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Pilot Microbial Electrolysis Cell Closes the Hydrogen Loop for Hydrothermal Wet Waste Conversion to Jet Fuel 中试微生物电解池为水热法将湿垃圾转化为喷气燃料建立了氢回路
IF 12.8 1区 环境科学与生态学 Q1 ENGINEERING, ENVIRONMENTAL Pub Date : 2024-10-16 DOI: 10.1016/j.watres.2024.122644
Jinyue Jiang, Lin Du, Buchun Si, Harshal D. Kawale, Zixin Wang, Sabrina Summers, Juan A. Lopez-Ruiz, Shuyun Li, Yuanhui Zhang, Zhiyong Jason Ren
The global shift toward net-zero emissions necessitates resource recovery from wet waste. In this study, we demonstrate the first feasibility of combining pilot-scale microbial electrolytic cells (MECs) with hydrothermal liquefaction (HTL) for simultaneous post-hydrothermal liquefaction wastewater (PHW) treatment and efficient hydrogen (H₂) production to meet biocrude upgrading requirements. Long-term single reactor operation revealed that fixed anode potential enabled rapid startup, and low catholyte pH and high salinity were effective in suppression of cathodic methanogenesis and acetogenesis – resulting in high current density of 16.6 A m−2 and 9.3 A m−2 when feeding synthetic wastewater and PHW respectively. Additionally, the anode biofilm exhibited spatial variations in response to local environmental conditions. Onsite parallel or serial operations of multiple MECs showed good performance using actual PHW with a record-high H2 production rate of 0.5 L LR day−1 for MEC over 10 liters scale, and the optimal chemical oxygen demand (COD)-to-H2 yield reached 0.127 kg-H2 per kg-COD, supporting a self-sufficient, closed-loop upgrade to jet fuel.
全球向净零排放的转变需要从湿废物中回收资源。在这项研究中,我们首次证明了将中试规模的微生物电解池(MECs)与水热液化(HTL)相结合,同时进行水热液化后废水(PHW)处理和高效制氢(H₂)以满足生物原油升级要求的可行性。长期的单反应器运行表明,固定阳极电位可实现快速启动,而低阴极溶液 pH 值和高盐度则可有效抑制阴极甲烷生成和乙酰生成--从而在注入合成废水和 PHW 时分别产生 16.6 A m-2 和 9.3 A m-2 的高电流密度。此外,阳极生物膜还表现出空间变化,以应对当地的环境条件。多个 MEC 的现场并行或串行运行显示出使用实际 PHW 的良好性能,10 升以上规模的 MEC 的 H2 产率达到创纪录的 0.5 LR day-1,最佳化学需氧量 (COD) 转化为 H2 的产率达到 0.127 kg-H2/kg-COD,支持自给自足、闭环升级为喷气燃料。
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引用次数: 0
Different patterns of bacterioplankton in response to inorganic and organic phosphorus inputs in freshwater lakes - a microcosmic study 淡水湖中浮游细菌对无机磷和有机磷输入的不同反应模式--一项微观世界研究
IF 12.8 1区 环境科学与生态学 Q1 ENGINEERING, ENVIRONMENTAL Pub Date : 2024-10-16 DOI: 10.1016/j.watres.2024.122645
Tianhong Tu, Le Li, Wenkai Li, Shan Zhang, Hui Zhong, Gang Ge, Lan Wu, Yantian Ma
Phosphorus (P) is a limiting factor in fresh waters and is also the main cause of water eutrophication and deterioration, However, the practical effect of elevated P level on bacterioplankton is less evaluated. In this study, we investigated the bacterioplankton in a 96 hours microcosm experiment with P additions in two forms (organic/inorganic P, OP/IP) and three levels (final conc., 0.040, 0.065 and 0.125 g/L), aiming to find out the response pattern of bacterioplankton in coping with the increasing P levels. Results showed a more dramatic change of water properties and bacterioplankton between P forms (OP and IP) than among the addition levels, and a more remarkable effect of OP addition than the IP. Both OP and IP treatments significantly decreased the water pH, dissolved oxygen (DO), Electrical Conductivity (EC), Nitrate Nitrogen (NO3--N) and Total Organic Carbon (TOC), and reduced the α-diversity of bacterioplankton and relative abundance of Cyanobacteria, but increased the abundance of Proteobacteria. The IP addition decreased Actinobacteria abundance (especially for HgcI) and showed higher denitrification potentials, while the OP addition depressed the Bateroidota and exhibited lowed methylotrophic functions, but such trends decreased with increasing addition concentrations. The network analysis showed that both IP and OP additions increased the proportion of positively correlated edges and reduced the network complexity and stability, but the OP network was more stable than the IP network. The study clarifies the response pattern of bacterioplankton to the P input with different forms and levels, and deepens our understanding of the eutrophication process, which provides a scientific basis for the management and control of freshwater lakes facing eutrophication.
磷(P)是淡水中的限制因子,也是水体富营养化和恶化的主要原因。在本研究中,我们在一个 96 小时的微观世界实验中,以两种形式(有机/无机磷,OP/IP)和三种水平(最终浓度,0.040、0.065 和 0.125 克/升)添加磷,对浮游细菌进行了调查,旨在找出浮游细菌在应对磷含量增加时的反应模式。结果表明,不同磷形式(OP 和 IP)之间水质和浮游细菌的变化比不同添加水平之间的变化更剧烈,OP 的添加效果比 IP 更显著。OP 和 IP 处理都明显降低了水的 pH 值、溶解氧(DO)、电导率(EC)、硝酸盐氮(NO3--N)和总有机碳(TOC),减少了浮游细菌的α-多样性和蓝藻的相对丰度,但增加了变形菌的丰度。添加 IP 会降低放线菌的丰度(尤其是 HgcI),并显示出较高的反硝化潜力,而添加 OP 则会抑制类蝠鲼的生长,并显示出较低的养甲功能,但这种趋势会随着添加浓度的增加而减弱。网络分析显示,添加 IP 和 OP 都增加了正相关边的比例,降低了网络的复杂性和稳定性,但 OP 网络比 IP 网络更稳定。该研究阐明了不同形式和水平的浮游细菌对P输入的响应模式,加深了对富营养化过程的认识,为面临富营养化的淡水湖泊的管理和控制提供了科学依据。
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引用次数: 0
Deciphering the impact of cascade reservoirs on nitrogen transport and nitrate transformation: Insights from multiple isotope analysis and machine learning 解密级联水库对氮迁移和硝酸盐转化的影响:多同位素分析和机器学习的启示
IF 12.8 1区 环境科学与生态学 Q1 ENGINEERING, ENVIRONMENTAL Pub Date : 2024-10-16 DOI: 10.1016/j.watres.2024.122638
Yufei Bao, Yuchun Wang, Mingming Hu, Peng Hu, Nanping Wu, Xiaodong Qu, Xiaobo Liu, Wei Huang, Jie Wen, Shanze Li, Meng Sun, Qian Zhang
Construction of cascade reservoirs has altered nutrient dynamics and biogeochemical cycles, thereby influencing the composition and productivity of river ecosystems. The Lancang River (LCR), characterized by its cascade reservoir system, presents uncertainties in nitrogen transport and nitrate transformation mechanisms. Herein, we conducted monthly monitoring of hydrochemistry and multiple stable isotopes (δ15N-NO3-, δ18O-NO3-, δ18O-H2O, δD-H2O) throughout 2019 in both the natural river reach (NRR) and cascade reservoirs reach (CRR) of the LCR. Through the monthly detection of nitrogen forms and runoff in the import (M2) and export (M9) section, the average annual retention ratios for Total nitrogen (TN), Nitrate nitrogen (NO3--N), Particulate Nitrogen (PN) and Ammonium Nitrogen (NH4+-N) were about -35%, -53%, 48% and -65%, respectively. The retention rates were positively correlated with hydraulic retention time and negatively correlated with reservoir age, especially in the flood season. Compared to the NRR, the reservoir had significantly affected the nitrogen transport characteristics, especially for the large reservoirs (like Xiaowan and Nuozhadu), which enhanced phytoplankton uptake of NO3--N to form PN capabilities in the lentic environment and subsequently to precipitate or intercept it at the reservoir. This led to the overall decreasing trend of TN and PN concentrations along the CRR. The Bayesian stable isotope model quantified NO3--N sources from the NRR to the CRR. During this transition, soil nitrogen (SN) ratios decreased from 69.3% to 61.8%, while Manure & sewage (M&S) increased from 24.0% to 31.3%. Anthropogenic and natural factors, including urban sewage discharge, population density, and precipitation, were selected as key predictor variables. The eXtreme Gradient Boosting (XGBoost) model exhibited superior predictive performance for NO3--N concentrations, achieving an R2 of 0.70. These findings deepen our understanding of the impact of reservoirs on river ecology.
梯级水库的建设改变了养分动力学和生物地球化学循环,从而影响了河流生态系统的组成和生产力。以梯级水库系统为特征的澜沧江(LCR)在氮迁移和硝酸盐转化机制方面存在不确定性。在此,我们对澜沧江天然河段(NRR)和梯级水库河段(CRR)进行了水化学和多种稳定同位素(δ15N-NO3-、δ18O-NO3-、δ18O-H2O、δD-H2O)的月度监测。通过对进口段(M2)和出口段(M9)氮形态和径流的月度检测,总氮(TN)、硝酸盐氮(NO3--N)、颗粒氮(PN)和铵态氮(NH4+-N)的年均滞留率分别约为-35%、-53%、48%和-65%。滞留率与水力滞留时间呈正相关,与库龄呈负相关,尤其是在汛期。与泥沙淤积率相比,水库对氮迁移特性有明显的影响,尤其是大型水库(如小湾水库和糯扎渡水库),它增强了浮游植物吸收 NO3-N 在湖泊环境中形成 PN 的能力,并随后在水库中沉淀或拦截。这就导致了中沙河沿岸 TN 和 PN 浓度的总体下降趋势。贝叶斯稳定同位素模型量化了从北回归线到中游河段的 NO3-N 来源。在这一转变过程中,土壤氮(SN)比率从69.3%下降到61.8%,而粪便和污水(M&S)比率从24.0%上升到31.3%。人类活动和自然因素,包括城市污水排放、人口密度和降水量,被选为关键的预测变量。极端梯度提升(XGBoost)模型在预测 NO3-N 浓度方面表现出色,R2 达到 0.70。这些发现加深了我们对水库对河流生态影响的理解。
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引用次数: 0
Catalytic Oxidation of Mn(II) in the Co-presence of Fe(II) by Free Chlorine: Significance of In Situ Formed Mn(II)-Doped Fe(III) Oxides 游离氯在铁(II)共存下催化氧化锰(II):原位形成的掺杂锰(II)的铁(III)氧化物的意义
IF 12.8 1区 环境科学与生态学 Q1 ENGINEERING, ENVIRONMENTAL Pub Date : 2024-10-15 DOI: 10.1016/j.watres.2024.122630
Xuecong Qian, Shilong Wang, Haijun Cheng, Luwei Li, Yun Liu, Jinhao Duan, Da Wang, Jun Ma
Fe(II) and Mn(II) are abundant in groundwater and require operationally simple and efficient method to remove in drinking water treatment. The rapid oxidation of Mn(II) is essential in water treatment. This study investigates the efficiency of Mn(II) oxidation by free chlorine in the presence of Fe(II). The results demonstrate that the presence of Fe(II) significantly accelerates the oxidation rate of Mn(II) by free chlorine under neutral and alkaline conditions. The rapid oxidation of Fe(II) by free chlorine and the presence of Mn(II) promote the formation of in situ Mn(II)-doped ferrihydrite. Kinetic modeling and characterization of Fe(III) oxides confirm that the heterogeneous catalytic effect of the Mn(II)-doped ferrihydrite, rather than manganese oxides or their coupled catalytic effect, is responsible for the enhanced oxidation rates. The doped Mn(II) substitutes the tetrahedral Fe(III) ions in the ferrihydrite, introducing additional negative charges at the doped sites. The increased charge enhances Mn(II) adsorption and lowers its redox potential, thereby accelerating Mn(II) oxidation rate through direct electron transfer with adjacent free chlorine. Additionally, the lepidocrocite formed by the reaction between Fe(II) and dissolved oxygen significantly impedes the catalytic performance. These findings provide new insights into the catalytic co-oxidation mechanism of Fe(II) and Mn(II), and help the optimization of water treatment engineering practices.
地下水中含有大量的铁(II)和锰(II),在饮用水处理中需要操作简单、高效的去除方法。Mn(II) 的快速氧化在水处理中至关重要。本研究调查了游离氯在铁(II)存在下氧化锰(II)的效率。结果表明,在中性和碱性条件下,Fe(II) 的存在会明显加快游离氯氧化 Mn(II) 的速度。游离氯对 Fe(II) 的快速氧化和 Mn(II) 的存在促进了原位掺杂 Mn(II) 的铁水物的形成。动力学模型和铁(III)氧化物的表征证实,掺杂锰(II)的铁酸盐的异相催化作用,而不是锰氧化物或它们的耦合催化作用,是氧化速率提高的原因。掺杂的 Mn(II) 取代了铁酸盐中的四面体 Fe(III) 离子,在掺杂位点上引入了额外的负电荷。增加的电荷增强了对 Mn(II)的吸附并降低了其氧化还原电位,从而通过与邻近游离氯的直接电子转移加快了 Mn(II)的氧化速率。此外,Fe(II) 与溶解氧反应形成的鳞片二茂铁会严重影响催化性能。这些发现为了解铁(II)和锰(II)的催化协同氧化机理提供了新的视角,有助于优化水处理工程实践。
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引用次数: 0
Cooperation of rhamnolipid and thermophilic bacteria modifies proteinic structure, microbial community, and metabolic traits for efficient solubilization and acidogenesis of mariculture solid wastes 鼠李糖脂与嗜热菌的合作改变了蛋白质结构、微生物群落和代谢特征,从而实现了海产养殖固体废物的高效溶解和酸化
IF 12.8 1区 环境科学与生态学 Q1 ENGINEERING, ENVIRONMENTAL Pub Date : 2024-10-15 DOI: 10.1016/j.watres.2024.122634
Hutao Wang, Dongxu Xing, Chunji Jin, Yangguo Zhao, Liang Guo
Anaerobic fermentation combined with thermophilic bacteria (TB) pretreatment is a promising method to realize effective waste management and carbon resource recovery. However, undesirable properties of high-strength mariculture solid wastes (MSW) such as high solids concentration, excessive salinity and poor bioavailability limited the overall solubilization and acidogenic efficiency. This study innovatively introduced rhamnolipid (RL) to alleviate this adverse effect, and unveiled its cooperation with TB on enhancing organic matter dissolution and volatile fatty acids (VFAs) production. The results showed that VFAs yield from pretreated MSW was improved by 9.4-15.1 folds with enriched acetate (81.4%-94.4%) in the TB+RL groups. The co-pretreatment of RL and TB disintegrated substrate structure for efficient release of electron shuttles and biodegradable organics. This was because introducing RL reconstructed solid-liquid interfacial charge and molecular arrangement, improved thermophilic enzyme activity, and reduced apoptosis and necrosis cells of TB. Substrate bioavailability was further improved with proteinic structure shifted from α-helix and β-sheet to random coil and aggregated strands, and amide II and carboxyl groups interacted with RL molecules. These changes induced the selective enrichment of hydrolytic and acidogenic bacteria, and the upregulated expression of encoding genes responsible for transmembrane transport, protein hydrolysis, carbohydrate metabolism and acetate biosynthesis. This study provides a new strategy to overcome the bottlenecks of acidogenesis from high-strengthen organic wastes and deciphers the underlying mechanism.
厌氧发酵结合嗜热菌(TB)预处理是实现有效废物管理和碳资源回收的一种可行方法。然而,高强度海产养殖固体废物(MSW)的不良特性,如固体浓度高、盐度过高和生物利用率低等,限制了其整体增溶和产酸效率。本研究创新性地引入鼠李糖脂(RL)来缓解这一不利影响,并揭示了鼠李糖脂与 TB 在提高有机物溶解和挥发性脂肪酸(VFAs)产量方面的合作。结果表明,在 TB+RL 组中,经预处理的 MSW 的挥发性脂肪酸产量提高了 9.4-15.1 倍,富含醋酸盐(81.4%-94.4%)。RL 和 TB 的联合预处理可以分解基质结构,从而有效释放电子梭子和可生物降解的有机物。这是因为引入 RL 重建了固液界面电荷和分子排列,提高了嗜热酶的活性,减少了 TB 细胞的凋亡和坏死。随着蛋白质结构从 α 螺旋和 β 片转变为无规线圈和聚合链,以及酰胺 II 和羧基与 RL 分子的相互作用,底物的生物利用率进一步提高。这些变化诱导了水解菌和产酸菌的选择性富集,以及跨膜转运、蛋白质水解、碳水化合物代谢和醋酸生物合成等编码基因的表达上调。这项研究为克服高强度有机废物产酸的瓶颈问题提供了一种新策略,并揭示了其内在机理。
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引用次数: 0
Macrogenomic analysis of tolerance and degradation mechanisms of polycyclic aromatic hydrocarbon in carbon and nitrogen metabolic pathways and associated bacterial communities during endogenous partial denitrification 内源部分脱氮过程中多环芳烃在碳氮代谢途径和相关细菌群落中的耐受性和降解机制的宏基因组分析
IF 12.8 1区 环境科学与生态学 Q1 ENGINEERING, ENVIRONMENTAL Pub Date : 2024-10-15 DOI: 10.1016/j.watres.2024.122628
Baodan Jin, Ye Liu, Fukun Zhao, Yeyu Yan, Zhixuan Bai, Jingjing Du, Yuanqian Xu, Chuang Ma, Jiantao Ji
The effective production of NO2-N through endogenous partial denitrification (EPD) provides a promising perspective for the broader adoption and application of anaerobic ammonia oxidation. However, the accumulation of polycyclic aromatic hydrocarbons (PAHs) in the environment may worsen the operational challenges of the EPD system. This study evaluated the resilience of the EPD system to the toxic impacts of phenanthrene (PHE) and anthracene (ANT) through macrogenomic analysis. A control group was maintained under identical conditions for comparison. The results revealed that PHE and ANT had a relatively minimal impact on NO3-N transformation and organic matter removal but significantly affected PO43−-P removal and NO2-N accumulation in the EPD process. The PHE system achieved a higher NO2-N accumulation, with a maximum NO3-N to NO2-N conversion ratio of 90.08%. In contrast, the ANT system exhibited higher efficiency in the PO43−-P removal, achieving a peak removal rate of 74.94%. Macrogenomic analysis revealed that PAHs significantly enriched both denitrifying glycogen-accumulating organisms (including Candidatus_Competibacter) and denitrifying polyphosphate-accumulating organisms (such as Thauera, Candidatus_Contendobacter, and Candidatus_Accumulibacter). This enrichment stabilized these organisms, facilitating NO2-N accumulation and PO43−-P removal. Metabolic pathway analysis indicated that PHE promoted the enrichment of NO3-N reductase and inhibited NO2-N reductase activity. However, ANT stimulated oxidative phosphorylation and the phosphate cycle. Moreover, PAH metabolites enhanced the expression of key genes encoding succinate dehydrogenase and isocitrate dehydrogenase in the tricarboxylic acid cycle within the EPD process, leading to increase the synthesis and utilization of acetyl coenzyme-A. Notably, significant differences were observed between the effects of PHE and ANT on these metabolic processes. This study provides new methods for treating PAH-containing wastewater through the combination of EPD and anaerobic ammonia oxidation.
通过内源部分反硝化作用(EPD)有效地产生氮氧化物(NO2--N),为更广泛地采用和应用厌氧氨氧化技术提供了一个前景广阔的前景。然而,环境中多环芳烃(PAHs)的积累可能会加剧 EPD 系统的运行挑战。本研究通过宏基因组分析评估了 EPD 系统对菲(PHE)和蒽(ANT)毒性影响的适应能力。同时还在相同条件下保留了一个对照组进行比较。结果表明,PHE 和 ANT 对 NO3-N 转化和有机物去除的影响相对较小,但对 EPD 过程中 PO43-P 的去除和 NO2-N 的积累有显著影响。PHE 系统实现了更高的 NO2-N 积累,NO3-N 与 NO2-N 的最大转化率为 90.08%。相比之下,ANT 系统对 PO43-P 的去除效率更高,达到了 74.94% 的峰值去除率。宏基因组分析表明,多环芳烃显著富集了反硝化糖原累积型生物(包括Competibacter念珠菌)和反硝化聚磷酸酯累积型生物(如Thauera、Contendobacter念珠菌和Accumulibacter念珠菌)。这种富集稳定了这些生物,促进了 NO2-N 的积累和 PO43-P 的去除。代谢途径分析表明,PHE促进了NO3--N还原酶的富集,抑制了NO2--N还原酶的活性。然而,ANT能刺激氧化磷酸化和磷酸循环。此外,多环芳烃代谢物还能增强 EPD 过程中三羧酸循环中编码琥珀酸脱氢酶和异柠檬酸脱氢酶的关键基因的表达,从而增加乙酰辅酶 A 的合成和利用。值得注意的是,PHE 和 ANT 对这些代谢过程的影响存在明显差异。这项研究为通过结合 EPD 和厌氧氨氧化处理含 PAH 废水提供了新方法。
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引用次数: 0
Riverine connectivity modulates elemental fluxes through a 200- year period of intensive anthropic change in the Magdalena River floodplains, Colombia 哥伦比亚马格达莱纳河冲积平原 200 年人类活动剧烈变化期间河流连通性对元素通量的调节作用
IF 12.8 1区 环境科学与生态学 Q1 ENGINEERING, ENVIRONMENTAL Pub Date : 2024-10-15 DOI: 10.1016/j.watres.2024.122633
Jorge Salgado, Camila Jaramillo-Monroy, Andrés Link, Laura Lopera, Maria I. Velez, Catalina Gonzalez-Arango, Handong Yang, Virginia N. Panizzo, Suzanne McGowan
Tropical floodplain lakes are increasingly impacted by human activities, yet their pathways of spatial and temporal degradation, particularly under varying hydrological connectivity regimes and climate change, remain poorly understood. This study examines surface-sediment samples and 210Pb-dated sediment cores from six floodplain lakes, representing a gradient in hydrological connectivity in the lower Magdalena River Basin, Colombia. We analysed temporal and spatial variations in several sediment biogeochemical indicators: the concentration and flux of nutrients, heavy metals, and organic matter (OM), and redox conditions, flooding and erosion. Multiple factor analysis (MFA) of surface-sediments identified redox conditions, OM, flooding, heavy metals and lake connectivity as the main contributors to spatial variability within- and between-lakes sediments, accounting for 48% of the total variation. Additionally, no clear distinction was found between littoral and open-water sediment characteristics. Isolated lakes sediments exhibited reductive conditions rich in OM and nutrients, whereas connected lakes sediments showed greater heavy metal enrichment and higher concentrations of coarse river-fed material. Generalised additive models identified significant changes in the biogeochemical indicators since the late 1800s, that accelerated post-1980s. Shifts in OM, erosion, flooding, redox conditions, land-cover change, heavy metals and climate were identified by MFA as the main drivers of change, explaining 60%-71% of the variation in the connected lakes and 53%-72% in the isolated lakes. Post-1980s, connected lakes transitioned from conditions of higher accumulation of OM and little erosion to higher accumulation of heavy metals and river-fed material. Conversely, isolated lakes, shifted from detrital-heavy metal-rich sediments to OM-, and nutrient-rich, reductive sediments. Sedimentation rates also surged post-1980s, particularly in highly connected lakes, from 0.14 ± 0.07 g cm² yr⁻¹ to 0.5 ± 0.5 g cm² yr⁻¹, with elevated fluxes of metals, OM and nutrients. These changes in sediment biogeochemistry align with deforestation, river regulation and prolonged dry periods, highlighting the complexities behind establishing reliable reference conditions for pollution assessments in large, human-impacted tropical river systems.
热带洪泛平原湖泊正日益受到人类活动的影响,但人们对其空间和时间退化的途径,尤其是在不同的水文连通性机制和气候变化条件下的退化途径,仍然知之甚少。本研究考察了哥伦比亚马格达莱纳河流域下游代表水文连通性梯度的六个洪泛平原湖泊的表层沉积物样本和 210Pb 时间沉积物岩心。我们分析了几种沉积物生物地球化学指标的时空变化:营养物质、重金属和有机物(OM)的浓度和通量,以及氧化还原条件、洪水和侵蚀。表层沉积物的多因素分析(MFA)发现,氧化还原条件、OM、洪水、重金属和湖泊连通性是造成湖内和湖间沉积物空间变化的主要因素,占总变化的 48%。此外,沿岸沉积物特征与开阔水域沉积物特征之间没有明显区别。孤立湖泊的沉积物表现出富含 OM 和营养物质的还原性条件,而相连湖泊的沉积物则表现出更高的重金属富集度和更高的河流馈入粗物质浓度。广义加性模型发现,自 19 世纪末以来,生物地球化学指标发生了显著变化,这种变化在 20 世纪 80 年代后加速。多元回归分析法认为,OM、侵蚀、洪水、氧化还原条件、土地覆盖变化、重金属和气候的变化是导致变化的主要原因,可解释相连湖泊中 60%-71% 的变化,以及孤立湖泊中 53%-72% 的变化。20 世纪 80 年代后,相连湖泊从较高的 OM 积累和较少的侵蚀条件过渡到较高的重金属积累和河流饵料条件。与此相反,孤立湖泊则从富含碎屑重金属的沉积物转变为富含 OM 和营养物质的还原性沉积物。20 世纪 80 年代后,沉积速率也急剧上升,尤其是在高度连通的湖泊中,从 0.14 ± 0.07 g cm² yr-¹ 上升到 0.5 ± 0.5 g cm² yr-¹,金属、OM 和营养物质的通量也随之增加。沉积物生物地球化学的这些变化与森林砍伐、河流调节和长期干旱有关,凸显了在受人类影响的大型热带河流系统中建立可靠的污染评估参考条件的复杂性。
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引用次数: 0
Characterization of Natural and Anthropogenic Dissolved Organic Matter in the Yangtze River Basin Using FT-ICR MS 利用 FT-ICR MS 分析长江流域天然和人为溶解有机物的特征
IF 12.8 1区 环境科学与生态学 Q1 ENGINEERING, ENVIRONMENTAL Pub Date : 2024-10-15 DOI: 10.1016/j.watres.2024.122636
Cuiping Ning, Shuai Sun, Yuan Gao, Huaijun Xie, Lidong Wu, Haijun Zhang, Jiping Chen, Ningbo Geng
Dissolved organic matter (DOM) is a complex mixture that plays a crucial role in global carbon cycling and climate dynamics. Understanding the chemical composition of DOM is crucial for studying its biogeochemical behavior. However, identifying individual DOM molecules is challenging. Here, using ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry and an in-house database, we developed a framework to investigate DOM characteristics in natural water. Through the developed approach, we successfully identified thousands of individual DOM molecules in the water bodies of the Yangtze River Basin. For the first time, the proportions of natural and anthropogenic organics within DOM were revealed. In total, 9557 unambiguous molecular formulas were assigned to DOM in the Yangtze River Basin. The proportions of CHNO and CHOS compounds increased from upstream to downstream regions. Moreover, 1099 DOM compounds were tentatively identified, with 85% being endogenous organics and 15% being exogenous organics. Notably, lipids and pharmaceuticals and personal care products were the most frequently detected endogenous and exogenous compounds. The spatial variation of the identified DOM indicated anthropogenic discharges considerably increased both the number and abundance of DOM in the downstream Yangtze River Basin. This study highlighted the importance of anthropogenic impacts on DOM in water.
溶解有机物(DOM)是一种复杂的混合物,在全球碳循环和气候动力学中发挥着至关重要的作用。了解 DOM 的化学成分对研究其生物地球化学行为至关重要。然而,识别单个 DOM 分子具有挑战性。在此,我们利用超高分辨率傅立叶变换离子回旋共振质谱仪和内部数据库,开发了一种研究天然水中 DOM 特征的框架。通过所开发的方法,我们成功鉴定了长江流域水体中成千上万个独立的 DOM 分子。首次揭示了 DOM 中天然有机物和人为有机物的比例。共为长江流域的 DOM 分配了 9557 个明确的分子式。从上游到下游,CHNO 和 CHOS 化合物的比例有所增加。此外,还初步鉴定出 1099 种 DOM 化合物,其中 85% 为内源有机物,15% 为外源有机物。值得注意的是,脂类和药物及个人护理产品是最常检测到的内源和外源化合物。已鉴定 DOM 的空间变化表明,人为排放大大增加了长江下游流域 DOM 的数量和丰度。这项研究强调了人为因素对水中 DOM 影响的重要性。
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引用次数: 0
Picolinic acid promotes organic pollutants removal in Fe(III)/periodate process: Mechanism and relationship between removal efficiency and pollutant structure 苦味酸在铁(III)/过碘酸过程中促进有机污染物的去除:机理以及去除效率与污染物结构之间的关系
IF 12.8 1区 环境科学与生态学 Q1 ENGINEERING, ENVIRONMENTAL Pub Date : 2024-10-15 DOI: 10.1016/j.watres.2024.122631
Jiansen Lei, Linjie Ding, Yangju Li, Xiang Li, Siyuan Pan, Dapeng Wu, Kai Jiang
The application of Fe-catalyzed periodate (PI) processes is often limited by both the narrow applicable pH range and weak reaction between Fe(III) and oxidant. Here, the biodegradable picolinic acid (PICA) was used as one kind of chelating ligands (CLs) to enhance the removal of organic pollutants (OPs) at initial pH 3.0−8.0, which displayed superior properties than the other CLs in Fe(III)/PI process. The dominant reactive species produced in the Fe(III)-PICA/PI process turned out to be high-valent iron-oxo (FeIV=O) species and hydroxyl radical (OH) by quenching, sulfoxide probe transformation, and 18O isotope-labeling tests. The relative contribution of FeIV=O and OH was dependent on OPs ionization potential (IP) and energy gap (ΔE). The degradation of OPs was also directly associated with their structure, the apparent rate constants correlated well with the highest occupied molecular orbital energy (EHOMO), IP, and ΔE, and among them ΔE had a greater effect. Furthermore, Fe(III)-PICA complexes displayed excellent long-term effectiveness for OPs removal in actual water matrixes, along with the non-toxic conversion of PI, indicating a broad application perspective of Fe(III)-PICA/PI process. This study provides an efficient method to improve the performance of Fe(III)/PI process and reveals the mechanism and relationship between removal efficiency and pollutant structure.
铁催化高碘酸盐(PI)工艺的应用往往受到适用 pH 值范围窄和铁(III)与氧化剂反应弱的限制。本文采用可生物降解的吡啶甲酸(PICA)作为一种螯合配体(CLs),在初始 pH 值为 3.0-8.0 的条件下增强对有机污染物(OPs)的去除,在 Fe(III)/PI 过程中显示出优于其他 CLs 的特性。通过淬灭、亚砜探针转化和 18O 同位素标记测试,Fe(III)-PICA/PI 过程中产生的主要反应物是高价铁氧自由基(FeIV=O)和羟自由基(-OH)。FeIV=O 和 -OH 的相对贡献取决于 OPs 的电离势(IP)和能隙(ΔE)。OPs 的降解也与其结构直接相关,表观速率常数与最高占据分子轨道能(EHOMO)、IP 和 ΔE 有很好的相关性,其中 ΔE 的影响更大。此外,Fe(III)-PICA 复合物对实际水基质中 OPs 的去除显示出卓越的长期有效性,同时 PI 的转化也是无毒的,这表明 Fe(III)-PICA/PI 工艺具有广阔的应用前景。本研究为提高 Fe(III)/PI 工艺的性能提供了一种有效的方法,并揭示了去除效率与污染物结构之间的机理和关系。
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引用次数: 0
A single-atom manganese nanozyme mediated membrane reactor for water decontamination 用于水净化的单原子锰纳米酶介导膜反应器
IF 12.8 1区 环境科学与生态学 Q1 ENGINEERING, ENVIRONMENTAL Pub Date : 2024-10-13 DOI: 10.1016/j.watres.2024.122627
Jiahao Sun, Minjia Yan, Guangdong Tao, Runbin Su, Xuanming Xiao, Qiangshun Wu, Feng Chen, Xi-Lin Wu, Hongjun Lin
Single-atom nanozymes possess high catalytic activity and selectivity, and are emerging as advanced heterogeneous catalysts for environmental applications. Herein, we present the innovative synthesis and characterization of a single-atom manganese-doped carbon nitride (SA-Mn-CN) nanozyme, integrated into a polyvinylidene fluoride (PVDF) membrane for advanced water treatment applications. The SA-Mn-CN nanozyme demonstrates high peroxidase-like activity, efficiently catalyzing the oxidation of 3,3’,5,5’-tetramethylbenzidine (TMB) and generating reactive oxygen species (ROS) for effective antibacterial action. Notably, the SA-Mn-CN/PVDF membrane showcases enhanced water permeability, superior antifouling properties, and ultra-fast degradation kinetics of organic pollutants. Mechanistic studies reveal that the nanozyme selectively generates Mn(IV)-oxo species via peroxymonosulfate (PMS) activation, crucial for the efficient oxidation processes. Our integrated membrane system effectively removes (within 1 min, > 92% removal) a variety of organic micropollutants in continuous-flow operations, demonstrating excellent stability and minimal manganese leaching. Compared to conventional advanced oxidation process (AOPs)/membrane system, the SA-Mn-CN/PVDF/PMS system holds the advantages of high catalytic activity and selectivity for generation of reactive species, wide working pH range (pH3-11) and excellent stability and reusability under the backwashing conditions. The developed device-scale AOPs/membrane system was proven to be effective in bacterial inactivation and pollutants degradation, verifying the vast application potential of the SA-Mn-CN/PVDF membrane for practical water decontamination. This work pioneers the development of enzyme-mimicking nanozyme membranes, offering a sustainable and high-performance solution for wastewater treatment, and sets a new benchmark for the design of nanozyme-based catalytic membranes in environmental applications.
单原子纳米酶具有高催化活性和选择性,正在成为环境应用领域的先进异相催化剂。在本文中,我们介绍了单原子锰掺杂氮化碳(SA-Mn-CN)纳米酶的创新合成和表征,并将其集成到聚偏二氟乙烯(PVDF)膜中,用于先进的水处理应用。SA-Mn-CN 纳米酶具有很高的过氧化物酶样活性,能有效催化 3,3',5,5'-四甲基联苯胺(TMB)的氧化,并产生活性氧(ROS),从而有效抗菌。值得注意的是,SA-Mn-CN/PVDF 膜具有更强的透水性、优异的防污性能和超快的有机污染物降解动力学。机理研究表明,纳米酶通过过氧单硫酸盐(PMS)活化选择性地生成锰(IV)-氧物种,这对高效氧化过程至关重要。我们的集成膜系统可在连续流操作中有效去除(1 分钟内,去除率达 92%)各种有机微污染物,并表现出卓越的稳定性和极低的锰浸出率。与传统的高级氧化工艺(AOPs)/膜系统相比,SA-Mn-CN/PVDF/PMS 系统具有催化活性高、反应物生成选择性强、工作 pH 值范围宽(pH3-11)、反冲洗条件下稳定性和重复使用性好等优点。所开发的装置级 AOPs/膜系统已被证明能有效灭活细菌和降解污染物,从而验证了 SA-Mn-CN/PVDF 膜在实际水净化中的巨大应用潜力。这项工作开创了酶模拟纳米酶膜的开发先河,为废水处理提供了可持续的高性能解决方案,并为基于纳米酶的催化膜在环境应用中的设计树立了新的标杆。
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Water Research
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