Spatial patterns and environmental functions of dissolved organic matter in grassland soils of China.

Soil dissolved organic matter (DOM) is crucial to atmospheric, terrestrial and aquatic environments as well as human life. Here, by characterizing DOM from 89 grassland soils throughout China, we reveal the spatial association between DOM geochemistry in the dry season vs annual ecosystem exchange and cancer cases. The humic-like and high molecular weight (3.4-25 kDa) fractions with lower biodegradability, decline from the northern to the southern regions of China, and are correlated with lower soil respiration and net ecosystem productivity at the continental scale. The <1.2 kDa and proteinaceous fractions could serve as a geographical indicator of nasopharyngeal cancer incidence and mortality, while the 3.4-25 kDa and humified fractions are potentially associated with pancreatic cancer cases (P < 0.05). Our findings highlight that exploiting the environmental functions of soil DOM and mitigating the negative impacts are necessary, and require actions tailored to local soil DOM conditions.

Purifying surface water contaminated with azo dyes using nanofiltration: Interactions between dyes and dissolved organic matter.

In this research, the interactions of two azo dyes, Methyl Orange (MO) and Eriochrome Black T (EBT), with dissolved organic matter (DOM) in surface water were studied, emphasizing their removal using nano-filtration membranes (NF-270 and NF-90). High-Performance Size Exclusion Chromatography (HPSEC) findings indicated that the dyes' molecular weight in deionized (DI) water ranged from 500 to 15k Dalton (Da), adjusting peak intensities with Jingmi River (JM) water Beijing. Notably, when dyes were diluted in JM water, ultraviolet (UV533 & 466, and UV254), together with total organic carbon (TOC) parameters, revealed color removal rates of 99.49% (EBT), 94.2% (MO), 87.6% DOM removal, and 86% TOC removal for NF-90. The NF-90 membrane demonstrated a 75% flux decline for 50 mL permeate volume due to its finer pore structure and higher rejection effectiveness. In contrast, the NF-270 membrane showed a 60% decline in flux under the same conditions. Attenuated total reflection-Fourier transform infrared spectroscopy (ATR-FTIR) analysis of dye-treated membranes in JM water revealed that the NF-270 showed a CC bond peak at 1660 cm-1 across various samples, while analyzing NF-90, the peaks at 1400 cm-1, 1040 cm-1, 750 cm-1, and 620 cm-1 disappeared for composite sample removal. The hydrophobicity of each membrane is measured by the contact angle (CA), which identified that initial CAs for NF-270 and NF-90 were 460 and 700, respectively, that were rapidly declined but stabilized after a few seconds of processing. Overall, this investigation shows that azo dyes interact with DOM in surface waters and enhance the removal efficiency of NF membranes.

Molecular-weight dependent promotion and competition effects of natural organic matter on dissolved black carbon removal by coagulation.

Dissolved black carbon (DBC) is the ubiquitous component of dissolved organic matter pools with the high reactivity for disinfection byproducts formation. However, it is unknown that the influence of molecular weight (MW) of natural organic matter (NOM) on the DBC removal from potable water sources. Therefore, it was studied that the DBC removal by coagulation in the presence of the NOM with various molecular weights. The DBC removal was promoted due to the presence of NOM and the promotion degree decreased with decreasing MW of NOM. Furthermore, the removal ratio of humic-like component increased as the MW of NOM decreased, suggesting that the competition between DBC and NOM increased with decreasing MW. The functional groups after coagulation were the same with that before coagulation as the MW of NOM varied, suggesting that the molecular structure was not the key factor of influencing the DBC removal. This study will give the deep insight into the prediction of the DBC removal ratio by coagulation based on the MW of NOM in water sources.

Synergistically enhancing the selective adsorption of cationic dyes through copper impregnation and amino functionality into iron-based metal-organic frameworks.

Dyes contaminating the sewages have seriously threatened the living beings and their separation from wastewater in terms of potential resource recovery is of high value. Herein, both of metal node doping and ligand group grafting were taken into account to enhance the adsorption selectivity of Fe-MOFs towards cationic dyes. The positive correlation between copper doping amount and selective coefficient (∂MOMB) for methylene blue (MB) over methyl orange (MO) within a certain range was mainly attributed to the increased surface negative charges via partial replacement of Fe(III) with Cu(II). Moreover, the amount of surface negative charges was further increased after amino functionalization and there was a synergism between Cu(II) and -NH2 in selectivity enhancement. As a result, Fe0.6Cu0.4-BDC-NH2 exhibited a 22.5-times increase in ∂MOMB and other cationic dyes including malachite green (MG) and rhodamine B (Rh. B) could also be selectively separated from binary and quaternary mixed dye systems. Moreover, Fe0.6Cu0.4-BDC-NH2 showed many superiorities like a wide pH range of 4.0-8.0, strong anti-interference ability over various inorganic ions, good recyclability, and stability. The adsorption kinetics and isotherm suggested that the MB adsorption process was a homogeneous single-layer chemisorption. Additionally, the thermodynamics manifested that the overall process was exothermic and spontaneous. According to the FT-IR and XPS spectra analysis, the electrostatic interaction and hydrogen bonding were determined as the main driving forces, and π-π interaction also contributed to the adsorption process.

Visible-light-driven iron-based heterogeneous photo-Fenton catalysts for wastewater decontamination: A review of recent advances.

Visible-light-driven heterogeneous photo-Fenton process has emerged as the most promising Fenton-derived technology for wastewater decontamination, owing to its prominent superiorities including the potential utilization of clean energy (solar light), and acceleration of ≡Fe(II)/≡Fe(III) dynamic cycle. As the core constituent, catalysts play a pivotal role in the photocatalytic activation of H2O2 to yield reactive oxidative species (ROS). To date, all types of iron-based heterogeneous photo-Fenton catalysts (Fe-HPFCs) have been extensively reported by the scientific community, and exhibited satisfactory catalytic performance towards pollutants decomposition, sometimes even exceeding the homogeneous counterparts (Fe(II)/H2O2). However, the relevant reviews on Fe-HPFCs, especially from the viewpoint of catalyst-self design are extremely limited. Therefore, this state-of-the-art review focuses on the available Fe-HPFCs in literatures, and gives their classification based on their self-characteristics and modification strategies for the first time. Two classes of representative Fe-HPFCs, conventional inorganic semiconductors of Fe-containing minerals and newly emerging Fe-based metal-organic frameworks (Fe-MOFs) are comprehensively summarized. Moreover, three universal strategies including (i) transition metal (TMs) doping, (ii) construction of heterojunctions with other semiconductors or plasmonic materials, and (iii) combination with supporters were proposed to tackle their inherent defects, viz., inferior light-harvesting capacity, fast recombination of photogenerated carriers, slow mass transfer and low exposure and uneven dispersion of active sites. Lastly, a critical emphasis was also made on the challenges and prospects of Fe-HPFCs in wastewater treatment, providing valuable guidance to researchers for the reasonable construction of high-performance Fe-HPFCs.

Iron-nickel bimetallic metal-organic frameworks as bifunctional Fenton-like catalysts for enhanced adsorption and degradation of organic contaminants under visible light: Kinetics and mechanistic studies.

Iron-nickel bimetallic organic frameworks (FeNiX-BDC, H2BDC: terephthalic acid) were developed as bifunctional materials for adsorption and photo-Fenton degradation of organic dyes with different charge properties. Significantly enhanced adsorption capacity of FeNi1/15-BDC towards methylene blue (MB) and methyl orange (MO) was achieved, 5.3 and 2.6 times higher than that of pristine Fe-BDC, which was attributed to enlarged specific surface area and pore volume and the decreased surface charges induced by Ni doping. The adsorption kinetics demonstrated that chemisorption was dominant and intra-particle diffusion was the rate-controlling step. Two-stage degradation including slow induction stage and rapid oxidation stage fitted with pseudo-zero-order kinetics well. The increased rate constants (2.472 vs. 1.188 min-1 for MB; 0.616 vs. 0.421 min-1 for MO) in the induction stage as well as the superior removal capability by asynchronism relative to synchronism jointly corroborating the improved adsorption performance was favor for subsequent degradation. Notably, this heterogeneous system not only exhibited obvious advantages like wider pH working range (3-9), better stability and reusability of catalysts, but also achieved the dual objectives of in-situ decontamination and adsorbent regeneration. The coupling of adsorption and degradation along with synergism between photocatalysis and Fenton-like process are responsible for the reinforced removal of organic contaminants.