Department of Civil Engineering, University of Arkansas, Fayetteville, Arkansas 72701, United States.
U.S. Environmental Protection Agency, Cincinnati, Ohio 45268, United States.
Environ Sci Technol. 2023 Jul 4;57(26):9793-9801. doi: 10.1021/acs.est.3c01861. Epub 2023 Jun 21.
Mass transport in diffusive gradients in thin-film passive samplers is restricted to diffusion through a gel layer of agarose or agarose cross-linked polyacrylamide (APA). The gel layer diffusion coefficient, , is typically determined using a standard analysis (SA) based on Fick's first law from two-compartment diffusion cell (D-Cell) tests. The SA assumes pseudo-steady-state flux, characterized by linear sink mass accumulation-time profiles with a typical threshold ≥ 0.97. In 72 D-Cell tests with nitrate, 63 met this threshold, but the SA-determined ranged from 10.1 to 15.8 × 10 cm·s (agarose) and 9.5 to 14.7 × 10 cm·s (APA). A regression model developed with the SA to account for the diffusive boundary layer had 95% confidence intervals (CIs) on of 13 to 18 × 10 cm·s (agarose) and 12 to 19 × 10 cm·s (APA) at 500 rpm. A finite difference model (FDM) developed based on Fick's second law with non-steady-state (N-SS) flux decreased uncertainty in tenfold. The FDM-captured decreasing source compartment concentrations and N-SS flux in the D-Cell tests and, at 500 rpm, the FDM-determined ± 95% CIs were 14.5 ± 0.2 × 10 cm·s (agarose) and 14.0 ± 0.3 × 10 cm·s (APA), respectively.
在薄层层析扩散采样器中,质量传递仅限于通过琼脂或琼脂交联聚丙烯酰胺 (APA) 的凝胶层扩散。凝胶层扩散系数 ,通常使用基于双室扩散池 (D-Cell) 测试中菲克第一定律的标准分析 (SA) 来确定。SA 假设假稳态通量,其特征是具有典型阈值 ≥ 0.97 的线性汇质量积累时间曲线。在 72 个硝酸盐 D-Cell 测试中,有 63 个符合此阈值,但 SA 确定的 范围为 10.1 到 15.8 × 10 cm·s(琼脂)和 9.5 到 14.7 × 10 cm·s(APA)。使用 SA 开发的回归模型来解释扩散边界层,在 500 rpm 时,琼脂的 置信区间 (CI) 为 13 到 18 × 10 cm·s,APA 的 置信区间 (CI) 为 12 到 19 × 10 cm·s。基于菲克第二定律和非稳态 (N-SS) 通量的有限差分模型 (FDM) 可将不确定性降低十倍。FDM 捕获了 D-Cell 测试中源隔室浓度和 N-SS 通量的下降,并在 500 rpm 时,FDM 确定的 ± 95% CI 分别为 14.5 ± 0.2 × 10 cm·s(琼脂)和 14.0 ± 0.3 × 10 cm·s(APA)。
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