EFFECTS

OF

WATER-SOLUBLE

POLYMERS OF

AND

ELECTROLYTES CLAY SOILS

ON P E R M E A B I L I T Y

HEAVY

P. P. Olodovskii, M. G. M u r a s h k o , A. B. B o g d a n o v a , R. F. D o t s e n k o , G. A. Ivkovskaya, T. L. M a t v e e v a , and T. M. K h o r s e e v a

UDC 620.168.34

A study h a s been made of the e f f e c t s of w a t e r - s o l u b l e p o l y m e r s on the filtration and c h e m i c a l r e s p o n s e of g y p s u m - b e a r i n g soils f r o m the Hunger Steppe and t a k y r - l i k e soils f r o m the K a r s h a Steppe. M e a s u r e m e n t s have been made [1-3] on the e f f e c t s of w a t e r - s o l u b l e p o l y m e r s and e l e c t r o l y t e s on the p e r m e a b i l i t i e s of r o c k - f o r m i n g clay m i n e r a l s (the n a t u r a l and Na f o r m s of m o n t m o r i l l o n i t e and kaolinite), using the data f i l t r a t i o n , a d s o r p t i o n , and e l e c t r o n m i c r o s c o p y , and a m e c h a n i s m (physical model) has been defined for the interaction between the p o l y m e r m a c r o m o l e c u l e s and the active c e n t e r s on the clay m i n e r a l s . A p p r o p r i a t e concentrations of these p o l y m e r s can m a x i m i z e the p e r m e a b i l i t y , and functions have been defined f o r predicting the filtration coefficients as functions of p o l y m e r content and specific s u r f a c e . Detailed m e a s u r e m e n t s a r e of considerable i n t e r e s t because c u r r e n t p r a c t i c e in soil i m p r o v e m e n t p l a c e s p a r t i c u l a r e m p h a s i s on i m p r o v e d infiltration in heavy s o i l s , i.e., m e a n s of controlling w a t e r t r a n s p o r t . We have e x a m i n e d the effects of w a t e r - s o l u b l e p o l y m e r s on desalination of soils and infiltration i m p r o v e m e n t , which has defined the scope for using b r a c k i s h w a t e r s for i r r i g a t i o n , on account of the i m p r o v e d f i l t r a tion o c c u r r i n g in the soils. We used genetic h o r i z o n s I and III f r o m soils in the Hunger Steppe (collective f a r m No. 5) and genetic h o r i z o n s I and II f r o m t a k y r - l i k e soils in the K a r s h a Steppe. We used w a t e r - s o l u b l e p o l y m e r s K-4, K - 9 , SMMA, PEM, SVAN, and SVAM, which w e r e made at the Institute of C h e m i s t r y , A c a d e m y of Sciences of the Uzbek SSR. The infiltration fluids w e r e saline w a t e r s whose c h e m i c a l compositions w e r e s i m i l a r to that of the w a t e r in the southern Hunger Steppe canal and in the R i v e r Amu D a r ' y a , in addition to 0.01 M aqueous p o t a s s i u m nitrate. M e a s u r e m e n t s w e r e made to d e t e r m i n e the initial salinity in the h o r i z o n s , the gypsum content, the exchangeable s o d i u m , and the total a b s o r p t i o n capacity; x - r a y analysis defined the m i n e r a l c o m position, while adsorption studies defined the specific s u r f a c e . In addition, infiltration t e s t s and e l e c t r o n m i c r o s c o p y w e r e employed. The soils w e r e e x a m i n e d in t h r e e s t a t e s : 1) with the initial salt a n d gypsum cont e n t s , 2) f r e e d f r o m s a l t s , and 3) modified by a m i x t u r e of subsoil w a t e r and i r r i g a t i o n water. Table 1 gives the m a i n r e s u l t s f r o m the c h e m i c a l and x - r a y studies. The effects of saline w a t e r s on the p a r a m e t e r s w e r e e x a m i n e d by tenfold t r e a t m e n t with aqueous s o l u tions of s a l t s p r e s e n t in the subsoil w a t e r and i r r i g a t i o n w a t e r s with s o l i d - l i q u i d phase r a t i o s of 1:8, which was followed by r e p e a t e d washing with distilled w a t e r until a negative r e a c t i o n for chloride was obtained. The s a l t concentrations in the solutions w e r e made up 1/5 f r o m the subsoil w a t e r and 4/5 f r o m the i r r i g a tion w a t e r . T a b l e 2 gives data on the compositions of t h e s e w a t e r s . Methods. The m i n e r a l compositions w e r e d e t e r m i n e d f r o m the x - r a y p a t t e r n s r e c o r d e d with a DRONI2 d f f f r a c t o m e t e r with CuK~ radiation. C l a s s i c a l c h e m i c a l a n a l y s i s methods w e r e used [4-6] ( a r g e n t o m e t r i c , EDTA, f l a m e p h o t o m e t r y , etc.). Central W a t e r - R e s o u r c e Utilization R e s e a r c h Institute, Minsk. T r a n s l a t e d f r o m I n z h e n e r n o - F i z i c h e s k i i Zhurnal, Vol. 34, No. 2, pp. 236-242, F e b r u a r y , 1978. Original a r t i c l e submitted J a n u a r y 1, 1977.

154

0022-0841/78/3402- 0154 $07.50

9 1978 Plenum Publishing C o r p o r a t i o n

T A B L E 1. Mineralogical Composition and Chemical Characteristics

Mineral composition

84

Material

Form of soil

Hun~er Steppe (col,

lecttve ~arm No. 5

I ~with initial salt I and gypsum coal tent~ /2,1 14,4

!w .shed
salts

17,3 Io:8
17,0 0 7 16,5 10,75

quartz, calcite, ~ypsum, h~mmica, kaolimte~ and montmorillomte;

Takyr-like soil, Karsha Steppe

I modified by a mixture of subsoil water and irrigation water 6,5 Ill with initial salt and gypsum contents 1,7 154,~ c washed free from salts modif~d by a mi~ ture or SUDSOil water and irrigation water I with initial salt and gypsum con0 teut~ with initial salt and gypsum contents 0 II washed free from salts modified by a mixture of subsoil water and irrigation water

--9!

lomlt6; "fedspars, ~oartzt gypsum, hydromica, kablinite, and montmorillonite

8,8~ 0,7 16,4 1,4 18,3 1,2 16,0 0,66 15,2 2,33 quartz, feldspars, calcite, ~y_psum, and a mixe~I-'Iayerphase (transittoual from hydmmioa to kaolinite), hydromiea, and chlorite

TABLE 2. Salt Contents of Soil Water and I r r i g a t i o n Water

Ion contents, g/liter Object Water type
HCO~- Cl-

SO42 Ca+-" big+ZI Na+ 0,4 0,22 4,21

due 19,26 1.037 14,45

Hunger Steppe Subsoil waters (collective Iarm Irrigation water No. 5) Southern HuggerSteppe canal Takyr-like soil Karsha Steppe Subsoil waters Irrigation water Amu-Dafya

0,43 0,15
0,27

2,34 11,7 0,13 5,52 0,56

0,081 0,043!.0,05 0,73 3,31

4,89 0,62

0,07: 0,063 0,107 0,0691 0,003I 0,040] 0,3 &

T h e s p e c i f i c s u r f a c e w a s d e d u c e d by m e a s u r i n g the b o u n d - w a t e r c o n c e n t r a t i o n and the d e n s i t y c h a n g e of a d i s p e r s i o n m e d i u m m i x e d w i t h the s o l i d , w h i c h t o o k up the a d s o r b e d w a t e r [7]; t h e r m a l d e s o r p t i o n by n i t r o gen w a s a l s o e m p l o y e d . T h e f i l t r a t i o n s t u d i e s w e r e m a d e w i t h F - l m i n s t r u m e n t s by a n a l o g y with the m e t h o d of [8], w h i l e the e l e c t r o n m i c r o g r a p h s w e r e r e c o r d e d w i t h an E M - 9 . T a b l e 3 g i v e s the p a r t i c l e s i z e s , a s w e l l a s the m a i n r e s u i t s f r o m the f i l t r a t i o n s t u d i e s , w h i l e F i g . 1 s h o w s t h e c h l o r i d e c o n t e n t d u r i n g w a s h i n g f o r g e n e t i c h o r i z o n s I and III in the H u n g e r S t e p p e f o r v a r i o u s l e v e l s of w a t e r c o n t e n t and w a t e r - s o l u b l e p o l y m e r . E v e n a c r u d e a n a l y s i s of the r e s u l t s i n d i c a t e s the f o l l o w i n g : 1. The v a r i o u s w a t e r - s o l u b l e p o l y m e r s a c c e l e r a t e the d e s a l i n a t i o n f r o m the i n i t i a l l e v e l to the m i n i m u m l e v e l [9] by f a c t o r s of 2 - 2 . 5 . 92. T h e s e p o l y m e r s i n c r e a s e the p e r m e a b i l i t y f a c t o r s f o r the h i g h l y s a l i n e s o i l in the n a t u r a l p o r o s i t y r a n g e by f a c t o r s of 1.4-1.5, w h e r e a s the v a l u e s f o r the w a s h e d s t a t e a r e v i r t u a l l y u n a l t e r e d .

155

TABLE 3.

Infiltration and Structure Parameters of Softs

Polymer added
p " ermeability coefficients[ ~,~ -K 9 I0 '~ for given poro- ~ ~ ~'~ "~

Soil state

sity coefficients r Hunger Steppe, I soil hodzon Without polymer 0,05% K-4. K-9 w l m o m polym~ Washed free from salts 0,0'25% K-4, K-9, S MMA Modified by. irrigation waml Without polymer
aQd subsoil water mixture

[~ "-"~ s

With initial salt content

0,024 0,055 0,095 0,136 0,611 0,045 0,083 0,131 0,181 0,450 0,045 0,083 0,131 0,181 0,410 0,045 0,083 0,131 0,181 0,354

Hunger Steppe, HI soft horizon With initial salt content Without polymer 0,05% K-4, K-9

L% I
0,029 0,111 0,266 0,309 0,617 0,12110,212 0,383 0 , 4 2 9 [

0,025% K-4, K-9

Washed free from salts

Without polymer 0,121 0,212 0,383 0,429, 0,025% K-9, S ~lbiA, 0,121 0,212 0,383 0,429, 0,370 PEM

Modified by irrigation war.el Without polymer and subsoil water mixture Karsha Steppe, II soft horizon With initial salt content Washed free from salts

0,121
~0,9 0 ST~
=0,97

0--~

0,49

~=1

,05

e=l ,l 0

i 1 Without polymer 0,1032 0,155610,2238 0,2711l 0,05% K-4, K-9 I__ Without polymer 0,05% SVAM,S MMA,0,1532 0,230910,3320 0 , 4 0 2 2

SVAN

Modified b X irrigation water Without polymer and subsotl wafer mixture

0,1032 0,155610,2238 0.2711

i

_Note. a T is the p o r o s i t y of the s o i l in the natural state.

3. A c c e l e r a t e d elution of the gypsum f r o m the soil is accompanied by an increase in the w a t e r p e r m e ability by a f a c t o r 1.4-1.5. 4. Modification of a soil by means of m i x t u r e s of i r r i g a t i o n water and subsoil w a t e r does not alter the filtration coefficient appreciably by c o m p a r i s o n with s a l t - f r e e soils, nor is the m a x i m u m swelling, gypsum content, o r exchangeable sodium appreciably altered. All of the r e s u l t s are explained by the m e a s u r e m e n t s . Soluble salts in any d i s p e r s e d s y s t e m tend to c o m p r e s s the diffuse l a y e r s around the p a r t i c l e s and inc r e a s e the w a t e r p e r m e a b i l i t y ; r e s u l t s of this kind have been given for monothermite [10]. It has been shown [1] that the m a c r o m o l e c u l e s of a w a t e r - s o l u b l e p o l y m e r can regulate or adjust the b e havior of a finely divided s y s t e m , not only on account of particle coagulation but also because the exchangeable cations are partially bound; i.e., some of the exchangeable cations become l o c a l i z e d within the p o r e s r a t h e r than at the s o l i d - l i q u i d interfaces. The r e s u l t is a m a t e r i a l less r e s i s t a n t to external factors. This effect f r o m a polyelectrolyte d e t e r m i n e s the i n c r e a s e d t r a n s p o r t of inorganic salts and a c c e l e r a t e s the desalination during washing. Similar r e s u l t s have been obtained elsewhere. F o r instance, it has been shown [11] that an initially t a k y r - l i k e soil artificially treated with sodium chloride will yield up 52% of the salts during the f i r s t stage of washing after t r e a t m e n t , w h e r e a s only 26% of the NaC1 is lost under the same conditions with an untreated soil, while the rate of elution is i n c r e a s e d by a factor of 4.

156

cL

4f2

,~,08 ---

O,04

2o

4,3

6o

8s

Fig. 1. Variations in chloride content during washing for Hunger Steppe soils in relation to w a t e r content (P %) and content of w a t e r - s o l u b l e p o l y m e r s (C %). F i r s t genetic horizon: 1) P = 30, C =0; 6) P =34, C =0; 7) P =30, concentration of K - 9 = 0 . 0 5 ; 8) P =33, K-4 concentration 0.05. Third genetic horizon: 5) P = 17,8, C = 0; 2) P =22.3, C =0; 3) P =22.5, K-9 c o n c e n t r a tion 0.05; 4) P = 18.7, K-4 concentration 0.05. It has also been found [12] that the w a t e r p e r m e a b i l i t y and salt loss are i n c r e a s e d for a s a l t - m a r c h m e a dow soil in the p r e s e n c e of K-4; the a c c e l e r a t e d salt loss and w a t e r t r a n s p o r t go with a certain i n c r e a s e in the rate of gypsum loss in the p r e s e n c e of w a t e r - s o l u b l e p o l y m e r s . The gypsum c r y s t a l s in a soil f o r m clumps with the clay m i n e r a l s , and these produce conditions for additional hydration, which ultimately r e d u c e s the w a t e r permeability. It has also been found [13] that gypsum adv e r s e l y affects the physical p a r a m e t e r s of soils. In p a r t i c u l a r , the shape of the gypsum clumps can affect the w a t e r p e r m e a b i l i t y of an i r r i g a t e d soil. An i n c r e a s e in the w a t e r content tends to enlarge the gypsum c r y s t a l s , which itself r e d u c e s the p e r m e a b i l i t y and blocks the p o r e s . Accumulative s a l t - m a r s h soils show considerable difficulty in desalination due to the poor p e r m e a b i l i t y , since some of the toxic salts a r e trapped in the gypsum c r y s t a l s . In our e x p e r i m e n t s , the p e r m e a b i l i t y i n c r e a s e d by a f a c t o r 1.4-1.5 on reducing the gypsum content f r o m 15 to 7%. P r e v i o u s m e a s u r e m e n t s [3] have provided a basis for generalizing the filtration and adsorption data to define the relative changes in the filtration coefficients for clay soils modified With p o l y m e r s , where there is a specific effect on the particle surface for K-9, PAA, and K-4 w a t e r - s o l u b l e p o l y m e r s . These c u r v e s have been c o n s t r u c t e d for the modified soil at optimal p o l y m e r levels, and values were calculated for the mean p o r o s i t y using the filtration coefficients for the unmodified soil with the appropriate p o r o sity coefficients. The c u r v e s w e r e monotonic functions, and the ratios of the filtration coefficients for the modified soil and unmodified soil for specific s u r f a c e s of 200-240 m2/g w e r e close to 1. However, the specific s u r f a c e s of m e d i u m - g r a i n e d loams and clays in the Hunger Steppe and the t a k y r - l i k e clays in the Karsha steppe lie in this range. We have found [1-3] that K-9, PAA, and K-4 are adsorbed at free hydroxyl groups via their carboxyl groups, which tends to bind the p a r t i c l e s into clumps and thus i n c r e a s e the permeability. The increase is d e t e r m i n e d by the number of adsorption c e n t e r s (active groups) per unit length of the m a c r o m o l e c u l e as well as by the number of free hydroxyl groups, in addition to any effect f r o m the exchingeable cations per unit s u r face area. There are thus strong interactions between the p o l y m e r and the solid, p a r t i c u l a r l y for m o n t m o r i l lonite. Any excess content of carboxyl groups r e s u l t s in an additional content of charged particles when the pore space is at the natural level (in c o n t r a s t to a suspension), which causes repulsion between the p a r t i c l e s , and thus d i s p e r s a l of the a g g r e g a t e s , which may reduce the p e r m e a b i l i t y , as o c c u r s in kaolinite clays.

157

The clay fraction in these soils in the main consists of hydromica with a littlekaolinite and montmorillonite. The concentrations of active centers in such systems are intermediate between those for montmorillonite and kaolinite, which means that the conditions are intermediate between those discussed above, where conflicting tendencies from the polymers make themselves felt. Modification with a mixture of irrigationwater and subsoil water involves the introduction of additional sodium ions~ these are adsorbed by the active centers, which tends to disperse the particles and thus to reduce the permeability. However, our measurements showed that the permeability factors were unchanged, as were the levels of exchangeable sodium in the washed and modified Hunger Steppe soils, which is ascribed to the effects of gypsum in the adsorbed complex. The calcium in the gypsum is displaced by the sodium, which reduces the alkalinityof the soil and improves the physical properties, while causing irreversible coagulation of the colloids. A somewhat different situation occurs with takyr-like soils. There is an increase (Table 3) in the permeability of the washed specimens, namely, by 40% by comparison with the initialvalue, which is due to the elimination of gypsum and the partial dissolution of the calcite and dolomite. However, the secondary processing with a mixture of salts during the modification and subsequent washing to negative chloride reaction results in the accumulation of exchangeable sodium (increased from 0.66 to 2.33 mg-eq/10O g, Table 1), with a reduction in the permeability coefficientby a factor of 1.4. Modification of a takyr-like soil by subsoil water or any other combination of dissolved salts at high concentrations can increase the salt contamination of the soil and markedly reduce the water permeability. Therefore, the salinity of water, obtained by mixing irrigationwater and subsoil water in a ratio of 5:1, is such as to have no adverse effects due to the accumulation of exchangeable sodium in such a soil, and there is no appreciable deterioration in the water permeability, and therefore such a mixture can be used at periods when irrigation water is scarce.
LITERATURE CITED

1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13.

P . P . Olodovskii and M. G. Murashko, Inzh. -Fi z. Zh., 30, No. 2 (1976). M . G . Murashko, P. P. Olodovskii, G. A. Ivkovskaya, T. M. Kolotsei, and L. L. Kolosov, in: WaterResource Utilization [in Russian], No. 3 (1975). P . P . Olodovskii, M. G. Murashko, A. B. Bogdanova, T. M. Malashko, R. F. Dotsenko, and V. F. Kononyuk, Inzh. - Fi z . Zh., 32, No. 4 (1977). E . V . Arinushkina, Handbook on Chemical Analysis of Soils [in Russian], MGU (!970). E . G . II'kovskaya, Agronomic Methods of Soil Examination [in Russian], AN SSSR (1954). P . S . Panin, Salt-Loss P r o c e s s e s in Washed Soils [in Russian], Nauka, Novosibirsk (1968). P . P . Olodovskii, Inzh.-Fiz. Zh., 26, No. 4 (1974). M . G . Murashko, P. P. Podovskii, andG. A. Ivkovskaya, Inzh. -Fi z. Zh., 19, No. 12 (1970). V . V . Egorov and N. G. Kinashina (editors), [in Russian], Nauka, Moscow (1968). P . P . Olodovskii, M. G. Murashko, G. A. Ivkovskaya, and E. V. Kopets, in: Engineering Geology of Clay Rocks [in Russian], MGU (1972). Kh. Arbykbaeva and K. S. Akhmedov, in: Structures in Dispersed Systems in the Presence of Polyelectrolytes [in Russian], FAN, Tashkent (1970). L . B . Smolina, in: Structures in Dispersed Systems in the Presence of Polyelectrolytes [in Russian], FAN, Tashkent (1970). N . G . Minashina and V. V. Egorov, Pochvovedenie, No. 10 (1975).

158