腐植酸

腐植酸（Humic acid, 縮寫：HA），又稱胡敏酸，是一種天然有機高分子化合物，是腐殖質的主要組成部分^[1]。腐植酸不是一個單一的酸，而是一個複雜的含有羧基、酚羥基等官能團的混合物，所以該混合物表現出二元酸或偶爾三元酸的性質。腐植酸在自然界中通常與離子形成絡合物。

腐植質由死亡生物物質，如木質素，經微生物降解產生，難以進一步降解^[1]。其特定的性能和結構取決於給定樣本從水或土壤源中提取時的具體條件。然而，雖然腐植質的來源不同，性能卻非常相似。腐植質在土壤和沉積物中可分為三個主要部分：胡敏酸（Humic acid，HA），黃腐酸（英語：fulvic acid）（fulvic acid, FA）和胡敏素（英語：humin）（humin, HM）^[2]。其中胡敏酸溶於鹼不溶於酸；黃腐酸溶於鹼和酸；而胡敏素不溶於鹼和酸^[1]。

商業腐植酸主要有兩種來源：一種是從褐煤、風化煤和泥炭等原料中提取的，稱為礦源腐植酸；另一種則以動植物殘骸、有機廢物和動物糞便等生物質為原料，通過生物或非生物手段將其分解轉化而成，稱為生物腐植酸，其性質與礦源腐植酸相似。由於天然腐植酸的形成漫長且複雜，因此採用人工方法合成生物腐植酸被認為是一種良好的增值方法。^[1]

腐植酸是一種帶電的、複雜的高分子多相膠態混合物。其組成和結構受到來源、氣候、形成時間等多種因素的影響，因此不同來源或合成方法得到的腐植酸具有不同的元素組成、結構和多相分子組成。^[3]

雖然不同來源的腐植酸具有一定差異，但整體上具有相似的分子結構和性質。分子量大概在0.3~100 kDa之間^[4]，其主要元素組成為碳、氫、氧，同時含有微量元素如鎂、鐵、鈣、鉀等^[1]。腐植酸的分子單體以芳香環為核心，含有多種活性基團，如羧基、醇羥基、酚羥基、甲氧基、羰基等^[5]^[6]，並與側鏈上的多肽或脂族基團相連接^[1]。

腐植酸的多樣性結構決定了其多樣的物理化學性質。其具有抗氧化、離子交換、絡合、抗菌、吸附和氧化還原等特性，可與重金屬、放射性元素、農藥、染料等發生化學反應，從而降低毒性、減輕污染，具有環境保護和土壤修復功能。^[1]

腐植酸分子具有豐富的羥基、羧基等官能團，賦予其良好的親水性。這些官能團使腐植酸能夠與水分子發生氫鍵作用，形成溶液。其親水性有助於促進土壤顆粒的團聚和聚集，提高土壤的結構穩定性，並改善土壤的透水性和保水性。^[7]

腐植酸分子中的羧基、酚羥基等官能團具有良好的絡合能力，可與金屬離子形成絡合物^[8]。這種絡合作用能夠改變土壤中金屬離子的活性和可溶性，減少金屬的毒性。同時，腐植酸的絡合作用還能促進營養元素的釋放和供應，提高土壤肥力，促進植物的生長發育。^[9]

腐植酸分子表面帶有大量負電荷，具有良好的離子交換能力，可以增加土壤的離子交換容量，提高土壤的肥力和養分保持能力^[10]。此外，腐植酸還能吸附和解吸植物營養元素，調節土壤中營養元素的有效性和可利用性^[11]；同時降低土壤中有害物質的毒性，減少污染物的遷移和擴散^[12]；還能穩定土壤中的養分和水分，減少養分的流失和水分的蒸發^[13]^[14]。

微生物分解法: 利用真菌、細菌等微生物的分解轉化能力對原料進行降解，從而提取腐植酸^[1]。

水熱法: 利用高溫液態水作為反應介質和反應物，以加速有機物的溶解和轉化^[1]。

催化/氧化法: 利用催化劑或氧化劑對原料進行處理，促進大分子鏈結構向小分子鏈的轉化，從而提高腐植酸產量。氧化劑如硝酸和過氧化氫，以及催化劑如鐵等過渡金屬催化劑^[1]。

熱解法: 在無氧或少量空氣的條件下，通過熱化學轉化，將有機物轉變為氣、液、固三相產物，調節熱解條件可以控制產物的性質和產率^[15]。

腐植酸作為土壤改良劑，能夠改善土壤結構，提高養分利用效率，並促進土壤微生物活性^[1]。同時，腐植酸還能刺激種子萌發和植物生長^[16]，增加根系生長，提高植物吸收水分和養分的能力，從而提高作物產量和品質^[17]。

在工業領域，腐植酸鹽鑽井助劑以其優異的親水、絡合和分散特性，被廣泛應用於降濾失、降黏和頁岩抑制等方面。此外，經過改性的腐植酸還可以用作陶瓷減水劑和水煤漿分散劑，具有良好的性能和環保特性。^[1]

腐植酸在醫學領域具有抗炎、抗氧化、抗病毒和抗癌等作用^[1]。其結構特性決定了其在藥物中的廣泛應用，能夠有效治療類風濕性關節炎、濕疹、過敏性鼻炎等炎症性疾病^[18]，同時也被用於預防和治療癌症和病毒性疾病^[6]^[19]。

在環保領域，腐植酸作為吸附劑，能夠去除水體中的陽離子和有機污染物^[20]，同時也能與重金屬形成絡合物，從而降低其對環境的危害^[21]。此外，腐植酸還能促進土壤微生物活性，提高土壤中重金屬的固定化效果^[22]。

腐植酸還被應用於新型電極材料的製備中，如鈉/鋰離子電池和超級電容器。腐植酸製備的電極材料具有成本低廉、環境友好的特點，並且在電池和超級電容器中表現出優異的性能。^[1]

[1]
Zhao, Qifeng; Yang, Yue; Qiu, Xinyue; Yang, Bo; Zhao, Dongye; Zhang, Wei; Su, Xintai. Humic acid: research progress in its structural properties, sources, preparation and application. SCIENTIA SINICA Chimica. 2023-08-01, 53 (8): 1437–1454. doi:10.1360/SSC-2023-0080.
[2]
Chiou, Cary T.; Malcolm, Ronald L.; Brinton, Terry I.; Kile, Daniel E. Water solubility enhancement of some organic pollutants and pesticides by dissolved humic and fulvic acids. Environmental Science & Technology. 1986-05, 20 (5): 502–508. doi:10.1021/es00147a010.
[3]
Orlov, Alexey A.; Zherebker, Alexander; Eletskaya, Anastasia A.; Chernikov, Viktor S.; Kozlovskaya, Liubov I.; Zhernov, Yury V.; Kostyukevich, Yury; Palyulin, Vladimir A.; Nikolaev, Eugene N.; Osolodkin, Dmitry I.; Perminova, Irina V. Examination of molecular space and feasible structures of bioactive components of humic substances by FTICR MS data mining in ChEMBL database. Scientific Reports. 2019-08-19, 9 (1). doi:10.1038/s41598-019-48000-y.
[4]
Wallinga, J.; van Mourik, J.M.; Schilder, M.L.M. Identifying and dating buried micropodzols in Subatlantic polycyclic drift sands. Quaternary International. 2013-09, 306: 60–70. doi:10.1016/j.quaint.2013.05.030.
[5]
Lee, Jeong Gu; Yoon, Ho Young; Cha, Joon-Yung; Kim, Woe-Yeon; Kim, Pil Joo; Jeon, Jong-Rok. Artificial humification of lignin architecture: Top-down and bottom-up approaches. Biotechnology Advances. 2019-12, 37 (8): 107416. doi:10.1016/j.biotechadv.2019.107416.
[6]
de Melo, Bruna Alice Gomes; Motta, Fernanda Lopes; Santana, Maria Helena Andrade. Humic acids: Structural properties and multiple functionalities for novel technological developments. Materials Science and Engineering: C. 2016-05, 62: 967–974. doi:10.1016/j.msec.2015.12.001.
[7]
顧鑫; 任翠梅，楊麗. 天然煤炭腐植酸对盐碱土改良效果的研究①. 灌溉排水學報. 2017, 36 (9): 57–61 [2024-02-28]. （原始內容存檔於2024-02-28）.
[8]
Song, Jina; Jin, Xin; Wang, Xiaochang C.; Jin, Pengkang. Preferential binding properties of carboxyl and hydroxyl groups with aluminium salts for humic acid removal. Chemosphere. 2019-11, 234: 478–487. doi:10.1016/j.chemosphere.2019.06.107.
[9]
Jindo, Keiji; Martim, Silvia Aparecida; Navarro, Elena Cantero; Pérez-Alfocea, Francisco; Hernandez, Teresa; Garcia, Carlos; Aguiar, Natália Oliveira; Canellas, Luciano Pasqualoto. Root growth promotion by humic acids from composted and non-composted urban organic wastes. Plant and Soil. 2012-04, 353 (1-2): 209–220. doi:10.1007/s11104-011-1024-3.
[10]
Pandey, Ashok K.; Pandey, Shri Dhar; Misra, Virendra. Stability Constants of Metal–Humic Acid Complexes and Its Role in Environmental Detoxification. Ecotoxicology and Environmental Safety. 2000-10, 47 (2): 195–200. doi:10.1006/eesa.2000.1947.
[11]
Wang, Qiaozhi; Zhao, Hui; Qi, Na; Qin, Yan; Zhang, Xuejie; Li, Ying. Generation and Stability of Size-Adjustable Bulk Nanobubbles Based on Periodic Pressure Change. Scientific Reports. 2019-02-04, 9 (1). doi:10.1038/s41598-018-38066-5.
[12]
Yu, Yaqi; Liu, Meng; Yang, Jinyan. Characteristics of vanadium adsorption on and desorption from humic acid. Chemistry and Ecology. 2018-07-03, 34 (6): 548–564. doi:10.1080/02757540.2018.1452915.
[13]
Deng, Aini; Wu, Xiaofang; Su, Chulian; Zhao, Min; Wu, Bin; Luo, Jinhui. Enhancement of soil microstructural stability and alleviation of aluminium toxicity in acidic latosols via alkaline humic acid fertiliser amendment. Chemical Geology. 2021-11, 583: 120473. doi:10.1016/j.chemgeo.2021.120473.
[14]
Fashina, Bidemi; Novák, František; Kučerík, Jiří. Role of polar and apolar moieties in water adsorption by humic acids under arid conditions. Journal of Thermal Analysis and Calorimetry. 2021-09, 145 (6): 3031–3039. doi:10.1007/s10973-020-09964-6.
[15]
Qiao, Yingyun; Xu, Fanfan; Xu, Shili; Yang, Dan; Wang, Bo; Ming, Xue; Hao, Junhui; Tian, Yuanyu. Pyrolysis Characteristics and Kinetics of Typical Municipal Solid Waste Components and Their Mixture: Analytical TG-FTIR Study. Energy & Fuels. 2018-10-18, 32 (10): 10801–10812. doi:10.1021/acs.energyfuels.8b02571.
[16]
Tiwari, Jaya; Ramanathan, Al; Bauddh, Kuldeep; Korstad, John. Humic substances: Structure, function and benefits for agroecosystems—a review. Pedosphere. 2023-04, 33 (2): 237–249. doi:10.1016/j.pedsph.2022.07.008.
[17]
石冰; 章衛星. 腐殖酸在农业生产与土壤修复领域的作用和建议. 化肥工業. 2015, 42 (3): 86–89. doi:10.3969/j.issn.1006-7779.2015.03.028.
[18]
Junek, R.; Morrow, R.; Schoenherr, J.I.; Schubert, R.; Kallmeyer, R.; Phull, S.; Klöcking, R. Bimodal effect of humic acids on the LPS-induced TNF-α release from differentiated U937 cells. Phytomedicine. 2009-05, 16 (5): 470–476. doi:10.1016/j.phymed.2008.10.003.
[19]
Jacob, Kala K; Kj, Prashob Peter; N, Chandramohanakumar. HUMIC SUBSTANCES AS A POTENT BIOMATERIALS FOR THERAPEUTIC AND DRUG DELIVERY SYSTEM-A REVIEW. International Journal of Applied Pharmaceutics. 2019-03-06: 1–4. doi:10.22159/ijap.2019v11i3.31421.
[20]
Chianese, Simeone; Fenti, Angelo; Iovino, Pasquale; Musmarra, Dino; Salvestrini, Stefano. Sorption of Organic Pollutants by Humic Acids: A Review. Molecules. 2020-02-19, 25 (4): 918. doi:10.3390/molecules25040918.
[21]
Lin, Daohui; Tian, Xiaoli; Li, Tingting; Zhang, Zhiyong; He, Xiao; Xing, Baoshan. Surface-bound humic acid increased Pb2+ sorption on carbon nanotubes. Environmental Pollution. 2012-08, 167: 138–147. doi:10.1016/j.envpol.2012.03.044.
[22]
Xu, Miaomiao; Zhao, Zhuanjun; Song, Yiran; Li, Jing; You, Yang; Li, Jie. Evaluation of ferrihydrite-humic acid coprecipitate as amendment to remediate a Cd- and Pb-contaminated soil. Geoderma. 2020-03, 361: 114131. doi:10.1016/j.geoderma.2019.114131.

國際社會腐殖酸物質
Suprahumic研究小組（頁面存檔備份，存於互聯網檔案館）
溫德米爾腐殖酸水模型（沼澤地）（頁面存檔備份，存於互聯網檔案館）一個成熟的數據庫和建模方案離子結合的腐殖質。
中國腐植酸網（頁面存檔備份，存於互聯網檔案館）

[SSC-2023-0080-1] [1]
Zhao, Qifeng; Yang, Yue; Qiu, Xinyue; Yang, Bo; Zhao, Dongye; Zhang, Wei; Su, Xintai. Humic acid: research progress in its structural properties, sources, preparation and application. SCIENTIA SINICA Chimica. 2023-08-01, 53 (8): 1437–1454. doi:10.1360/SSC-2023-0080.

[2] [2]
Chiou, Cary T.; Malcolm, Ronald L.; Brinton, Terry I.; Kile, Daniel E. Water solubility enhancement of some organic pollutants and pesticides by dissolved humic and fulvic acids. Environmental Science & Technology. 1986-05, 20 (5): 502–508. doi:10.1021/es00147a010.

[3] [3]
Orlov, Alexey A.; Zherebker, Alexander; Eletskaya, Anastasia A.; Chernikov, Viktor S.; Kozlovskaya, Liubov I.; Zhernov, Yury V.; Kostyukevich, Yury; Palyulin, Vladimir A.; Nikolaev, Eugene N.; Osolodkin, Dmitry I.; Perminova, Irina V. Examination of molecular space and feasible structures of bioactive components of humic substances by FTICR MS data mining in ChEMBL database. Scientific Reports. 2019-08-19, 9 (1). doi:10.1038/s41598-019-48000-y.

[4] [4]
Wallinga, J.; van Mourik, J.M.; Schilder, M.L.M. Identifying and dating buried micropodzols in Subatlantic polycyclic drift sands. Quaternary International. 2013-09, 306: 60–70. doi:10.1016/j.quaint.2013.05.030.

[5] [5]
Lee, Jeong Gu; Yoon, Ho Young; Cha, Joon-Yung; Kim, Woe-Yeon; Kim, Pil Joo; Jeon, Jong-Rok. Artificial humification of lignin architecture: Top-down and bottom-up approaches. Biotechnology Advances. 2019-12, 37 (8): 107416. doi:10.1016/j.biotechadv.2019.107416.

[j.msec.2015.12.001-6] [6]
de Melo, Bruna Alice Gomes; Motta, Fernanda Lopes; Santana, Maria Helena Andrade. Humic acids: Structural properties and multiple functionalities for novel technological developments. Materials Science and Engineering: C. 2016-05, 62: 967–974. doi:10.1016/j.msec.2015.12.001.

[7] [7]
顧鑫; 任翠梅，楊麗. 天然煤炭腐植酸对盐碱土改良效果的研究①. 灌溉排水學報. 2017, 36 (9): 57–61 [2024-02-28]. （原始內容存檔於2024-02-28）.

[8] [8]
Song, Jina; Jin, Xin; Wang, Xiaochang C.; Jin, Pengkang. Preferential binding properties of carboxyl and hydroxyl groups with aluminium salts for humic acid removal. Chemosphere. 2019-11, 234: 478–487. doi:10.1016/j.chemosphere.2019.06.107.

[9] [9]
Jindo, Keiji; Martim, Silvia Aparecida; Navarro, Elena Cantero; Pérez-Alfocea, Francisco; Hernandez, Teresa; Garcia, Carlos; Aguiar, Natália Oliveira; Canellas, Luciano Pasqualoto. Root growth promotion by humic acids from composted and non-composted urban organic wastes. Plant and Soil. 2012-04, 353 (1-2): 209–220. doi:10.1007/s11104-011-1024-3.

[10] [10]
Pandey, Ashok K.; Pandey, Shri Dhar; Misra, Virendra. Stability Constants of Metal–Humic Acid Complexes and Its Role in Environmental Detoxification. Ecotoxicology and Environmental Safety. 2000-10, 47 (2): 195–200. doi:10.1006/eesa.2000.1947.

[11] [11]
Wang, Qiaozhi; Zhao, Hui; Qi, Na; Qin, Yan; Zhang, Xuejie; Li, Ying. Generation and Stability of Size-Adjustable Bulk Nanobubbles Based on Periodic Pressure Change. Scientific Reports. 2019-02-04, 9 (1). doi:10.1038/s41598-018-38066-5.

[12] [12]
Yu, Yaqi; Liu, Meng; Yang, Jinyan. Characteristics of vanadium adsorption on and desorption from humic acid. Chemistry and Ecology. 2018-07-03, 34 (6): 548–564. doi:10.1080/02757540.2018.1452915.

[13] [13]
Deng, Aini; Wu, Xiaofang; Su, Chulian; Zhao, Min; Wu, Bin; Luo, Jinhui. Enhancement of soil microstructural stability and alleviation of aluminium toxicity in acidic latosols via alkaline humic acid fertiliser amendment. Chemical Geology. 2021-11, 583: 120473. doi:10.1016/j.chemgeo.2021.120473.

[14] [14]
Fashina, Bidemi; Novák, František; Kučerík, Jiří. Role of polar and apolar moieties in water adsorption by humic acids under arid conditions. Journal of Thermal Analysis and Calorimetry. 2021-09, 145 (6): 3031–3039. doi:10.1007/s10973-020-09964-6.

[15] [15]
Qiao, Yingyun; Xu, Fanfan; Xu, Shili; Yang, Dan; Wang, Bo; Ming, Xue; Hao, Junhui; Tian, Yuanyu. Pyrolysis Characteristics and Kinetics of Typical Municipal Solid Waste Components and Their Mixture: Analytical TG-FTIR Study. Energy & Fuels. 2018-10-18, 32 (10): 10801–10812. doi:10.1021/acs.energyfuels.8b02571.

[16] [16]
Tiwari, Jaya; Ramanathan, Al; Bauddh, Kuldeep; Korstad, John. Humic substances: Structure, function and benefits for agroecosystems—a review. Pedosphere. 2023-04, 33 (2): 237–249. doi:10.1016/j.pedsph.2022.07.008.

[17] [17]
石冰; 章衛星. 腐殖酸在农业生产与土壤修复领域的作用和建议. 化肥工業. 2015, 42 (3): 86–89. doi:10.3969/j.issn.1006-7779.2015.03.028.

[18] [18]
Junek, R.; Morrow, R.; Schoenherr, J.I.; Schubert, R.; Kallmeyer, R.; Phull, S.; Klöcking, R. Bimodal effect of humic acids on the LPS-induced TNF-α release from differentiated U937 cells. Phytomedicine. 2009-05, 16 (5): 470–476. doi:10.1016/j.phymed.2008.10.003.

[19] [19]
Jacob, Kala K; Kj, Prashob Peter; N, Chandramohanakumar. HUMIC SUBSTANCES AS A POTENT BIOMATERIALS FOR THERAPEUTIC AND DRUG DELIVERY SYSTEM-A REVIEW. International Journal of Applied Pharmaceutics. 2019-03-06: 1–4. doi:10.22159/ijap.2019v11i3.31421.

[20] [20]
Chianese, Simeone; Fenti, Angelo; Iovino, Pasquale; Musmarra, Dino; Salvestrini, Stefano. Sorption of Organic Pollutants by Humic Acids: A Review. Molecules. 2020-02-19, 25 (4): 918. doi:10.3390/molecules25040918.

[21] [21]
Lin, Daohui; Tian, Xiaoli; Li, Tingting; Zhang, Zhiyong; He, Xiao; Xing, Baoshan. Surface-bound humic acid increased Pb2+ sorption on carbon nanotubes. Environmental Pollution. 2012-08, 167: 138–147. doi:10.1016/j.envpol.2012.03.044.

[22] [22]
Xu, Miaomiao; Zhao, Zhuanjun; Song, Yiran; Li, Jing; You, Yang; Li, Jie. Evaluation of ferrihydrite-humic acid coprecipitate as amendment to remediate a Cd- and Pb-contaminated soil. Geoderma. 2020-03, 361: 114131. doi:10.1016/j.geoderma.2019.114131.

[1]

[2]

[3]

[4]

[5]

[6]

[7]

[8]

[9]

[10]

[11]

[12]

[13]

[14]

[15]

[16]

[17]

[18]

[19]

[20]

[21]

[22]

腐植酸

Wikiwand in your browser!

腐植酸

Wikiwand in your browser!

形成和來源

結構

功能

製備

應用

參考資料

外部連結