γ-Al2O3 was the main remaining solid phase at pH 6.5, whereas ZnO NPs were the main residual solid phases at pH 9.5. Formation of amorphous Zn(OH)2 was also observed at both pH values, likely due to Zn2+ release at low pH and Al(OH)4- adsorption at high pH. It is proposed that the formation of Zn-Al LDH occurs via a dissolution-sorption-coprecipitation process, where the solubility of ZnO NPs or γ-Al2O3 solid phases determines the reaction pathways and kinetics under varied pH conditions. The results from this work revealed the transformation mechanisms for ZnO NPs under conditions from weakly acidic to alkaline pH with highly available Al particles and shed light on the environmental fate of ZnO NPs in Zn or ZnO NP contaminated environments.

Catalytic oxidation of arsenite and reaction pathways on the surface of CuO nanoparticles at a wide range of pHs.

Recently, the wide application of CuO nanoparticles (NPs) in engineering field inevitably leads to its release into various geologic settings, which has aroused great concern about the geochemical behaviors of CuO NPs due to its high surface reactivity and impact on the fate of co-existing contaminants. However, the redox transformation of pollutants mediated by CuO NPs and the underlying mechanism still remain poorly understood. Here, we studied the interaction of CuO NPs with As(III), and explored the reaction pathways using batch experiments and multiple spectroscopic techniques. The results of in situ quick scanning X-ray absorption spectroscopy (Q-XAS) analysis verified that CuO NPs is capable of catalytically oxidize As(III) under dark conditions efficiently at a wide range of pHs. As(III) was firstly adsorbed on CuO NPs surface and then gradually oxidized to As(V) with dissolved O2 as the terminal electron acceptor. As(III) adsorption increased to the maximum at a pH close to PZC of CuO NPs (~ pH 9.2), and then sharply decreased with increasing pH, while the oxidation capacity monotonically increased with pH. X-ray photoelectron spectroscopy and electron paramagnetic resonance characterization of samples from batch experiments indicated that two pathways may be involved in As(III) catalytic oxidation: (1) direct electron transfer from As(III) to Cu(II), followed by concomitant re-oxidation of the produced Cu(I) by dissolved O2 back to Cu(II) on CuO NPs surface, and (2) As(III) oxidation by reactive oxygen species (ROS) produced from the above Cu(I) oxygenation process. These observations facilitate a better understanding of the surface catalytic property of CuO NPs and its interaction with As(III) and other elements with variable valence in geochemical environments.

Transformations of Phosphorus Speciation during (Hydro)thermal Treatments of Animal Manures.

Phosphorus (P) in animal manures is an important P pool for P recycling and reclamation. In recent years, thermochemical techniques have gained much interests for effective waste treatment and P recycling. This study comparatively characterized the transformation of P during two representative thermochemical treatments (pyrolysis and hydrothermal carbonization, HTC) of four animal manures (swine, chicken, beef, and dairy manures) by combining nuclear magnetic resonance spectroscopy, X-ray absorption spectroscopy, and sequential extraction. For both pyrolysis and HTC treatments, degradation of organic phosphate and crystallization of Ca phosphate minerals were observed and were highly dependent on treatment temperature. Extensive crystallization of Ca phosphate minerals occurred at temperatures above 450 °C during pyrolysis, compared to the lower temperature (175 and 225 °C) requirements during HTC. As a result, P was immobilized in the hydrochars and high temperature pyrochars, and was extracted primarily by HCl. Because Ca is the dominating P-complexing cation in all four manures, all manures showed similar P speciation and transformation behaviors during the treatments. Results from this work provided deeper insights into the thermochemical processes occurred during the pyrolysis and HTC treatments of biological wastes, as well as guidance for P reclamation and recycling from these wastes.

Phosphatase-Mediated Hydrolysis of Linear Polyphosphates.

Polyphosphates are a group of phosphorus (P) containing molecules that are produced by a wide range of microorganisms and human activities. Although polyphosphates are ubiquitous in aquatic environments and are of environmental significance, little is known about their transformation and cycling. This study characterized the polyphopshate-hydrolysis mechanisms of several representative phosphatase enzymes and evaluated the effects of polyphosphate chain length, light condition, and calcium (Ca2+). 31P nuclear magnetic resonance (NMR) spectroscopy was used to monitor the dynamic changes of P molecular configuration during polyphosphate hydrolysis and suggested a terminal-only degradation pathway by the enzymes. Such mechanism enabled the quantification of the hydrolysis rates by measuring orthophosphate production over time. At the same initial concentration of polyphosphate molecules, the hydrolysis rates were independent of chain length. The hydrolysis of polyphosphate was also unaffected by light condition, but was reduced by the presence of Ca2+. The released orthophosphates formed Ca-phosphate precipitates in the presence of Ca2+, likely in amorphous phases. Results from this study lay the foundation for better understanding the chemical processes governing polyphosphate transport and transformation in various environmental settings.

Speciation evolution of zinc and copper during pyrolysis and hydrothermal carbonization treatments of sewage sludges.

Thermal and hydrothermal treatments are promising techniques for sewage sludge management that can potentially facilitate safe waste disposal, energy recovery, and nutrient recovery/recycling. Content and speciation of heavy metals in the treatment products affect the potential environmental risks upon sludge disposal and/or application of the treatment products. Therefore, it is important to study the speciation transformation of heavy metals and the effects of treatment conditions. By combining synchrotron X-ray spectroscopy/microscopy analysis and sequential chemical extraction, this study systematically characterized the speciation of Zn and Cu in municipal sewage sludges and their chars derived from pyrolysis (a representative thermal treatment technique) and hydrothermal carbonization (HTC; a representative hydrothermal treatment technique). Spectroscopy analysis revealed enhanced sulfidation of Zn and Cu by anaerobic digestion and HTC treatments, as compared to desulfidation by pyrolysis. Overall, changes in the chemical speciation and matrix properties led to reduced mobility of Zn and Cu in the treatment products. These results provide insights into the reaction mechanisms during pyrolysis and HTC treatments of sludges and can help evaluate the environmental/health risks associated with the metals in the treatment products.

Insights into the attenuated sorption of organic compounds on black carbon aged in soil.

Sorption of organic compounds on fresh black carbons (BCs) can be greatly attenuated in soil over time. We examined herein the changes in surface properties of maize straw-derived BCs (biochars) after aged in a black soil and their effects on the sorptive behaviors of naphthalene, phenanthrene and 1,3-dinitrobenzene. Dissolved fulvic and humic acids extracted from the soil were used to explore the role of dissolved organic carbon (DOC) in the aging of biochars. Chromatography analysis indicated that DOC molecules with relatively large molecular weight were preferentially adsorbed on the biochars during the aging processes. DOC sorption led to blockage of the biochar's micropores according to N2 and CO2 adsorption analyses. Surface chemistry of the biochars was also substantially modified, with more O-rich functional groups on the aged biochars compared to the original biochars, as evidenced by Near-edge X-ray absorption fine structure (NEXAFS) spectroscopy and X-ray photoelectron spectroscopy (XPS) analyses. The changes in both the physical and chemical surface properties of biochars by DOC led to significant attenuation of the sorption capacity and nonlinearity of the nonionic organic compounds on the aged biochars. Among the tested organic compounds, phenanthrene was the most attenuated in its sorption by the aging treatments, possibly because of its relatively large molecular size and hydrophobicity. The information can help gain a mechanistic understanding of interactions between BCs and organic compounds in soil environment.

Transformation of Phosphorus during (Hydro)thermal Treatments of Solid Biowastes: Reaction Mechanisms and Implications for P Reclamation and Recycling.

Phosphorus (P) is an essential nutrient for all organisms, thus playing unique and critical roles at the food-energy-water nexus. Most P utilized by human activities eventually converges into various solid biowastes, such as crop biomass, animal manures, and sewage sludges. Therefore, integration of efficient P recovery practices into solid biowaste management will not only significantly reduce the dependence on limited geological P resources but also reduce P runoff and related water contamination issues associated with traditional waste management strategies. This study reviews the applications of (hydro)thermal techniques for the treatment of solid biowastes, which can greatly facilitate P recovery in addition to waste volume reduction, decontamination, and energy recovery. Research showed that P speciation (including molecular moiety, complexation state, and mineralogy) can experience significant changes during (hydro)thermal treatments, and are impacted by treatment techniques and conditions. Changes in P speciation and overall properties of the products can alter the mobility and bioavailability of P, and subsequent P reclamation and recycling efficiency of the treatment products. This review summarizes recent progresses in this direction, identifies the challenges and knowledge gaps, and provides a foundation for future research efforts targeting at sustainable management of nutrient-rich biowastes.

Probing the interactions of organic molecules, nanomaterials, and microbes with solid surfaces using quartz crystal microbalances: methodology, advantages, and limitations.

Quartz crystal microbalances (QCMs) provide a new analytical opportunity and prospect to characterize many environmental processes at solid/liquid interfaces, thanks to their almost real-time measurement of physicochemical changes on their quartz sensor. This work reviews the applications of QCMs in probing the interactions of organic molecules, nanomaterials (NMs) and microbes with solid surfaces. These interfacial interactions are relevant to critical environmental processes such as biofilm formation, fate and transport of NMs, fouling in engineering systems and antifouling practices. The high sensitivity, real-time monitoring, and simultaneous frequency and dissipation measurements make QCM-D a unique technique that helps reveal the interaction mechanisms for the abovementioned processes (e.g., driving forces, affinity, kinetics, and the interplay between surface chemistry and solution chemistry). On the other hand, QCM measurement is nonselective and spatially-dependent. Thus, caution should be taken during data analysis and interpretation, and it is necessary to cross-validate the results using complementary information from other techniques for more quantitative and accurate interpretation. This review summarizes the general methodologies for collecting and analyzing raw QCM data, as well as for evaluating the associated uncertainties. It serves to help researchers gain deeper insights into the fundamentals and applications of QCMs, and provides new perspectives on future research directions.

Evolution of phosphorus complexation and mineralogy during (hydro)thermal treatments of activated and anaerobically digested sludge: Insights from sequential extraction and P K-edge XANES.

(Hydro)thermal treatments of sewage sludge is a promising option that can simultaneously target safe waste disposal, energy recovery, and nutrient recovery/recycling. The speciation of phosphorus (P) in sludge is of great relevance to P reclamation/recycling and soil application of sludge-derived products, thus it is critical to understand the effects of different treatment techniques and conditions on P speciation. This study systematically characterized P speciation (i.e. complexation and mineral forms) in chars derived from pyrolysis and hydrothermal carbonization (HTC) of municipal sewage sludges. Combined sequential extraction and P K-edge X-ray absorption near edge structure (XANES) spectroscopy analysis revealed the dependence of P transformation on treatment conditions and metal composition in the feedstocks. Pyrolysis of sludges decreased the relative abundance of phytic acid while increased the abundance of Al-associated P. HTC thoroughly homogenized and exposed P for interaction with various metals/minerals, with the final P speciation closely related to the composition/speciation of metals and their affinities to P. Results from this study revealed the mechanisms of P transformation during (hydro)thermal treatments of sewage sludges, and might be applicable to other biosolids. It also provided fundamental knowledge basis for the design and selection of waste management strategies for better P (re)cycling and reclamation.

Biomolecule-nanoparticle interactions: Elucidation of the thermodynamics by isothermal titration calorimetry.

BACKGROUND: Nanomaterials (NMs) are often exposed to a broad range of biomolecules of different abundances. Biomolecule sorption driven by various interfacial forces determines the surface structure and composition of NMs, subsequently governs their functionality and the reactivity of the adsorbed biomolecules. Isothermal titration calorimetry (ITC) is a nondestructive technique that quantifies thermodynamic parameters through in-situ measurement of the heat absorption or release associated with an interaction. SCOPE OF REVIEW: This review highlights the recent applications of ITC in understanding the thermodynamics of interactions between various nanoparticles (NPs) and biomolecules. Different aspects of a typical ITC experiment that are crucial for obtaining accurate and meaningful data, as well as the strengths, weaknesses, and challenges of ITC applications to NP research were discussed. MAJOR CONCLUSIONS: ITC reveals the driving forces behind biomolecule-NP interactions and the effects of the physicochemical properties of both NPs and biomolecules by quantifying the crucial thermodynamics parameters (e.g., binding stoichiometry, ΔH, ΔS, and ΔG). Complimentary techniques would strengthen the interpretation of ITC results for a more holistic understanding of biomolecule-NP interactions. GENERAL SIGNIFICANCE: The thermodynamic information revealed by ITC and its complimentary characterizations is important for understanding biomolecule-NP interactions that are fundamental to the biomedical and environmental applications of NMs and their toxicological effects.

Biochar-Facilitated Microbial Reduction of Hematite.

As an important component of soil organic matter (SOM), the transformation of pyrogenic carbon plays a critical role in the biogeochemical cycles of carbon and other redox-active elements such as iron (Fe). Herein, we studied the influences of wheat straw-derived biochars on the microbial reduction of 100 mM of hematite by the dissimilatory metal reducing bacteria Shewanella oneidensis MR-1 under anoxic conditions. The long-term microbial reduction extent and initial reduction rate of hematite were accelerated by more than 2-fold in the presence of 10 mg L(-1) biochar. Soluble leachate from 10 mg L(-1) biochar enhanced Fe(III) reduction to a similar degree. Microbially prereduced biochar leachate abiotically reduced hematite, consistent with the apparent electron shuttling capacity of biochar leachate. Electron paramagnetic resonance (EPR) analysis suggested that biochar leachate-associated semiquinone functional groups were likely involved in the redox reactions. In addition to electron shuttling effects, biochar particles sorbed 0.5-1.5 mM biogenic Fe(II) and thereby increased the long-term extent of hematite reduction by 1.4-1.7 fold. Our results suggest that Fe redox cycling may be strongly impacted by pyrogenic carbon in soils with relatively high content of indigenous pyrogenic carbon or substantial application of biochar.