【歡迎您關注--農業環境科學】
簡 介
東北農業大學楊帆教授課題組近期在環境及化學領域主流學術期刊Angewandte Chemie International Edition、Chemical Engineering Journal、ACS Sustainable Chemistry & Engineering、Science of the Total Environment發表系列論文，在模擬地球化學過程基礎上合成了多種土壤成分，首次提出了「水熱腐殖化」合成策略，將生物質中主要成分進行裂解-重組合成人造腐殖質，進一步地與沙質土壤有序結合形成類黑土結構，實現了「黑土再造」。進一步地，提出了採用水熱溼法技術溶解-重構潛力固廢資源，同步實現了磷素回收和難溶性磷礦物增溶，為典型固體廢棄物的資源化利用和土壤磷素的可持續循環提供了可行途徑。這些原創性科研成果，為解決土壤資源退化、土壤養分可持續發展和潛力資源的合理化利用奠定了重要理論基礎。
01
人造腐殖質的宏量製備
第一作者：楊帆
通訊作者：Markus Antonietti，楊帆
通訊單位：東北農業大學、德國馬普膠體與界面研究所
DOI：10.1016/j.scitotenv.2019.06.045
Abstract
A novel preparation protocol for synthetic, look-a-like humic substances (i.e., fulvic and humic acids) simulating geochemical processes through hydrothermal reaction is presented, with crude waste biomass as an omnipresent and universal precursor. The chemical nature of the organic scaffold and the type and abundance of oxygen containing functional groups of the synthetic humic substances (A-FA and A-HA) are revealed by a series of examinations. Results from EA, XPS analyze, FTIR spectra and NMR technology matched well each other, suggesting high similarity on chemical structure (abundant aromatic frameworks) and contents (e.g. N and S elements) in both humic acids. Pyrolysis-gas-chromatography/mass spectrometry (Py-GC/MS) analysis is employed on the organic structure and is directly compared to extracted natural humic matter from black soils (Harbin, China). Dehydrated carbohydrates and their condensates with low molecular weight that are rich in oxygen are the main structural components of the artificial fulvic acids, while aromatic structures and aliphatic side chains are almost absent. Aromatics (7.43%) and in some cases long-chain aliphatics (7.15%) are more prominent in the A-HA sample. The combination of the diverse analytical techniques not only allows a better understanding of artificial fulvic and humic acids, but also supports the high similarity to natural humic substances in structure and morphology. As the technology can be easily scaled and is comparable cheap, the as obtained products can be discussed to rehabilitate used up farm land.
摘 要
本文提出了一種通過水熱反應模擬地球化學過程，以普遍存在的廢棄生物質為前驅體合成人造腐殖質。相關表徵結果揭示了人造腐殖質（腐植酸和富裡酸）的結構和物理化學性質。EA、XPS、FTIR以及NMR的分析結果顯示兩種合成物質在化學結構(芳香族結構)和元素含量(如N和S元素)方面均具有較高的相似性。採用熱解-氣相色譜/質譜(Py-GC/MS)分析人造腐殖質和天然腐殖質的組成單元和成分結構，發現富含氧元素的低分子量的脫水碳水化合物及其縮合物是人造富裡酸的主要結構成分，而芳香結構和較長的脂類鏈則幾乎不存在。人造腐植酸中則含有較多的芳烴(7.43%)和長鏈脂肪烴(7.15%)結構，並且發現其與天然腐植酸在結構和形態上具有高度相似性。由於該技術易於規模化生產，且成本相當低廉，因此本研究所獲得的人造腐殖質有望實現推廣。
該篇文章題為「A hydrothermal process to turn waste biomass into artificial fulvic and humic acids for soil remediation」，發表於Science of the Total Environment。該研究在革新傳統水熱碳化技術的基礎上，模擬地球化學過程，首次提出了水熱腐殖化合成策略，對生物質主要成分裂解形成的脂肪類、糖類及酚類等物質進行合理重組，成功合成與黑土提取腐殖質結構和功能高度相似的人造腐殖質（如圖1和2）。特別地，我們選擇小分子葡萄糖為模式物成功合成了人造富裡酸，選擇木屑和樹葉為模式物合成了人造腐植酸。該工作創新性地通過化學合成手段利用廢棄生物質成功合成人造腐殖質。更重要的是，該方法反應時間短、製備成本低，大大加快了生物質腐殖化進度，為大規模實際應用提供可能。
圖1. 人造腐殖質的合成策略
圖2. 人造腐殖質與天然腐殖質的結構和成分分析
文章連結：
https://doi.org/10.1016/j.scitotenv.2019.06.045
02
增溶難溶磷素, 提高養分利用效率
第一作者：楊帆
通訊作者：Markus Antonietti，楊帆
通訊單位：東北農業大學、德國馬普膠體與界面研究所
DOI：10.1002/ange.201911060
Abstract
Artificial humic acids (A-HA) made from biomass in a hydrothermal process turn otherwise highly insoluble phosphates (e.g. iron phosphate as a model) into highly available phosphorus, which contributes to the fertility of soils and the coupled plant growth. A detailed electron microscopy study revealed etching of the primary iron phosphate crystals by the -COOH and phenolic groups of humic acids, but also illustrated the importance of the redox properties of humic matter on the nanoscale. The combined effects result in the formation of then bioavailable phosphate nanoparticles stabilized by humic matter. Typical agricultural chemical tests indicate that the content of total P and directly plant-available P improved largely. Comparative pot planting experiments before and after treatment of phosphates with A-HA demonstrate significantly enhanced plant growth, as quantified in higher aboveground and belowground plant biomass.
摘 要
人造腐植酸是由生物質在水熱過程中合成的，它可以將高度不溶性的磷酸鹽(以磷酸鐵為例)轉化為植物可利用磷素，這有助於增加土壤的肥力以及促進植物的生長。相關表徵手段揭示了人造腐植酸功能性基團對磷酸鐵晶體的蝕刻效果，同時也說明了基於氧化還原反應的蝕刻機理。典型的室內盆栽試驗表明，添加腐植酸蝕刻磷酸鐵晶體後的液體產物可以明顯提高土壤總磷和有效磷含量，且植物各生長指標得到了顯著提高，其地上和地下植物生物量均有所增加。
磷是作物生長不可缺少的必需營養元素之一，其在土壤中的含量和有效性決定最終的農業生產力，促進土壤難溶磷素的有效化是實現節本節肥、合理施肥的迫切需求。基於此，我們通過模擬天然植物根系在貧磷環境下的響應機制，提出了利用人造腐殖質增溶難溶性磷素的可行途徑（如圖3）。得到的液體磷肥施加到土壤中可以快速提高土壤有效磷素含量，明顯增加土壤肥力，生長25天後的玉米幼苗、根和莖的乾重得到了顯著地增加，分別是未添加磷肥對照組的2.5、2.78和2.25倍。研究成果首次揭示了難溶磷礦石結構轉變的宏觀根源和納米根源，提出了腐植酸對難溶磷素的增溶過程符合經典的有機酸蝕刻機理，還與腐植酸的聚合物性質和所涉及的氧化還原過程有關。
圖3. 人造腐殖質促進難溶磷素有效化
文章連結：
http://dx.doi.org/10.1002/ange.201911060
03
介導磷素循環, 實現可持續發展
第一作者：張帥帥
通訊作者：Markus Antonietti，楊帆
通訊單位：東北農業大學、德國馬普膠體與界面研究所
DOI：10.1016/j.cej.2020.124832
Abstract
This publication presents a simple and low-cost hydrothermal humification (HTH) treatment of sewage sludge (SS) together with alkali ash (AA) and biomass for simultaneous implementation of heavy metal removal, nutrient recovery (P) and ash refining. The H/C and O/C atomic ratio plots obtained from elemental analysis demonstrate that dehydration and decarboxylation under hydrothermal conditions are elemental reactions leading to sludge/biomass decomposition and artificial humic matter formation. Introduction of plant biomass into sludge-derived samples and adjustment of KOH or alkali ash (AA) mass effectively improve the recovery of P element, realizing high contents of dissolved phosphorus (DP) (from 7045 to 10075 mg/L) at appropriate pH values (6.5 to 7.7). ICP-AES results indicate the drop of Cr and Cd content below detection limit together with a sharp decrease of the elements Cu (from 0.07 to 0.46 mg/g), Zn (from 0.15 to 0.98 mg/g) and Pb (from 0.067 to 0.142 mg/g) after HTH treatment in sludge-derived liquid products and the heavy metal elements enriched in sludge-derived solids can be recovered into industrial salts by subsequent treatment. Pot planting experiments are conducted to investigate the P-availability in both sludge-derived liquids and solids (after treatment of heavy metal recovery) for promotion of plant growth. A higher proportion of shoot-to-root weight (62.1 % versus 46.2 %) and preserved moisture contents (84.7 % versus 83.7 %) when compared to the control groups demonstrate the effect of the presence of more nutrients after addition of sludge-derived liquid products. This work could provide a smart, energy utilization and sustainable fertilization route for planting growth.
摘 要
本篇文章介紹了一種簡單和經濟的水熱腐殖質化技術用於處理廢水汙泥、鹼灰和廢棄生物質，以實現重金屬去除、磷素回收和鹼灰的精煉。通過元素分析得到，水熱條件下的脫水和脫羧反應是導致汙泥/生物質分解和人造腐殖質形成的主要因素。將生物質引入汙泥處理過程中，並且調整添加的強鹼或鹼灰質量以有效提高磷素的回收效率，獲得適宜的pH值。ICP-AES結果顯示，汙泥水熱腐殖化技術處理後的液體產物，Cr、Cd含量均低於檢出限，Cu、Zn、Pb等元素含量均急劇下降，Cu從0.46降至0.07 mg/g，Zn從0.98降至0.15 mg/g, Pb從0.142降至0.067 mg/g，而固體產物中富集的重金屬元素經後續處理可回收為工業鹽。後續的盆栽試驗研究了汙泥水熱腐殖化處理後的液體和固體(重金屬回收處理後)中磷的有效性以及對於作物生長的促進作用。與對照組相比，實驗組作物具有較高的芽-根重量比例(62.1 % vs 46.2 %)和含水率(84.7 % vs 83.7 %)，且明顯增加土壤中的有效磷素含量。本研究可為促進植物生長提供一條有效的、綠色的和可持續的施肥途徑。
文章連結：
https://doi.org/10.1016/j.cej.2020.124832
第一作者：杜慶
通訊作者：楊帆、Markus Antonietti
通訊單位：東北農業大學、德國馬普膠體與界面研究所
DOI：10.1021/acssuschemeng.0c02233
Abstract
Lack of available phosphorus (P) minerals and their very localized regional distribution threatens world food production. Traditional farming methods that recycle various biological wastes and manure for localized fertilization of farmland are our role model, but come with risks such as hygiene, water toxification and passed-on diseases. Here, we present a simple hydrothermal process which turns animal bones of kitchen wastes into secondary P sources for fertilization. It is shown that this hydrothermal humification (HTH) process completely disintegrates texture and chemical structure of the biomass, while the simultaneously in-situ prepared artificial humic acid (A-HA) etches even macroscopic bones. Notably, A-HA can solubilize the insoluble P existing in animal bones partly as directly soluble phosphorus (DP), accounting for 6.48 % of total phosphorus (TP) in the bone wastes. Characterization methods indicate that oxygen-containing functional groups (i.e., -COOH and phenolic-OH) of A-HA can help to corrode bones, causing Ca5(PO4)3(OH) to be decomposed into a large number of more active minerals with much smaller grain size, furthermore, leading to high DP (98.65 mg/L) content and the formation of new P-based species. Pot planting experiments show that the resulting liquids can be applied as a fertilizer and lead to a significant promotion of the growth of seedlings.
摘 要
有效磷素的缺乏及區域分布不均等問題威脅著世界糧食安全。傳統的耕種方式通過回收各種廢棄生物質和動物糞便用於農田的局部施肥耕作，但是這種方式存在嚴重衛生問題和傳播傳染病等風險。在這裡，我們通過水熱腐殖化工藝，將餐廚垃圾中的動物骨骼轉變成富含豐富有效磷素的液體肥料。結果表明，水熱腐殖化過程可將骨骼中原有結構完全轉化，同時合成的人造腐植酸可以蝕刻骨骼中的難溶性磷成分轉化為可溶性磷酸鹽。通過相關表徵結果得到，人造腐植酸豐富的含氧官能團對於骨骼的刻蝕起到了關鍵作用，從而形成大量的高活性的可溶性磷溶液（98.65 mg/L），並且生成了新的含磷晶體。後續盆栽試驗表明，從骨骼中回收的可溶性磷肥可以顯著促進玉米幼苗的生長。
文章連結：
https://doi.org/10.1021/acssuschemeng.0c02233