Chemical Weathering Rates of Silicate Minerals (Reviews in Mineralogy & Geochemistry)

Volume 31 of Reviews in Mineralogy reviews current thinking on the fundamental processes that control chemical weathering of silicates, including the physical chemistry of reactions at mineral surfaces, the role of experimental design in isolating and quantifying these reactions, and the complex roles that water chemistry, hydrology, biology, and climate play in weathering of natural systems. The chapters in this volume are arranged to parallel this order of development from theoretical considerations to experimental studies to characterization of natural systems. Secondly, the book is meant to serve as a reference from which researchers can readily retrieve quantitative weathering rate data for specific minerals under detailed experimental controls or for natural weathering conditions. Toward this objective, the authors were encouraged to tabulate available weathering rate data for their specific topics. Finally this volume serves as a forum in which suggestions and speculations concerning the direction of future weathering research are discussed. Page 1 Titles REVIEWS in MINERALOGY Volume 31 Editors: Arthur F. White u.s. Geological Survey, Menlo Park, CA Susan L. Brantley Pennsylvania State University Mineralogical Society of America Page 1 Page 1 Titles iii Page 1 Titles Chemical Weathering Rates of ................................................................. iii v Page 2 Titles vi Page 3 Page 4 Titles viii Page 5 Titles ix Page 6 Titles x Page 7 Titles xi Page 8 Titles xii Page 9 Titles H. Sverdrup and P. Warfvinge USING LABORATORY KINETICS Page 10 Titles xiv Page 11 Titles xv Page 12 Page 1 Titles Chapter 1 CHEMICAL WEATHERING RATES OF SILICATE MINERALS: AN OVERVIEW Art F. White Susan L. Brantley Page 2 Page 3 Page 4 Tables Table 1 Page 5 Tables Table 1 Page 6 Titles £>.0 .• Slope = -0.5 ~···o • -. rfir ~. o. T t z Tables Table 1 Page 7 Page 8 Page 9 Page 10 Page 11 Page 12 Page 13 Page 14 Page 15 Page 16 Page 17 Page 18 Page 19 Tables Table 1 Page 20 Page 21 Titles White & Brantley: Overview of Chemical Weathering Rates of Silicates 21 weathering currently underway will serve to push our understanding forward in the next REFERENCES Page 22 Titles 22 White & Brantley: Overview of Chemical Weathering Rates of Silicates Page 1 Titles Chapter 2 FUNDAMENTAL APPROACHES IN DESCRIBING MINERAL Antonio C. Lasaga Page 2 Titles (1) Page 3 Titles (2) (3) (4) Page 4 Titles 26 Lasaga: Approaches to Describing Dissolution/Precipitation Rates 4 ADATOM 2 3 .... ~- ... - .. --.- .... -~-.- (7) (8) Page 7 Titles (10) (ll) R"et = R+ - R_ = 0 (12) (13) (15) (16) Page 8 Titles k~ c~q Tables Table 1 Table 2 Page 9 Page 10 Titles r II2 f(b.Gr) f(b.Gr) Page 11 Titles (32) (33) Page 12 Titles 34 Lasaga: Approaches to Describing Dissolution/Precipitation Rates h x (35) k _ BulkRate flow v = ~ (- 'ilP + pg) R t - k A -Ea/RT nH+ II ni f(AG) a e - 0 min e a H+ ai Ll r (37) Page 13 Titles _ 8lnRate _ Eapp _ Ea _ n 8InXH+,ads _ '\' n. 8lnXi,ads _ 8ln f(b.Gr) 8(1/T) - R - R H+,ads 8(1/T) L: i.ads 8(1/T) 8(1/T) Page 14 Titles pH DEPENDENCE Tables Table 1 Page 15 Titles IONIC STRENGTH AND SOLUTION COMPOSITION Page 16 Titles ,- Ii: Page 17 Titles :r: \ o \ 1'\ 12 ~ .. \ '2.,~ \ Tables Table 1 Page 18 Titles , I· DE 30CJ0.tIOO , Tables Table 1 Page 19 Page 20 Page 21 Titles Lasaga: Approaches to Describing Dissolution/Precipitation Rates 43 RHF/STO-36 n-Alkanes • Carbons RHF/6-31I ++6** n-Alkanes b Tables Table 1 Table 2 Page 22 Page 23 Titles Lasaga: Approaches to Describing DissolutioniPrecipitation Rates 45 H If Si AI 0- H stretching out-of-plane H in-plane ~ I ~ O-H bending /0"", Si AI Tables Table 1 Page 24 Titles 46 Lasaga: Approaches to Describing Dissolution/Precipitation Rates Page 25 Page 26 Titles Table 4. SCF optimized structural parameters computed for different models. Tables Table 1 Table 2 Page 27 Titles H 0 10.965 ~ H "J ~JJ)~ V /674 o 50 0 Page 28 Page 29 Page 30 Page 31 Titles Lasaga: Approaches to Describing Dissolution/Precipitation Rates 53 a Kaolinite cluster SVWN/3-21G* Page 32 REV031C002_p55-86.pdf Page 1 Titles Lasaga: Approaches to Describing Dissolution/Precipitation Rates 55 ~/"" l' ~ ~ b Table 5. Hydrolysis of feldspar. Page 2 Page 3 Titles ? G '-'.643 H g~ ~ Page 4 Titles 58 Lasaga: Approaches to Describing Dissolution/Precipitation Rates II IV .,. C?l-3 " -, Q'~ \\ til :S/ 2: \ I c-;: , Page 5 Titles H-if' , ~~® r "< 59 Page 6 Titles b ... ' ~: i~~ ~~ Page 7 Titles a b c Page 8 Titles 62 Lasaga: Approaches to Describing Dissolution/Precipitation Rates , , ',., \ .~ , ,~ » , " ~J: ~------- 0.970 C"? I ,0 ~I \ --; ·:t"!1·1J-" ~ ~~ ~ \ , , ' ~: : \~ , ::Jl Page 9 Page 10 Page 11 Titles A. B. c. D. I I; I 51 SI ........... H 51 /,~,~,~ o y ? Y ? Y ? , , , Page 12 Titles Rate = ks[H4SiO:dS] = kI[H20ads• Si] Page 13 Titles 1.+1.+1.+1. Page 14 Titles (0 Tables Table 1 Table 2 Table 3 Page 15 Page 16 Titles (62) MONTE CARLO METHODS AND RATE LAWS (63) Page 17 Titles Lasaga: Approaches to Describing DissolutionlPrecipitation Rates 71 Comparison of Monte Carlo Results "' o t Time (in arbitrary units) (64) Page 18 Titles 72 Lasaga: Approaches to Describing DissolutionlPrecipitation Rates Si - -0 - -Si + H20 --t Si - OH + Si - OH (65) Si - -0 - -Al2 + H20 --t Al- OH - Al + Si - OH (66) Al - OH - Al + H20 --t Al - OH + Al - OH2 (67) Page 19 Titles ° + Tables Table 1 Page 20 Titles 74 Lasaga: Approaches to Describing Dissolution/Precipitation Rates Page 21 Titles Lasaga: Approaches to Describing DissolutionlPrecipitation Rates 75 a b I -... I =« d \ ~ ~I \ ~ J , ==-, . .. ,. ,. l ~ a c : \ , , , -1 Z ~ 11'\1\- ~ -. ~. / ''\'''' " ks, = 0.69 kAl = 4.86 Page 24 Tables Table 1 Page 25 Titles -£ • Tables Table 1 Page 26 Page 27 Titles Lasaga: Approaches to Describing DissolutionlPrecipitation Rates 81 REFERENCES Page 28 Titles 82 Lasaga: Approaches to Describing DissolutionlPrecipitation Rates Page 29 Titles Lasaga: Approaches to Describing DissolutionlPrecipitation Rates 83 Page 30 Titles 84 Lasaga: Approaches to Describing Dissolution/Precipitation Rates Page 31 Titles Lasaga: Approaches to Describing Dissolution/Precipitation Rates 85 Page 32 Titles 86 Lasaga: Approaches to Describing Dissolution/Precipitation Rates Page 1 Titles Chapter 3 SILICATE MINERAL DISSOLUTION William H. Casey and Christian Ludwig INTRODUCTION Tables Table 1 Page 2 Titles a) b) Dissociative . __ /,--C-···.. -: L······ . 10000 553 10 100 1000 10000 Mean Runoff (mm vr') Tables Table 1 Page 12 Titles 554 Page 13 Titles (10) Tables Table 1 Page 14 Titles 556 Tables Table 1 Page 15 Titles 557 o o '-:;; 1 1-------------- o - as a: Tables Table 1 Page 16 Titles 558 Page 17 Titles Stallard: Relating Chemical and Physical Erosion 559 Predicted solid yields Tables Table 1 Page 18 Titles 560 • 1 E ~ - as o Mean Runoff (mm vr') Tables Table 1 Page 19 Titles 561 100 10 5 V ' , , , , I II' "" , ",I "" , ,,,I 10000 }1000 10 100 1 000 10000 Mean annual runoff (mm) Page 20 Titles 562 Page 21 Titles Stallard: Relating Chemical and Physical Erosion 563 Page 22 Titles 564 Stallard: Relating Chemical and Physical Erosion Page 1 Titles Chapter 13 CHEMICAL WEATHERING AND ITS EFFECT Robert A. Berner Page 2 Page 3 Titles (6) Page 4 Page 5 Page 6 Page 7 Titles Climate Page 8 Titles ~ ~ co co s: }- - Temperature (0G) Page 9 Page 10 Page 11 Titles Berner: Chemical Weathering: Effect on Atmospheric CO2 and Climate 575 - 10~m Page 12 Page 13 Page 14 Titles I I ~ ., il ) ;:, H i , , , , , I ! I n! , ,. : l:: , .. . " . " , .. , " . i Ai: Page 15 Tables Table 1 Page 16 Titles 580 Berner: Chemical Weathering: Effect on Atmospheric CO2 and Climate Tables Table 1 Table 2 Page 17 Page 18 Titles 582 Berner: Chemical Weathering: Effect on Atmospheric CO2 and Climate Page 19 Titles Berner: Chemical Weathering: Effect on Atmospheric CO2 and Climate 583 Page 20