Variable aging and storage of dissolved black carbon in the ocean.

During wildfires and fossil fuel combustion, biomass is converted to black carbon (BC) via incomplete combustion. BC enters the ocean by rivers and atmospheric deposition contributing to the marine dissolved organic carbon (DOC) pool. The fate of BC is considered to reside in the marine DOC pool, where the oldest BC 14C ages have been measured (>20,000 14C y), implying long-term storage. DOC is the largest exchangeable pool of organic carbon in the oceans, yet most DOC (>80%) remains molecularly uncharacterized. Here, we report 14C measurements on size-fractionated dissolved BC (DBC) obtained using benzene polycarboxylic acids as molecular tracers to constrain the sources and cycling of DBC and its contributions to refractory DOC (RDOC) in a site in the North Pacific Ocean. Our results reveal that the cycling of DBC is more dynamic and heterogeneous than previously believed though it does not comprise a single, uniformly "old" 14C age. Instead, both semilabile and refractory DBC components are distributed among size fractions of DOC. We report that DBC cycles within DOC as a component of RDOC, exhibiting turnover in the ocean on millennia timescales. DBC within the low-molecular-weight DOC pool is large, environmentally persistent and constitutes the size fraction that is responsible for long-term DBC storage. We speculate that sea surface processes, including bacterial remineralization (via the coupling of photooxidation of surface DBC and bacterial co-metabolism), sorption onto sinking particles and surface photochemical oxidation, modify DBC composition and turnover, ultimately controlling the fate of DBC and RDOC in the ocean.

Dissolved Black Carbon Facilitates the Photodegradation of Microplastics via Molecular Weight-Dependent Generation of Reactive Intermediates.

Photodegradation of microplastics (MPs) induced by sunlight plays a crucial role in determining their transport, fate, and impacts in aquatic environments. Dissolved black carbon (DBC), originating from pyrolyzed carbon, can potentially mediate the photodegradation of MPs owing to its potent photosensitization capacity. This study examined the impact of pyrolyzed wood derived DBC (5 mg C/L) on the photodegradation of polystyrene (PS) MPs in aquatic solutions under UV radiation. It revealed that the photodegradation of PS MPs primarily occurred at the benzene ring rather than the aliphatic segments due to the fast attack of hydroxyl radical (•OH) and singlet oxygen (1O2) on the benzene ring. The photosensitivity of DBC accelerated the degradation of PS MPs, primarily attributed to the increased production of •OH, 1O2, and triplet-excited state DBC (3DBC*). Notably, DBC-mediated photodegradation was related to its molecular weight (MW) and chemical properties. Low MW DBC (<3 kDa) containing more carbonyl groups generated more •OH and 1O2, accelerating the photodegradation of MPs. Nevertheless, higher aromatic phenols in high MW DBC (>30 kDa) scavenged •OH and generated more O2•-, inhibiting the photodegradation of MPs. Overall, this study offered valuable insights into UV-induced photodegradation of MPs and highlighted potential impacts of DBC on the transformation of MPs.

Appearance of Recalcitrant Dissolved Black Carbon and Dissolved Organic Sulfur in River Waters Following Wildfire Events.

Increasing wildfire frequency, a consequence of global climate change, releases incomplete combustion byproducts such as aquatic pyrogenic dissolved organic matter (DOM) and black carbon (DBC) into waters, posing a threat to water security. In August 2022, a series of severe wildfires occurred in Chongqing, China. Samples from seven locations along the Yangtze and Jialing Rivers revealed DBC, quantified by the benzene poly(carboxylic acid) (BPCA) method, comprising 9.5-19.2% of dissolved organic carbon (DOC). High concentrations of BPCA-DBC with significant polycondensation were detected near wildfire areas, likely due to atmospheric deposition driven by wind. Furthermore, Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) revealed that wildfires were associated with an increase in condensed aromatics, proteins, and unsaturated hydrocarbons, along with a decrease in lignins. The condensed aromatics primarily consisted of dissolved black nitrogen (DBN), contributing to abundant high-nitrogen-containing compounds in locations highly affected by wildfires. Meanwhile, wildfires potentially induced the input of recalcitrant sulfur-containing protein-like compounds, characterized by high oxidation, aliphatic nature, saturation, and low aromaticity. Overall, this study revealed the appearance of recalcitrant DBC and dissolved organic sulfur in river waters following wildfire events, offering novel insights into the potential impacts of wildfires on water quality and environmental biogeochemistry.

Revealing Molecular Structures of Nitrogen-Containing Compounds in Dissolved Black Carbon Using Ultrahigh-Resolution Mass Spectrometry Combined with Thermodynamic Calculations.

Landscape wildfires generate a substantial amount of dissolved black carbon (DBC) annually, yet the molecular nitrogen (N) structures in DBC are poorly understood. Here, we systematically compared the chemodiversity of N-containing molecules among three different DBC samples from rice straw biochar pyrolyzed at 300, 400, and 500 °C, one leached dissolved organic carbon (LDOC) sample from composted rice straw, and one fire-affected soil dissolved organic matter (SDOMFire) sample using Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR MS). N-Containing molecules contributed 20.0%, 36.1%, and 43.7% of total compounds in Combined DBC (pooling together the three DBC), LDOC, and SDOMFire, respectively, and molecules with fewer N atoms had higher proportions (i.e., N1 > N2 > N3). The N-containing molecules in Combined DBC were dominated by polycyclic aromatic (62.2%) and aromatic (14.4%) components, while those in LDOC were dominated by lignin-like (50.4%) and aromatic (30.1%) components. The composition and structures of N-containing molecules in SDOMFire were more similar to those in DBC than in LDOC. As the temperature rose, the proportion of the nitrogenous polycyclic aromatic component in DBC significantly increased with concurrent enhanced oxidation and unsaturation of N. As indicated by density functional theory (DFT)-based thermodynamic calculations, the proportion of aliphatic amide N decreased from 23.2% to 7.9%, whereas that of nitroaromatic N increased from 10.0% to 39.5% as the temperature increased from 300 to 500 °C; alternatively, the proportion of aromatic N in the 5/6 membered ring remained relatively stable (∼31%) and that of aromatic amide N peaked at 400 °C (32.7%). Our work first provides a comprehensive and thorough description of molecular N structures of DBC, which helps to better understand and predict their fate and biogeochemical behavior.

Benzenepoly(carboxylic acid)s as Exclusive Intrinsic Markers to Assess Riverine Export of Dissolved Black Carbon.

Landscape fires annually generate large quantities of black carbon. The water-soluble fraction of black carbon (i.e., dissolved black carbon/DBC) is an important constituent of the dissolved organic carbon (DOC) pool, playing a crucial role in the global budget of refractory carbon and climate change. A key challenge in constraining the flux and fate of riverine DBC is to develop targeted and accurate quantification methods. Herein, we report that benzenepentacarboxylic acid (B5CA) intrinsically present in DBC can be used as an exclusive and holistic marker (representing both condensed aromatics and less-/nonaromatic fractions) for DBC quantification. B5CA was universally detected in water extractions of biochar and fire-affected soils with relatively large abundance but not produced by nonthermogenic processes. It has good mobility in the environment as it is not readily precipitated by cations or adsorbed by common geosorbents. B5CA also represents the recalcitrant components of DBC with excellent stability against photodegradation and biodegradation. Applying B5CA as the DBC marker in surface waters of the Changjiang River (i.e., the third largest river in the world), we calculate the DBC concentration in the downstream Changjiang River to be 4.8 ± 5.5% of the DOC flux. Our work provides a simple and reliable approach for the accurate quantification and source tracking of DBC in the soil and aquatic carbon pools.

Mechanistic and Kinetic Consideration of the Photochemically Generated Oxidative Organic Radicals in Dissolved Black Carbon Solutions under Simulated Solar Irradiation.

The photochemically generated oxidative organic radicals (POORs) in dissolved black carbon (DBC) was investigated and compared with that in dissolved organic matter (DOM). POORs generated in DBC solutions exhibited higher one-electron reduction potential values (1.38-1.56 V) than those in DOM solutions (1.22-1.38 V). We found that the photogeneration of POORs from DBC is enhanced with dissolved oxygen (DO) increasing, while the inhibition of POORs is observed in reference to DOM solution. The behavior of the one-electron reducing species (DBC•-/DOM•-) was employed to explain this phenomenon. The experimental results revealed that the DO concentration had a greater effect on DBC•- than on DOM•-. Low DO levels led to a substantial increase in the steady-state concentration of DBC•-, which quenched the POORs via back-electron reactions. Moreover, the contribution of POORs to the degradation of 19 emerging organic contaminants (EOCs) in sunlight-exposed DBC and DOM solutions was estimated. The findings indicate that POORs play an important role in the photodegradation of EOCs previously known to react with triplets, especially in DBC solutions. Compared to DOM solutions, POOR exhibits a lower but considerable contribution to EOC attenuation. This study enhances the understanding of pollutant fate in aquatic environments by highlighting the role of DBC in photochemical pollutant degradation and providing insights into pollutant transformation mechanisms involving POORs.

Different photoreduction processes of Cr(VI) on cellulose-rich and lignin-rich biochar.

In this study, a series of biochar were prepared via pyrolyzing cellulose-rich pakchoi (PBC) and lignin-rich corncob (CBC) to explore the photoreduction process of Cr(VI). X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy confirmed higher oxygenated functional groups in PBC (48.9%-57.1%), whereas CBC exhibited more aromatization properties due to the stable aromatic network in lignin. For PBC, the valence bands decreased from 1.42 eV to 1.20 eV with the increase of pyrolysis temperature from 300 °C to 500 °C; however, an opposite trend was observed for CBC. The photoreduction of Cr(VI) clearly showed that both PBC and CBC had the best performance at the carbonization temperature of 300 °C (named PBC300 and CBC300). It is noted that PBC300 exhibited the most effective photoreduction of Cr(VI), which was about 1.3 times higher than that of CBC300. The maximum reduction capacities of Cr(VI) were 68.2 mg g-1 on PBC300 and 66.1 mg g-1 on CBC300 at pH∼2.0. Compared with the insoluble char substances, dissolved black carbons made more contributions for Cr(VI) photoreduction, ∼70% in PBC and almost 100% in CBC, which suggested that in the case of PBC, the insoluble char and the corresponding dissolved black carbons play an important role in the photoreduction of Cr(VI). However, only dissolved black carbons contributed to Cr(VI) photoreduction on CBC. As the key reaction pathway, the interfacial electron transport dominated Cr(VI) reduction on PBC and CBC. Moreover, the radical of •O2- had some contribution to the reduction of Cr(VI) only in the PBC system. Interestingly, •OH could promote the photoreduction of Cr(VI) in both PBC and CBC systems, which might be due to the fact that •OH facilitated the formation of small molecule fragments. These findings provide an essential basis for evaluating the environmental impact of photocatalytic behaviors of biochar.

Microheterogeneous Triplet Oxidation of Hydrophobic Organic Contaminants in Dissolved Black Carbon Solutions under Simulated Solar Irradiation.

Dissolved black carbon (DBC) is proven to accelerate the triplet-mediated photodegradation of hydrophobic organic contaminants (HOCs). However, its photosensitization mechanisms are not clear. In this study, five HOCs including 2,4,6-trimethylphenol, N,N-dimethylaniline, 17ß-estradiol, 17α-ethinylestradiol, and bisphenol A were selected as model compounds to explore the triplet-mediated phototransformation of HOCs in illuminated DBC solutions. All five HOCs presented high organic carbon-water partition coefficient (KOC) values in DBC solutions, indicating the strong sorption capacity of DBC for HOCs. When reaching sorption equilibrium, the apparent pseudo-first-order rate constants of HOCs vs log[DBC] were well fitted with a sorption-enhanced phototransformation model (R2 > 0.98). Using the sorption-enhanced phototransformation model, the degradation rates of HOCs determined at intra-DBC (kDBC,HOCs') were 1-2 orders of magnitude higher than those observed in aqueous bulk solution (kHOCsaq). Moreover, typical triplet quenchers (2,4,6-trimethylphenol and oxygen) exhibited a microheterogeneous quenching effect on the triplet-mediated photodegradation of 17ß-estradiol. Therefore, our results suggested that HOCs underwent a microheterogeneous photooxidative degradation process in DBC solutions. Furthermore, a sorption-enhanced phototransformation mechanism was proposed to elucidate the microheterogeneous photooxidative behavior of HOCs in DBC solutions. This study provides new insights into the fate and transport of HOCs in aquatic environments.

Natural Asphalt Seeps Are Potential Sources for Recalcitrant Oceanic Dissolved Organic Sulfur and Dissolved Black Carbon.

Natural oil seepages contribute about one-half of the annual petroleum input to marine systems. Yet, environmental implications and the persistence of water-soluble hydrocarbons from these seeps are vastly unknown. We investigated the release of oil-derived dissolved organic matter (DOM) from natural deep sea asphalt seeps using laboratory incubation experiments. Fresh asphalt samples collected at the Chapopote asphalt volcano in the Southern Gulf of Mexico were incubated aerobically in artificial seawater over 4 weeks. The compositional changes in the water-soluble fraction of asphalt-derived DOM were determined with ultrahigh-resolution mass spectrometry (Fourier-transform ion cyclotron resonance mass spectrometry, FT-ICR-MS) and by excitation-emission matrix spectroscopy to characterize fluorescent DOM (FDOM) applying parallel factor (PARAFAC) analysis. Highly reduced aliphatic asphalt-derived DOM was readily biodegraded, while aromatic and sulfur-enriched DOM appeared to be less bioavailable and accumulated in the aqueous phase. A quantitative molecular tracer approach revealed the abundance of highly condensed aromatic molecules of thermogenic origin. Our results indicate that natural asphalt and potentially other petroleum seepages can be sources of recalcitrant dissolved organic sulfur and dissolved black carbon to the ocean.

Effect of root exudates on the release, surface property, colloidal stability, and phytotoxicity of dissolved black carbon.

In this study, the release of dissolved black carbon (DBC) from bulk-BC, its surface properties, colloidal stability, and oxidative stress to rice seedlings in the presence and absence of rice root exudates were compared. The bulk-BCs were prepared at 550 °C and derived from wood chips and pig manure, respectively. The release of DBC from bulk-BC was significantly enhanced (20.19-23.63%) by the introduction of root exudates, where low molecular weight organic acids played a dominating role in the dissociation of DBC from carbon skeleton. The surface properties of DBC were greatly modified by root exudates including decreases in the surface area (18.13%) and mineral contents (43.90-69.57%). The O-containing groups and graphitization were also enhanced by 11.46% and 18.65%, respectively. Meanwhile, the presence of root exudates not only reduced the colloidal stability of DBC but also lowered the intensity of free radicals (19.44-22.22%) in DBC. Consequently, the oxidative stress of DBC to rice seedlings was significantly (p < 0.05) alleviated, evidenced by reduced antioxidative enzyme activities (5.67-29.25%) and soluble protein content (15.75-46.79%) in rice plants. These results indicate that the interaction between DBC and root exudates could remarkably modify the surface properties and reactivity of DBC, which has profound implications for understanding the behavior and functions of DBC in the environment.

Dissolved black carbon enhanced the aquatic photo-transformation of chlortetracycline via triplet excited-state species: The role of chemical composition.

Dissolved black carbon (DBC), widely distributed in the aquatic environments, can accelerate sunlight-driven photo-transformation of micropollutants, however the photosensitization mechanisms are not clear. Herein, the DBC was extracted from bamboo biochar and fractionated by molecular weight (i.e. <10 k, <3 k, and <1 k Da). The effects of DBC on chlortetracycline (CTC) photolysis behaviors, and the role of chemical composition (i.e., molecular weight and chemical structure) in DBC-mediated photo-transformation were investigated. The results showed that DBC could accelerate CTC photodegradation significantly. At low DBC concentrations (<6.0 mg C/L), the photodegradation rate constant of CTC increased from 0.0299 to 0.0416 min-1 with the increasing DBC concentration. Via quenching experiment, the triplet excited-state of DBC was identified as the dominant reactive intermediate with >90% contribution to total CTC photodegradation. In addition, it was found that the photosensitive efficiency of DBC increased as the molecular weight decreased, and the stronger photosensitization ability exhibited in DBC with low-molecular weight was potentially attributed to its higher content of carbonyl compounds. The observed photosensitive efficiency of DBC sharply decreased after reduction by NaBH4, further confirming the key role of carbonyl compounds in the photosensitization process. Moreover, based on the result of photoproducts, the amidogen in CTC was verified to be susceptible to react with 3DBC*.

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.

How does adsorptive fractionation of dissolved black carbon on ferrihydrite affect its copper binding behaviors? A molecular-scale investigation.

Adsorptive fractionation of dissolved black carbon (DBC) on minerals is proven to alter its molecular composition, which will inevitably affect the environment fate of heavy metals. However, the effects of molecular fractionation on the interaction between DBC and heavy metals remain unclear. Herein, we observed that the selective adsorption of ferrihydrite caused molecular changes of DBC from high molecular weight/unsaturation/aromaticity to low molecular weight/saturation/aliphatics. This process accompanied by a retention of carbohydrate and a reduction of oxygen-rich functional groups (e.g., polyphenols and carboxyl) and long carbon chain in DBC. The residual DBC in aqueous phase demonstrated a weaker binding affinity to copper compared to the original DBC. This decrease in binding affinity was primarily attributed to the adsorption of polycyclic condensed aromatic compounds of 200-250 Da, oxygen-rich polycyclic condensed aromatic compounds of 250-300 Da, oxygen-rich non-polycyclic aromatic compounds of 300-450 Da, and non-polycyclic aromatic compounds of 450-700 Da in DBC by ferrihydrite. Additionally, the retention of carbohydrates and aliphatic compounds of 300-450 Da also made a significant contribution. Notably, carboxylic groups rather than phenolic groups were the dominant oxygen-containing functional groups responsible for this affinity reduction. This study has significant implications for understanding of the biogeochemical processes of DBC at soil-water interface and surface water, especially its role in the transportation of heavy metals.

Dual role of dissolved black carbon in sensitized ofloxacin photooxidation: Mechanism and influential factors.

Dissolved black carbon (DBC) is the more photoactive component of dissolved organic matter (DOM) pool, which plays a dual role in the photoconversion of aquatic contaminants, acting as both a photosensitizer and an inhibitor. However, little is known about the more systematic mechanism by which DBC exhibits a dual effect, which is closely related to the structure composition of DBC. In this study, the differences in characteristics of DBC obtained from 300 °C and 500 °C were compared via UV-vis absorption spectrum, Fluorescence excitation emission matrix spectra (3D-EEM), Fourier transform infrared (FT-IR), and X-ray photoelectron spectroscopy (XPS), and evaluated the promoting and inhibiting effects of DBC on ofloxacin (OFL) photodegradation. It was found that higher pyrolysis temperature reduced the UV absorbance, molecular weight, aromaticity, and phenolics of DBC while increasing the content of quinone/aromatic ketone and humic substances. Photochemical data showed that 3DBC*, 1O2 and ·OH were all participated in the DBC-mediated OFL photodegradation. Wherein, DBC300 (DBCT, where T = pyrolysis temperature) had strong light screening and dynamic quenching effect, but the formation ability of 3DBC*, 1O2 and ·OH was poor, which significantly retarded the photodegradation of OFL. While DBC500 exhibited a slight promotion effect due to its higher formation ability of reactive species and weak light screening effect. Moreover, DBC500 had higher steady-state concentration and (kOFL,3DBC⁎) than DBC300, which might be due to the higher contents of quinone/aromatic ketone and the lower contents of phenol in DBC500, thus enhancing the reactivity of 3DBC* and OFL. Our research systematically revealed the trade-off mechanism of DBC on the photodegradation of fluoroquinolones, and provided an important theoretical guidance for the photodegradation of fluoroquinolones under the evolution of DBC composition.

Molecular-level transformations of dissolved black carbon in UV-based advanced oxidation processes.

Dissolved black carbon (DBC) released from biochar, is an essential group in the dissolved organic matter (DOM) pool and is widely distributed in aquatic environments. In various advanced oxidation processes (AOPs), DBC exhibits enhanced free radical scavenging compared to typical DOM, attributed to its smaller molecular weight and more compacted aromatic structure; however, the molecular-level transformations of DBC in different AOPs, such as UV/H2O2, UV/PDS, and UV/Chlorine, remain unclear. This study employed a DBC derived from wheat biochar for experimentation. Characterization involved ultraviolet-visible (UV-Vis) spectroscopy and fluorescence excitation-emission-matrix (EEM) spectroscopy, revealing the transformation of DBC through diminished SUVA254 values and reduced intensity of three-dimensional fluorescence peaks. Further insights into the transformation were gained through Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). After each UV-AOP treatment, a conspicuous augmentation in the oxygen content of DBC was observed. The detailed oxygenation processes were elucidated through mass difference analysis, based on 23 types of typical reactions. Results indicated that oxygenation reactions were most frequently detected in all three UV-AOP treatments. Specifically, the hydroxylation (+O) predominated in UV/H2O2, while the di-hydroxylation (+2O) prevailed in UV/PDS. UV/Chlorine treatments commonly exhibited tri-hydroxylation (+3O), with the identification of 1194 Cl-BPs of unknown structures. This study contributes to a comprehensive understanding of the molecular transformations of DBC induced by various free radicals in different UV-AOP processes, leading to a better understanding of the different fates of DBC in UV-AOP processes. In addition, the identification of DBC as a precursor of by-products will also contribute to the understanding of how to inhibit the generation of by-products.

Disinfection byproducts and their cytotoxicity contribution from dissolved black carbon in source water during chlor(am)ination.

Dissolved black carbon (DBC), the soluble component of black carbon, which mainly comes from the incomplete combustion of fossil fuels or biomass, is widely spread in source water and significantly contributes to the formation of dissolved organic matter (DOM). However, the origin of DBC in different types of source water in China has not been well studied, as well as its subsequent transformation and toxicity contribution during disinfection of source water DOM by chlor(am)ine. In this study, DBC from 17 different source water in East China at different seasons was collected. The δ13C compositions indicated that straw burning was the main origin of DBC in source water. After simulated chlor(am)ination of DBC, 5 categories of aliphatic disinfection byproducts (DBPs) including trihalomethanes, haloacetic acids, haloacetonitriles, haloketones, halonitromethanes and 6 categories of aromatic DBPs including halophenols, halonitrophenols, halohydroxybenzaldehyde, halohydroxybenzoic acid, halobenzoquinones and haloaniline were detected. Compared with chlorination of DBC, higher levels of nitrogenous DBPs and aromatic DBPs were generated during chloramination. Detected DBPs accounted for 42 % of total organic halogen. What's more, Chinese hamster ovary cells cytotoxicity tests showed that the cytotoxicity of DBPs formed by chlor(am)ination of DBC was 4 times higher than that by chlor(am)ination of DOM. Haloacetonitriles contributed to the highest cytotoxicity in the chloramination of DBC, and haloacetic acids contributed to the highest cytotoxicity in chlorination. 67 % of the total cytotoxicity attributed to the undetected DBPs. As a result, DBPs generated from DBC contributed to 11.7 % of the total cytotoxicity in the chlor(am)ination of the source water DOM although DBC only took up 2 % of DOC in the source water. Results obtained from this study systematically revealed the DBPs formation from DBC and their potential cytotoxicity contribution in the chlor(am)ination of source water DOM, which should not be ignored in drinking water treatment.

Refining metallic nano-copper by electron-rich black carbon for superior Fenton-like catalysis in water purification: The capacitive regulation of corrosive electron transfer.

Transition metals are promising catalysts for environmental remediation. However, their low reactivity, poor stability and weak reusability largely limit practical applications. Herein, we report that the electron-rich dissolved black carbon (DBC) incorporated into the nanoscale zero-valent copper (nZVCu) can boost intrinsic reactivity, structural stability and cyclic reusability for superior peroxymonosulfate (PMS) activation and pollutant degradation. A series of refractory pollutants can be effectively removed on the DBC/nZVCu, in comparison with the nZVCu reference. Hydroxyl radical (‧OH) is identified as the dominant reactive oxygen species by electron spin resonance (ESR) and chemical quenching tests, mediated by the metastable Cu(III) as the key reactive intermediate. The electron-rich DBC protects nanoscale Cu from oxidative corrosion to slow down the surface formation of inert CuO layer, rendered by the thermodynamically and dynamically capacitive regulation of corrosive electron transfer from metallic core. By this refining way, the conducive DBC improves the neighboring utilization of reactive electron during metal corrosion, oxidant activation, radical generation and pollutant degradation in Fenton-like catalysis. Our findings suggest that the ubiquitous DBC can be an efficient chelating agent to refine transition metals by serving as the surface deactivator and electron mediator, and take new insights into their environmental and agricultural geochemistry.

Photo-Reactivity of dissolved black carbon unveiled by combination of optical spectroscopy and FT-ICR MS analysis: Effects of pyrolysis temperature.

Dissolved black carbon (DBC) has high photoactivity, which plays an important role in contaminants photodegradation. However, it is unclear how pyrolysis temperatures would affect the composition and photo-reactivity of DBC at the molecular level. Herein, we combined complementary techniques to study the characteristics of DBC pyrolyzed at 200 - 500 ℃, as well as the photoproduction of reactive species and the photodegradation of tetracycline (TC). Bulk composition characterization found that condensed aromatic carbonyl compounds (ConAC) with narrow molecular weights in DBC experienced an increase from 200 to 500 °C, which enhanced the photoproduction of 3DBC*,1O2, and ·OH. Molecular-level data suggested that 3DBC* and 1O2 were both related to the same DBC compounds. Comparatively, the patterns for ·OH were less pronounced, implying its precursor was not 3DBC* and had more complexity. Plentiful CHOx species of ConAC in DBC400 and DBC500 (DBCT, where T = pyrolysis temperature) accelerated the generation of 3DBC* and 1O2, enhancing the photodegradation of TC, and mainly triplet states of quinones reacted with TC. In contrast, DBC200 and DBC300 exhibited inhibition since massive CHOx species in lignin-like reduced 3TC* to TC. Our data revealed the diverse photochemical behavior mechanisms of DBC pyrolyzed at 200 - 500 ℃ at the molecular level and the implications for aquatic contaminants photochemistry.

Novel insights into the temporal molecular fractionation of dissolved black carbon at the iron oxyhydroxide - water interface.

As the most reactive and mobile fraction of black carbon, dissolved black carbon (DBC) inexorably interacts with minerals in the biosphere. Nevertheless, the research on the mechanisms and compositions of DBC assembly at the mineral-water interface remains limited. In this study, we revealed the "kinetic architecture" of DBC on iron oxyhydroxide at novel insights based on quantitative and qualitative approaches. The results indicated that high molecular weight, highly unsaturated, oxygen-rich (such as carboxyl-rich fraction, phenolics), aliphatics, and long C chains compounds were preferentially adsorbed on the iron oxyhydroxide. 2D-COS analyses directly disclosed the sequential fractionation: aromatic and phenolic groups > aliphatic groups, and few aromatics were continuously adsorbed after the rapid adsorption. Quantitative determinations identified that aromatic and phenolic components were adsorbed rapidly over the first 60 min, while aromatics achieved the dynamic equilibrium until ∼300 min, which was consistent with the 2D-COS observations. Our findings supported the hypothesis that "mineral-OM" and "OM-OM" interactions worked simultaneously, and the adsorption might be co-driven by ligand exchange, hydrophobic interactions, and other mechanisms. This work provided the theoretical basis for organic carbon storage and turnover, and it was valuable for predicting the behaviors and fates of contaminants at the soil-water interface and surface water.

Structural characteristics of dissolved black carbon and its interactions with organic and inorganic contaminants: A critical review.

Biochar (BC) is a sustainable and renewable carbonaceous material, and its soluble component, dissolved black carbon (DBC), is the key to understanding BC's geological and environmental processes. Although the relationship between the changes in DBC structure and its properties, functions, and associated environmental risks has been explored, a gap remains in our understanding of DBC's fate and behavior in the natural environment. Thus, in this review, we have highlighted the molecular and chemical compositions and the structural evolution of DBC during pyrolysis, the influence of DBC's physicochemical properties on its fate and transport, DBC's interaction with soil and its contaminants, and DBC stability in soil and water environments along with potential risks. Based on our in-depth assessment of DBC and its biogeochemical roles, we believe that future studies should focus on the following: (1) using advanced techniques to understand the chemical and molecular structure of DBC deeply and concisely and, thus, determine its fundamental role in the natural environment; (2) investigating the multi-functional properties of DBC and its interaction mechanisms; and (3) evaluating the environmental behaviors of and risks associated with DBC after BC application. In future, it is necessary to gain a deeper insight into the fate and transport of DBC with contaminants and study its associated risks under BC application in the environment.