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絮体老化过程中 NOM 的变化:典型铝基混凝剂和不同粒径的影响。

Variations in NOM during floc aging: Effect of typical Al-based coagulants and different particle sizes.

机构信息

State Key Laboratory of Environmental Aquatic Chemistry, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085, China; Yangtze River Delta Branch, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Yiwu City, Zhejiang Province 322000, China; University of Chinese Academy of Sciences, Beijing 100049, China.

State Key Laboratory of Environmental Aquatic Chemistry, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085, China; Yangtze River Delta Branch, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Yiwu City, Zhejiang Province 322000, China.

出版信息

Water Res. 2022 Jun 30;218:118486. doi: 10.1016/j.watres.2022.118486. Epub 2022 Apr 21.

Abstract

Most studies on the interaction between coagulation and NOM (natural organic matter) currently focus on pollutant removal and coagulant species distribution, while studies on floc aging are lacking. Investigation onto the effects of floc aging could guide further processes that utilize flocs, such as densadeg sludge recirculation, floc predeposition for ultrafiltration, sludge condensation, and other traditional sludge reflux processes. In this study, flocs generated by Al and AlCl in microparticle- and nanoparticle-containing water were investigated, and the effect of floc aging on NOM was quantified based on several organic matter characterization techniques. Flocs absorb and release organics during aging. The flocs generated from micro-SiO have a significant absorbing effect for LWM-N (low-molecular-weight neutral substances) and protein-like substances, while the absorption of NOM by flocs generated from nano-SiO is insignificant. HS (humic substances) with high aromaticity are released during floc aging. From the molecular perspective, the molecules released during floc aging are those with higher double bond equivalents and higher aromaticity, while the absorbed molecules are those with lower double bond equivalents and lower aromaticity. 2D-COS (two-dimensional correlation spectroscopy) demonstrated that the flocs generated by Al and AlCl had the same organic release patterns but different intensities, while the flocs generated in the micro-SiO and nano-SiO systems had different organics release patterns. Abundant aluminum hydrolysates with low polymerization and amorphous Al(OH) would be produced from AlCl during the coagulation process and then undergo hydroxyl‑bridging reaction and crystallization during floc aging, thus releasing more HS with high aromaticity into the supernatant; in comparison, prehydrolyzed Al produces a more stable floc and releases less HS during aging. The flocs produced by nano-SiO and Al-based coagulants release higher aromaticity HS into the water than those produced by micro-SiO, which may be related to the formation of more highly polymerized degree hydrolysates and nanocrystalline Al(OH) in the nano-SiO system. The flocs generated in water with micro-SiO may contain a large amount of Al-OH and have a loose structure, thus further absorbing NOM, such as protein-like substances and LWM-N. In contrast, the flocs generated from nano-SiO possess abundant adsorbed water and a denser structure; thus, organic matter cannot be absorbed stably.

摘要

大多数关于凝血与天然有机物(NOM)相互作用的研究目前主要集中在污染物去除和混凝剂种类分布上,而对絮体老化的研究则相对较少。对絮体老化效应的研究可以指导进一步的利用絮体的过程,如浓缩污泥再循环、用于超滤的絮体预沉淀、污泥浓缩和其他传统的污泥回流过程。本研究考察了含有微纳米颗粒的水中由 Al 和 AlCl 生成的絮体,并基于几种有机物特性技术定量研究了絮体老化对 NOM 的影响。絮体在老化过程中会吸收和释放有机物。微 SiO2 生成的絮体对低分子量中性物质和类蛋白物质有显著的吸收作用,而纳米 SiO2 生成的絮体对 NOM 的吸收作用不明显。富芳香度的 HS(腐殖质)在絮体老化过程中被释放出来。从分子角度来看,絮体老化过程中释放的分子具有更高的双健当量和芳香度,而吸收的分子具有更低的双健当量和芳香度。二维相关光谱(2D-COS)表明,Al 和 AlCl 生成的絮体具有相同的有机物释放模式,但强度不同,而在微 SiO2 和纳米 SiO2 体系中生成的絮体具有不同的有机物释放模式。在混凝过程中,AlCl 会产生低聚合度和无定形的 Al(OH)3 等丰富的铝水解产物,然后在絮体老化过程中进行羟基桥联反应和结晶,从而将更多富芳香度的 HS 释放到上清液中;相比之下,预水解 Al 在老化过程中产生更稳定的絮体,释放的 HS 较少。与微 SiO2 相比,纳米 SiO2 和基于 Al 的混凝剂生成的絮体将更多具有高芳香度的 HS 释放到水中,这可能与纳米 SiO2 体系中形成更多高聚合度水解产物和纳米晶相 Al(OH)3 有关。微 SiO2 水中生成的絮体可能含有大量的 Al-OH,并具有疏松的结构,因此可以进一步吸收类蛋白物质和低分子量中性物质等 NOM。相比之下,纳米 SiO2 生成的絮体含有丰富的吸附水,结构更致密;因此,有机物不能稳定地被吸收。

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