Geochemical Processes at Mineral Surfaces

Downloaded by UNIV OF PRINCE EDWARD ISLAND on September 15, 2015 | http://pubs.acs.org Publication Date: November 13, 1987 | doi: 10.1021/bk-1987-0323.ix002

Author Index

Ambe, F., 403 Ambe, S., 403 Anderson, Μ. Α., 142 Bousse, L u c , 79 B r a n t l e y , S. L., 635 Chan, Derek Y. C , 99 C o s t a n z o , P. Μ., 37 Crane, S. R., 635 Cremers, Α., 254 C r e r a r , D. Α., 635 C u r t i s , Gary P., 191 D a v i e s , Simon H. R., 487 D a v i s , James A., 2 D i l l a r d , John G., 503 D r i e s s e n s , F e r d i n a n d C. M., 524 E b e r l , Dennis D., 296 G i e s e , R. F., J r . , 37 Goodman, Β. Α., 342 G o u l d i n g , K e i t h W. T., 327 Hayes, Kim F., 2, 114 Hellmann, R., 635 Honeyman, Bruce D., 162 I k e d a , T e t s u y a , 230 Koutsoukos, P. G., 650 L e c k i e , James 0., 114, 162 Machesky, M. L., 142 Maes, Α., 254 M c B r i d e , Murray B., 362 M e i n d l , J . D., 79

M u l l a , David J . , 20 N a n c o l l a s , G. Η., 650 N i e l s e n , Arne E., 600 N o r t h r o p , H. Roy, 296 Okada, T., 403 P e r r y , Dale L., 389 P i n g i t o r e , N i c h o l a s E., J r . , 574 Plummer, L. N i e l , 561 R e i n h a r d , M a r t i n , 191, 462 R o b e r t s , P a u l V., 191 S a l i m i , M. H., 650 Schenck, C a t h e r i n e V., 503 Sekizawa, H., 403 S p o s i t o , G a r r i s o n , 217 Srodon, J a n , 296 S t a l l a r d , R., 635 Stone, A l a n T., 446 T e j e d o r - T e j e d o r , M. I . , 142 V e l b e l , M i c h a e l Anthony, 615 V o u d r i a s , Evangelos Α., 462 W a i t e , T. D a v i d , 426 W e s t a l l , John C , 54 White, A r t F., 587 Yasunaga, T a t s u y a , 230 Yee, Andy, 587 Y o s t , E. C , 142 Zawacki, S. J . , 650 Z e l t n e r , W. Α., 142

Subject Index

A

Acidity (Continued) e f f e c t on i n t e r c a l a t i o n phenomena, 250-252 A c i d i t y constants adsorption-desorption of p o t e n t i a l - d e t e r m i n i n g i o n s , 234t d i p r o t i c s u r f a c e group model, 69-71 A c t i v a t i o n energy d i f f u s i o n i n a l k a l i g l a s s e s , 593 d i f f u s i o n i n c r y s t a l l i n e and g l a s s s i l i c a t e s , 597 d i s s o l u t i o n o f q u a r t z , 644 A c t i v a t i o n p o t e n t i a l s , k i n e t i c model o f l e a d - i o n a d s o r p t i o n , 127 Activity components o f o l i v i n e s , 533 h y d r o x y a p a t i t e and f l u o r a p a t i t e , 545-552

Abiological nitrogen p h o t o f i x a t i o n , 428-429 A b i o t i c organic reactions a t mineral s u r f a c e s , 462-483 Absorption d e f i n i t i o n , 217 light metal o x i d e b u l k , 427-429 surface-located chromophores, 429-441 A c i d i c s i t e s on s o l i d s u r f a c e s , c h a r a c t e r i z a t i o n , 345 Acidity clay minerals, reaction promotion, 464-479 663

In Geochemical Processes at Mineral Surfaces; Davis, J., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 1987.


664

G E O C H E M I C A L P R O C E S S E S AT M I N E R A L S U R F A C E S

A c t i v i t y (Continued) KCl-KBr-water system, 563-566 Activity coefficients KCl-KBr-water system, 564-566 t r i p l e l a y e r model, 120-121 Adsorbate s u r f a c e r e a c t i o n s , s u r f a c e - c o m p l e x a t i o n models, l 6 3 t Adsorbed antimony-119 i o n s , c h e m i c a l forms, 420 Adsorbed copper on l a y e r s i l i c a t e s , 376-387 Adsorbed d i v a l e n t Co-57 i o n s , c h e m i c a l forms, 419 Adsorbed n i t r o x i d e s p i n probes on l a y e r s i l i c a t e s , 366-367 Adsorption a n i o n s on g o e t h i t e , 142 B a ( I I ) on c a l c i t e , 577-579 c o b a l t o u s i o n s on h e m a t i t e , 406-409 complexes on m i n e r a l s , 353-354 d i s t i n g u i s h i n g from s u r f a c e p r e c i p i t a t i o n , 217-226 d i v a l e n t Co-57, e f f e c t s o f p e n t a v a l e n t Sb and Sb i o n s , 414,423 g e n e r a l d i s c u s s i o n , 5-7 i n o r g a n i c s u r f a c e s , 204-208 l e a d i o n a t the g o e t h i t e - w a t e r i n t e r f a c e , mechanism, 114-140 manganese(II) m e t a l oxide s u r f a c e s , 490-491 sodium p e r c h l o r a t e and sodium c h l o r i d e , 497t metal ions a l u m i n o s i l i c a t e m i n e r a l s , 342-358 macroscopic p a r t i t i o n i n g c o e f f i c i e n t , 162-188 o r g a n i c r e d u c t a n t s and subsequent e l e c t r o n t r a n s f e r on m e t a l oxide s u r f a c e s , 446-460 o r g a n i c s o l u t e s on s u r f a c e s , 192-193 p e n t a v a l e n t antimony i o n s on h e m a t i t e , 409 p r e c u r s o r complex f o r m a t i o n , 454 p r e d i c t i n g over a range o f a d s o r p t i o n d e n s i t i e s , 179-181 s i l i c a t e m i n e r a l s , 50-51 w a t e r , 41-43 Adsorption density r e l a t i o n t o macroscopic p r o t o n c o e f f i c i e n t , 169,172,175 r e l a t i o n t o metal i o n a d s o r p t i o n , 167 r e l a t i o n to p a r t i t i o n i n g c o e f f i c i e n t , 175-178 Adsorption-desorption k i n e t i c s c o u n t e r i o n s , 236-241 d i v a l e n t metal i o n s , 241-244 metal o x i d e - s o l u t i o n i n t e r f a c e , s t u d i e d by r e l a x a t i o n methods, 230-252 p o t e n t i a l - d e t e r m i n i n g i o n s , 233-235

Adsorption enthalpies, f a c t o r s a f f e c t i n g , 144 Adsorption isotherms, d i s t i n g u i s h i n g a d s o r p t i o n from s u r f a c e p r e c i p i t a t i o n , 218-220 Adsorption layer concentration, c r y s t a l growth i n s o l u t i o n , 606 Adsorption reaction c o n c e p t u a l model, 57-59 net p r o t o n r e l e a s e and l i g a n d number, 136-137 A d s o r p t i o n s i t e s on m i n e r a l s u r f a c e s , o r i g i n and n a t u r e , 345 Adsorptive p r o p e r t i e s , v e r m i c u l i t e s and s m e c t i t e s , 364 A f f i n i t y term, e f f e c t on r e a c t i o n r a t e , 630 A l k a l i and a l k a l i n e e a r t h m e t a l - i o n exchange i n i l l i t e , 274-278 A l k a l i elements i n o b s i d i a n , d i f f u s i o n c o e f f i c i e n t s , 593t A l k a l i metal c a t i o n exchange, thermodynamic d a t a , 257t A l k a l i radionuclide diffusion, role i n g l a s s y and c r y s t a l l i n e s i l i c a t e s , 587-597 A l k a l i n e e a r t h c a t i o n s , e f f e c t on c a l c i u m phosphate p r e c i p i t a t i o n , 653 A l u m i n o s i l i c a t e minerals a d s o r p t i o n o f metal i o n s and complexes, 342-358 p o t a s s i u m - c a l c i u m exchange e q u i l i b r i a , 330-334 s u r f a c e charge, 344-345 types of s t r u c t u r e s , 344 Aluminum, auger parameters, 400t Ammonia c o o r d i n a t e d t o C o ( I I I ) , XPS s t u d i e s , 509 sorbed on sodium b i r n e s s i t e , XPS s t u d i e s , 509-510 Ammonium c a t i o n exchange, i n c l a y m i n e r a l s , 260-262 Amphoteric s u r f a c e e q u a t i o n o f s t a t e , 100-102 w i t h c o m p l e x a t i o n , 86-89 w i t h o u t c o m p l e x a t i o n , 80,82-85 Angle o f t e t r a h e d r a l r o t a t i o n , s m e c t i t e s , 310,314 A n g l e - r e s o l v e d XPS a n a l y s i s , t o produce e l e m e n t a l p r o f i l e s w i t h d e p t h , 592 Anion a d s o r p t i o n g o e t h i t e , 142-159 l e p i d o c r o c i t e s u r f a c e , 494t mechanism, 147 A n i s o t r o p y o f motion, h e c t o r i t e , 373 Antimony-119, decay t o Sn-119, 404 Antimony-119 i o n s , Mossbauer s t u d i e s o f m e t a l oxide-aqueous s o l u t i o n i n t e r f a c e s , 403-423


INDEX

665

A p a t i t e systems, i n c o n t a c t w i t h aqueous s o l u t i o n s , 544-558 Aqueous-phase n o n i d e a l i t i e s , 200-203 Aqueous s o l u t i o n s i n contact with i o n i c s o l i d


s o l u t i o n s , 524-558 i n contact with s o l i d s o l u t i o n s , approach t o e q u i l i b r i u m , 561-573 KBr and K C l , approach t o e q u i l i b r i u m , 561-573 Aragonite, i n s o l i d solutions i n c o n t a c t w i t h aqueous s o l u t i o n s , 540-544 Argon i o n s p u t t e r i n g i n o b s i d i a n , 590 Aromatic compounds e f f e c t on o r g a n i c exchange, 273 p o l y m e r i z a t i o n , t r e n d s , 471 A r r h e n i u s e x p r e s s i o n , temperature dependence o f d i f f u s i o n c o e f f i c i e n t s , 593 Auger d a t a , c h a l c o c i t e and c o v e l l i t e , 400t Auger e l e c t r o n s p e c t r o s c o p y (AES), c h e m i c a l bonding s t u d i e s o f m i n e r a l s , 395-397 Auger parameters aluminum, 400t d e f i n i t i o n , 397 s i l i c o n , 400t A x i a l l y symmetric s p i n system, ESR spectra, 379,38lf Axis spacings of l a y e r s i l i c a t e c l a y s , 366t

Β

B a c t e r i a , e f f e c t on M n ( I I ) o x i d a t i o n , 500 B a r i u m ( I I ) , modes o f c o p r e c i p i t a t i o n w i t h c a l c i t e , 574-585 Beidellite copper-doped f i l m s , ESR s p e c t r a , 379,380f,383,384f ESR s p e c t r a , 376,371-378f B e n t o n i t e , p o t a s s i u m - c a l c i u m exchange e q u i l i b r i a , 330-334 Benzene, r e a c t i o n w i t h metal-exchanged c l a y s , 355-356 Benzidine o x i d a t i o n i n the presence o f v a r i o u s c l a y s , 467-468 p r o t o n a t i o n , 468 r e a c t i o n w i t h metal-exchange c l a y s , 356 Benzoate, CIR-FTIR spectrum, 156f B i d e n t a t e bonding o f phosphate on g o e t h i t e , 148 B i n d i n g energy, XPS, 391-392 Binding s t r e n g t h , potassium-calcium exchange i n s o i l s , 337

Birnessite, synthetic, interaction w i t h c o b a l t complexes, 503-521 B j e r r u m s u r f a c e complex f o r m a t i o n f u n c t i o n , 269-270 Boltzmann d i s t r i b u t i o n , s o l u t i o n concentration of p o t e n t i a l - d e t e r m i n i n g i o n s , 101 Bond s t r e n g t h , p o t a s s i u m - c a l c i u m exchange, 331 Bonding s t u d i e s o f m i n e r a l s , a p p l i c a t i o n s of surface t e c h n i q u e s , 389-401 Bronsted a c i d i t y o f c l a y m i n e r a l s g e n e r a l d i s c u s s i o n , 471-474 r e a c t i o n p r o m o t i o n , 464-479

C C a l c i f i e d tissues, mineral phases, 557t Calcite modes o f c o p r e c i p i t a t i o n w i t h B a ( I I ) and S r ( I I ) , 574-585 s o l i d s o l u t i o n s i n contact with aqueous s o l u t i o n s , 540-544 s o r p t i o n o f phosphate, 224 C a l c i u m , exchange w i t h p o t a s s i u m , a l u m i n o s i l i c a t e m i n e r a l s , 327-339 C a l c i u m c a r b o n a t e , i n systems w i t h magnesium c a r b o n a t e , 540-544 Calcium c a t i o n a d s o r p t i o n on and i n t e r a c t i o n s w i t h the l e p i d o c r o c i t e s u r f a c e , 494t e f f e c t on M n ( I I ) o x i d a t i o n , 492-497 C a l c i u m i o n , c o o r d i n a t i o n modes, 575 C a l c i u m phosphates and c a l c i f i e d t i s s u e s , 554-558 g r o w t h , 650-661 r e l e v a n t t o aqueous systems, 555t Calciumhydroxyapatite i n systems w i t h l e a d h y d r o x y a p a t i t e , 554 i n systems w i t h s t r o n t i u m h y d r o x y a p a t i t e , 554 C a l c u l a t i o n o f d i f f u s i o n parameters, r u b i d i u m , cesium, and s t r o n t i u m i n o b s i d i a n , 592-594 C a l i c y l a t e on g o e t h i t e , CIR-FTIR spectrum, 157f Capacitance amphoteric surface without c o m p l e x a t i o n model, 83 c o n s t r a i n t , d i p r o t i c s u r f a c e group model, 74 d i v a l e n t m e t a l - i o n b i n d i n g , 243t s t e r n , on o x i d e s , 89,91 C a t a l y t i c i n t e r c a l a t i o n phenomena, 250 Cation(s) h i g h p o l a r i z a b i l i t y , i o n exchange i n c l a y m i n e r a l s , 265-274 homovalent exchange i n c l a y m i n e r a l s , 256-260



666


C a t i o n ( s ) (Continued) layer s i l i c a t e s ESR, 364-365 h y d r a t i o n , 362-364 o r g a n i c ammonium, exchange i n c l a y m i n e r a l s , 260-262 s e l e c t i v i t y dependence on l o a d i n g , i o n exchange i n c l a y s , 265 Cation-exchange c a p a c i t y , a l u m i n o s i l i c a t e m i n e r a l s , 345 Cation-exchange r e a c t i o n , f r e e energy change, 255 Cesium calculation of diffusion parameters, 592-594 exchange i n i l l i t e - s m e c t i t e i n t e r l a y e r s and i n reduced charge m o n t m o r i l l o n i t e s , 278-280 high-temperature d i f f u s i o n s t u d i e s , 595 uptake by f e l d s p a r and o b s i d i a n , 588-591 Chalcocite copper and s u l f u r XPS s p e c t r a , 394f XPS and AES d a t a , 400t Charge amphoteric surface w i t h complexation model, 86-87 amphoteric surface without c o m p l e x a t i o n model, 84-85 Charge b a l a n c e s , t r i p l e - l a y e r model s u r f a c e complexes, 118-119 Charge d e n s i t y e f f e c t on i o n exchange i n c l a y m i n e r a l s , 256-265 See a l s o S u r f a c e charge d e n s i t y Charge-potential r e l a t i o n s h i p s e l e c t r i c double l a y e r , 233 o v e r l a p p i n g d i f f u s e l a y e r s , 109-110 C h a r g e - t r a n s f e r complex f o r m a t i o n and oxidation r e a c t i o n s , at mineral s u r f a c e s , 464,467-468 Charged i n t e r f a c e , f r e e energy o f f o r m a t i o n , 106-107 Charged s u r f a c e , f r e e energy o f f o r m a t i o n , 109-110 C h a r g i n g , XPS and AES, 390 Chelate o f g o e t h i t e and s a l i c y l a t e , 156-157 o f i r o n and s a l i c y l a t e , 156-157 C h e m i c a l a f f i n i t y o f the w e a t h e r i n g r e a c t i o n , e f f e c t on m i n e r a l w e a t h e r i n g r a t e s , 630-631 Chemical and e l e c t r o s t a t i c models f o r r e a c t i o n s a t the o x i d e - s o l u t i o n i n t e r f a c e , 54-77 Chemical bonding s t u d i e s o f m i n e r a l s , applications of surface t e c h n i q u e s , 389-401 Chemical c h a r a c t e r i s t i c s o f o r g a n i c r e d u c t a n t s , e f f e c t on r e d u c t i v e d i s s o l u t i o n , 457

Chemical c o n s t r a i n t s , oxide-electrolyte interface models, 66 Chemical c o n t r i b u t i o n , f r e e energy o f f o r m a t i o n o f a charged i n t e r f a c e , 107-108 Chemical forms o f adsorbed m e t a l i o n s , c h a r a c t e r i z a t i o n , 348-353 Chemical r e a c t i o n s , o x i d e s u r f a c e , 59-61 Chemical r e a c t i v i t y , m i n e r a l - w a t e r interface, 3 Chemical r e l a x a t i o n methods a p p a r a t u s , m a t e r i a l s , and sample p r e p a r a t i o n , 231-232 p r i n c i p l e s , 231 study o f a d s o r p t i o n - d e s o r p t i o n k i n e t i c s a t the metal oxide-solution i n t e r f a c e , 230-252 Chemical v e r s u s e l e c t r o s t a t i c i n t e r a c t i o n s , i n surface phenomena, 56-57 Chemisorption, organic molecules with metal-exchanged c l a y s , 355-357 Chloride ion e f f e c t on h y d r o x y a p a t i t e c r y s t a l growth, 655-657 e f f e c t on M n ( I I ) o x i d a t i o n , 492-497 Chromate, a d s o r p t i o n r a t e c o n s t a n t s , 239,241 Chromium, r e a c t i o n w i t h g a l e n a , XPS s t u d i e s , 394f,396t Chromium i o n s , a d s o r p t i o n on c l a y m i n e r a l s , 349 Chromophores, l i g h t a b s o r p t i o n i n c o r p o r a t i n g the oxide l a t t i c e m e t a l , 429-441 C i t r a t e , e f f e c t on d i s s o l u t i o n o f i r o n o x i d e , 431-433 Clay(s) h y d r a t i o n , 40 i n i t i a t i o n of polymerization r e a c t i o n s , 468-471 nature o f s u r f a c e s , 344-345 s i l i c a t e , groups o f exchange s i t e s , 332t See a l s o s i l i c a t e s Clay f i l m s ESR parameters o f copper i o n , 385t h y p e r f i n e s p l i t t i n g and e l e c t r o n g - v a l u e , 367-373 Clay minerals a c i d i t y , r e a c t i o n p r o m o t i o n , 464-479 B r o n s t e d a c i d i t y , 471-474 highly selective ion exchange, 256-283 Lewis a c i d i t y , 464-466 s t r u c t u r e s , 38-43 C l a y - w a t e r m i x t u r e s , water p r o p e r t i e s , 42



INDEX

667

Closed d i s s o l u t i o n experiments, q u a r t z , 639-642 C o b a l t , 2p s p l i t t i n g , XPS s t u d i e s o f complexes on b i r n e s s i t e , 510-511 C o b a l t ( I I ) , oxidation to c o b a l t ( I I I ) d u r i n g s o r p t i o n on b i r n e s s i t e , 510-511 Cobalt-57 decay t o i r o n - 5 7 , 404 i o n s , Mossbauer s t u d i e s o f metal oxide-aqueous s o l u t i o n i n t e r f a c e s , 403-423 C o b a l t complexes on sodium b i r n e s s i t e SIMS s t u d i e s , 514-519 XPS s t u d i e s , 507-514 on s y n t h e t i c b i r n e s s i t e , 503-521 Cobalt ions a d s o r p t i o n on c l a y m i n e r a l s , 349,351 a d s o r p t i o n on h e m a t i t e , 406-409 exchange i n Y z e o l i t e , 285 C o l l o i d surface charge, s t a b i l i z a t i o n o f p h o t o p r o d u c t s , 441,443 C o l l o i d a l metal o x i d e s , photoredox c h e m i s t r y , 426-443 Complex(es) a d s o r b e d , c h a r a c t e r i z a t i o n , 353-354 a d s o r p t i o n on m i n e r a l s , 353-354 inner c o o r d i n a t i o n sphere, p h o t o l y s i s , 431-441 m e t a l , a d s o r p t i o n on a l u m i n o s i l i c a t e m i n e r a l s , 342-358 t r a n s i t i o n metal i o n , exchange, 288 Complex c a t i o n exchange, i n c l a y m i n e r a l s , 265-273 Complex f o r m a t i o n m i n e r a l s u r f a c e s , 464,467-468 t r a n s i t i o n m e t a l c a t i o n w i t h an uncharged l i g a n d , 269 Complex i d e a l s o l i d s o l u t i o n s , d i s t r i b u t i o n l a w s , 530 C o m p l e x a t i o n models, s u r f a c e , 59-63 Complexing l i g a n d s , e f f e c t on a d s o r p t i o n o f m e t a l i o n s , 347 Computer-generated f i t t i n g o f s u r f a c e charge, amphoteric s u r f a c e w i t h o u t c o m p l e x a t i o n model, 85 Computer s i m u l a t i o n s o f i n t e r f a c i a l w a t e r , weaknesses and d i s a d v a n t a g e s , 32-33 Concentration a d s o r p t i o n l a y e r , c r y s t a l growth i n s o l u t i o n , 606 dependence o f r e l a x a t i o n t i m e , 233-236,239 C o n c e p t u a l model o f an a d s o r p t i o n r e a c t i o n , 57-59 C o n s e r v a t i o n - o f - s i t e equation amphoteric surface with complexation model, 86 amphoteric surface without c o m p l e x a t i o n model, 82

C o n v e c t i o n , c r y s t a l growth i n s o l u t i o n , 603-604 C o o r d i n a t i v e environment, t r a n s i t i o n m e t a l i o n s , 451-453 Copper, adsorbed on l a y e r s i l i c a t e s , 376-387 C o p p e r ( I I ) , s o r p t i o n by h e c t o r i t e , 225-226 Copper-aquo complexes i n l a y e r s i l i c a t e s , stereochemical arrangements, 383,385f Copper complexes, 353-357 Copper i o n s , a d s o r p t i o n on c l a y m i n e r a l s , 349-353 Coprecipitation B a ( I I ) and S r ( I I ) w i t h c a l c i t e , 574-585 Doerner-Haskins d i s t r i b u t i o n law, 528 Corundum-type magnetic o x i d e s u r f a c e s , 416-419 C o v e l l i t e , X-ray p h o t o e l e c t r o n and Auger d a t a , 400t C r i t i c a l concentration, etch p i t f o r m a t i o n , 638 C r y s t a l growth e l e c t r o l y t e , mechanisms and r a t e laws, 600-611 h y d r o x y a p a t i t e , 655-657 in solution e s t i m a t e s o f p a r a m e t e r s , 606-607 p r e d i c t i o n , 607-610 r a t e c o n t r o l , 601 transport-controlled k i n e t i c s , 601-604 C r y s t a l l i n e s i l i c a t e s , r o l e of nearsurface a l k a l i r a d i o n u c l i d e , 587-597 C r y s t a l l i t e , single, layer s i l i c a t e s , 362-363f C r y s t a l l i z a t i o n experiments, calcium phosphates, 654 Crystallographically different site groups, h i g h l y s e l e c t i v e i o n exchange, 283-287 Cylindrical internal reflectionF o u r i e r t r a n s f o r m IR s p e c t r o s c o p y (CIR-FTIR) a n i o n a d s o r p t i o n , 150-158 g e n e r a l d i s c u s s i o n , 150-151 methods, 151-152

D Dehydration s u r f a c e s p e c t r o s c o p y , 225 XPS and AES, 390 Density o s c i l l a t i o n s , s i m u l a t i o n r e s u l t s o f i n t e r f a c i a l w a t e r , 30 D e n t a l c a l c u l u s , m i n e r a l phases, 557t Deprotonation r e a c t i o n , e q u i l i b r i u m c o n s t a n t , 120-121



668

G E O C H E M I C A L PROCESSES AT M I N E R A L SURFACES

Depth p r o f i l i n g s t u d i e s , m i n e r a l samples, 399 Desorption-adsorption kinetics d i v a l e n t m e t a l i o n s , 241-244 metal o x i d e - s o l u t i o n i n t e r f a c e , 230-252 p o t e n t i a l - d e t e r m i n i n g i o n s , 233-235 D i c a l c i u m phosphate d i h y d r a t e , e f f e c t o f magnesium and s t r o n t i u m i o n s on c r y s t a l l i z a t i o n , 657-661 D i f f u s e double l a y e r , e q u a t i o n o f s t a t e , 102-103 Diffusion a l k a l i radionuclide, r o l e i n glassy and c r y s t a l l i n e s i l i c a t e s , 587-597 c r y s t a l growth i n s o l u t i o n , 603 F i c k ' s f i r s t law, 617 Diffusion coefficients a l k a l i elements i n o b s i d i a n , 593t comparison w i t h p e n e t r a t i o n d e p t h , 593 single-component model, 592 temperature dependence, 593 D i f f u s i o n model, s o r p t i o n k i n e t i c s , 209-211 D i f f u s i o n parameters, r u b i d i u m , cesium, and s t r o n t i u m i n o b s i d i a n , c a l c u l a t i o n , 590,592-594 D i f f u s i o n rates, control of reaction k i n e t i c s and t r a n s p o r t p r o p e r t i e s , 31 Diffusion reaction, relaxation t i m e , 236 D i f f u s i o n s t u d i e s , rubidium, cesium, and s t r o n t i u m , a t h i g h t e m p e r a t u r e s , 595 Dioctahedral clays, tetrahedral r o t a t i o n s , 314 D i p o l e r e l a x a t i o n t i m e , study by m o l e c u l a r dynamics, 31-32 D i p r o t i c s u r f a c e groups g e n e r a l d i s c u s s i o n , 61-62 model, 68-75 D i s e q u i l i b r i u m i n d e x , d e f i n i t i o n , 630 D i s l o c a t i o n etch p i t s i n q u a r t z , 635-647 Dislocations i n a c r y s t a l , r e l a t i o n to e t c h p i t s , 622 D i s o r d e r parameter, o l i v i n e s , 533 D i s s o c i a t i o n r e a c t i o n s , oxide s u r f a c e , 100-101 Dissolution d e s c r i p t i o n on a m o l e c u l a r l e v e l , 451-459 e f f e c t o f o x i d e m i n e r a l o g y , 458 f e l d s p a r w e a t h e r i n g , 626 g e n e r a l d i s c u s s i o n , 10-11 k i n e t i c s a t e t c h p i t s , 638-639 n u c l e u s , f r e e energy o f f o r m a t i o n , 636-638 r a t e , d e f i n i t i o n , 622 r e a c t i o n scheme, 447-448

D i s s o l u t i o n (Continued) reduced s u r f a c e s i t e s , 457-458 D i s s o l v e d humic m a t e r i a l , e f f e c t on humic p o l y m e r s , 200-202 Distribution coefficients adsorbate-solid i n t e r a c t i o n s , 163-164 a d s o r p t i o n on i n o r g a n i c s u r f a c e s , 204,205f a p p l i c a t i o n i n a n a l y t i c a l and i n o r g a n i c c h e m i s t r y , 535-539 i d e a l s o l i d s o l u t i o n s , 528,530 KCl-KBr-water system, 565-566 r e g u l a r s o l i d s o l u t i o n s , 531 D i s t r i b u t i o n laws complex i d e a l s o l i d s o l u t i o n s , 530 r e g u l a r s o l i d s o l u t i o n s , 531-532 simple i d e a l s o l i d s o l u t i o n s , 527-530 s o l i d s o l u t i o n s i n g e n e r a l , 533-558 D i t r i g o n a l h o l e s , hydrated k a o l i n i t e s , 46,48 D i v a l e n t Co-57, on h e m a t i t e , i n s i t u Mossbauer measurement, 406-409 D i v a l e n t Co-57 i o n s , on h e m a t i t e , 419-420 Divalent metal i o n ( s ) , adsorptiond e s o r p t i o n k i n e t i c s , 241-244 Divalent metal-ion hydroxides, s o l u b i l i t y p r o d u c t c o n s t a n t s , 458t Doerner-Hoskins d i s t r i b u t i o n law f o r c o p r e c i p i t a t i o n , 528 Dolomite, i n s o l i d s o l u t i o n s i n c o n t a c t w i t h aqueous s o l u t i o n s , 540-544 Double-bond a d d i t i o n , promotion by a c i d i t y o f mineral s u r f a c e s , 478-479 Double-layer capacitance, amphoteric surface without complexation model, 83 Drying-wetting, potassium f i x a t i o n i n s m e c t i t e , 296-324 Drying-wetting c y c l e s i n water, response o f p o t a s s i u m s m e c t i t e s , 303-317 Drying-wetting experiments m i n e r a l s used, 300t s t r u c t u r a l formulas of smectites used, 302t Ε

E l e c t r i c double l a y e r a p p l i c a t i o n o f models, 67-68 e l e c t r o s t a t i c models, 64-68 E l e c t r i c a l c o n t r i b u t i o n , f r e e energy o f f o r m a t i o n o f a charged i n t e r f a c e , 107-108 E l e c t r i c a l double l a y e r a t the o x i d e s o l u t i o n i n t e r f a c e , f r e e energy, 99-112 f o r m a t i o n , f r e e energy change, 106-109


669


INDEX

E l e c t r i c a l double l a y e r ( C o n t i n u e d ) p r o p e r t i e s , 3-5 E l e c t r o k i n e t i c behavior, d i s t i n g u i s h i n g a d s o r p t i o n from s u r f a c e p r e c i p i t a t i o n , 222-223 E l e c t r o k i n e t i c phenomenon, d e f i n i t i o n , 222 E l e c t r o l y t e , e f f e c t on hydroxyapatite c r y s t a l l i z a t i o n r a t e , 655-657 Electrolyte activity amphoteric s u r f a c e w i t h c o m p l e x a t i o n model, 86-87 c a l c u l a t i o n , 221 E l e c t r o l y t e c r y s t a l growth from aqueous s o l u t i o n , 600-611 p r e d i c t i o n o f r a t e s , 608-609t E l e c t r o l y t e - i n s u l a t o r - s i l i c o n (EIS) s t r u c t u r e , 80 E l e c t r o l y t e i n t e r f a c e theory, importance o f s u r f a c e p o t e n t i a l - p H c h a r a c t e r i s t i c s , 79-96 Electrolyte-oxide interface in g e o c h e m i s t r y , 55-59 E l e c t r o l y t e surface reactions, t r i p l e l a y e r model, 123t E l e c t r o n g - v a l u e , c l a y f i l m s , 367-372 E l e c t r o n g r a z i n g a n g l e a n a l y s i s , 399 E l e c t r o n paramagnetic resonance (EPR), s t u d i e s o f S r ( I I ) and B a ( I I ) i n c a l c i t e , 583-584 E l e c t r o n spectroscopy f o r chemical a n a l y s i s (ESCA), c h e m i c a l bonding s t u d i e s o f m i n e r a l s , 391-395 E l e c t r o n s p i n double resonance s p e c t r o s c o p y , m e t a l i o n s adsorbed on c l a y m i n e r a l s , 352 E l e c t r o n s p i n echo m o d u l a t i o n complexes adsorbed on c l a y m i n e r a l s , 353 m e t a l i o n s adsorbed on c l a y minerals, 352 E l e c t r o n s p i n l e v e l s i n a magnetic f i e l d , 367,368f E l e c t r o n s p i n resonance (ESR) spectroscopy b e i d e l l i t e , 376,377-378f b e i d e l l i t e f i l m s , copperdoped, 379,380f,383,384f c a t i o n s on l a y e r s i l i c a t e s , 364-365 complexes adsorbed on c l a y m i n e r a l s , 353-354 d i s t i n g u i s h i n g a d s o r p t i o n from s u r f a c e s p e c t r o s c o p y , 225-226 m e t a l i o n s adsorbed on c l a y m i n e r a l s , 349-352 n i t r o x i d e s p i n probe, 367,369f s a p o n i t e , 371f,372 s a p o n i t e f i l m s , copperdoped, 379,382f tempamine adsorbed on sodium s m e c t i t e f i l m s , 370,371f

Electron transfer m e t a l o x i d e s u r f a c e s , 446-460 m i n e r a l - w a t e r i n t e r f a c e , 13 E l e c t r o p h o r e s i s , d e f i n i t i o n , 222 E l e c t r o p h o r e t i c m o b i l i t y of h y d r o x y a p a t i t e , 655-658 E l e c t r o s m o s i s , d e f i n i t i o n , 222 E l e c t r o s t a t i c models e l e c t r i c double l a y e r , 64-68 r e a c t i o n s a t the o x i d e - s o l u t i o n i n t e r f a c e , 54-77 E l e c t r o s t a t i c versus chemical i n t e r a c t i o n s , surface phenomena, 56-57 Elemental r a t i o s , Co(III) complexes-birnessite, 518t E l i m i n a t i o n r e a c t i o n s , p r o m o t i o n by a c i d i t y of m i n e r a l s u r f a c e s , 478-479 E m p i r i c a l models o x i d e - e l e c t r o l y t e i n t e r f a c e , 55 sorption processes, 7 Energies allowed, unpaired e l e c t r o n , 366 Energy l e v e l diagram, s p i n s t a t e s o f copper i o n , 376,378f Energy o f i n t e r a c t i o n between the magnetic f i e l d and the e l e c t r o n s p i n , 366 Enthalpies a d s o r p t i o n , f a c t o r s a f f e c t i n g , 144 exchange o f p y r i d i n i u m and b i p y r i d i u m s a l t s , 275t p o t a s s i u m - c a l c i u m exchange i n aluminosilicate m i n e r a l s , 330-333 p o t a s s i u m - c a l c i u m exchange i n s o i l s , 334-338 E n t h a l p y of m i x i n g hydroxyapati t e - f l u o r a p a t i te systems, 546-552 r e g u l a r s o l i d s o l u t i o n s , 531 s o l i d s o l u t i o n s , 534-535 Entropies p o t a s s i u m - c a l c i u m exchange i n aluminosilicate m i n e r a l s , 330-331 p o t a s s i u m - c a l c i u m exchange i n s o i l s , 337-338 Entropy o f m i x i n g complex i d e a l s o l i d s o l u t i o n s , 530 s i m p l e i d e a l s o l i d s o l u t i o n s , 527 Environmental relevance, h i g h l y s e l e c t i v e ion-exchange r e a c t i o n s , 290 Equations of s t a t e , oxide s u r f a c e , d i f f u s e double l a y e r , and e q u i l i b r i u m p o i n t , 100-106 Equilibrium KCl-KBr-water system, 563-566 p o t a s s i u m - c a l c i u m exchange, 328



670


E q u i l i b r i u m (Continued) s o l i d solution-aqueous s o l u t i o n systems, 561-573 E q u i l i b r i u m constants a d s o r p t i o n , c r y s t a l growth i n s o l u t i o n , 606 adsorption-desorption of c o u n t e r i o n s , 237,239 adsorption-desorption of d i v a l e n t m e t a l i o n s , 241 d e p r o t o n a t i o n r e a c t i o n , 120-121 d e t e r m i n a t i o n f o r a s u r f a c e , 89-94 f a c t o r s a f f e c t i n g , 231 KCl-KBr-water system, 566-567 p r e s s u r e dependence, 133 s u r f a c e r e a c t i o n k i n e t i c s , 232-233 Equilibrium expressions, reactions, t r i p l e - l a y e r model, 123t E q u i l i b r i u m model, r e a c t i o n s a t charged i n t e r f a c e s , 117-118 Equilibrium point, oxide-solution i n t e r f a c e , equation of s t a t e , 103-106 Equilibrium r e s u l t s , lead-ion a d s o r p t i o n a t the g o e t h i t e - w a t e r i n t e r f a c e , 121-125 E q u i l i b r i u m s l o p e , KCl-KBr-water system, 570-571 E q u i l i b r i u m solid-aqueous s o l u t i o n p r o p e r t i e s , 570t E q u i l i b r i u m t e s t s , KCl-KBr-water system, 567-572 Estimates of parameters, c r y s t a l growth i n s o l u t i o n , 606-607 Estuarine water, Mn(II) o x i d a t i o n , 497-498 Etch p i t s d i s s o l u t i o n k i n e t i c s 638-639 f o r m a t i o n , t h e o r y , 636-639 n a t u r a l l y weathered f e l d s p a r , 620-623 quartz d i s l o c a t i o n , 635-647 t e s t o f f o r m a t i o n t h e o r y , 639-645 t e r r a c e d , q u a r t z s u r f a c e s , 645 w i d t h s on q u a r t z etched i n f l o w systems, 644t E t c h t u b e s , q u a r t z s u r f a c e s , 645 Etching, quartz surfaces, l o w - t e m p e r a t u r e , 642 Exchange e n t h a l p i e s , c l a y minerals, 278 Exchange i s o t h e r m s , d i v a l e n t c a t i o n s w i t h Na m o n t m o r i l l o n i t e , 346 E x p o n e n t i a l r a t e law, c r y s t a l growth i n s o l u t i o n , 608-611

F e l d s p a r , cesium u p t a k e , 588-591 Feldspar weathering f a c t o r s a f f e c t i n g r a t e s , 615-632 g e n e r a l d i s c u s s i o n , 616 l a b o r a t o r y s t u d i e s , 625-626 n a t u r a l weathering p r o f i l e s , 627-629 r a t e s , 626-627 F e r r i c ions at surface metal ion s i t e s , Weiss f i e l d c a l c u l a t i o n , 416 F e r r i c o x i d e — S e e Iron oxide F e r r u g i n o u s s m e c t i t e s , k i n e t i c s o f the t r a n s f o r m a t i o n toward i l l i t e , 314-317 F e r t i l i z e r s , e f f e c t on p o t a s s i u m s e l e c t i v i t y i n s o i l s , 334,337 F i c k ' s f i r s t law o f d i f f u s i o n , 617 F i r s t - o r d e r k i n e t i c model, s o r p t i o n k i n e t i c s , 208-209 F i x a t i o n i n s m e c t i t e by w e t t i n g and d r y i n g , p o t a s s i u m , 296-324 F l a t - b a n d v o l t a g e o f an EIS s t r u c t u r e , 80 Flow d i s s o l u t i o n e x p e r i m e n t s , q u a r t z , 639-642 F l u o r a p a t i t e , i n systems w i t h h y d r o x y a p a t i t e , 544-554 F l u o r i d e a d s o r p t i o n on g o e t h i t e , 148 F r e e energy between two p l a t e s , i n t e r a c t i o n , 109-112 c a t i o n - e x c h a n g e r e a c t i o n , 255 complex c a t i o n exchange, 271 e l e c t r i c a l d o u b l e l a y e r s a t the o x i d e - s o l u t i o n i n t e r f a c e , 99-112 of formation d i s s o l u t i o n n u c l e u s , 636-638 one s u r f a c e , 106-109 o f m i x i n g , s o l i d s o l u t i o n s , 541 o f t r a n s f e r , c a l c i u m phosphate i o n , 651 p o t a s s i u m - c a l c i u m exchange i n aluminosilicate m i n e r a l s , 330-331 p o t a s s i u m - c a l c i u m exchange i n s o i l s , 337 Free enthalpy of mixing, hydroxyapatite-fluorapatite systems, 546-552 F r e s h w a t e r , M n ( I I ) o x i d a t i o n , 497-498 F u l v i c acids e f f e c t on d i s s o l u t i o n o f i r o n o x i d e , 438,439f e f f e c t on d i s s o l u t i o n o f manganese o x i d e , 438,440f

F G F-function amphoteric surface w i t h complexation model, 86 amphoteric surface without c o m p l e x a t i o n model, 82-83

Galena XPS spectrum i n chromium r e g i o n , 394f XPS spectrum i n s u l f u r r e g i o n ,


393f

671


INDEX

Galena (Continued) XPS survey s c a n , 393f Galena-chromium r e a c t i o n , XPS d a t a , 396t Geochemical mass b a l a n c e s t u d i e s , f e l d s p a r w e a t h e r i n g , 627-629 Geochemical p r o c e s s e s a t m i n e r a l s u r f a c e s , o v e r v i e w , 2-14 Geochemistry, o x i d e - e l e c t r o l y t e i n t e r f a c e , 55-59 Glassy s i l i c a t e s , r o l e of near-surface a l k a l i r a d i o n u c l i d e , 587-597 Goethite anion adsorption c h a r a c t e r i z a t i o n , 142-159 CIR-FTIR s p e c t r a , 153-154f G o e t h i t e - w a t e r i n t e r f a c e , mechanism o f l e a d - i o n a d s o r p t i o n , 114-140 Growth, c a l c i u m phosphates, 650-661 Growth r a t e s c a l c i u m phosphates, 652t c r y s t a l s i n s o l u t i o n , 601 prediction, crystals i n s o l u t i o n , 607-610 Growth r e a c t i o n , h y d r o x y a p a t i t e , 655-657 H H a l f - l i v e s , M n ( I I ) o x i d a t i o n , 498t H a l l o y s i t e , adsorbed w a t e r , 40-41 Heat c a p a c i t y measurements and i n t e r l a y e r water s t r u c t u r e , 48-50 H e a t i n g e f f e c t s , p e n t a v a l e n t Sb-119 i o n s on h e m a t i t e , 420 Hectorite a n i s o t r o p y o f motion, 373 orientation-dependence of hyperfine s p l i t t i n g , 370-371f o x i d a t i o n o f b e n z i d i n e , 467 s o r p t i o n o f C u ( I I ) , 225-226 Hematite corundum-type s t r u c t u r e , 416-419 d i v a l e n t Co-57 i o n s , 419-420 magnetic i n t e r a c t i o n s on s u r f a c e s , 414-416 Mossbauer s t u d i e s o f metal oxide-solution i n t e r f a c e s , 405-406 p e n t a v a l e n t Sb-119 i o n s , 420-423 suspensions containing S(IV), s o l u b i l i z a t i o n , 432,434f See a l s o I r o n o x i d e H e m a t i t e - d i v a l e n t Co-57, i n s i t u Mossbauer measurement, 406-409 H e m a t i t e - p e n t a v a l e n t Sb-119, i n s i t u Mossbauer measurement, 409-414 H e t e r o v a l e n t exchange, c l a y m i n e r a l s , 262-265 High-temperature d i f f u s i o n s t u d i e s , r u b i d i u m , cesium, and s t r o n t i u m , 595 H i g h l y s e l e c t i v e i o n exchange i n c l a y m i n e r a l s and z e o l i t e s , 254-290

Homogeneity, p r e c i p i t a t e o f a s o l i d s o l u t i o n , 539 Homovalent exchange o f i n o r g a n i c c a t i o n s , c l a y m i n e r a l s , 256-260 Hydrated k a o l i n i t e s , IR s p e c t r a , 45-48 Hydration c a t i o n s o f l a y e r s i l i c a t e s , 362-364 c l a y s , 40 e f f e c t s on i o n exchange i n c l a y m i n e r a l s , 256-265 f o r c e , i n t e r f a c i a l w a t e r , 30 s u r f a c e , e f f e c t on a l k a l i d i f f u s i o n , 597 Hydrogen b o n d i n g , l a y e r s i l i c a t e s , 364 Hydrogen-exchange r e a c t i o n s , promotion by B r o n s t e d o r Lewis a c i d i t y , 479 Hydrogen-ion a c t i v i t y i n s o l u t i o n , d i p r o t i c s u r f a c e group model, 71 Hydrogen-ion exchange, f e l d s p a r w e a t h e r i n g , 625-626 Hydrogen p e r o x i d e , c a t a l y t i c d e c o m p o s i t i o n by c a t i o n s , 483 H y d r o l y s i s , m e t a l - i o n complexes, homogeneous s o l u t i o n s o f i n c r e a s i n g pH, 453 Hydrolysis reactions m i n e r a l s u r f a c e s , 474-478 s u r f a c e groups on a m e t a l o x i d e , 491 Hydrophobic e f f e c t , i n t e r f a c i a l w a t e r , 30 Hydrophobic o r g a n i c s o l u t e s , s o r p t i o n by sediments, 191-213 Hydrothermal e t c h i n g , q u a r t z , 639-642 Hydroxyapatite c r y s t a l growth, 655-661 e f f e c t o f magnesium and s t r o n t i u m i o n s on c r y s t a l l i z a t i o n , 657-661 i n systems w i t h f l u o r a p a t i t e , 544-554 H y p e r f i n e i n t e r a c t i o n , magnetic, t e t r a v a l e n t Sn-119 i o n s , 416 H y p e r f i n e magnetic f i e l d s a c t i n g on Fe-57 n u c l e i , 419 a c t i n g on Sn-119 n u c l e i , 420 Hyperfine s p l i t t i n g c l a y f i l m s , 367-373 tempamine adsorbed on c l a y f i l m s , 372t I Illite a l k a l i and a l k a l i n e e a r t h m e t a l - i o n exchange, 274-278 i o n exchange, 256-283 p o t a s s i u m - c a l c i u m exchange e q u i l i b r i a , 330-334 I l l i t e layers p o t a s s i u m k i n n e y , temperature e f f e c t s , 321t potassium smectites subjected t o w e t t i n g and d r y i n g , 308t,310 sodium k i n n e y , e f f e c t o f p o t a s s i u m m i n e r a l , 323t



672


I l l i t e - s m e c t i t e i n t e r l a y e r s , cesium and r u b i d i u m exchange, 278-280 I n e f f i c i e n c y o f p a r t i t i o n i n g , 203-204 I n e l a s t i c electron tunneling s p e c t r o s c o p y , complexes adsorbed on c l a y m i n e r a l s , 353 Infrared spectroscopy complexes adsorbed on c l a y m i n e r a l s , 354 i n t e r l a y e r w a t e r , 45-48 I n n e r - s p h e r e mechanism r e d u c t i o n o f t e r v a l e n t m e t a l i o n by p h e n o l , 448,449f r e d u c t i v e d i s s o l u t i o n o f metal o x i d e s u r f a c e , 448,450f Inner-sphere surface r e a c t i o n , t r i p l e - l a y e r model, 123t Inorganic cations, clay minerals, homovalent exchange, 256-260 Inorganic surfaces, a d s o r p t i o n , 204-208 Integration rate constant, c r y s t a l growth i n s o l u t i o n , 607 I n t e r a c t i o n f r e e energy between two p l a t e s , 109-112 I n t e r a c t i o n parameter, s o l i d s o l u t i o n s , 534 Interaction potential, i n t e r f a c i a l water s i m u l a t i o n s , 23-28 I n t e r a c t i o n p o t e n t i a l energy, p a r t i c l e s i n a c e l l , 21 Intercalation e f f e c t o f a c i d i c p r o p e r t i e s , 250-252 k i n e t i c s , 244-252 m o l e c u l e s i n t o the i n t e r l a m e l l a r l a y e r , 244 Interdiffusion coefficient, N e r n s t - P l a n k e q u a t i o n , 592-593 I n t e r f a c i a l t e n s i o n , c r y s t a l growth i n s o l u t i o n , 607 I n t e r f a c i a l water s i m u l a t i o n s g e n e r a l d i s c u s s i o n , 28-32 i n t e r a c t i o n p o t e n t i a l s , 23-28 s u r f a c e p o t e n t i a l s , 25-28 water p o t e n t i a l s , 24-25 I n t e r l a y e r chemistry, potassium s m e c t i t e s s u b j e c t e d t o w e t t i n g and d r y i n g , 308t Interlayer distance, i n t e r c a l a t i o n s t u d i e s , 247-248t I n t e r l a y e r water c h a r a c t e r i z a t i o n , 45-48 heat c a p a c i t y measurements o f s t r u c t u r e , 48-50 I n t r i n s i c constants, d i v a l e n t metali o n b i n d i n g , 243t I n t r i n s i c surface reaction constants, d e t e r m i n a t i o n , 89-94 Ion(s) adsorption-desorption k i n e t i c s , 233-244

I o n ( s ) (Continued) e f f e c t on M n ( I I ) o x i d a t i o n i n the presence o f l e p i d o c r o c i t e , 492-497 m e t a l , a d s o r p t i o n on a l u m i n o s i l i c a t e m i n e r a l s , 342-358 Ion exchange g e n e r a l d i s c u s s i o n , 7-9 use i n complex f o r m a t i o n c o n s t a n t measurement, 269-270 Ion-pair s t a b i l i t y constant, c r y s t a l growth i n s o l u t i o n , 606 Ion-sensitive f i e l d effect transistor ( I S F E T ) , 80 Ion s i z e , e f f e c t on r a t e s o f i n t e r c a l a t i o n , 245-250 Ion s p u t t e r i n g , m i n e r a l samples, 399 I o n i c a c t i v i t y products c a l c i u m phosphate s o l u t i o n s , 651 d i s t i n g u i s h i n g a d s o r p t i o n from s u r f a c e p r e c i p i t a t i o n , 220-222 I o n i c compound, g e n e r a l f o r m u l a , 524 Ionic solid solution g e n e r a l f o r m u l a , 524 i n c o n t a c t w i t h aqueous s o l u t i o n , 524-528 I o n i c s t r e n g t h , e f f e c t on a d s o r p t i o n of metal i o n s , 346 Iron-57, e l e c t r o n i c environment, 404-405 I r o n complexes, a d s o r p t i o n on c l a y m i n e r a l s , 354-356 I r o n ( I I I ) hydroxy s p e c i e s , p h o t o r e d u c t i o n , 429 Iron oxide e f f e c t o f c i t r a t e on d i s s o l u t i o n , 431-433 p h o t o d i s s o l u t i o n , 429-431,437t photoredox c h e m i s t r y , 429-441 photoredox r e a c t i o n s , 431 See a l s o Hematite and Lepidocrocite Iron oxyhydroxide, photodissolution p r o c e s s , 435 I r o n redox c h e m i s t r y , h e m a t i t e suspensions containing S ( I V ) , 432,434f I r o n - s a l i c y l a t e complex, CIR-FTIR spectrum, 157f Isotherm a n a l y s i s , macroscopic proton c o e f f i c i e n t , mathematical development, 187-188 Isotherm s u b t r a c t i o n , macroscopic proton c o e f f i c i e n t d e t e r m i n a t i o n , 172 Κ Kaolin minerals b e h a v i o r o f water on the s u r f a c e , 37-52


673


INDEX

K a o l i n minerals (Continued) e x p e r i m e n t a l s t u d i e s o f adsorbed w a t e r , 43-50 Kaolinite groups o f exchange s i t e s , 336t h y d r o l y s i s o f p a r a t h i o n , 477 i o n exchange, 256-265 p o t a s s i u m - c a l c i u m exchange e q u i l i b r i a , 330-334 K a o l i n i t e hydrates IR s p e c t r a , 45-48 s y n t h e s i s , 44-45 Kinetics a d s o r p t i o n - d e s o r p t i o n a t the m e t a l oxide-solution i n t e r f a c e , 230-252 c r y s t a l growth i n s o l u t i o n s u r f a c e - c o n t r o l l e d , 604-606 t r a n s p o r t - c o n t r o l l e d , 601-604 d i s s o l u t i o n a t e t c h p i t s , 638-639 e v i d e n c e f o r i n c r e a s e d Bronsted a c i d i t y a t c l a y s u r f a c e s , 476 i n t e r c a l a t i o n , 244-252 l e a d - i o n a d s o r p t i o n a t the goethite-water i n t e r f a c e , 127-132 methods, d i s t i n g u i s h i n g a d s o r p t i o n from s u r f a c e p r e c i p i t a t i o n , 222-224 mineral d i s s o l u t i o n experiments, p a r a b o l i c , 616-620 model, l e a d - i o n a d s o r p t i o n a t the goethite-water i n t e r f a c e , 125-127 reductive dissolution mechanisms, 451 s o r p t i o n , 208-211 s u r f a c e r e a c t i o n , 232-244 Kinney s m e c t i t e s , k i n e t i c s o f t h e t r a n s f o r m a t i o n toward i l l i t e , 314-317 Kurbatov c o e f f i c i e n t s , a d s o r p t i o n p r e d i c t i o n , 179-181 Kurbatov p l o t s , m a c r o s c o p i c p r o t o n c o e f f i c i e n t d e t e r m i n a t i o n , 169-172

L Langmuir e q u a t i o n , 219 Langmuir i s o t h e r m , s o l i d - a q u e o u s s o l u t i o n i n t e r f a c e , 167 L a t t i c e s t r u c t u r e , e f f e c t on r a t e s o f l i g a n d s u b s t i t u t i o n , 454-455 L a t t i c e s u b s t i t u t i o n , B a ( I I ) and S r ( I I ) on c a l c i t e , 576-579 Layer s i l i c a t e s adsorbed copper, 376-387 adsorbed n i t r o x i d e s p i n p r o b e s , 366-376 e x p a n s i o n i n w a t e r , 364 paramagnetic probes o f s u r f a c e s , 362-387

Lead i o n s , a d s o r p t i o n on c l a y m i n e r a l s , 349 Lead o x i d e m i n e r a l s , X-ray induced AES s p e c t r a , 398f L e a d h y d r o x y a p a t i t e , i n systems w i t h c a l c i u m h y d r o x y a p a t i t e , 554 Lennard-Jones p o t e n t i a l , i n t e r f a c i a l w a t e r s i m u l a t i o n s , 25-28 Lepidocrocite o x i d a t i o n o f M n ( I I ) , 487-500 photoredox c h e m i s t r y , 429-431 p r e p a r a t i o n and c h a r a c t e r i z a t i o n , 489 s u r f a c e p r o p e r t i e s , 489t See a l s o I r o n o x i d e Lewis a c i d i t y o f c l a y m i n e r a l s , r e a c t i o n p r o m o t i o n , 464-479 L i g a n d ( s ) , e f f e c t on a d s o r p t i o n o f m e t a l i o n s , 347-348 L i g a n d complexes, t r a n s i t i o n m e t a l i o n , 288 L i g a n d exchange e f f e c t on M n ( I I ) o x i d a t i o n , 492 r a t e i n p r e c u r s o r complex f o r m a t i o n , 454 L i g a n d number, a d s o r p t i o n r e a c t i o n s , 136-137 Light absorption metal o x i d e b u l k , 427-429 surface-located chromophores, 429-441 L i n e w i d t h s o f n i t r o x i d e ESR s p e c t r a , 370,371f L i n e a r growth r a t e , c r y s t a l s i n s o l u t i o n , 601,605 L i n e a r r a t e l a w , c r y s t a l growth i n s o l u t i o n , 608-609 L i q u i d water near h y d r o p h o b i c m i n e r a l s u r f a c e s , methods and l i m i t a t i o n s o f s i m u l a t i o n , 20-34 Low-temperature e t c h i n g , q u a r t z s u r f a c e s , 642

M M a c r o s c o p i c c o e f f i c i e n t s and s u r f a c e - s i t e h e t e r o g e n e i t y , 181 Macroscopic p a r t i t i o n i n g c o e f f i c i e n t s , m e t a l - i o n a d s o r p t i o n , 162-188 Macroscopic p r o p e r t i e s , canonical ensemble, 22 Macroscopic proton c o e f f i c i e n t d e s c r i p t i o n , 164-169 d e t e r m i n a t i o n , 169-186 m a t h e m a t i c a l development o f i s o t h e r m a n a l y s i s , 187-188 m i c r o s c o p i c s u b r e a c t i o n s , 181-185 r e l a t i o n t o pH and a d s o r p t i o n d e n s i t y , 172,175 Magnesite, i n s o l i d s o l u t i o n s i n c o n t a c t w i t h aqueous s o l u t i o n s , 540-544


G E O C H E M I C A L PROCESSES AT M I N E R A L S U R F A C E S


674

Magnesium c a r b o n a t e , i n systems w i t h c a l c i u m c a r b o n a t e , 540-544 Magnesium c a t i o n a d s o r p t i o n on and i n t e r a c t i o n s w i t h the l e p i d o c r o c i t e s u r f a c e , 494t e f f e c t on M n ( I I ) o x i d a t i o n , 492-497 Magnesium i o n s e f f e c t on c a l c i u m phosphate c r y s t a l l i z a t i o n r a t e s , 657-661 e f f e c t on e l e c t r o p h o r e t i c m o b i l i t y o f h y d r o x y a p a t i t e , 657,658f Magnesium w h i t l o c k i t e , f o r m a t i o n , 555 M a g n e t i c i n t e r a c t i o n s on hematite s u r f a c e s , 414-416 Magnetic oxide s u r f a c e s , corundum-type, 416-419 Manganese n a t u r a l w a t e r s , removal t i m e s , 499t o x i d a t i o n s t a t e s , 487-488 Manganese-cobalt r a t i o s SIMS s t u d i e s o f c o b a l t complexes on b i r n e s s i t e , 514-519 XPS s t u d i e s o f c o b a l t complexes on b i r n e s s i t e , 507-514 Manganese i o n s , a d s o r p t i o n on c l a y m i n e r a l s , 350 Manganese(II) o x i d a t i o n comparison w i t h p r e d i c t i o n s based on l a b o r a t o r y d a t a , 499-500 i m p l i c a t i o n s of experimental s t u d i e s , 497-500 i n f l u e n c e o f o t h e r i o n s , 497-499 m e t a l o x i d e s , 491-492 presence o f l e p i d o c r o c i t e , 487-500 Manganese o x i d e s d i s s o l u t i o n , 438,440f r e a c t i o n s w i t h m e t a l s , 504 Mass a c t i o n e x p r e s s i o n s l i n e a r i z a t i o n , 170 s u r f a c e r e a c t i o n k i n e t i c s , 232 t r i p l e - l a y e r model s u r f a c e complexes, 118 Mass b a l a n c e s t u d i e s , f e l d s p a r w e a t h e r i n g , , 627-629 M a t h e m a t i c a l development o f i s o t h e r m a n a l y s i s , macroscopic proton c o e f f i c i e n t , 187-188 Mechanisms a d s o r p t i o n o f o r g a n i c s o l u t e s onto s u r f a c e s , 192-193 e l e c t r o l y t e c r y s t a l growth from aqueous s o l u t i o n , 600-611 l e a d - i o n a d s o r p t i o n a t the goethite-water i n t e r f a c e , 114-140 M n ( I I ) o x i d a t i o n on m e t a l o x i d e s , 492,493f oxide-electrolyte i n t e r f a c e , 55-56 s o r p t i o n p r o c e s s e s , 5-6

M e r c a p t a n s , o x i d a t i o n by a m e t a l o x i d e s u r f a c e , 456 M e r c a p t o a c e t i c a c i d , e f f e c t on dissolution of iron oxide, 44l,442f Mercury s u r f a c e , e q u a t i o n o f s t a t e , 100 M e t a l complexes, a d s o r p t i o n on a l u m i n o s i l i c a t e m i n e r a l s , 342-358 Metal ions adsorbed c h a r a c t e r i z a t i o n , 348-353 r e a c t i o n s i n v o l v i n g , 355-357 adsorption a l u m i n o s i l i c a t e m i n e r a l s , 342-358 Langmuirian d e s c r i p t i o n , 167 macroscopic p a r t i t i o n i n g c o e f f i c i e n t s , 162-188 mixtures of m u l t i p l e s o l i d phases, 178,179t complexes, r e d u c t i o n by o r g a n i c compounds, 446-447 divalent, adsorption-desorption k i n e t i c s , 241-244 r e d u c t i o n , XPS and AES, 390 M e t a l o r g a n i c complexes, p r e p a r a t i o n u s i n g c l a y m i n e r a l s , 356 Metal oxide(s) a d d i t i v e - f r e e media, p h o t o d i s s o l u t i o n , 429-431 b u l k , l i g h t a b s o r p t i o n , 427-429 c o l l o i d a l , photoredox c h e m i s t r y , 426-443 M n ( I I ) o x i d a t i o n , 491-492 photoredox r e a c t i o n s , 431 surfaces adsorption of organic reductants and subsequent e l e c t r o n t r a n s f e r , 446-460 e f f e c t on photoinduced redox r e a c t i o n s , 441-443 M n ( I I ) a d s o r p t i o n , 490-491 Metal o x i d e - s o l u t i o n i n t e r f a c e s adsorption-desorption k i n e t i c s , 230-252 i n s i t u Mossbauer s t u d i e s w i t h adsorbed Co-57 and Sb-119 i o n s , 403-423 M e t a l - p r o t o n exchange r e a c t i o n , 164 Mica number o f charges per u n i t c e l l , 26t p o t a s s i u m - c a l c i u m exchange e q u i l i b r i a , 330-334 M i c r o s c o p i c s u b r e a c t i o n s and macroscopic p r o t o n c o e f f i c i e n t s , 181-185 Mineral(s) a l u m i n o s i l i c a t e , potassiumc a l c i u m exchange e q u i l i b r i a , 330-334 c h e m i c a l bonding s t u d i e s , applications of surface t e c h n i q u e s , 389-401


675


INDEX

M i n e r a l ( s ) (Continued) clay, highly selective ion exchange, 256-283 o x i d a t i o n of organic compounds, 480-483 used i n w e t t i n g and d r y i n g e x p e r i m e n t s , d e s c r i p t i o n , 300t M i n e r a l phases c a l c i f i e d t i s s u e s , 557t d e n t a l c a l c u l u s , 557t Mineral surfaces a b i o t i c o r g a n i c r e a c t i o n s , 462-483 overview o f geochemical p r o c e s s e s , 2-14 s o r p t i o n , 204-208 Mineral-water i n t e r f a c e p h y s i c a l p r o p e r t i e s , 3-5 t r a n s f o r m a t i o n r e a c t i o n s , 13-14 M i n e r a l o g y , o x i d e , e f f e c t on r e d u c t i v e d i s s o l u t i o n , 458-459 Mixed a d s o r b a t e s , d e f i n i t i o n , 218 Modes o f c o p r e c i p i t a t i o n o f B a ( I I ) and S r ( I I ) w i t h c a l c i t e , 574-585 M o i s t u r e content e f f e c t on Bronsted a c i d i t y o f c l a y m i n e r a l s , 472 e f f e c t on Bronsted s u r f a c e a c i d i t y , 476-477 M o l e c u l a r dynamics simulations of i n t e r f a c i a l systems, 22-23 s i m u l a t i o n s o f i n t e r f a c i a l w a t e r , 33 s i m u l a t i o n s o f water near hydrophobic s u r f a c e s , 29t Molecular l e v e l d e s c r i p t i o n of r e d u c t i v e d i s s o l u t i o n , 451-459 Molecular simulations of i n t e r f a c i a l w a t e r , m e r i t s and s t r e n g t h s , 32 M o l e c u l e - f i x e d axes, a n i s o t r o p i c motion o f s p i n probes on hydrated s m e c t i t e s , 373 M o n o p r o t i c s u r f a c e groups g e n e r a l d i s c u s s i o n , 62-63 model, i n t e r p r e t a t i o n o f d a t a , 75 Monte C a r l o s i m u l a t i o n s i n t e r f a c i a l systems, 22 i n t e r f a c i a l water, f u t u r e u s e s , 33 water near hydrophobic s u r f a c e s , 28t Montmorillonites cesium and r u b i d i u m exchange, 278-280 groups o f exchange s i t e s , 335t h y d r o l y s i s o f phosmet, 477-478 i o n exchange, 256-283 o r i e n t a t i o n dependence o f h y p e r f i n e s p l i t t i n g , 370-371f potassium-calcium exchange e q u i l i b r i a , 330-334 Mossbauer s t u d i e s , m e t a l oxide-aqueous solution interfaces p r i n c i p l e s , 403-405 w i t h adsorbed i o n s , 403-423

Multilayer adsorption d e f i n i t i o n , 218 w a t e r , 41-43 M u l t i p l e t s p l i t t i n g , XPS, 395

Ν N a t u r a l o r g a n i c m a t t e r - w a t e r systems, p a r t i t i o n i n g , 196-197 Nernst-Plank equation, i n t e r d i f f u s i o n c o e f f i c i e n t , 592-593 Net p r o t o n r e l e a s e and l i g a n d number, a d s o r p t i o n r e a c t i o n s , 136-137 Nitrogen p h o t o f i x a t i o n , a b i o l o g i c a l , 428-429 XPS s t u d i e s o f c o b a l t complexes on b i r n e s s i t e , 507-514 N i t r o x i d e s p i n probes adsorbed on l a y e r s i l i c a t e s , 366-376 ESR s p e c t r a , 367,369f Nonidealities humic polymers, 197-203 w a t e r - s a t u r a t e d o c t a n o l , 195-196 N u c l e a t i o n c o n t r o l , c r y s t a l growth i n s o l u t i o n , 605 0

O b s i d i a n , cesium and r u b i d i u m u p t a k e , 588-591 O c c l u s i o n , r e l a t i o n t o t h e speed o f f o r m a t i o n o f a p r e c i p i t a t e , 539 O c t a c a l c i u m phosphate, e f f e c t o f magnesium and s t r o n t i u m i o n s on c r y s t a l l i z a t i o n , 657-661 Octanol, water-saturated, n o n i d e a l i t i e s , 195-196 O c t a n o l - w a t e r systems, p a r t i t i o n i n g , 194-195 O l i v i n e s , s t r u c t u r a l f o r m u l a , 533 Order parameter s o l i d s o l u t i o n s of calcium carbonate and magnesium c a r b o n a t e , 542 s u r f a c e s , 372 O r d e r i n g , s o l i d s o l u t i o n s , 534-535 O r g a n i c ammonium c a t i o n exchange, c l a y m i n e r a l s , 260-262 O r g a n i c c a t i o n exchange, c l a y m i n e r a l s , 273-274 O r g a n i c compounds i n f l u e n c e o f m i n e r a l s u r f a c e s on s o r p t i o n , 206,207f o x i d a t i o n by o x i d e s and p r i m a r y m i n e r a l s , 480-483 s o r p t i o n processes, 7 O r g a n i c c o s o l v e n t s , e f f e c t on humic p o l y m e r s , 202-203 O r g a n i c l i g a n d s , e f f e c t on a d s o r p t i o n o f m e t a l i o n s , 347-348 Organic matter, s o i l s , r o l e i n r e a c t i o n s a t m i n e r a l s u r f a c e s , 479



676

G E O C H E M I C A L PROCESSES AT M I N E R A L SURFACES

O r g a n i c m a t t e r - w a t e r systems, p a r t i t i o n i n g , 196-197 Organic-phase n o n i d e a l i t i e s , 197-200 O r g a n i c r a d i c a l scavengers, photoredox r e a c t i o n s o f metal o x i d e s , 431 Organic r e a c t i o n s a b i o t i c , m i n e r a l s u r f a c e s , 462-483 a f f e c t e d by s u r f a c e B r o n s t e d a c i d i t y o f c l a y m i n e r a l s , 475t a f f e c t e d by s u r f a c e Lewis a c i d i t y o f c l a y m i n e r a l s , 466t Organic r e d u c t a n t s , a d s o r p t i o n and subsequent e l e c t r o n t r a n s f e r on metal o x i d e s u r f a c e s , 446-460 O r g a n i c r e s i d u e s , e f f e c t on potassium s e l e c t i v i t y i n s o i l s , 337-338 Organic s o l u t e s a d s o r p t i o n onto s u r f a c e s , 192-193 h y d r o p h o b i c , s o r p t i o n by sediments, 191-213 Osmotic c o e f f i c i e n t , KCl-KBr-water system, 566-567 O u t e r - s p h e r e mechanism r e d u c t i o n o f t e r v a l e n t metal i o n by p h e n o l , 448,449f r e d u c t i v e d i s s o l u t i o n o f metal o x i d e s u r f a c e , 448,450f Outer-sphere surface r e a c t i o n , t r i p l e - l a y e r model, 123t Oxidation b e n z i d i n e i n the presence o f v a r i o u s c l a y s , 467-468 C o ( I I ) t o C o ( I I I ) d u r i n g s o r p t i o n on b i r n e s s i t e , 510-511 manganese(II) i n n a t u r a l w a t e r s , 497-500 i n sodium p e r c h l o r a t e and sodium c h l o r i d e , 497t i n the presence o f l e p i d o c r o c i t e , 487-500 on metal o x i d e s , 491-492 mercaptans by a metal o x i d e s u r f a c e , 456 o r g a n i c compounds by o x i d e s and primary m i n e r a l s , 480-483 Oxidation polymerization reactions, m i n e r a l s u r f a c e s , 468-471 Oxidation reactions, mineral s u r f a c e s , 464,467-468 O x i d a t i o n s t a t e s , manganese, 487-488 Oxide(s) c o m p o s i t i o n , e f f e c t on r a t e s o f l i g a n d s u b s t i t u t i o n , 454-455 m i n e r a l o g y , e f f e c t on r e d u c t i v e d i s s o l u t i o n , 458-459 oxidation of organic compounds, 480-483 s t e r n c a p a c i t a n c e , 89,91 Oxide-electrolyte interface g e o c h e m i s t r y , 55-59 t h e o r y , 79-96

Oxide-solution interface f r e e e n e r g i e s o f e l e c t r i c a l double l a y e r s , 99-112 r e a c t i o n s , c h e m i c a l and e l e c t r o s t a t i c models, 54-77 Oxide s u r f a c e c h e m i c a l r e a c t i o n s , 59-61 e q u a t i o n o f s t a t e , 100-102 Oxygen e f f e c t on d i s s o l u t i o n o f manganese o x i d e , 438,440f i s o t o p i c d a t a f o r s m e c t i t e s , 319t Ρ

Parabolic k i n e t i c s , mineral d i s s o l u t i o n experiments, 616-620 P a r a b o l i c r a t e law, c r y s t a l growth i n s o l u t i o n , 608-611 Paramagnetic probes o f l a y e r s i l i c a t e s u r f a c e , 362-387 P a r a t h i o n , h y d r o l y s i s on k a o l i n i t e s , 477 P a r t i c l e s i n a c e l l , i n t e r a c t i o n s , 21 Partitioning metal between s o l i d and s o l u t i o n , 165 t r a c e elements i n t o c a l c i t e , 584-585 Partitioning coefficients as a f u n c t i o n o f pH and a d s o r p t i o n d e n s i t y , 175-178 d e f i n i t i o n , 201-202 m e t a l - i o n a d s o r p t i o n , 162-188 r e l a t i o n t o macroscopic proton c o e f f i c i e n t s , 165-169 P a r t i t i o n i n g e q u i l i b r i u m constant, d e f i n i t i o n , 201 P a r t i t i o n i n g experiments B a ( I I ) i n t o c a l c i t e , 577-583 S r ( I I ) i n t o c a l c i t e , 575-576 P a r t i t i o n i n g theory, l i m i t a t i o n s , 203-208 P a r t i t i o n i n g thermodynamics, 194-197 P e n e t r a t i o n depths, comparison w i t h d i f f u s i o n c o e f f i c i e n t s , 593 P e n t a v a l e n t Sb-119, on h e m a t i t e , 409-414 P e n t a v a l e n t Sb-119 i o n s , on h e m a t i t e , 420-423 Pétrographie o b s e r v a t i o n s , weathered f e l d s p a r , 620-623 pH amphoteric surface w i t h complexation model, 87-89 c u r v e s , i n t e r p r e t a t i o n , 91,94 dependence o f a d s o r p t i o n o f metal i o n s , 347 dependence o f c h e m i c a l s t r u c t u r e o f adsorbed p e n t a v a l e n t Sb-119, 411 dependence o f phosphate a d s o r p t i o n , 237,238f


INDEX


pH

677

(Continued) e f f e c t on copper a d s o r p t i o n on c l a y m i n e r a l s , 351 e f f e c t on s o r p t i o n o f c o b a l t complexes on sodium b i r n e s s i t e , 507-519 e f f e c t s on d i v a l e n t Co-57 i o n s on h e m a t i t e , 419 e f f e c t s on p e n t a v a l e n t Sb-119 i o n s on h e m a t i t e , 420 importance i n the t h e o r y o f the oxide-electrolyte i n t e r f a c e , 79-96 r e l a t i o n t o macroscopic p r o t o n c o e f f i c i e n t , 172,175 r e l a t i o n to p a r t i t i o n i n g c o e f f i c i e n t , 175-178 Phenol CIR-FTIR spectrum, 156f p o l y m e r i z a t i o n through r a d i c a l c a t i o n s , 468-469 Phosmet, h y d r o l y s i s by m o n t m o r i l l o n i t e , 477-478 Phosphate b i d e n t a t e a d s o r p t i o n on g o e t h i t e , 148 c a l c i u m , g r o w t h , 650-661 e f f e c t on M n ( I I ) o x i d a t i o n , 492-497 pH dependence o f a d s o r p t i o n , 237,238f s o r p t i o n by c a l c i t e , 224 Photoacoustic spectroscopy, monitoring o f s u r f a c e s p e c i e s , 357 Photocatalyzed r e a c t i o n s , semiconducting metal oxide s u r f a c e s , 428 Photodissolution of iron oxide, measured and f i t t e d p a r a m e t e r s , 437t P h o t o d i s s o l u t i o n o f metal o x i d e s i n a d d i t i v e - f r e e media, 429-431 P h o t o f i x a t i o n , n i t r o g e n , 428-429 Photolysis of surface-located inner c o o r d i n a t i o n sphere complexes, 431-441 P h o t o m i c r o g r a p h s , SEM, q u a r t z s u r f a c e s , 641f,643,646f Photopeaks f o r n i t r o g e n , XPS s t u d i e s o f c o b a l t complexes on b i r n e s s i t e , 507-514 Photoredox c h e m i s t r y o f c o l l o i d a l metal o x i d e s , 426-443 Photoredox r e a c t i o n s o f metal o x i d e s i n t h e presence o f o r g a n i c r a d i c a l s c a v e n g e r s , 431 P h o t o r e d u c t i o n , XPS and AES, 390 P h t h a l a t e , e f f e c t on M n ( I I ) o x i d a t i o n , 492-497 P h t h a l i c a c i d , e f f e c t on d i s s o l u t i o n o f i r o n o x i d e , 438 P h y l l o s i l i c a t e minerals, p o t a s s i u m - c a l c i u m exchange e q u i l i b r i a , 330-334

P h y s i c a l p r o p e r t i e s of the m i n e r a l - w a t e r i n t e r f a c e , 3-5 P i t d e n s i t i e s , quartz s u r f a c e s , 640-642 P i t f o r m a t i o n , t h e o r y , 636-638 P i t growth r a t e s , q u a r t z s u r f a c e s , 642-645 Plagiclase feldspars, susceptibility t o w e a t h e r i n g , 616 P l a n a r double l a y e r s , i n t e r a c t i o n f r e e energy, 109-112 P l a t e l e t , l a y e r s i l i c a t e s , 362-363f P o l a r i z a b i l i t y , c a t i o n s , i o n exchange i n c l a y m i n e r a l s , 265-274 P o l y m e r i c metal i o n s , f o r m a t i o n on m i n e r a l s u r f a c e s , 348 Polymerization reactions, oxidative, a t m i n e r a l s u r f a c e s , 468-471 P o l y m e r s , humic, n o n i d e a l i t i e s , 197-203 Potassium-bearing minerals, r e a c t i o n w i t h sodium k i n n e y , 320-322 Potassium bromide-potassium c h l o r i d e aqueous system, 561-573 P o t a s s i u m - c a l c i u m exchange e q u i l i b r i a i n a l u m i n o s i l i c a t e m i n e r a l s and s o i l s , 327-339 Potassium c h l o r i d e , e f f e c t on hydroxyapatite c r y s t a l l i z a t i o n r a t e , 655-657 Potassium-exchanged s m e c t i t e s w i t h o u t w e t t i n g and d r y i n g , b e h a v i o r , 303 Potassium f i x a t i o n i n s m e c t i t e background, 297-298 by w e t t i n g and d r y i n g , 296-324 m a t e r i a l s and methods, 299-302 P o t a s s i u m - i o n exchange i n Y z e o l i t e , 285 Potassium k i n n e y r e a c t i o n , e f f e c t o f temperature, 320 P o t a s s i u m n i t r a t e , e f f e c t on hydroxyapatite c r y s t a l l i z a t i o n r a t e , 655-657 Potassium s m e c t i t e s e f f e c t o f s o l u t i o n c o m p o s i t i o n on r e a c t i o n s , 317-320 response t o w e t t i n g and d r y i n g i n w a t e r , 303-317 X-ray d i f f r a c t i o n p a t t e r n s , 303-310 Potential r e l a t i o n s h i p t o charge, e l e c t r i c double l a y e r , 233 See a l s o S u r f a c e p o t e n t i a l P o t e n t i a l energy o f i n t e r a c t i o n s , p a r t i c l e s i n a c e l l , 21 P r e c i p i t a t e f o r m a t i o n , o c c l u s i o n , 539 Precipitation c a l c i u m carbonate-magnesium carbonate system, 544 c a l c i u m phosphate, 651 d e f i n i t i o n , 217 g e n e r a l d i s c u s s i o n , 11-12


G E O C H E M I C A L PROCESSES AT MINERAL SURFACES


678

P r e c u r s o r complex f o r m a t i o n between r e d u c t a n t m o l e c u l e s and o x i d e s u r f a c e s i t e s , 453-455 r a t e , 455 P r e d i c t i o n o f growth r a t e s , c r y s t a l s i n s o l u t i o n , 607-610 Pressure-jump a p p a r a t u s w i t h c o n d u c t i v i t y d e t e c t i o n , 133-135 Pressure-jump k i n e t i c e x p e r i m e n t s , l e a d - i o n adsorption a t the g o e t h i t e - w a t e r i n t e r f a c e , 128-132 Probes o f l a y e r s i l i c a t e s u r f a c e s , p a r a m a g n e t i c , 362-387 P r o t o n a d s o r p t i o n on g o e t h i t e , t i t r a t i o n calorimetry r e s u l t s , 146-147 Proton c o e f f i c i e n t a d s o r p t i o n p r e d i c t i o n , 179-181 comparison, I85t c o n d i t i o n a l , I68t m a c r o s c o p i c d e s c r i p t i o n s , 164-169 See a l s o M a c r o s c o p i c p r o t o n coefficient Proton-exchange r e a c t i o n , m e t a l , 164 P r o t o n s t o i c h i o m e t r y a t v a r i a b l e pH and a d s o r p t i o n d e n s i t y , 162-188 P r o t o n a t i o n o f b e n z i d i n e , 468 Protonation-deprotonation reactions, hydrated metal oxide surface s i t e s , 453 P r o t o n i c surface charge, d i p r o t i c s u r f a c e group model, 71-72 P r o v i s i o n a l a c t i v i t i e s and a c t i v i t y c o e f f i c i e n t s , KCl-KBr-water system, 568t P r o v i s i o n a l equilibrium constants, KCl-KBr-water system, 568t P y r i d i n i u m and b i p y r i d i u m s a l t s , e n t h a l p i e s o f exchange, 275t Q Q u a r t z , d i s l o c a t i o n e t c h p i t s , 635-647 Q u a r t z s u r f a c e s , SEM photomicrographs, 641f,643f,646f R R a d i c a l scavengers, organic, photoredox r e a c t i o n s o f m e t a l o x i d e s , 431 Radionuclide d i f f u s i o n , a l k a l i , r o l e i n g l a s s y and c r y s t a l l i n e s i l i c a t e s , 587-597 Rapid k i n e t i c s , s o r p t i o n p r o c e s s , 224 Rate e t c h p i t f o r m a t i o n , 638 f e l d s p a r w e a t h e r i n g , 626-629 M n ( I I ) o x i d a t i o n , 488,491,497 p i t growth, q u a r t z s u r f a c e s , 642-645 p r e c u r s o r complex f o r m a t i o n , 455-456

Rate c o n s t a n t s a d s o r p t i o n - d e s o r p t i o n o f phosphate and chromate, 239t adsorption-desorption of p o t e n t i a l - d e t e r m i n i n g i o n s , 234t a d s o r p t i o n - d e s o r p t i o n o f the c o u n t e r i o n , 237t i n t e r c a l a t i o n s t u d i e s , 247-248t k i n e t i c model o f l e a d - i o n a d s o r p t i o n , 127,132 M n ( I I ) o x i d a t i o n , 495 Rate c o n t r o l c r y s t a l growth i n s o l u t i o n , 601 m i n e r a l d i s s o l u t i o n , 620 Rate laws, e l e c t r o l y t e c r y s t a l growth from aqueous s o l u t i o n , 600-611 Reaction(s) and e q u i l i b r i u m e x p r e s s i o n s , t r i p l e - l a y e r model, 123t i n v o l v i n g m e t a l i o n s adsorbed on m i n e r a l s , 355-357 promoted by the Lewis and B r o n s t e d a c i d i t y of clay m i n e r a l s , 464-479 Reaction k i n e t i c s , d i s t i n g u i s h i n g a d s o r p t i o n from s u r f a c e p r e c i p i t a t i o n , 223-224 R e a c t i o n p a t t e r n s , w e t t i n g and d r y i n g o f p o t a s s i u m s m e c t i t e s , 310 Reaction quotients, d i p r o t i c surface group model, 69-71 R e c r y s t a l l i z a t i o n i n the K C l - K B r - w a t e r system, 561-573 Redox d i s p r o p o r t i o n a t i o n , d e f i n i t i o n , 468 Reduced m a g n e t i z a t i o n , s u r f a c e f e r r i c i o n s , 414 Reduced s u r f a c e s i t e s , d i s s o l u t i o n , 457-458 Reduction m e t a l i o n , XPS and AES, 390 m e t a l i o n complexes by o r g a n i c compounds, 446-447 Reduction p o t e n t i a l s , t r a n s i t i o n metal o x i d e - h y d r o x i d e s , 448t Reductive d i s s o l u t i o n d e s c r i p t i o n on a m o l e c u l a r l e v e l , 451-459 e f f e c t o f o x i d e m i n e r a l o g y , 458-459 m e t a l o x i d e s u r f a c e s , 448-451 r e a c t i o n scheme, 447-448 Regular s o l i d s o l u t i o n s d i s t r i b u t i o n l a w s , 531-532 s u b s t i t u t i o n a l d i s o r d e r , 534 R e l a x a t i o n methods adsorption-desorption k i n e t i c s at the m e t a l o x i d e - s o l u t i o n i n t e r f a c e , 230-252 See a l s o Chemical r e l a x a t i o n methods


679


INDEX

R e l a x a t i o n time adsorption-desorption k i n e t i c s , concentration dependence, 233-239 adsorption-desorption of divalent metal i o n s , 243 d i f f u s i o n r e a c t i o n , 236 d i v a l e n t Co-57 i o n s on h e m a t i t e , 420 i n t e r c a l a t i o n k i n e t i c s , 244-245 R e l a x a t i o n time c o n s t a n t s lead-ion adsorption at the goethite-water i n t e r f a c e , 128-132 r e l a t i o n s h i p t o the c o n c e n t r a t i o n o f the r e a c t i n g s p e c i e s , 138-139 Removal t i m e s , manganese i n n a t u r a l w a t e r s , 499t R e s i d u a l l a y e r c o m p o s i t i o n s , weathered f e l d s p a r , 623-625 Reversibility i o n exchange i n c l a y m i n e r a l s , 280,283 i o n exchange i n z e o l i t e s , 290 Roozeboom c l a s s i f i c a t i o n , systems o f two isomorphous s a l t s , 525-527 Rubidium calculation of diffusion parameters, 592-594 exchange i n i l l i t e - s m e c t i t e i n t e r l a y e r s and i n m o n t m o r i l l o n i t e s , 278-280 high-temperature d i f f u s i o n s t u d i e s , 595 uptake by o b s i d i a n , 588,589

S Salicylate a d s o r p t i o n on g o e t h i t e , 148-150 CIR-FTIR spectrum, 156f complex w i t h i r o n , CIR-FTIR spectrum, 157f e f f e c t on M n ( I I ) o x i d a t i o n , 492-497 S a l i c y l i c a c i d , e f f e c t on i r o n o x i d e d i s s o l u t i o n r a t e , 435,436f Sand g r a i n s from bedrock, s u r f a c e m o r p h o l o g i e s , 642,643f S a p o n i t e , ESR s p e c t r a , 371f,372 S a p o n i t e f i l m s , copper-doped, ESR s p e c t r a , 379,382f S a t e l l i t e s t r u c t u r e , XPS, 392 Scanning e l e c t r o n m i c r o s c o p i c s t u d i e s , weathered f e l d s p a r s , 625 Scanning e l e c t r o n p h o t o m i c r o g r a p h s , quartz s u r f a c e s , 641f,643f,646f Seawater, M n ( I I ) o x i d a t i o n , 498-499 Secondary i o n mass s p e c t r o s c o p y (SIMS), c o b a l t complex i n t e r a c t i o n s on b i r n e s s i t e , 506 Sediments, s o r p t i o n o f h y d r o p h o b i c o r g a n i c s o l u t e s , 191-213

Seeds used t o i n i t i a t e c a l c i t e g r o w t h , 583 S e l e c t i v e i o n exchange i n c l a y m i n e r a l s and z e o l i t e s , 254-290 Selectivity a d s o r p t i o n o f metal i o n s , 346 a l k a l i m e t a l c a t i o n s , 277 p o t a s s i u m - c a l c i u m exchange, 330-331 S e l e c t i v i t y - c o m p l e x formation f u n c t i o n , 270 Semiconducting metal oxide s u r f a c e s , p h o t o c a t a l y z e d r e a c t i o n s , 428 Semiconducting p r o p e r t i e s of t r a n s i t i o n metal o x i d e s , importance i n r e d u c t i v e d i s s o l u t i o n , 459 Semiconductors, e l e c t r i c a l c o n d u c t i o n , 427 Silicate(s) e f f e c t on M n ( I I ) o x i d a t i o n , 492-497 g l a s s y and c r y s t a l l i n e , r o l e o f near-surface a l k a l i r a d i o n u c l i d e , 587-597 See a l s o C l a y s S i l i c a t e c l a y s , groups o f exchange s i t e s , 332t S i l i c a t e minerals, adsorption of w a t e r , 50-51 S i l i c a t e s u r f a c e s , paramagnetic p r o b e s , 362-387 Silicon Auger p a r a m e t e r s , 400t e f f e c t o f c o n c e n t r a t i o n on e t c h p i t d e n s i t i e s on q u a r t z s u r f a c e s , 640-642 S i l v e r - s o d i u m exchange i n NaY z e o l i t e , 283-285 Simple i d e a l s o l i d s o l u t i o n s , d i s t r i b u t i o n laws, 527-530 S i m u l a t i n g l i q u i d water near hydrophobic mineral s u r f a c e s , methods and l i m i t a t i o n s , 20-34 S i m u l a t i o n approaches, g e n e r a l , 21-23 Simulations of i n t e r f a c i a l w a t e r , 28-32 Site density of goethite, e s t i m a t i o n , 115-117 Slow k i n e t i c s , s o r p t i o n p r o c e s s , 224 Smectites adsorbed w a t e r , 41 angle o f t e t r a h e d r a l r o t a t i o n , 310,314 oxygen i s o t o p i c d a t a , 319t p o t a s s i u m f i x a t i o n by w e t t i n g and d r y i n g , 296-324 s t r u c t u r e , 38,39f,344 s u r f a c e s , number o f charges per u n i t c e l l , 26t w e t t i n g and d r y i n g e x p e r i m e n t s c h e m i c a l a n a l y s e s , 301t s t r u c t u r a l f o r m u l a s , 302t w i t h exchangeable c a t i o n s , 364



680

G E O C H E M I C A L PROCESSES AT M I N E R A L S U R F A C E S

Sodium c h l o r i d e , e f f e c t on hydroxyapatite c r y s t a l l i z a t i o n r a t e , 655-657 Sodium-ion exchange i n Y z e o l i t e , 285 Sodium-ion s a t u r a t e d l a y e r s i l i c a t e c l a y s , u n i t c e l l formulas and s o u r c e s , 365t Sodium k i n n e y , r e a c t i o n w i t h potassium-bearing m i n e r a l s , 320-322 Sodium p e r c h l o r a t e , M n ( I I ) o x i d a t i o n , 497-498 S o d i u m - s i l v e r exchange i n NaY z e o l i t e , 283-285 Soils groups o f exchange s i t e s , 337t p o t a s s i u m - c a l c i u m exchange e q u i l i b r i a , 334-338 r o l e of organic matter i n r e a c t i o n s a t m i n e r a l s u r f a c e s , 479 Solid-phase mixtures, metal-ion a d s o r p t i o n , 178,179t Solid solution(s) d i s t r i b u t i o n laws and s u b s t i t u t i o n a l d i s o r d e r , 533-558 g e n e r a l d i s c u s s i o n , 12-13 i d e a l , d i s t r i b u t i o n laws, 527-530 i o n i c , i n c o n t a c t w i t h aqueous s o l u t i o n s , 524-558 r e g u l a r , d i s t r i b u t i o n l a w s , 531-532 s o l u b i l i t y b e h a v i o r , 536-537t S o l i d solution-aqueous s o l u t i o n systems, approach t o e q u i l i b r i u m , 561-573 Solubility h y d r o x y a p a t i t e systems, 544-552 KCl-KBr-water system, 561-573 s o l i d solution i n equilibrium with aqueous s o l u t i o n of i t s i o n s , 541 s o l i d s o l u t i o n s , 536-537t s o l u t e i n the presence o f d i s s o l v e d humic m a t e r i a l , 201 S o l u b i l i t y methods, d i s t i n g u i s h i n g a d s o r p t i o n from s u r f a c e p r e c i p i t a t i o n , 218-222 S o l u b i l i t y product e q u i l i b r i u m between an i o n i c compound and an aqueous s o l u t i o n , 524-525 e q u i l i b r i u m between an i o n i c s o l i d s o l u t i o n and an aqueous s o l u t i o n , 525 S o l u b i l i t y product c o n s t a n t s , d i v a l e n t m e t a l - i o n h y d r o x i d e s , 458t S o l u b i l i z a t i o n , hematite suspensions c o n t a i n i n g S ( I V ) , 432,434f Solute a d s o r p t i o n , macroscopic d e s c r i p t i o n s , 164-169 S o l u t i o n complex f o r m a t i o n , e f f e c t on M n ( I I ) o x i d a t i o n , 492

S o l u t i o n composition e f f e c t on the r e a c t i o n s o f p o t a s s i u m s m e c t i t e s , 317-320 i n f l u e n c e on f e l d s p a r w e a t h e r i n g r a t e s , 615-632 Solution concentration of potential-determining ions, Boltzmann d i s t r i b u t i o n , 101 Solution-metal oxide i n t e r f a c e adsorption-desorption k i n e t i c s , 230-252 f r e e e n e r g i e s o f e l e c t r i c a l double l a y e r s , 99-112 Solution-phase r e a c t i o n s , surface c o m p l e x a t i o n models, l63t Sorbent p r o p e r t i e s used t o e s t i m a t e the time to e q u i l i b r i u m , 211t Sorption c o b a l t complexes on sodium birnessite s u r f a c e a n a l y s i s , 507-519 XPS, 507-514 h y d r o p h o b i c o r g a n i c s o l u t e s by s e d i m e n t s , 191-213 m i n e r a l s u r f a c e s , 204-211 o r g a n i c compounds, 7 See a l s o A d s o r p t i o n S o r p t i o n processes d e f i n i t i o n , 217 mechanisms, 5-6 t y p e s , 343 S p e c t r a l s h i f t s i n sorbed m o l e c u l e s , e f f e c t o f m e t a l o x i d e s , 441 Spectroscopic techniques, s t u d i e s of s u r f a c e a d s o r p t i o n , 343-344 Speed r u n s , c o p r e c i p i t a t i o n o f B a ( I I ) and S r ( I I ) w i t h c a l c i t e , 579-583 S p i n d e n s i t i e s on m e t a l i o n s , magnetic metal o x i d e s , 414 Spin l e v e l s , electron i n t e r a c t i n g with a n i t r o g e n atom, 367,368f S p i n - o r b i t s p l i t t i n g , XPS, 395 S p i n s t a t e s o f copper i o n , energy l e v e l diagram, 376,378f S p i n system, a x i a l l y symmetric, ESR s p e c t r a , 379,381f S p i r a l step c o n t r o l , s u r f a c e , c r y s t a l growth i n s o l u t i o n , 605-606 S p l i t t i n g s p i n o r b i t and m u l t i p l e t , XPS, 395 S p u t t e r i n g t e c h n i q u e , to produce e l e m e n t a l p r o f i l e s w i t h d e p t h , 590 S t a b i l i z a t i o n f a c t o r , complex c a t i o n exchange, 270 S t a t i c d i e l e c t r i c constant, i n t e r f a c i a l w a t e r , 30-31 S t e r e o c h e m i c a l arrangements, copper-aquo complexes i n l a y e r s i l i c a t e s , 383,385f S t e r e o c h e m i s t r y and d - o r b i t a l energy diagram, copper adsorbed on l a y e r s i l i c a t e s , 376,378f


681


INDEX

S t e r e o s e l e c t i v e i n t e r c a l a t i o n , 245-250 S t e r n c a p a c i t a n c e on o x i d e s , 89-91 S t e r n model, e l e c t r i c double l a y e r , 64-67 Stoichiometric saturation, KCl-KBr-water system, 564 S t o i c h i o m e t r i c versus nonstoichiometric dissolution, elements o f f e l d s p a r , 619-620 S t o i c h i o m e t r y o f s u r f a c e complexes, importance i n determining e l e c t r o n - t r a n s f e r r a t e , 456-457 Streaming p o t e n t i a l , d e f i n i t i o n , 222 Strontium calculation of diffusion parameters, 592-594 high-temperature diffusion s t u d i e s , 595 Strontium(II) e f f e c t on B a ( I I ) p a r t i t i o n i n g e x p e r i m e n t s , 579 i n c o r p o r a t i o n i n t o c a l c i t e , 575-576 modes o f c o p r e c i p i t a t i o n w i t h c a l c i t e , 574-585 S t r o n t i u m i o n s , e f f e c t on c a l c i u m phosphate c r y s t a l l i z a t i o n , 657-661 S t r o n t i u m h y d r o x y a p a t i t e , i n systems w i t h c a l c i u m h y d r o x y a p a t i t e , 554 Structural differences, a l k a l i glasses and c r y s t a l l i n e s i l i c a t e s , 595 Subreactions, r e l a t i o n t o macroscopic p r o t o n c o e f f i c i e n t s , 181-185 Substitutional disorder, solid s o l u t i o n s , 533-558 S u l f a t e , e f f e c t on M n ( I I ) o x i d a t i o n , 492-497 S u l f u r and copper XPS s p e c t r a , c h a l c o c i t e , 394f S u p e r s a t u r a t i o n , c a l c i u m phosphate s o l u t i o n s , 651 S u p e r t r a n s f e r r e d h y p e r f i n e magnetic f i e l d , a c t i n g on t h e s u r f a c e Sn-119 i o n s , 416-419 Surface(s) a c c e l e r a t i o n o f Mn(II) o x i d a t i o n , 488 l a y e r s i l i c a t e , paramagnetic probes, 362-387 mineral, a b i o t i c organic r e a c t i o n s , 462-483 Surface a n a l y s i s , s o r p t i o n of c o b a l t complexes on sodium b i r n e s s i t e , 507-519 S u r f a c e area assessment, 345 e f f e c t o f i n c r e a s e s on m i n e r a l d i s s o l u t i o n e x p e r i m e n t s , 623 i n f l u e n c e on f e l d s p a r w e a t h e r i n g r a t e s , 615-632 S u r f a c e c h a r a c t e r i s t i c s , i n f l u e n c e on f e l d s p a r w e a t h e r i n g r a t e s , 615-632

Surface c h a r a c t e r i z a t i o n , c o b a l t complex i n t e r a c t i o n s on b i r n e s s i t e , 503-521 S u r f a c e charge a l u m i n o s i l i c a t e m i n e r a l s , 344-345 amphoteric s u r f a c e with complexation model, 86-87 amphoteric s u r f a c e without c o m p l e x a t i o n model, 84-85 t r i p l e - l a y e r model s u r f a c e complexes, 118-119 S u r f a c e charge d e n s i t y adsorption-desorption of divalent metal i o n s , 241,243 d i f f u s e d o u b l e l a y e r , 102-103 oxide-solution interface equilibrium p o i n t , 103-106 o x i d e s u r f a c e , 101-102 S u r f a c e charge-pH c u r v e s , i n t e r p r e t a t i o n , 91,94 S u r f a c e c h e m i c a l r e a c t i o n mechanism, r e d u c t i v e d i s s o l u t i o n o f metal o x i d e s u r f a c e s , 448-451 S u r f a c e complex(es) e f f e c t o f f o r m a t i o n on M n ( I I ) o x i d a t i o n , 492 t r i p l e - l a y e r model, 118-120 S u r f a c e c o m p l e x a t i o n models oxide-solution interface r e a c t i o n s , 59-63 solid-solution interface i n t e r a c t i o n s , 162-164 S u r f a c e c o m p o s i t i o n , weathered f e l d s p a r s , 623-625 Surface c o n c e n t r a t i o n s , amphoteric surface without complexation model, 82-83 Surface-controlled kinetics, crystal growth i n s o l u t i o n , 604-606 S u r f a c e c o v e r a g e , o r g a n i c compounds on metal o x i d e s u r f a c e s , 455-456 S u r f a c e d e n s i t y , d i f f u s e double l a y e r , 102-103 Surface d i s s o c i a t i o n constant, d i p r o t i c s u r f a c e group model, 71 Surface e q u i l i b r i u m constants, d e t e r m i n a t i o n , 89-94 S u r f a c e h y d r a t i o n , e f f e c t on a l k a l i d i f f u s i o n , 597 S u r f a c e - l o c a t e d chromophores, l i g h t absorption i n c o r p o r a t i n g the oxide l a t t i c e m e t a l , 429-441 Surface-located inner coordination sphere complexes, p h o t o l y s i s , 431-441 S u r f a c e measurements as p a r t o f a g e o c h e m i c a l s t u d y , advantages, 390 Surface n u c l e a t i o n c o n t r o l , c r y s t a l growth i n s o l u t i o n , 605 S u r f a c e o r d e r i n g parameter, 372



682

G E O C H E M I C A L PROCESSES AT MINERAL SURFACES

S u r f a c e peak e f f e c t , r u b i d i u m and strontium d i f f u s i o n i n vitreous s i l i c a , 597 S u r f a c e phenomena, e l e c t r o s t a t i c versus chemical i n t e r a c t i o n s , 56-57 Surface p o t e n t i a l adsorption-desorption of divalent metal i o n s , 241,243 amphoteric s u r f a c e w i t h c o m p l e x a t i o n model, 87-89 amphoteric s u r f a c e w i t h o u t c o m p l e x a t i o n model, 83-84 i n t e r f a c i a l water s i m u l a t i o n , 25-28 k i n e t i c model o f l e a d - i o n a d s o r p t i o n , 127 o x i d e s u r f a c e , 101-102 oxide-solution interface equilibrium p o i n t , 103-106 Surface potential-pH c h a r a c t e r i s t i c s , importance i n t h e o r y o f o x i d e - e l e c t r o l y t e i n t e r f a c e , 79-96 Surface potential-pH curves, measurement, 80-81f Surface p r e c i p i t a t i o n , d i s t i n g u i s h i n g from a d s o r p t i o n , 217-226 S u r f a c e p r o c e s s e s , c r y s t a l growth i n s o l u t i o n , 600-601 Surface p r o p e r t i e s l e p i d o c r o c i t e , 489t metal o x i d e , e f f e c t on photoinduced redox r e a c t i o n s , 441-443 Surface p r o t o l y s i s r e a c t i o n s , t r i p l e - l a y e r model, 123t S u r f a c e p r o t o n a d s o r p t i o n on g o e t h i t e , 148 Surface r e a c t i o n s k i n e t i c s , 232-244 s u r f a c e c o m p l e x a t i o n models, 163t Surface s i t e s heterogeneity e v a l u a t i o n s , 185-186 r e l a t i o n t o macroscopic p r o t o n c o e f f i c i e n t , 165-169,181 n o n u n i f o r m i t y , e f f e c t on s u r f a c e complex f o r m a t i o n , 455 reduced, d i s s o l u t i o n , 457-458 Surface spectroscopy d i s t i n g u i s h i n g a d s o r p t i o n from s u r f a c e p r e c i p i t a t i o n , 224-226 g e n e r a l d i s c u s s i o n , 9-10 Surface s p i r a l step c o n t r o l , c r y s t a l growth i n s o l u t i o n , 605-606 Surface techniques, a p p l i c a t i o n s to c h e m i c a l bonding s t u d i e s o f m i n e r a l s , 389-401 S y n t h e s i s o f k a o l i n i t e h y d r a t e s , 44-45 Synthetic birnessite, interaction with c o b a l t complexes, 503-521

Τ T a r t a r i c a c i d , e f f e c t on i r o n o x i d e d i s s o l u t i o n r a t e , 435,436f Tempamine adsorbed on c l a y f i l m s , h y p e r f i n e s p l i t t i n g v a l u e s , 372t adsorbed on sodium s m e c t i t e f i l m s , 370-371f m o l e c u l a r s t r u c t u r e , 367 p o s s i b l e o r i e n t a t i o n s , 375f Temperature dependence o f d i f f u s i o n c o e f f i c i e n t s , 593 e f f e c t on the r e a c t i o n o f p o t a s s i u m k i n n e y , 320 Terraced etch p i t s , quartz s u r f a c e s , 645 Tetrahedral rotations i n dioctahedral c l a y s , 314 Theory, KCl-KBr-water system s o l u b i l i t y , 563-566 Thermodynamic a c t i v i t i e s , h y d r o x y a p a t i t e and f l u o r a p a t i t e , 549-552 Thermodynamic background, i o n exchange i n c l a y m i n e r a l s and z e o l i t e s , 255-256 Thermodynamic d a t a a l k a l i metal c a t i o n exchange, 257t t r a n s i t i o n metal i o n exchange, 266-267t Thermodynamic p r o p e r t i e s c l a y - w a t e r m i x t u r e s , 42-43 KCl-KBr-water system, 564-566 Thermodynamics, p a r t i t i o n i n g , 194-197 Time t o e q u i l i b r i u m , s o r b e n t p r o p e r t i e s used t o e s t i m a t e , 211t Tin-119, e l e c t r o n i c environment, 404-405 Titration calorimetry a n i o n a d s o r p t i o n on g o e t h i t e , 143-150 g e n e r a l d i s c u s s i o n , 143-144 methods, 144-146 p r o t o n a d s o r p t i o n on g o e t h i t e , 146-147 T r a n s f o r m a t i o n r e a c t i o n s a t the m i n e r a l - w a t e r i n t e r f a c e , 13-14 T r a n s i t i o n metal complexes, a d s o r p t i o n on m i n e r a l s , 353-354 T r a n s i t i o n metal i o n c o o r d i n a t i v e environment, 451-453 T r a n s i t i o n metal i o n exchange, thermodynamic d a t a , 266-267t T r a n s i t i o n m e t a l i o n uncharged l i g a n d complexes, exchange, 288 T r a n s i t i o n metal oxide-hydroxides, r e d u c t i o n p o t e n t i a l s , 448t Transport-controlled kinetics, crystal growth i n s o l u t i o n , 600-604


683

INDEX

T r a p p i n g , B a ( I I ) on c a l c i t e , 577-579 T r i p l e - l a y e r model c a l c u l a t i o n s to estimate s i t e d e n s i t y o f g o e t h i t e , 115-117 e l e c t r i c d o u b l e l a y e r , 64-66 r e a c t i o n s and e q u i l i b r i u m e x p r e s s i o n s , 121-125 r e a c t i o n s a t charged i n t e r f a c e s , 118-121 Two-surface Langmuir e q u a t i o n , 219


U

U l t r a v i o l e t - v i s i b l e absorption s p e c t r o s c o p y , 354 Uncertainty associated with c a l c u l a t i o n o f n a t u r a l weathering r a t e s , 629-630 Unpaired e l e c t r o n e n e r g i e s , 366

V Vacuum-oriented s u r f a c e t e c h n i q u e s , problems, 390 Vanadium i o n s , a d s o r p t i o n on c l a y m i n e r a l s , 350-351 Vermiculite adsorbed w a t e r , 41 e x p a n s i o n i n w a t e r , 364 i o n exchange, 256-283 p o t a s s i u m - c a l c i u m exchange e q u i l i b r i a , 330-334 s t r u c t u r e , 38,39f V e r n a d i t e d i s s o l u t i o n , 438,440f

W Water e f f e c t on Bronsted a c i d i t y o f c l a y m i n e r a l s , 472 e f f e c t on Bronsted s u r f a c e a c i d i t y , 476-477 i n t e r l a y e r , c h a r a c t e r i z a t i o n , 45-48 m u l t i l a y e r a d s o r p t i o n , 41-43 n a t u r a l , M n ( I I ) o x i d a t i o n , 497-500 on h a l l o y s i t e , 40-41 on k a o l i n m i n e r a l s , 37-52 on s m e c t i t e s , 41 on v e r m i c u l i t e , 41 p o t e n t i a l s , i n t e r f a c i a l water s i m u l a t i o n s , 24-25 W a t e r - g o e t h i t e i n t e r f a c e , mechanism o f l e a d - i o n a d s o r p t i o n , 114-140 W a t e r - o r g a n i c m a t t e r systems, p a r t i t i o n i n g , 196-197 Water-saturated o c t a n o l , n o n i d e a l i t i e s , 195-196

Water-surface i n t e r a c t i o n p o t e n t i a l , s i m u l a t i o n s o f s m e c t i t e on mica s u r f a c e s , 26 Watershed g e o c h e m i c a l mass b a l a n c e s t u d i e s , f e l d s p a r w e a t h e r i n g , 629 Weathering e f f e c t on p o t a s s i u m s e l e c t i v i t y i n s o i l s , 337-338 f e l d s p a r , g e n e r a l d i s c u s s i o n , 616 Weathering r a t e s f e l d s p a r , f a c t o r s a f f e c t i n g , 615-632 g e o c h e m i c a l mass balance s t u d i e s , 628-629 Weiss f i e l d , r e d u c t i o n f a c t o r due t o the s u r f a c e e f f e c t , 416 W e t t i n g and d r y i n g , p o t a s s i u m f i x a t i o n i n s m e c t i t e , 296-324 W e t t i n g and d r y i n g e x p e r i m e n t s chemical analyses of smectites used, 301t m i n e r a l s used, 300t s t r u c t u r a l formulas o f s m e c t i t e s used, 302t Wheatstone b r i d g e , pressure-jump a p p a r a t u s , 133-135

X X-ray d i f f r a c t i o n complexes adsorbed on c l a y m i n e r a l s , 354 p o t a s s i u m s m e c t i t e s , 303-310 X-ray p h o t o e l e c t r o n s p e c t r o s c o p y (XPS) c h a l c o c i t e and c o v e l l i t e , 400t c h e m i c a l bonding s t u d i e s o f m i n e r a l s , 391-395 c o b a l t complex i n t e r a c t i o n s on b i r n e s s i t e , 505-506 metal i o n s adsorbed on c l a y m i n e r a l s , 348-349 s o r p t i o n o f c o b a l t complexes on sodium b i r n e s s i t e , 507-514 weathered f e l d s p a r s , 623-625 X-ray photoelectron/X-ray-induced Auger s p e c t r o s c o p y , c h e m i c a l bonding s t u d i e s o f m i n e r a l s , 397-401

Ζ Zeolites highly selective ion exchange, 283-290 s t r u c t u r e , 344 Zeta p o t e n t i a l d e f i n i t i o n , 222 r e l a t i o n t o pH, 223


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