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.

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.

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.

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.

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.

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.

Speciation Dynamics of Phosphorus during (Hydro)Thermal Treatments of Sewage Sludge.

(Hydro)thermal treatments of sewage sludge from wastewater treatment process can significantly reduce waste volume and transform sludge into valuable products such as pyrochar and hydrochar. Given the global concern with phosphorus (P) resource depletion, P recycling/reclamation from or direct soil application of the derived chars can be potential P recycling practices. In order to evaluate P recyclability as well as the selection and optimization of treatment techniques, it is critical to understand the effects of different treatment techniques and conditions on P speciation and distribution. In the present study, we systematically characterized P speciation in chars derived from thermal (i.e., pyrolysis) and hydrothermal treatments of municipal sewage sludge using complementary chemical extraction and nuclear magnetic resonance (NMR) spectroscopy methods. P species in the raw activated sludge was dominated by orthophosphate and long-chain polyphosphates, whereas increased amounts of pyrophosphate and short-chain polyphosphates formed after pyrolysis at 250-600 °C. In contrast, hydrothermal treatments resulted in the production of only inorganic orthophosphate in the hydrochar. In addition to the change of molecular speciation, thermal treatments also altered the physical state and extractability of different P species in the pyrochars from pyrolysis, with both total P and polyphosphate being less extractable with increasing pyrolysis temperature. Results from this study suggest that P speciation and availability in sludge-derived chars are tunable by varying treatment techniques and conditions, and provide fundamental knowledge basis for the design and selection of waste management strategies for better nutrient (re)cycling and reclamation.