铁/钙改性膨润土控制底泥磷释放效果的对比研究

doi:10.19965/j.cnki.iwt.2025-0329

摘要/Abstract

摘要：

对比研究了铁改性膨润土（Fe-BT）和钙改性膨润土（Ca-BT）对水中磷酸盐的吸附效果及其抑制底泥磷释放的能力。结果显示，Fe-BT对水中磷酸盐的吸附动力学符合Elovich模型。溶液初始pH升高会抑制Fe-BT对磷酸根离子的吸附；高NaCl浓度有利于Fe-BT对磷酸盐的吸附；阳离子，尤其是二价阳离子能促进Fe-BT对磷酸盐的吸附，而HCO₃ ^-抑制吸附过程。Fe-BT对磷酸盐的吸附机理是Fe—OH与磷酸盐形成Fe—O—P内层络合物。底泥培养实验结果表明，Fe-BT能够有效抑制底泥磷释放，但其所固定的磷酸盐主要是以氧化还原敏感态磷（BD-P）存在，在缺氧状态下存在二次释放的风险。Ca-BT对水体磷酸盐具有一定吸附能力，最大吸附量为0.113 mg/g，且去除效果随投加量增加而提升。Ca-BT添加初期能有效抑制底泥磷释放，但长期抑制效果有限，且其固定的磷酸盐中高达40%为易解吸磷形态，易再次释放。相比Ca-BT，Fe-BT在抑制底泥磷释放方面效果更优，可作为磷污染底泥修复的潜力材料。

关键词: 铁改性膨润土, 钙改性膨润土, 底泥, 磷释放

Abstract:

The comparative study was conducted on the ability of iron-modified bentonite (Fe-BT) and calcium-modified bentonite (Ca-BT) to regulate phosphorus release from sediment. The experimental results showed that the adsorption kinetics characteristics of phosphate on Fe-BT were in good agreement with the Elovich model. An increase in the initial pH of the solution would inhibit the adsorption of phosphate ions by Fe-BT. High NaCl concentration was conducive to the adsorption of phosphate ions by Fe-BT, and the presence of HCO₃⁻ would inhibit the adsorption process. The adsorption mechanism of Fe-BT was that Fe—OH formed Fe—O—P inner-sphere complexes with phosphate ions. During the sediment culture experiment, it was found that the addition of Fe-BT could effectively control the phosphorus release from sediment, but the phosphorus fixed by Fe-BT was mainly retained in the oxidized-reduced sensitive state (BD-P) form, and there was a risk of secondary release under anoxic conditions. Ca-BT had a certain adsorption capacity for phosphate ions in water, and its removal efficiency increased with the increase of the dosage. The maximum unit adsorption capacity of Ca-BT was 0.113 mg/g. Ca-BT could effectively inhibit the phosphorus release from sediment in the short term, but it would gradually lose the ability to control the phosphorus release over time. Among the phosphorus fixed by Ca-BT, up to 40% appeared in an easily releasable form, and this part of phosphorus was prone to secondary release. Compared with Ca-BT, Fe-BT had a better effect in inhibiting the phosphorus release from sediment.

Key words: iron-modified bentonite, calcium-modified bentonite, sediment, phosphorus release

中图分类号:

X703.1

王凤君, 詹艳慧, 林建伟, 柏晓云. 铁/钙改性膨润土控制底泥磷释放效果的对比研究[J]. 工业水处理, 2026, 46(3): 127-135.

Fengjun WANG, Yanhui ZHAN, Jianwei LIN, Xiaoyun BAI. Comparison of the efficiencies of iron- and calcium-modified bentonite to control phosphorus release from sediment[J]. Industrial Water Treatment, 2026, 46(3): 127-135.

https://www.iwt.cn/CN/Y2026/V46/I3/127

图/表 11

表1 R-BT、Ca-BT和Fe-BT的化学组成

Table 1 Chemical composition of R-BT，Ca-BT and Fe-BT

化学组成	R-BT/%	Ca-BT/%	Fe-BT/%
Na₂O	4.787	1.765	2.557
MgO	1.858	1.803	1.803
Al₂O₃	18.791	18.562	18.440
SiO₂	65.150	66.123	65.121
K₂O	1.205	1.065	1.118
CaO	2.733	4.855	1.483
TiO₂	0.642	0.662	0.647
MnO	0.153	0.124	0.067
Fe₂O₃	4.442	4.891	8.517

图1 R-BT、Ca-BT和Fe-BT的XRD（a）和N₂吸附-解吸曲线（b）

Fig.1 XRD patterns（a） and N₂ adsorption-desorption curves（b） of R-BT，Ca-BT and Fe-BT

图2 吸附剂投加量对Fe-BT和Ca-BT去除水中磷酸盐效果的影响

Fig.2 Effect of adsorbent dosage on phosphate removal from aqueous solution by Fe-BT and Ca-BT

图3 反应时间对Fe-BT吸附水中磷酸盐效果的影响 t为反应时间；q_t 为t时刻吸附剂对水中磷酸盐的单位吸附量。

Fig.3 Effect of reaction time on phosphate adsorption from aqueous solution by Fe-BT

图4 溶液pH对Fe-BT吸附水中磷酸盐效果的影响

Fig.4 Effect of solution pH on phosphate adsorption from aqueous solution by Fe-BT

图5 离子强度（a）和共存离子（b）对Fe-BT吸附水中磷酸盐效果的影响

Fig.5 Effects of ion strength（a） and coexisting ions（b） on phosphate adsorption from aqueous solution by Fe-BT

图6 吸附磷酸盐前后Fe-BT的XPS （a）全谱图；（b）P 2p谱图；（c）原始Fe-BT的Fe 2p谱图；（d）吸附磷酸盐后Fe-BT的Fe 2p谱图；（e）原始Fe-BT的O 1s谱图；（f）吸附磷酸盐后Fe-BT的O 1s谱图。

Fig.6 XPS spectra of original and phosphate-loaded Fe-BT samples

图7 吸附磷酸盐前后Ca-BT（a）及Fe-BT（b）中磷形态分布

Fig.7 P fraction of fresh and phosphate-loaded Ca-BT and Fe-BT samples

图8 上覆水DO（a）和pH（b）随培养时间的变化规律

Fig.8 Variation of DO（a） and pH（b） in overlying water with incubation time

图9 上覆水SRP浓度（a）和SRP的削减率（b）的变化规律

Fig.9 Variation of SPR in overlying water（a） and the reduction rates of SRP（b）

图10 Ca-BT和Fe-BT对间隙水中SRP的削减率

Fig.10 The reduction rates of SRP in interstitial water by Ca-BT and Fe-BT addition

参考文献 35

[1]	RAVINDIRAN G， RAJAMANICKAM S， RAMALINGAM M，et al. Conversion of seaweed waste to biochar for the removal of heavy metal ions from aqueous solution：A sustainable method to address eutrophication problem in water bodies［J］. Environmental Research，2024，241：117551. doi:10.1016/j.envres.2023.117551
[2]	HO J C， MICHALAK A M， PAHLEVAN N. Widespread global increase in intense lake phytoplankton blooms since the 1980s［J］. Nature，2019，574：667-670. doi:10.1038/s41586-019-1648-7
[3]	HU Minqi， MA Ronghua， XUE Kun，et al. Eutrophication evolution of lakes in China：Four decades of observations from space［J］. Journal of Hazardous Materials，2024，470：134225. doi:10.1016/j.jhazmat.2024.134225
[4]	邓素炎，郭雯，温雯雯，等. 水体富营养化及物种入侵对星云湖食物网的影响［J］. 中国环境科学，2024，44（2）：932-943. doi:10.3969/j.issn.1000-6923.2024.02.034
	DENG Suyan， GUO Wen， WEN Wenwen，et al. The effects of water eutrophication and species invasion on the food web of Xingyun Lake［J］. China Environmental Science，2024，44（2）：932-943. doi:10.3969/j.issn.1000-6923.2024.02.034
[5]	SCHINDLER D W， HECKY R E， FINDLAY D L，et al. Eutrophication of lakes cannot be controlled by reducing nitrogen input：Results of a 37-year whole-ecosystem experiment［J］. Proc Natl Acad Sci USA，2008，105（32）：11254-11258. doi:10.1073/pnas.0805108105
[6]	LIN Songshun， SHEN Shuilong， ZHOU Annan，et al. Assessment and management of lake eutrophication：A case study in Lake Erhai，China［J］. Science of the Total Environment，2021，751：141618. doi:10.1016/j.scitotenv.2020.141618
[7]	LÜRLING M， VAN OOSTERHOUT F. Controlling eutrophication by combined bloom precipitation and sediment phosphorus inactivation［J］. Water Research，2013，47（17）：6527-6537. doi:10.1016/j.watres.2013.08.019
[8]	WANG Jinglong， CHEN Qinyi， HUANG Shun，et al. Cyanobacterial organic matter（COM） positive feedback aggravates lake eutrophication by changing the phosphorus release characteristics of sediments［J］. Science of the Total Environment，2023，892：164540. doi:10.1016/j.scitotenv.2023.164540
[9]	QIN Boqiang， ZHANG Yunlin， ZHU Guangwei，et al. Eutrophication control of large shallow lakes in China［J］. Science of the Total Environment，2023，881：163494. doi:10.1016/j.scitotenv.2023.163494
[10]	WANG Changhui， JIANG Helong. Chemicals used for in situ immobilization to reduce the internal phosphorus loading from lake sediments for eutrophication control［J］. Critical Reviews in Environmental Science and Technology，2016，46（10）：947-997. doi:10.1080/10643389.2016.1200330
[11]	OLDENBORG K A， STEINMAN A D. Impact of sediment dredging on sediment phosphorus flux in a restored riparian wetland［J］. Science of the Total Environment，2019，650：1969-1979. doi:10.1016/j.scitotenv.2018.09.298
[12]	HUSER B J， EGEMOSE S， HARPER H，et al. Longevity and effectiveness of aluminum addition to reduce sediment phosphorus release and restore lake water quality［J］. Water Research，2016，97：122-132. doi:10.1016/j.watres.2015.06.051
[13]	LIU Mengshuo， LI Tingting， WANG Zhongchen，et al. Effect of aeration on water quality and sediment humus in rural black-odorous water［J］. Journal of Environmental Management，2022，320：115867. doi:10.1016/j.jenvman.2022.115867
[14]	ZHANG Shengrui， WANG Ao， LI Luyao，et al. Phosphorus immobilization in sulfide-ferrous oxidation process driven by nitrate reduction during black-odorous sediment remediation［J］. Bioresource Technology，2024，407：131130. doi:10.1016/j.biortech.2024.131130
[15]	XU Di， DING Shiming， SUN Qin，et al. Evaluation of in situ capping with clean soils to control phosphate release from sediments［J］. Science of the Total Environment，2012，438：334-341. doi:10.1016/j.scitotenv.2012.08.053
[16]	柏晓云，林建伟，詹艳慧，等. 利用铁改性方解石作为活性覆盖材料控制水体内源磷的释放［J］. 环境科学，2020，41（3）：1296-1307. doi:10.13227/j.hjkx.201908127
	BAI Xiaoyun， LIN Jianwei， ZHAN Yanhui，et al. Use of iron-modified calcite as an active capping material to control phosphorus release from sediments in surface water bodies［J］. Environmental Science，2020，41（3）：1296-1307. doi:10.13227/j.hjkx.201908127
[17]	杨海全，陈敬安，刘文，等. 草海底泥原位钝化工程示范及其生态环境效应［J］. 环境工程学报，2017，11（7）：4437-4444. doi:10.12030/j.cjee.201604152
	YANG Haiquan， CHEN Jing’an， LIU Wen，et al. Eco-environment effect of in situ sediment inactivation in Lake Caohai，Southwest China［J］. Chinese Journal of Environmental Engineering，2017，11（7）：4437-4444. doi:10.12030/j.cjee.201604152
[18]	贾陈蓉，吴春芸，梁威，等. 污染底泥的原位钝化技术研究进展［J］. 环境科学与技术，2011，34（7）：118-122. doi:10.3969/j.issn.1003-6504.2011.07.028
	JIA Chenrong， WU Chunyun， LIANG Wei，et al. Research advances on in situ inactivation technology for contaminated sediment［J］. Environmental Science & Technology，2011，34（7）：118-122. doi:10.3969/j.issn.1003-6504.2011.07.028
[19]	马鑫雨，杨盼，张曼，等. 湖泊沉积物磷钝化材料的研究进展［J］. 湖泊科学，2022，34（1）：1-17. doi:10.18307/2022.0101
	MA Xinyu， YANG Pan， ZHANG Man，et al. Advances in researches on phosphorous inactivation materials in lake sediment［J］. Journal of Lake Sciences，2022，34（1）：1-17. doi:10.18307/2022.0101
[20]	WANG Bin， ZHANG Heng， HU Xiaoling，et al. Efficient phosphate elimination from aqueous media by La/Fe bimetallic modified bentonite：Adsorption behavior and inner mechanism［J］. Chemosphere，2023，312：137149. doi:10.1016/j.chemosphere.2022.137149
[21]	ZHANG Bo， ZHU Weiyu， HOU Rongbo，et al. Recent advances of application of bentonite-based composites in the environmental remediation［J］. Journal of Environmental Management，2024，362：121341. doi:10.1016/j.jenvman.2024.121341
[22]	BAO Teng， DAMTIE M M， WANG CHU yan，et al. Iron-containing nanominerals for sustainable phosphate management：A comprehensive review and future perspectives［J］. Science of the Total Environment，2024，926：172025. doi:10.1016/j.scitotenv.2024.172025
[23]	SPEARS B M， MACKAY E B， YASSERI S，et al. A meta-analysis of water quality and aquatic macrophyte responses in 18 lakes treated with lanthanum modified bentonite（Phoslock®）［J］. Water Research，2016，97：111-121. doi:10.1016/j.watres.2015.08.020
[24]	张巧颖，杜瑛珣，罗春燕，等. 镧改性膨润土钝化湖泊中的磷及其生态风险的研究进展［J］. 湖泊科学，2019，31（6）：1499-1509. doi:10.18307/2019.0620
	ZHANG Qiaoying， DU Yingxun， LUO Chunyan，et al. Advances in researches on phosphorus immobilization by lanthanum modified bentonite in lakes and its ecological risk［J］. Journal of Lake Sciences，2019，31（6）：1499-1509. doi:10.18307/2019.0620
[25]	D’HAESE P C， DOUGLAS G， VERHULST A，et al. Human health risk associated with the management of phosphorus in freshwaters using lanthanum and aluminium［J］. Chemosphere，2019，220：286-299. doi:10.1016/j.chemosphere.2018.12.093
[26]	SANTOS A F， LOPES D V， ALVARENGA P，et al. Phosphorus removal from urban wastewater through adsorption using biogenic calcium carbonate［J］. Journal of Environmental Management，2024，351：119875. doi:10.1016/j.jenvman.2023.119875
[27]	LIN Jianwei， HE Siqi， ZHANG Honghua，et al. Effect of zirconium-modified zeolite addition on phosphorus mobilization in sediments［J］. Science of the Total Environment，2019，646：144-157. doi:10.1016/j.scitotenv.2018.07.281
[28]	SONG Langrun， Jun NAN， LIU Bohan，et al. Novel three-dimensional Ti₃C₂-MXene embedded zirconium alginate aerogel adsorbent for efficient phosphate removal in water［J］. Chemosphere，2023，319：138016. doi:10.1016/j.chemosphere.2023.138016
[29]	CORNEJO-LEÓN S， GÓMEZ-NAVARRO C S， CONTRERAS-ATRISCO Z A，et al. Development of a sustainability-oriented university laboratory：Insight into adsorption kinetics models for the removal of pollutants from aqueous solution［J］. Environ Research，2024，258：119422.
[30]	LIN Jianwei， WANG Xingxing， ZHAN Yanhui. Effect of precipitation pH and coexisting magnesium ion on phosphate adsorption onto hydrous zirconium oxide［J］. Journal of Environmental Sciences，2019，76：167-187. doi:10.1016/j.jes.2018.04.023
[31]	SU Yu， CUI Hang， LI Qi，et al. Strong adsorption of phosphate by amorphous zirconium oxide nanoparticles［J］. Water Research，2013，47（14）：5018-5026. doi:10.1016/j.watres.2013.05.044
[32]	LIN Jianwei， ZHAO Yuying， ZHAN Yanhui，et al. Influence of coexisting calcium and magnesium ions on phosphate adsorption onto hydrous iron oxide［J］. Environmental Science and Pollution Research，2020，27（10）：11303-11319. doi:10.1007/s11356-020-07676-w
[33]	MEIS S， SPEARS B M， MABERLY S C，et al. Sediment amendment with phoslock^® in clatto reservoir（Dundee，UK）：Investigating changes in sediment elemental composition and phosphorus fractionation［J］. Journal of Environmental Management，2012，93（1）：185-193. doi:10.1016/j.jenvman.2011.09.015
[34]	DING Shiming， HAN Chao， WANG Yanping，et al. In situ，high-resolution imaging of labile phosphorus in sediments of a large eutrophic lake［J］. Water Research，2015，74：100-109. doi:10.1016/j.watres.2015.02.008
[35]	Yaobin LÜ， ZHANG Man， YIN Hongbin. Phosphorus release from the sediment of a drinking water reservoir under the influence of seasonal hypoxia［J］. Science of the Total Environment，2024，917：170490. doi:10.1016/j.scitotenv.2024.170490

选择文件类型/文献管理软件名称

选择包含的内容