RESUMO
The uptake of carbon dioxide (CO2) by terrestrial ecosystems is critical for moderating climate change1. To provide a ground-based long-term assessment of the contribution of forests to terrestrial CO2 uptake, we synthesized in situ forest data from boreal, temperate and tropical biomes spanning three decades. We found that the carbon sink in global forests was steady, at 3.6 ± 0.4 Pg C yr-1 in the 1990s and 2000s, and 3.5 ± 0.4 Pg C yr-1 in the 2010s. Despite this global stability, our analysis revealed some major biome-level changes. Carbon sinks have increased in temperate (+30 ± 5%) and tropical regrowth (+29 ± 8%) forests owing to increases in forest area, but they decreased in boreal (-36 ± 6%) and tropical intact (-31 ± 7%) forests, as a result of intensified disturbances and losses in intact forest area, respectively. Mass-balance studies indicate that the global land carbon sink has increased2, implying an increase in the non-forest-land carbon sink. The global forest sink is equivalent to almost half of fossil-fuel emissions (7.8 ± 0.4 Pg C yr-1 in 1990-2019). However, two-thirds of the benefit from the sink has been negated by tropical deforestation (2.2 ± 0.5 Pg C yr-1 in 1990-2019). Although the global forest sink has endured undiminished for three decades, despite regional variations, it could be weakened by ageing forests, continuing deforestation and further intensification of disturbance regimes1. To protect the carbon sink, land management policies are needed to limit deforestation, promote forest restoration and improve timber-harvesting practices1,3.
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Dióxido de Carbono , Sequestro de Carbono , Florestas , Internacionalidade , Árvores , Dióxido de Carbono/metabolismo , Dióxido de Carbono/análise , Mudança Climática , Conservação dos Recursos Naturais , Ecossistema , Agricultura Florestal/legislação & jurisprudência , Agricultura Florestal/estatística & dados numéricos , Agricultura Florestal/tendências , Combustíveis Fósseis/efeitos adversos , Combustíveis Fósseis/provisão & distribuição , Taiga , Árvores/metabolismo , Árvores/crescimento & desenvolvimento , Clima TropicalRESUMO
Intact tropical rainforests have been exposed to severe droughts in recent decades, which may threaten their integrity, their ability to sequester carbon, and their capacity to provide shelter for biodiversity. However, their response to droughts remains uncertain due to limited high-quality, long-term observations covering extensive areas. Here, we examined how the upper canopy of intact tropical rainforests has responded to drought events globally and during the past 3 decades. By developing a long pantropical time series (1992 to 2018) of monthly radar satellite observations, we show that repeated droughts caused a sustained decline in radar signal in 93%, 84%, and 88% of intact tropical rainforests in the Americas, Africa, and Asia, respectively. Sudden decreases in radar signal were detected around the 1997-1998, 2005, 2010, and 2015 droughts in tropical Americas; 1999-2000, 2004-2005, 2010-2011, and 2015 droughts in tropical Africa; and 1997-1998, 2006, and 2015 droughts in tropical Asia. Rainforests showed similar low resistance (the ability to maintain predrought condition when drought occurs) to severe droughts across continents, but American rainforests consistently showed the lowest resilience (the ability to return to predrought condition after the drought event). Moreover, while the resistance of intact tropical rainforests to drought is decreasing, albeit weakly in tropical Africa and Asia, forest resilience has not increased significantly. Our results therefore suggest the capacity of intact rainforests to withstand future droughts is limited. This has negative implications for climate change mitigation through forest-based climate solutions and the associated pledges made by countries under the Paris Agreement.
Assuntos
Secas , Floresta Úmida , Mudança Climática , Árvores/fisiologia , Clima TropicalRESUMO
Stoichiometric rules may explain the allometric scaling among biological traits and body size, a fundamental law of nature. However, testing the scaling of elemental stoichiometry and growth to size over the course of plant ontogeny is challenging. Here, we used a fast-growing bamboo species to examine how the concentrations and contents of carbon (C), nitrogen (N) and phosphorus (P), relative growth rate (G), and nutrient productivity scale with whole-plant mass (M) at the culm elongation and maturation stages. The whole-plant C content vs M and N content vs P content scaled isometrically, and the N or P content vs M scaled as a general 3/4 power function across both growth stages. The scaling exponents of G vs M and N (and P) productivity in newly grown mass vs M relationships across the whole growth stages decreased as a -1 power function. These findings reveal the previously undocumented generality of stoichiometric allometries over the course of plant ontogeny and provide new insights for understanding the origin of ubiquitous quarter-power scaling laws in the biosphere.
Assuntos
Fósforo , Plantas , Desenvolvimento Vegetal , Tamanho Corporal , NitrogênioRESUMO
Hydroxyl radical (HOâ¢) and chlorine atom (Clâ¢) are common reactive species in aqueous environments. However, the intrinsic difference in their reactions with organic compounds has not been revealed. This study compared the reaction mechanisms of HO⢠and Cl⢠with 13 aromatic and 11 aliphatic compounds by quantum chemical calculation and laser flash photolysis. Both HO⢠and Cl⢠can spontaneously react with aromatic compounds via radical adduct formation (RAF), hydrogen atom transfer (HAT), and single electron transfer (SET) pathways. The SET reactions of Cl⢠were more thermodynamically favorable than HOâ¢, but contrary results were obtained for HAT reactions. According to the free energy of activation (ΔGaq), the dominant oxidation mechanisms of aromatic compounds were RAF and SET by HO⢠and SET by Clâ¢. The important role of SET in the HO⢠reactions with aromatic compounds was further verified by accurately calculating the solvation free energy of HOâ¢/HO- and experimentally tracking the radical cations, which were generally neglected in previous studies. Meanwhile, the ΔGaq value of each reaction pathway of Cl⢠was lower than that of HOâ¢, resulting in higher rate constants of Cl⢠with aromatic compounds than HOâ¢. For saturated aliphatic compounds, HAT was found to be the only mechanism accounting for their transformation by HO⢠and Clâ¢. This study proposed general rules for the reaction mechanisms of HO⢠and Cl⢠and unraveled their differences in the aspects of thermodynamics and kinetics, providing fundamental information for understanding contaminant transformation in processes involving HO⢠and Clâ¢.
Assuntos
Cloro , Radical Hidroxila , Compostos Orgânicos , Termodinâmica , Radical Hidroxila/química , Cloro/química , Cinética , Compostos Orgânicos/química , OxirreduçãoRESUMO
Recently, reactive cobalt (Co) species, including Co(IV)-oxo and Co(II)-OOSO3- complexes, were proposed to be the primary intermediates formed during the process of activating peroxymonosulfate (PMS) by Co(II), mainly based on the observation that the methyl phenyl sulfoxide (MPSO) probe was transformed to methyl phenyl sulfone (MPSO2) in this process. However, in this work, we rationalized the results of the MPSO probe assay based on the chemistry of aqueous Co(III), an alternative reactive Co species. Moreover, 18O-labeled water experiments and Raman spectroscopy analysis clearly proved the Co(III) formation in the Co(II)/PMS system. In parallel, sulfate radicals (SO4â¢-) and hydroxyl radicals (HOâ¢) were also involved in this system. Further, the relative contribution of Co(III) to the abatement of carbamazepine (CBZ), a representative micropollutant, in the Co(II)/PMS system was significantly increased by increasing the Co(II) dosage but was dramatically decreased by improving the PMS dosage and increasing the pH from 3 to 7. Additionally, the degradation pathway of CBZ by Co(III) and the Co(II)/PMS system was comparatively explored, confirming that Co(III) participated in the hydroxylation, carbonylation, deacetylation, and ring reduction of CBZ by the Co(II)/PMS system. Our work addresses the controversy regarding the reactive Co species involved in the Co(II)/PMS system with evidence of Co(III) as the chief one, which highlights the significance of re-evaluating the relative contribution of Co(III) in relevant environmental decontamination processes.
RESUMO
Herein, we propose preferential dissolution paired with Cu-doping as an effective method for synergistically modulating the A- and B-sites of LaMnO3 perovskite. Through Cu-doping into the B-sites of LaMnO3, specifically modifying the B-sites, the double perovskite La2CuMnO6 was created. Subsequently, partial La from the A-sites of La2CuMnO6 was etched using HNO3, forming novel La2CuMnO6/MnO2 (LCMO/MnO2) catalysts. The optimized catalyst, featuring an ideal Mn:Cu ratio of 4.5:1 (LCMO/MnO2-4.5), exhibited exceptional catalytic ozonation performance. It achieved approximately 90% toluene degradation with 56% selectivity toward CO2, even under ambient temperature (35 °C) and a relatively humid environment (45%). Modulation of A-sites induced the elongation of Mn-O bonds and decrease in the coordination number of Mn-O (from 6 to 4.3) in LCMO/MnO2-4.5, resulting in the creation of abundant multivalent Mn and oxygen vacancies. Doping Cu into B-sites led to the preferential chemisorption of toluene on multivalent Cu (Cu(I)/Cu(II)), consistent with theoretical predictions. Effective electronic supplementary interactions enabled the cycling of multiple oxidation states of Mn for ozone decomposition, facilitating the production of reactive oxygen species and the regeneration of oxygen vacancies. This study establishes high-performance perovskites for the synergistic regulation of O3 and toluene, contributing to cleaner and safer industrial activities.
Assuntos
Ozônio , Tolueno , Catálise , Ozônio/química , Tolueno/química , Titânio/química , Óxidos/química , Compostos de Cálcio/químicaRESUMO
BACKGROUND: Septic myocardial injury is one of the most life-threatening organ dysfunction. The γ-secretase-based approaches have been developed as potential strategies for diverse diseases management. Unfortunately, the role of γ-secretase inhibitor in septic myocardial injury is unclarified. The present study aims to investigate the effect of γ-secretase inhibitor in septic myocardial injury and reveal its mechanism. METHODS: The mouse model of septic myocardial injury was established by intraperitoneally injection of lipopolysaccharide (LPS), and γ-secretase inhibitor MW167 was applied in this model. RNA-sequencing analysis and further bioinformatics analyses were used to screen differential expressed genes (DEGs) and potentially enriched pathways between LPS and LPS + MW167 mice. Pathological examination was performed using haematoxylin and eosin (HE) staining. SD-1029 was used to block JAK2/STAT3 signaling in H9C2 cells and western blot analysis quantified JAK2/STAT3-related proteins. RESULTS: LPS induced myocardial injury accompanied with significant inflammatory infiltration and more apoptotic cells. Transcriptome sequencing screened 36 DEGs and bioinformatics identified JAK2/STAT3 signaling pathway was significantly enriched. Further in vitro experiments showed that γ-secretase inhibitor MW167 activated JAK2/STAT3 pathway. Additionally, MW167 restored cell viability, decreased myocardial injury markers including cardiac troponin I (cTnI) and brain natriuretic peptide (BNP), inhibited pro-inflammatory cytokines such as interleukin (IL)-1ß and tumor necrosis factor-α (TNF-α) and reduced nitric oxide (NO), cyclooxygenase-2 (COX2) and inducible nitric oxide synthase (iNOS) release. Application of SD-1029 reversely deteriorated LPS-induced myocardial injury and inflammatory response in γ-secretase inhibitor-treated myocardial cells. CONCLUSION: The results demonstrate that γ-secretase inhibitor alleviates septic myocardial injury via activating JAK2/STAT3 signaling, and provide novel therapeutic direction for septic myocardial injury.
Assuntos
Secretases da Proteína Precursora do Amiloide , Lipopolissacarídeos , Camundongos , Animais , Lipopolissacarídeos/toxicidade , Secretases da Proteína Precursora do Amiloide/metabolismo , Transdução de Sinais , Citocinas/metabolismo , Miocárdio/metabolismo , Fator de Transcrição STAT3/metabolismo , Janus Quinase 2/metabolismoRESUMO
Using steady-state photosynthesis-intercellular CO2 concentration (A-Ci) response curves to obtain the maximum rates of ribulose-1,5-bisphosphate carboxylase oxygenase carboxylation (Vcmax) and electron transport (Jmax) is time-consuming and labour-intensive. Instead, the rapid A-Ci response (RACiR) technique provides a potential, high-efficiency method. However, efficient parameter settings of RACiR technique for evergreen broadleaved species remain unclear. Here, we used Li-COR LI-6800 to obtain the optimum parameter settings of RACiR curves for evergreen broadleaved trees and shrubs. We set 11 groups of CO2 gradients ([CO2]), i.e. R1 (400-1500 ppm), R2 (400-200-800 ppm), R3 (420-20-620 ppm), R4 (420-20-820 ppm), R5 (420-20-1020 ppm), R6 (420-20-1220 ppm), R7 (420-20-1520 ppm), R8 (420-20-1820 ppm), R9 (450-50-650 ppm), R10 (650-50 ppm) and R11 (650-50-650 ppm), and then compared the differences between steady-state A-Ci and RACiR curves. We found that Vcmax and Jmax calculated by steady-state A-Ci and RACiR curves overall showed no significant differences across 11 [CO2] gradients (P > 0.05). For the studied evergreens, the efficiency and accuracy of R2, R3, R4, R9 and R10 were higher than the others. Hence, we recommend that the [CO2] gradients of R2, R3, R4, R9 and R10 could be applied preferentially for measurements when using the RACiR technique to obtain Vcmax and Jmax of evergreen broadleaved species.
Assuntos
Dióxido de Carbono , Ribulose-Bifosfato Carboxilase , Ribulose-Bifosfato Carboxilase/metabolismo , Fotossíntese/fisiologia , Transporte de Elétrons , Folhas de Planta/fisiologiaRESUMO
Because of the deterioration of global water quality, the occurrence of chemical and microbial contaminants in water raises serious concerns for the health of the population. Identifying and developing effective and environmentally friendly water treatment technologies are critical to obtain clean water. Among the various technologies for the purification of water, ultraviolet photolysis of chlorine (UV/chlorine), an emerging advanced oxidation process (AOP), has multiple functions for the control of contaminants via the production of hydroxyl radicals (HO·) and reactive chlorine species (RCS), such as Cl·, ClO·, and Cl2·-.This Account centers around the radical chemistry of RCS and HO· in different water matrices and their roles and mechanisms in the abatement of contaminants. The concentrations of Cl·, ClO·, and Cl2·- are comparable to or higher than those of HO· (10-14 to 10-13 M). The reactivities of RCS are more selective than HO· with a broader range of second-order rate constants (k). The k values of Cl· toward most aromatics are higher or similar as compared to those of HO·, while those of Cl2·- and ClO· are less reactive but more selective toward aromatics containing electron-donating functional groups. Their major reaction mechanisms with Cl· are electron transfer and addition, while those with ClO· and Cl2·- primarily involve electron transfer. As for aliphatics, their reactivities with both HO· and RCS are much lower than those of aromatics. The reaction mechanisms for most of them with Cl· and Cl2·- are hydrogen abstraction, except for olefins, which are addition. In addition, RCS greatly contribute to the inactivation of microbial contaminants.Toward future application, the UV/chlorine process has both pros and cons. Compared with the traditional HO·-based AOP of UV/H2O2, UV/chlorine is more efficient and energy-saving for oxidation and disinfection, and its efficiency is less affected by water matrix components. However, the formation of toxic byproducts in UV/chlorine limits its application scenarios. In dissolved organic matter (DOM)-rich water, the formation of halogenated byproducts is enhanced in UV/chlorine. In the presence of ammonia, reactive nitrogen species (RNS) (e.g., ·NO and ·NO2) are involved, and highly toxic nitro(so) products such as nitro(so)-phenolics and N-nitrosodimethylamine are generated. For a niche application, the UV/chlorine process is recommended to be utilized in water with low levels of DOM and ammonia.Strategies should be developed to make full use of highly reactive species (RCS and HO·) for the abatement of target contaminants and to reduce the formation of toxic byproducts. For example, the UV/chlorine process can be used in tandem with other treatments to create multiple barriers for the production of safe water. In addition, halogen radicals are very important in ecosystems as well as other areas such as medical therapy and organic synthesis. UV/chlorine is the most efficient homogeneous system to generate halogen radicals, and thus it provides a perfect system to investigate the fates of halogen radicals for interdisciplinary research.
Assuntos
Poluentes Químicos da Água , Purificação da Água , Cloro , Ecossistema , Peróxido de Hidrogênio , Cinética , Oxirredução , Raios Ultravioleta , Poluentes Químicos da Água/análiseRESUMO
Formation of nitrogenous disinfection byproducts from aliphatic amines is a widespread concern owing to the serious health risks associated with them. However, the mechanisms of transforming aliphatic amines and forming nitro products in the UV/chlorine process have rarely been discussed, which are investigated in this work. Initially, secondary amines (R1R2NH) are transformed into secondary organic chloramines (R1R2NCl) via chlorination. Subsequently, radicals, such as HO⢠and Clâ¢, are found to contribute predominantly to such transformations. The rate constants at which HOâ¢, Clâ¢, and Cl2â¢- react with R1R2NCl are (2.4-5.1) × 109, (1.5-3.8) × 109, and (1.2-6.1) × 107 M-1 s-1, respectively. Consequently, R1R2NCl are transformed into primary amines (R1NH2/R2NH2) and chlorinated primary amines (R1NHCl/R2NHCl and R1NCl2/R2NCl2) by excess chlorine. Furthermore, primarily driven by UV photolysis, chlorinated primary amines can be transformed into nitroalkanes with conversion rates of â¼10%. Dissolved oxygen and free chlorine play crucial roles in forming nitroalkanes, and post-chlorination can further form chloronitroalkanes, such as trichloronitromethane (TCNM). Radicals are involved in forming TCNM in the UV/chlorine process. This study provides new insights into the mechanisms of transforming aliphatic amines and forming nitro products using the UV/chlorine process.
Assuntos
Poluentes Químicos da Água , Purificação da Água , Cloro , Poluentes Químicos da Água/análise , Aminas , Halogenação , Desinfecção , Raios UltravioletaRESUMO
Reactive bromine species (RBS) are gaining increasing attention in natural and engineered aqueous systems containing bromide ions (Br-). However, their roles in the degradation of structurally diverse micropollutants by advanced oxidation processes (AOPs) were not differentiated. In this study, the second-order rate constants (k) of Brâ¢, Br2â¢-, BrOâ¢, and ClBrâ¢- were collected and evaluated. Br⢠is the most reactive RBS toward 21 examined micropollutants with k values of 108-1010 M-1 s-1. Br2â¢-, ClBrâ¢-, and BrO⢠are selective for electron-rich micropollutants with k values of 106-108 M-1 s-1. The specific roles of RBS in aqueous micropollutant degradation in AOPs were revealed by using simplified models via sensitivity analysis. Generally, RBS play minimal roles in the UV/H2O2 process but are significant in the UV/peroxydisulfate (PDS) and UV/chlorine processes in the presence of trace Br-. In UV/PDS with ≥1 µM Br-, Br⢠emerges as the major RBS for removing electron-rich micropollutants. In UV/chlorine, BrO⢠contributes to the degradation of specific electron-rich micropollutants with removal percentages of ≥20% at 1 µM Br-, while the contributions of BrO⢠and Br⢠are comparable to those of reactive chlorine species as Br- concentration increases to several µM. In all AOPs, Br2â¢- and ClBrâ¢- play minor roles at 1-10 µM Br-. Water matrix components such as HCO3-, Cl-, and natural organic matter (NOM) significantly inhibit Brâ¢, while BrO⢠is less affected, only slightly scavenged by NOM with a k value of 2.1 (mgC/L)-1 s-1. This study sheds light on the differential roles of multiple RBS in micropollutant abatement by AOPs in Br--containing water.
Assuntos
Poluentes Químicos da Água , Purificação da Água , Bromo , Brometos , Água , Cloro/análise , Peróxido de Hidrogênio , Poluentes Químicos da Água/análise , Raios Ultravioleta , Oxirredução , CloretosRESUMO
The ultraviolet (UV)/chlorine process has attracted increasing attention for micropollutant abatement. However, the limited hydroxyl radical (HOâ¢) generation and the formation of undesired disinfection byproducts (DBPs) are the two major issues in this process. This study investigated the roles of activated carbon (AC) in the UV/chlorine/AC-TiO2 process for micropollutant abatement and DBP control. The degradation rate constant of metronidazole by UV/chlorine/AC-TiO2 was 3.44, 2.45, and 1.58 times higher than those by UV/AC-TiO2, UV/chlorine, and UV/chlorine/TiO2, respectively. AC acted as an electron conductor and dissolved oxygen (DO) adsorbent, resulting in the steady-state concentration of HO⢠that was â¼2.5 times that of UV/chlorine. Compared with UV/chlorine, the formation of total organic chlorine (TOCl) and known DBPs in UV/chlorine/AC-TiO2 was reduced by 62.3 and 75.7%, respectively. DBP could be controlled via adsorption on AC, and the increased HO⢠and decreased chlorine radical (Clâ¢) and chlorine exposure reduced DBP formation. UV/chlorine/AC-TiO2 efficiently abated 16 structurally different micropollutants under environmentally relevant conditions owing to the enhanced generation of HOâ¢. This study provides a new strategy for designing catalysts with photocatalytic and adsorption properties for UV/chlorine to promote micropollutant abatement and DBP control.
Assuntos
Poluentes Químicos da Água , Purificação da Água , Cloro , Carvão Vegetal , Poluentes Químicos da Água/análise , Purificação da Água/métodos , Raios Ultravioleta , Desinfecção , Halogenação , CloretosRESUMO
Nutrient availability significantly regulates plant growth and metabolic functions, but whether and how the long-term exposure of ancestral plants to contrasting nutrient environments influences offspring phenotypic performance (i.e., transgenerational plasticity) remain poorly addressed. Here we conducted experimental manipulations using Arabidopsis thaliana with the ancestral plants grown in different nitrogen (N) and phosphorus (P) availabilities over eleven consecutive generations, and then examined the offspring phenotypic performance under the interactive effects of current and ancestral nutrient environments. We found that current rather than ancestral nutrient environments dominantly explained the variations in offspring plant traits (i.e., flowering time, aboveground biomass and biomass allocation fractions), suggesting the relatively weak transgenerational effects of ancestral N and P availabilities on offspring phenotypes. In contrast, increasing N and P availabilities in the offspring generation remarkably shortened the flowering time, increased the aboveground biomass, and altered biomass allocation fractions differentially among organs. Despite the overall weak transgenerational phenotypic plasticity, under the low nutrient environment, the offspring of ancestral plants from the low nutrient environment had a significantly higher fruit mass fraction than those from the suitable nutrient environment. Taken together, our findings suggest that A. thaliana exhibits a much stronger within- than trans-generational trait plasticity under contrasting nutrient availabilities, and may provide important insights into the understanding of plant adaptation and evolutionary processes under changing nutrient environments.
Assuntos
Arabidopsis , Fósforo , Fósforo/metabolismo , Nitrogênio/metabolismo , Fenótipo , BiomassaRESUMO
Increased nitrogen (N) inputs are widely recognised to reduce soil respiration (Rs), but how N deposition affects the temporal dynamics of Rs remains unclear. Using a decade-long fertilisation experiment in a boreal larch forest (Larix gmelini) in northeast China, we found that the effects of N additions on Rs showed a temporal shift from a positive effect in the short-term (increased by 8% on average in the first year) to a negative effect over the longer term (decreased by 21% on average in the 11th year). The rates of decrease in Rs for the higher N levels were almost twice as high as those of the low N level. Our results suggest that the reduction in Rs in response to increased N input is accelerated by high-level N additions, and experimental high N applications are likely to overestimate the contribution of N deposition to soil carbon sequestration in a boreal forest.
Assuntos
Nitrogênio , Solo , Carbono , Sequestro de Carbono , China , Florestas , Nitrogênio/análise , Respiração , TaigaRESUMO
Nitrogen (N) deposition is known to increase carbon (C) sequestration in N-limited boreal forests. However, the long-term effects of N deposition on ecosystem carbon fluxes have been rarely investigated in old-growth boreal forests. Here we show that decade-long experimental N additions significantly stimulated net primary production (NPP) but the effect decreased with increasing N loads. The effect on soil heterotrophic respiration (Rh) shifted from a stimulation at low-level N additions to an inhibition at higher levels of N additions. Consequently, low-level N additions resulted in a neutral effect on net ecosystem productivity (NEP), due to a comparable stimulating effect on NPP and Rh, while NEP was increased by high-level N additions. Moreover, we found nonlinear temporal responses of NPP, Rh and NEP to low-level N additions. Our findings imply that actual N deposition in boreal forests likely exerts a minor contribution to their soil C storage.
Assuntos
Ecossistema , Nitrogênio , Carbono , Florestas , Nitrogênio/análise , Solo , TaigaRESUMO
The formation of disinfection byproducts (DBPs) during UV/chlorine treatment, especially nitrogenous DBPs, is not well understood. This study investigated the formation mechanisms for dichloroacetonitrile (DCAN) from typical amino compounds during UV/chlorine treatment. Compared to chlorination, the yields of DCAN increase by 88-240% during UV/chlorine treatment from real waters, while the yields of DCAN from amino compounds increase by 3.3-5724 times. Amino compounds with electron-withdrawing side chains show much higher DCAN formation than those with electron-donating side chains. Phenylethylamine, l- phenylalanine, and l-phenylalanyl-l-phenylalanine were selected to represent amines, amino acids, and peptides, respectively, to investigate the formation pathways for DCAN during UV/chlorine treatment. First, chlorination of amines, amino acids, and peptides rapidly forms N-chloramines via chlorine substitution. Then, UV photolysis but not radicals promotes the transformation from N-chloramines to N-chloroaldimines and then to phenylacetonitrile, with yields of 5.4, 51.0, and 19.8% from chlorinated phenylethylamine, l-phenylalanine, and l-phenylalanyl-l-phenylalanine to phenylacetonitrile, respectively. Finally, phenylacetonitrile is transformed to DCAN with conversion ratios of 14.2-25.6%, which is attributed to radical oxidation, as indicated by scavenging experiments and density functional theory calculations. This study elucidates the pathways and mechanisms for DCAN formation from typical amino compounds during UV/chlorine treatment.
Assuntos
Poluentes Químicos da Água , Purificação da Água , Acetonitrilas , Aminoácidos , Cloraminas/química , Cloro/química , Desinfecção , Halogenação , Fenetilaminas , Fenilalanina , Poluentes Químicos da Água/químicaRESUMO
Permanganate [Mn(VII)] has gained broad attention in water treatment. However, its limited reactivity toward some refractory micropollutants hinders its application for micropollutant degradation. Herein, we introduced UVA-LED photolysis of Mn(VII) (UVA-LED/Mn(VII)) to degrade micropollutants (diclofenac (DCF), 4-chlorophenol (4-CP), atrazine, and nitrobenzene) by selecting DCF and 4-CP as target micropollutants. The effects of operating conditions (e.g., light intensity, radiation wavelengths, pH, and water constituents) on DCF and 4-CP degradation as well as the underlying mechanisms were systematically studied. The degradation rates of DCF and 4-CP linearly decreased with increasing radiation wavelengths (from 365 to 405 nm), likely due to the decreased molar absorption coefficients and quantum yields of Mn(VII). Reactive manganese species (RMnS), including Mn(V), Mn(III), and HOâ¢, were generated in the UVA-LED/Mn(VII) process. Mn(V) and HO⢠were responsible for DCF degradation, while Mn(III), HOâ¢, and likely Mn(V) accounted for 4-CP degradation. Competitive kinetic results revealed that contributions of RMnS and HO⢠decreased with increasing radiation wavelengths, wherein RMnS played the dominant role. Increasing pH displayed opposite effects on DCF and 4-CP degradation with higher degradation efficiency obtained at acidic pH for the former one but alkaline pH for the latter one. The presence of water background ions (e.g., Cl-, HCO3-, and Ca2+) barely influenced DCF and 4-CP degradation. Finally, in comparison with Mn(VII) alone, enhanced degradation of DCF and 4-CP by UVA-LED/Mn(VII) was observed in real waters. This work advances the understanding of the photochemistry of manganese species in micropollutant degradation and facilitates Mn(VII) oxidation in practical application.
Assuntos
Poluentes Químicos da Água , Purificação da Água , Manganês , Radical Hidroxila , Óxidos , Compostos de Manganês , Oxirredução , Diclofenaco , Poluentes Químicos da Água/análise , Purificação da Água/métodosRESUMO
Above- and belowground biomass allocation is an essential plant functional trait that reflects plant survival strategies and affects belowground carbon pool estimation in grasslands. However, due to the difficulty of distinguishing living and dead roots, estimation of biomass allocation from field-based studies currently show large uncertainties. In addition, the dependence of biomass allocation on plant species, functional type as well as plant density remains poorly addressed. Here, we conducted greenhouse manipulation experiments to study above- and belowground biomass allocation and its density regulation for six common grassland species with different functional types (i.e., C3 vs C4; annuals vs perennials) from temperate China. To explore the density regulation on the biomass allocation, we used five density levels: 25, 100, 225, 400, and 625 plant m-2. We found that mean root to shoot ratio (R/S) values ranged from 0.04 to 0.92 across the six species, much lower than those obtained in previous field studies. We also found much lower R/S values in annuals than in perennials (C. glaucum and S. viridis vs C. squarrosa, L. chinensis, M. sativa and S. grandis) and in C4 plants than in C3 plants (C. squarrosa vs L. chinensis, M. sativa and S. grandis). In addition to S. grandis, plant density had significant effects on the shoot and root biomass fraction and R/S for the other five species. Plant density also affected the allometric relationships between above- and belowground biomass significantly. Our results suggest that R/S values obtained from field investigations may be severely overestimated and that R/S values vary largely across species with different functional types. Our findings provide novel insights into approximating the difficult-to-measure belowground living biomass in grasslands, and highlight that species composition and intraspecific competition will regulate belowground carbon estimation.
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Pradaria , Plantas , Biomassa , Carbono , China , Ecossistema , Raízes de PlantasRESUMO
UV irradiation and chlorination have been widely used for water disinfection. However, there are some limitations, such as the risk of generating viable but nonculturable bacteria and bacteria reactivation when using UV irradiation or chlorination alone. This study comprehensively evaluated the feasibility of the UV/chlorine process in drinking water disinfection, and Pseudomonas aeruginosa was selected as the target microorganism. The number of culturable cells was effectively reduced by more than 5 orders of magnitude (5-log10) after UV, chlorine, and UV/chlorine treatments. However, intact and VBNC cells were detected at 103 to 104 cells/mL after UV and chlorine treatments, whereas they were undetectable after UV/chlorine treatment due to the primary contribution of reactive chlorine species (Clâ¢, Cl2â¢-, and ClOâ¢). After UV/chlorine treatment, the metabolic activity determined using single cell Raman spectroscopy was much lower than that after UV. The level of toxic opr gene in P. aeruginosa decreased by more than 99% after UV/chlorine treatment. Importantly, bacterial dark reactivation was completely suppressed by UV/chlorine treatment but not UV or chlorination. This study suggests that the UV/chlorine treatment can completely damage bacteria and is promising for pathogen inactivation to overcome the limitations of UV and chlorine treatments alone.