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冷冻与溶液酸度是影响矿物风化溶解的关键环境因子，但二者对磷灰石溶解的相对贡献及其耦合调控机制尚不明确。本研究以氟磷灰石为对象，设置多级温度梯度(-80～15℃)与pH值梯度(pH=1～5)，结合柠檬酸络合体系，采用电感耦合等离子体发射光谱法(ICP-OES)定量监测磷与钙的溶出浓度，系统区分酸溶作用与冷冻过程对磷灰石溶解的影响。结果表明：冷冻处理可通过晶间液态边界(LIB)溶质浓缩效应在反应初期加速磷的释放，但非冻结对照组(4℃)的最终磷溶出浓度(92 mg/L)略高于冷冻处理组(-20℃，80 mg/L)，说明冷冻仅提升了初期释放速率，并未改变磷的最终溶出总量。溶液H⁺浓度是控制磷灰石溶解程度的主导因子，其对磷最终释放总量的贡献远超冷冻过程的物理作用。在-15～-25℃，冷冻温度变化对磷溶出量无显著影响。本研究明确了酸性环境中磷灰石溶解的主控机制，可为冰川及永冻土消融区磷的活化迁移与生物地球化学循环提供理论依据。
Abstract：Freezing and solution acidity are key environmental factors that drive mineral weathering and dissolution in terrestrial and aquatic environments. However, the relative contributions of these two factors to apatite dissolution,as well as their coupled regulatory mechanisms during the weathering process, remain unclear and lack systematic quantitative evaluation. In this study, fluorapatite was selected as the target mineral to investigate its dissolution behavior under coupled freezing and acidic conditions. A set of batch dissolution experiments was conducted with multi-level temperature gradients ranging from-80 to 15 ℃ and pH value gradients from 1 to 5, combined with a citric acid complexation system to mimic natural acidic environments with organic ligands. The dissolved concentrations of phosphorus(P) and calcium(Ca) in the solution at different reaction time points were quantitatively monitored via inductively coupled plasma optical emission spectrometry(ICP-OES), based on which the individual effects of acid dissolution and freezing process on apatite dissolution were systematically distinguished and compared.The experimental results demonstrated that freezing treatment could accelerate phosphorus release at the initial stage of the reaction, which was mainly driven by the solute concentration effect occurring in the Liquid Intergrain Boundary(LIB) during ice formation. However, the final phosphorus dissolution concentration in the non-freezing control group(4 ℃, 92 mg/L) was slightly higher than that in the freezing treatment group(-20 ℃, 80 mg/L). This comparative result indicated that freezing only enhanced the initial release rate of phosphorus from apatite, but did not alter the total amount of phosphorus dissolved at equilibrium. Furthermore, solution H⁺ concentration was identified as the dominant factor controlling the dissolution extent of apatite, and its contribution to the final total phosphorus release far outweighed the physical effect induced by the freezing process. In addition, within the freezing temperature range of-15 to-25 ℃, variations in freezing temperature exerted no significant influence on the phosphorus dissolution amount of fluorapatite. This study clarifies the dominant controlling mechanism of apatite dissolution in acidic environments, and quantifies the differential roles of freezing and acidity in regulating apatite weathering. The conclusions can provide a solid theoretical basis for understanding phosphorus mobilization,migration and biogeochemical cycling in cold region environments such as glacial zones and permafrost thaw areas.
[1] Hugonnet R, McNabb R, Berthier E, et al. Accelerated global glacier mass loss in the early twenty-first century[J].Nature, 2021, 592(7856):726-731.
[2] Rantanen M, Karpechko A Y, Lipponen A, et al. The Arctic has warmed nearly four times faster than the globe since 1979[J]. Communications Earth&Environment, 2022, 3:168. DOI:10.1038/s43247-022-00498-3.
[3] Slater D A, Straneo F. Submarine melting of glaciers in Greenland amplified by atmospheric warming[J]. Nature Geoscience, 2022, 15(10):794-799.
[4] Pokrovsky O S, Karlsson J, Giesler R. Freeze-thaw cycles of Arctic thaw ponds remove colloidal metals and generate low-molecular-weight organic matter[J]. Biogeochemistry, 2018, 137(3):321-336.
[5] Tank S E, McClelland J W, Spencer R G M, et al. Recent trends in the chemistry of major northern rivers signal widespread Arctic change[J]. Nature Geoscience, 2023, 16(9):789-796.
[6] Bartels-Rausch T, Jacobi H W, Kahan T F, et al. A review of air–ice chemical and physical interactions(AICI):liquids, quasi-liquids, and solids in snow[J]. Atmospheric Chemistry and Physics, 2014, 14(3):1587-1633.
[7] Chen Tao, Bui Thi T M, Luo Tao, et al. Redox-driven formation of Mn(III)in ice[J]. Environmental Science&Technology, 2024:acs.est.4c03850. DOI:10.1021/acs.est.4c03850.
[8] Sun Yuqi, Li Juan, Li Shengnan, et al. Inorganic substrates in frozen solutions:transformation mechanisms and interactions with organic compounds:a review[J]. Water Research, 2025, 273:123068.DOI:10.1016/j.watres.2024.123068.
[9] Cho H, Shepson P B, Barrie L A, et al. NMR investigation of the quasi-brine layer in ice/brine mixtures[J]. The Journal of Physical Chemistry B, 2002, 106(43):11226-11232.
[10] Lv Jiaxin, Zuo Wenping, Tian Chen, et al. Freeze-accelerated reactions on environmental relevant processes[J].Cell Reports Physical Science, 2023, 4(6):101456. DOI:10.1016/j.xcrp.2023.101456.
[11] Sebaaly A P, van Rijn F, Hanna K, et al. Ice as a kinetic and mechanistic driver of oxalate-promoted iron oxyhydroxide dissolution[J]. Proceedings of the National Academy of Sciences of the United States of America, 2025,122(35):e2507588122. DOI:10.1073/pnas.2507588122.
[12] Song Junwei, Werner L, Da Silva Y C M, et al. Spontaneous production of H2O2 at the liquid–ice interface:a potential source of atmospheric oxidants[J]. Environmental Science&Technology, 2024, 58(51):22691-22699.
[13] Lin Qiuxun, Song Zhenyang, Qi Mengting, et al. Spatial and historic changes of nutrients across the Changjiang river and associated major tributaries[J]. Water Research, 2026, 290:125140. DOI:10.1016/j.watres.2025.125140.
[14]刁星，万欣，丛志远，等.高压密闭消解-电感耦合等离子体质谱(ICP-MS)法测定青藏高原气溶胶样品中磷及其他18种元素[J].中国无机分析化学，2023, 13(1):19-24.Diao Xing, Wan Xin, Cong Zhiyuan, et al. Determination of phosphorus and other 18 elements in Tibetan Plateau aerosol samples by inductively coupled plasma mass spectrometry with high-pressure bomb digestion[J]. Chinese Journal of Inorganic Analytical Chemistry, 2023, 13(1):19-24.
[15] Guo Licheng, Xiong Shangfa, Mills B J W, et al. Acceleration of phosphorus weathering under warm climates[J].Science Advances, 2024, 10(28):eadm7773. DOI:10.1126/sciadv.adm7773.
16] Herbert R J, Krom M D, Carslaw K S, et al. The effect of atmospheric acid processing on the global deposition of bioavailable phosphorus from dust[J]. Global Biogeochemical Cycles, 2018, 32(9):1367-1385.
[17] Stockdale A, Krom M D, Mortimer R J G, et al. Understanding the nature of atmospheric acid processing of mineral dusts in supplying bioavailable phosphorus to the oceans[J]. Proceedings of the National Academy of Sciences of the United States of America, 2016, 113(51):14639-14644.
[18] Nenes A, Krom M D, Mihalopoulos N, et al. Atmospheric acidification of mineral aerosols:a source of bioavailable phosphorus for the oceans[J]. Atmospheric Chemistry and Physics, 2011, 11(13):6265-6272.
[19] Li Ziliang, Kang Luyao, Wang Lu, et al. Accelerated soil phosphorus cycling upon abrupt permafrost thaw[J].Nature Climate Change, 2025, 15(11):1234-1240.
[20] Liao Ning, Jiang Lai, Li Jia, et al. Effects of freeze-thaw cycles on phosphorus from sediments in the middle reaches of the Yarlung Zangbo River[J]. International Journal of Environmental Research and Public Health, 2019,16(19):3783. DOI:10.3390/ijerph16193783.
[21] Barczok M, Smith C, Kinsman-Costello L, et al. Iron transformation mediates phosphate retention across a permafrost thaw gradient[J]. Communications Earth&Environment, 2024, 5:635.DOI:10.1038/s43247-024-01810-z.
[22] Berens M J, Michaud A B, VanderJeugdt E, et al. Phosphorus interactions with iron in undisturbed and disturbed Arctic tundra ecosystems[J]. Environmental Science&Technology, 2024, 58(26):11400-11410.
[23] Xu Renkou, Zhu Yongguan, Chittleborough D. Phosphorus release from phosphate rock and iron phosphate by low-molecular-weight organic acids[J]. Journal of Environmental Sciences, 2004, 16(1):5-8.
[24] Wei Wei, Zhang Xiao, Cui Jing, et al. Interaction between low molecular weight organic acids and hydroxyapatite with different degrees of crystallinity[J]. Colloids and Surfaces A:Physicochemical and Engineering Aspects, 2011, 392(1):67-75.
[25] Goyne K W, Brantley S L, Chorover J. Effects of organic acids and dissolved oxygen on apatite and chalcopyrite dissolution:implications for using elements as organomarkers and oxymarkers[J]. Chemical Geology, 2006, 234(1/2):28-45.
[26] Jeong D, Kim K, Min D W, et al. Freezing-enhanced dissolution of iron oxides:effects of inorganic acid anions[J]. Environmental Science&Technology, 2015, 49(21):12816-12822.
[27] Jeong D, Kim K, Choi W. Accelerated dissolution of iron oxides in ice[J]. Atmospheric Chemistry and Physics,2012, 12(22):11125-11133.
[28] Bower J P, Anastasio C. Using singlet molecular oxygen to probe the solute and temperature dependence of liquid-like regions in/on ice[J]. The Journal of Physical Chemistry A, 2013, 117(30):6612-6621.
[29] Moreno E C, Kresak M, Zahradnik R T. Physicochemical aspects of fluoride-apatite systems relevant to the study of dental caries[J]. Caries Research, 1977, 11(S1):142-171.
[30] Chen Tao, Luo Tao, Bui Thi T M, et al. Ice amplifies ligand-controlled mineral dissolution in microscale hot spots[J]. Proceedings of the National Academy of Sciences of the United States of America, 2026, 123(17):e2532599123. DOI:10.1073/pnas.2532599123.
[31] Avnimelech Y, Moreno E C, Brown W E. Solubility and surface properties of finely divided hydroxyapatite[J].Journal of Research of the National Bureau of Standards Section A:Physics and Chemistry, 1973, 77A(1):149.DOI:10.6028/jres.077a.008.
[32] Rahbar Kafshboran H, Aminnezhad N. Novel formulations of hydroxyapatite in hard tissue engineering:an overview[J]. Micro Nano Bio Aspects, 2025, 4(3):13-25.
[33]汝琳琳，陈天虎，邹雪华，等.胶磷矿氟磷灰石对水中低浓度磷的去除作用[J].硅酸盐学报，2021, 49(8):1776-1784.Ru Linlin, Chen Tianhu, Zou Xuehua, et al. Effect of collophanite on removal of low-concentration phosphorus in water[J]. Journal of the Chinese Ceramic Society, 2021, 49(8):1776-1784.
[34] Oztas T, Fayetorbay F. Effect of freezing and thawing processes on soil aggregate stability[J]. Catena, 2003,52(1):1-8.
[35] YarbaşıN, Kalkan E, Akbulut S. Modification of the geotechnical properties, as influenced by freeze–thaw, of granular soils with waste additives[J]. Cold Regions Science and Technology, 2007, 48(1):44-54.
[36] Serreze M C, Barry R G. Processes and impacts of Arctic amplification:a research synthesis[J]. Global and Planetary Change, 2011, 77(1/2):85-96.
[37] Serreze M C, Cassano E, Crawford A, et al. The observed evolution of Arctic amplification over the past 45years[J]. The Cryosphere, 2026, 20(1):411-425.
基本信息:
中图分类号:P593;P574;O657.3
引用信息:
[1]冉雪莉,杨冰清,万雨函,等.冷冻与酸溶解对氟磷灰石中磷释放的影响[J].中国无机分析化学().
基金信息:
国家自然科学基金资助项目(42401148);国家自然科学基金重点项目(42330515); 中国博士后科学基金会与湖北省联合资助(特别资助)项目(2025T036HB); 中国工程院院地合作项目(HB2025B19)
2026-09-03
2026-09-03
2026-09-03