Abstract
Descriptions of chemical transformation kinetics and hydrologic transport need to be coupled to understand the composition of flowing waters. The coupling of a bimolecular transformation reaction (reactant 1 + reactant 2 → product; rate \( r = \kappa c_{1} c_{2} \)) with spatially heterogeneous subsurface flows is addressed here. The flow microstructure—that controls the spreading rate of solutes and the mean reactant concentrations (C 1, C 2)—creates concentration microstructure whose intensity is characterized by the variances \( \sigma_{{c_{1} }}^{2} \), \( \sigma_{{c_{2} }}^{2} \), and the cross-covariance \( \overline{{c_{1} c_{2} }} \). In addition to the macroscopic overlap of the reactants, that is quantified by the product of the mean concentrations that are routinely modeled using effective dispersion coefficients \( D_{ij} \), the concentration microstructure plays an important role in determining reaction macro-kinetics as the mean reaction rate is \( \overline{r} = \kappa (C_{1} C_{2} + \overline{{c_{1} c_{2} }} ) \). For initially non-overlapping reactants \( \overline{{c_{1} c_{2} }} + C_{1} C_{2} = 0 \) and \( \overline{r} = 0 \) under pure advection. It is shown that due to the action of local dispersion, at large time, the \( \overline{{c_{1} c_{2} }} \) budget is characterized by a balance between its rate of production and dissipation, which results in \( \overline{{c_{1} c_{2} }} \approx 2\tau D_{ij} ({{\partial C_{1} } \mathord{\left/ {\vphantom {{\partial C_{1} } {\partial x_{i} )({{\partial C_{2} } \mathord{\left/ {\vphantom {{\partial C_{2} } {\partial x_{j} )}}} \right. \kern-0pt} {\partial x_{j} )}}}}} \right. \kern-0pt} {\partial x_{i} )({{\partial C_{2} } \mathord{\left/ {\vphantom {{\partial C_{2} } {\partial x_{j} )}}} \right. \kern-0pt} {\partial x_{j} )}}}} \), where τ is the dissipation time-scale characteristic to the destruction of concentration fluctuation by local dispersion. This results in \( \overline{r} = \kappa_{\text{eff}} C_{1} C_{2} \), where \( \kappa_{\text{eff}} \approx \kappa [1 + 2\tau D_{ij} ({{\partial { \ln }C_{1} } \mathord{\left/ {\vphantom {{\partial { \ln }C_{1} } {\partial x_{i} )({{\partial { \ln }C_{2} } \mathord{\left/ {\vphantom {{\partial { \ln }C_{2} } {\partial x_{j} )}}} \right. \kern-0pt} {\partial x_{j} )}}}}} \right. \kern-0pt} {\partial x_{i} )({{\partial { \ln }C_{2} } \mathord{\left/ {\vphantom {{\partial { \ln }C_{2} } {\partial x_{j} )}}} \right. \kern-0pt} {\partial x_{j} )}}}}] \), which accounts for the influence of concentration microstructure and small-scale mixing on the macroscopic bimolecular kinetics. The effective rate parameter κeff is greater than the intrinsic rate constant κ measured under well-mixed conditions if the macroscopic concentration gradients have the same sign (initially overlapping reactants). For the initially non-overlapping reactants which result in macroscopic gradients having opposite signs, κ eff < κ. The macroscopic reactant concentration gradients, effective dispersion coefficients, and the dissipation time-scale control the reaction macro-kinetics, in addition to the intrinsic rate constant κ and the mean reactant concentrations. The formulation for reaction macro-kinetics developed here helps explain previously reported disparities between laboratory and field-scale transformation rates and also provides a way to represent the influence of reactant concentration microstructure in large-scale descriptions of reactive transport.
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References
Acharya RC, Valocchi AJ, Werth CJ, Willingham TW (2007) Pore-scale simulation of dispersion and reaction along a transverse mixing zone in two-dimensional media. Water Resour Res 43:W10435. doi:10.1029/2007WR005969
Ames WF (1992) Numerical methods for partial differential equations, 3rd edn. Academic Press, USA
Anmala J (2000) Mixing and bimolecular reaction kinetics in heterogeneous porous media flows. Ph.D thesis, Georgia Institute of Technology
Anmala J, Kapoor V (2012) Mixing and bimolecular reaction kinetics in a plane Poisseulle flow. Flow Turbul Combust 88:387–405
Battiato I, Tartakovsky DM (2011) Applicability regimes for macroscopic models of reactive transport in porous media. J Contam Hydrol 120–121:18–26
Battiato I, Tartakovsky DM, Tartakovsky AM, Scheibe TD (2009) On breakdown of macroscopic models of mixing-controlled heterogeneous reactions in porous media. Adv Water Resour 32:1664–1673
Battiato I, Tartakovsky DM, Tartakovsky AM, Scheibe TD (2011) Hybrid models of reactive transport in porous and fractured media. Adv Water Resour 34:1140–1150
Cirpka OA, Kitanidis PK (2000a) Characterization of mixing and dilution in heterogeneous aquifers by means of local temporal moments. Water Resour Res 36(5):1221–1236
Cirpka OA, Kitanidis PK (2000b) An advective dispersive streamtube approach for the transfer of conservative tracer data to reactive transport. Water Resour Res 36(5):1209–1220
Dentz M, Borgne TL, Englert A, Bijeljic B (2011) Mixing, spreading and reaction in heterogeneous media: a brief review. J Contam Hydrol 120–121:1–17
Dykaar B, Kitanidis PK (1992) Determination of effective hydraulic conductivity in heterogeneous porous media using a numerical spectral approach, 1, Method. Water Resour Res 28(4):1155–1166
Friedly JC, Davis JA, Kent DB (1995) Modeling hexavalent chromium reduction in groundwater in field-scale transport and laboratory batch experiments. Water Resour Res 31(11):2783–2794
Gelhar LW (1993) Stochastic subsurface hydrology. Prentice-Hall, Englewood-Cliffs
Gelhar LW, Axness CL (1983) Three-dimensional stochastic analysis of macrodispersion in aquifers. Water Resour Res 19(1):161–180
Kapoor V, Anmala J (1998) Lower bounds on scalar dissipation rate in bounded rectilinear flows. Flow Combust Turbul 60(2):125–156
Kapoor V, Gelhar LW (1994a) Transport in three-dimensionally heterogeneous aquifers. 1. Dynamics of concentration fluctuations. Water Resour Res 30(6):1775–1788
Kapoor V, Gelhar LW (1994b) Transport in three-dimensionally heterogeneous aquifers. 2. Predictions and observations of concentration fluctuations. Water Resour Res 30(6):1789–1801
Kapoor V, Kitanidis PK (1997) Advection-diffusion in spatially random flows: formulation of concentration covariance. Stoch Hydrol Hydraul 11(5):397–422
Kapoor V, Kitanidis PK (1998) Concentration fluctuations and dilution in aquifers. Water Resour Res 34(5):1181–1194
Kapoor V, Gelhar LW, Wilhelm FM (1997) Bimolecular second order reactions in spatially varying flows: segregation induced scale dependence of transformation. Water Resour Res 33(4):527–536
Kapoor V, Jafvert CT, Lyn DA (1998) Experimental study of a bimolecular reaction in Poiseuille flow. Water Resour Res 34(8):1997–2004
LeBlanc DR, Garabedian SP, Hess KM, Gelhar LW, Quadri RD, Stollenwerk KG, Wood WW (1991) Large-scale natural gradient tracer test in sand and gravel, Cape Cod, Massachusetts: 1. Experimental design and observed tracer movement. Water Resour Res 27(5):895–910
Lichtner PC, Tartakovsky DM (2003) Stochastic analysis of effective rate constant for heterogeneous reaction. Stoch Environ Res Risk Assess 17:419–429
Luo J, Dentz M, Carrera J, Kitanidis P (2008) Effective reaction parameters for mixing controlled reactions in heterogeneous media. Water Reour Res 44:W02416. doi:10.1029/2006WR005658
Mo Z, Friedly JC (2000) Local reaction and diffusion in porous media transport models. Water Resour Res 36(2):431–438
Molz FJ, Widdowson MA (1988) Internal inconsistencies in dispersion-dominated models that incorporate chemical and microbial kinetics. Water Resour Res 24(4):615–619
Pannone M, Kitanidis PK (1999) Large-time behavior of concentration variance and dilution in heterogeneous formations. Water Resour Res 35(3):623–634
Raje D, Kapoor V (2000) Experimental study of bimolecular reaction kinetics in porous media. Environ Sci Tech 34:1234–1239
Semprini L, McCarty PL (1991) Comparison between model simulations and field results for in situ biorestoration of chlorinated aliphatics: part 1. Biostimulation of methanotrophic bacteria. Groundwater 29(3):365–374
Srinivasan G, Tartakovsky DM, Robinson BA, Aceeves AB (2007) Quantification of uncertainty in geochemical reactions. Water Resour Res 43:W12415. doi:10.1029/2007WR006003
Sturman PJ, Stewart PS, Cunningham AB, Bouwer EJ, Wolfram JH (1995) Engineering scale-up of in situ bioremediation processes: a review. J Contam Hydrol 19:171–203
Wang J, Kitanidis PK (1999) Analysis of macrodispersion through volume averaging: comparison with stochastic theory. Stoch Env Res Risk Assess 13:66–84
Webb BW, Walling DE (1996) Water quality, II, chemical characteristics. In: Petts G, Calow P (eds) River flows and channel forms. Blackwell, Cambridge, Chap. 6, pp 102–129
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Anmala, J., Kapoor, V. Dynamics of mixing and bimolecular reaction kinetics in aquifers. Stoch Environ Res Risk Assess 27, 1005–1020 (2013). https://doi.org/10.1007/s00477-012-0679-5
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DOI: https://doi.org/10.1007/s00477-012-0679-5