Enhanced Nitrite Production from the Aqueous Photolysis of Nitrate in the Presence of Vanillic Acid and Implications for the Roles of Light-Absorbing Organics.

A prominent source of hydroxyl radicals (•OH), nitrous acid (HONO) plays a key role in tropospheric chemistry. Apart from direct emission, HONO (or its conjugate base nitrite, NO2-) can be formed secondarily in the atmosphere. Yet, how secondary HONO forms requires elucidation, especially for heterogeneous processes involving numerous organic compounds in atmospheric aerosols. We investigated nitrite production from aqueous photolysis of nitrate for a range of conditions (pH, organic compound, nitrate concentration, and cation). Upon adding small oxygenates such as ethanol, n-butanol, or formate as •OH scavengers, the average intrinsic quantum yield of nitrite [Φ(NO2-)] was 0.75 ± 0.15%. With near-UV-light-absorbing vanillic acid (VA), however, the effective Φ(NO2-) was strongly pH-dependent, reaching 8.0 ± 2.1% at a pH of 8 and 1.5 ± 0.39% at a more atmospherically relevant pH of 5. Our results suggest that brown carbon (BrC) may greatly enhance the nitrite production from the aqueous nitrate photolysis through photosensitizing reactions, where the triplet excited state of BrC may generate solvated electrons, which reduce nitrate to NO2 for further conversion to nitrite. This photosensitization process by BrC chromophores during nitrate photolysis under mildly acidic conditions may partly explain the missing HONO in urban environments.

Diverse molecular compositions of dissolved organic matter derived from different composts using ESI FT-ICR MS.

Dissolved organic matter (DOM) derived from various composts can promote significant changes of soil properties. However, little is known about the DOM compositions and their similarities and differences at the molecular level. In this study, the molecular compositions of DOM derived from kitchen waste compost (KWC), green waste compost (GWC), manure waste compost (MWC), and sewage sludge compost (SSC) were characterized by electrospray ionization coupled with Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS). The molecular formulas were classified into four subcategories: CHO, CHON, CHOS, and CHONS. The KWC, MWC, and SSC DOM represented the highest fraction (35.8%-47.4%) of CHON subcategory, while the GWC DOM represented the highest fraction (68.4%) of CHO subcategory. The GWC DOM was recognized as the nitrogen- and sulfur-deficient compounds that were less saturated, more aromatic, and more oxidized compared with other samples. Further analysis of the oxygen, nitrogen-containing (N-containing), and sulfur-containing (S-containing) functional groups in the four subcategories revealed higher organic molecular complexity. Comparison of the similarities and differences of the four samples revealed 22.8% ubiquitous formulas and 17.4%, 11.1%, 10.7%, and 6.3% unique formulas of GWC, KWC, SSC, and MWC DOM, respectively, suggesting a large proportion of ubiquitous DOM as well as unique, source-specific molecular signatures. The findings presented herein provide new insight into the molecular characterization of DOM derived from various composts and demonstrated the potential role of these different compounds for agricultural utilization.

Carbon fixation via volatile fatty acids recovery from sewage sludge through electrochemical-pretreatment-based anaerobic digestion.

Capturing the carbon in volatile fatty acids (VFA) produced from the anaerobic digestion (AD) of sewage sludge has the potential to not only provide economic benefits but also reduce greenhouse gas production. This study demonstrates a chemical-free method to collect VFA from an AD instead of methane that involves electrochemical pretreatment (EPT) of sludge. Experimental results show that applying 15 V EPT for 45 min enhances acidogenesis and selectively inhibits methanogenesis, leading to a substantial VFA accumulation (2563.1 ± 307.9 mg COD/L) and achieving 2.5 times more carbon fixation than via methane production. Interfacial thermodynamic analysis shows that EPT induces a decrease in both the repulsive electrostatic energy (from 152.9 kT to 12.2 kT) and the energy barrier (from 57.0 kT to 2.6 kT) in the sludge, leading to increased sludge aggregation and entrapment of microorganisms. Molecular docking sheds lights on how the methanogens interacts with the organic matter released from EPT (e.g., alanine-tRNA ligase), showing that these interactions potentially interfere with the proteins that are associated with the activities of the methanogens and the electron transfer pathways, thereby impeding methanogenesis. Integrating EPT into AD therefore facilitates the recovery of valuable VFA and the capture of carbon from freshwater sludge, providing notable economic and environmental benefits in sewage sludge treatment.

Emerging electrochemistry-based process for sludge treatment and resources recovery: A review.

The electrochemical process is gaining widespread interest as an emerging alternative for sludge treatment. Its potentials for sludge stabilization and resources recovery have been well proven to date. Despite the high effectiveness of the electrochemical process having been highlighted in several studies, concerns about the electrochemical sludge treatment, including energy consumption, scale-up feasibility, and electrode stability, have not yet been addressed. The present paper critically reviews the versatile uses of the electrochemical processes for sludge treatment and resource recovery, from the fundamentals to the practical applications. Particularly considered are the enhancement of the digestion of the anaerobic sludge and dewaterability, removal of pathogens and heavy metals, and control of sludge malodor. In addition, the opportunities and challenges of the sludge-based resource recovery (i.e., nitrogen, phosphorus, and volatile fatty acids) are discussed. Insights into the working mechanisms (e.g., electroporation, electrokinetics and electrooxidation) of electrochemical processes are reviewed, and perspectives and future research directions are proposed. This work is expected to provide an in-depth understanding and broaden the potential applications of electrochemical processes for sludge treatment and resource recovery.