Effects of Freeze-Thaw Cycles on Transport Behavior of Chlorobenzene Following Spontaneous Infiltration
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摘要:
探明包气带重非水相液体（dense non-aqueous phase liquids, DNAPLs）自发入渗稳定后受冻融循环作用的再运移规律及机制对季节性冻融区污染场地修复至关重要.选取氯苯作为典型DNAPL，以西藏色季拉山口的粉质黏土为多孔介质，利用分层核磁共振技术定量测试不同入渗时间及冻融循环次数后在土柱垂向空间位置的氯苯含量.研究表明：随着入渗时间的增加，无量纲入渗深度0~0.375范围内氯苯浓度呈下降趋势，0.375~0.750范围内氯苯浓度呈上升趋势.冻结产生的冻结诱导压力驱动入渗稳定后的氯苯向下再运移，但驱动能力有限，不同冻融循环后氯苯浓度变化率最小的为3.51%，最大的不超过24%.自发入渗和冻融循环过程中，毛细力、重力和冻结诱导压力的相互作用控制着氯苯在不同垂向深度的运移和分布.
Abstract:Elucidating the re-transport patterns and mechanisms of dense non-aqueous phase liquids (DNAPLs) in the vadose zone after spontaneous infiltration and stabilization under freeze-thaw cycles is crucial for the remediation of contaminated sites in seasonal freeze-thaw zones. Chlorobenzene (CB) was selected as a typical DNAPL, and silty clay from the Sejila Pass in Xizang was used as the porous medium. A stratified nuclear magnetic resonance (NMR) technology was used to quantitatively test the CB content at the vertical spatial location of the soil column after different infiltration times and freeze-thaw cycles. Studies have shown that as infiltration time increases, the concentration of CB decreases in the dimensionless infiltration depth range of 0-0.375, and increases in the dimensionless infiltration depth range of 0.375-0.750. The freeze-induced pressure generated by freezing drives the downward transport of CB after it has stabilized, but the driving ability is limited. The smallest change rate of CB concentration after different freeze-thaw cycles is 3.51%, and the largest does not exceed 24%. During spontaneous infiltration and freeze-thaw cycles, the interaction of capillary force, gravity, and freeze-induced pressure controls the transport and distribution of CB at different vertical depths.
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图 2 核磁信号强度与氯苯体积的相关性
Fig. 2. Correlation between NMR signal intensity and the volume of chlorobenzene
图 3 入渗过程中不同入渗深度氯苯的T2谱图
Fig. 3. T2 spectra of chlorobenzene at different infiltration depths during infiltration
图 4 不同入渗深度氯苯浓度随入渗时间的变化
Fig. 4. Changes of CB concentration at different infiltration depths with infiltration time
图 5 冻融循环作用后不同垂向深度的氯苯T2谱
Fig. 5. T2 spectra of CB at different vertical depths after freeze-thaw cycles
图 6 不同垂向深度氯苯浓度随冻融循环次数的变化
Fig. 6. The variation of CB concentration at different vertical depths with the number of freeze-thaw cycles
图 7 入渗过程中不同浓度氯苯的受力情况模型
Fig. 7. Force model diagram of CB at different concentrations during infiltration
图 8 冻结过程中不同浓度氯苯的受力模型图
Fig. 8. Force model diagram of CB at different concentrations during freezing process
表 1 本研究所用粉质黏土的理化性质
Table 1. The physicochemical properties of the silty clay used in the study
孔隙度
(%)黏粒含量
(%)粉粒含量
(%)砂粒含量
(%)D10
(mm)D30
(mm)D60
(mm)总黏土矿物
(%)43.55 6.44 60.84 32.72 0.003 33 0.015 1 0.038 2 73.67 
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表 2 SE-SPI序列的主要操作参数
Table 2. Main operation parameters of the SE-SPI sequence
参数 SE-SPI 主频频率(MHz) 13 90°脉冲宽度(μs) 12 180°脉冲宽度(μs) 23.04 等待时间(ms) 6 000 累加次数 8 回波个数 10 000 回波时间(ms) 0.18 相位编码梯度方向 Z 视野范围(mm) 66 层数 13
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表 3 不同垂向深度氯苯浓度的变化率对冻融循环次数的响应
Table 3. Response of the rate of change of CB concentration at different vertical depths to the number of freeze-thaw cycles
冻融循环次数 氯苯浓度 0~0.125(%) 0.125~0.250(%) 0.250~0.375(%) 0.375~0.500(%) 0.500~0.625(%) 0.625~0.750(%) FT 1 6.36 9.90 3.51 8.79 17.75 4.01 FT 3 7.18 11.19 4.40 9.43 18.78 10.26 FT 5 7.86 12.67 5.24 10.47 18.16 19.23 FT 7 10.06 14.21 6.38 14.73 19.19 23.08
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