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Zinc deficiency in a soil toposequence, grown to rice, at Tiaong, Quezon province, Philippines
CATENA
Vol. 10, 115-132
Braunschweig 1983
ZINC DEFICIENCY IN A SOIL TOPOSEQUENCE, GROWN TO RICE, AT TIAONG, QUEZON PROVINCE, PHILIPPINES H.W. Scharpenseel, E. Eichwald, Ch. Haupenthai, H.U. Neue, Hamburg ABSTRACT After scrutiny of the pertinent literature analytical and tracer experiments with 65Zn along a toposequence office paddies in Tiaong, Quezon Province, Philippines are described. The higher catena member is moderately Zn deficient, the lower member extremely Zn deficient. Soil analysis reveals Tiaong soil to be slightly alkaline, smectitic, strongly humic, of high CEC and base saturation, of low plant available Zn (Bray method). The higher catena member (H) leads in Si, Al, K, Na, Zn, Cu, Ni, Co, Cr, Ba, the lower member (L) in C, Ca, Mg, Mn, P. The very high deficiency in (L) corresponds with higher humus-, Ca-, Mg, and P concentrations, all potential agents to Zn fixation. Clay minerals are higher in less deficient (H). This, and studies of VAN BREMEN et al. (1980) would point to strong Zn organic fixation. However, DTPA-, dithionite- and oxalate-extracts represent only 2.5-25% pedogenlc zinc, the rest is lithogenic and insoluble. Previous combustion scarcely increases these rates• This points against Zn organic linkages as predominating Zn fixation mechanism. Partial correlation, applied to VAN BREMEN's data also annihilates the high correlation between zinc and organic maAter, which is replaced by strong Zn-Mg and Zn-bicarbonate correlations. Field tests with °°ZnSO4 in plastic tubes of 35 and 25 cm diameter,inserted in the rice fields, showed, that mobility, i.e. lateral and vertical translocation of the zinc was much more pronounced at (H) than at(L). After air drying the removed soil cores replanting was accompanied by much less Zn deficiency than in loco in the rice field• Drainage and at least temporary oxidation seems to be the primary requirement for soil rehabilitation. Adsorption - desorption isotherms followed the Freundlich relation. K-values were very high, especially in (L), indicating strong adsorption of Zn. K-values of the DTPA desorption extracts were quite low, representative for easy desorption by chelate solution, whereas the 0.1 M HC1 extract after DTPA elution had again high K-values as a sign of strong adsorption of the non DTPA extractable Zn. For rehabilitation mixed rice - fish farming with fishponds in the lowest points of the relief seems to be best with propagation ofazolla as N-green manure for the rice and feed for the fish. 1. INTRODUCTION Zinc is in soils, grown to rice, next to N the second most important element. Along with the pH value of submerged rice soils near neutrality and with a syndrom of other factors, such as overwetting and extreme reduction, which consumes protons and lifts up the pH, and with lithogenic inhefitage ofMg > Ca, it is estimated, that about 50% ofaU paddy rice soils are Zn-deficient or depleted to the extent, that the rice plant responds favorably upon Zn application. The strong Zn deficiency of the rice soil toposequence at Tiaong, Quezon Province, Philippines, varies greatly in effect with just slight differences of altitude and slope position. By means of analysis and tracer work with Zn it is tried, to expose the differences between an upper Zn deficient catena member, where rice grows fairly well after seedling dipping in ZnO suspension and a just 2 m lower catena member, where Zn deficiency is lethal to the plant despite of Zn treatment. •
65
•
116 2.
2.1.
SCHARPENSEEL,EICHWALD,HAUPENTHAL& NEUE LITERATURE REVIEW
OCCURRENCE IN SOIL
Zinc contents are about 60 ppm in felsic, 130 ppm in mafic rocks, 10 to 300 ppm in soils and 15 to 60 ppm in plant dry matter (MITCHELL 1955, SWAINE 1955). The soil solution contains 1-80 ppb of Zn and up to several, hundred ppb of Zn in submerged rice soils (MIKKELSEN & KUO 1977). Zn concentrations below 1 ppm in a 0,05 N HCI extract express Zn-deficiency (PONNAMPERUMA 1979); 0.05 M cu-acetate and EUF (electro ultra filtration) extracts have been likewise tested (MURTHY 1980). Other inorganic or chelate extractants are compared by HAQ et al. (1980) as well as HAVLIN et al. (1981). Numerous factors influence Zn availability and fixation. Zn mobility and plant uptake of Zn depends partly of the form of Zn in the soil, especially on soil pH (GERTH et al. 1981, HERMS & BR'IJMMER 1980). Zinc may be present as ZnCO3, ZnS, Zns(CO3)2(OH)6 (KALBASI 1975), adsorbed at Fe and Al oxides as aquo and hydroxo complexes (KIEKENS 1975), eventually as ZnFe204 with Ferrihydrit (BAR-YOSEF et al. 1980), Zn-phosphate and adsorbed or isomorl?.hically exchanged f.ex. in trioctahedric Mg-smectites. Contrary to BRUMMER (198 I), who expected in soils with neutral to alkaline pH rather formation of Zn-silicates than precipitation of ZnCO3, OSMAN et al. (1980) noticed in calcareous soils of Egypt stronger Zn fixation as ZnCO3 than by silicate clays. Zinc can be fixed by adsorption at negative charge points of the soil humic matter as well as by incorporation into clay-Zn-organic matter complexes. Zinc surpasses Ca and Mg in forming clay-metal-humic acid complexes (TIWARI et al. 1976). Zn humic coils are too big (3-8 nm) to allow a full intercalation between smectite layers, but they could penetrate between oriented clay domains in a swollen soil, such as in submerged soil of neutral pH (AYLMORE & QUIRK 1959, 1960, GILES et al. 1974).The polarizing power of Zn for water molecules and the electrostatic energy of interaction between exchangeable Zn and a water molecule in the primary hydration shell of montmorillonite suggest, that the contribution of clay-Zn- organic matter complexes to the total of Zn fixation might be considerable (ELGABALI 1950, MACKENZIE 1964, THENG & SCHARPENSEEL 1976, VAN BREEMEN et al. 1980, ZUNINO et al. 1979). Abasic study by ZUNINO et al. (1979), regarding sorption points and competition between Zn and Mg for binding sites in humic and fulvic polymers, indicates, that Zn is mostly favoured by the terminal groups. Also McBRIDE et al. (1979) exclude simple precipitation as Zn-hydroxide or -carbonate to be an important mechanism of zinc fixation in soils of a pH level below 7.0, while at high pH > 7.5 they regard increase in Zn solubility as result of organic complex formation. They consider nucleation of Zn on clay minerals or interaction with hydrated oxide surfaces important in the moderately acidic pH-range. Similarly, HERMS et al. (1980), studying the influence of organic matter on Zn solubility in soils, observed decreasing Zn solubility after organic matter application within a range from pH 4-6, while between pH 7 and 8 Zn solubility increased. VAN BREEMEN (1980) observed in connection with a soil, near to the experimental site of this report, highest correlation between Zn deficiency and soil organic matter. In important studies of chemical equilibria in soils LINDSAY (1979) expresses the solubility isotherm for Zn in soils as soil Zn + 2H + ~- Zn2; log Zn 2+ = 5.80 - 2 pH. Provided Zn concentrations are high enough, the increase of Zn-solubility with pH equals -2
RADIOMETRICSTUDIESON Zn DEFICIENTRICESOILCATENA
117
at pH 7 and up; at acidic pH it can change to 0 till -1. A basic study, aimed to elucidate and model the Zn 2+ transport as well as possible improvement of the Zn 2+ transport to the plant root was carried out by BAR YOSEF et al. (1980).
2.2.
CONDITIONS FOR Zn DEFICIENCY
PONNAMPERUMA (1979), after defining about 30 Zn deficient areas in the Philippines with pH values of the soils between 5.2 and 8.2, has layed down a combination of soil conditions, framing most of the Zn deficient soils: Perennial wetness - low reliefposition artesian water condition - interflow/upweUing - pH > 7 - calcareous soil - Mg > Ca organic matter > 3% - available Zn in 0.05 N HCI extract < 1 ppm - Aquent/Aquept/hydric Hemist Suborder or Great Soil Group. Besides of the mainly geomorphological syndrom of preconditions for Zn deficiency specific lithological and chemical factors can contribute. Alcali soils, being inherently liable to Zn fLxation (SINGH & SEKHON 1977, KUO & MIKKELSEN 1979), were subjected to Zn adsorption studies. Among various sources of Zn for alleviation of the deficiency, ZnSO4 ranked first (NAYYAR & TAKKAR 1980). Also the possible Zn fLxing interaction with P-fertilization required elucidation," While studies with corn (REHM et al. 1980, MANDAL & HALDAR 1980, FRIESEN et al. 1980, TRIER & BERGMANN 1974) did not reveal any depression of Zn availability, soybeans and bushbeans, grown in nutrient solution (SAEED & FOX 1979), responded pH dependent with higher Zn uptake upon P application at lower pH, with Zn stress after P application at high pH. Hawaiian soils, high in colloids of variable charge, decreased in Zn availability, whereas those with predominantly constant charge colloids released Zn upon P application (WALLACE et al. 1978). In the rice field, P application was depressing Zn availability, more with regard to the native Zn in the soil than to the newly applied Zn (MANDAL & HALDAR 1980). Decrease of Zn concentration in aquaeus extracts of non calcareous soil was lower after phosphate plus ZnSO4 treatment than after ZnSO4 application only (KALBASI et al. 1978). Other authors observed in Vertisols, grown to rice, mutual antagonism between Zn and Fe. While Fe was highest under water lagged conditions, Zn concentration climaxed at field capacity (TIWARI et al. 1976). FRANCK & FINCK (1980) determined yield related Znrequirements for oats and wheat by means of hydroculture and statistic evaluation of data collective, derived from field experiments. -
2.3.
ADSORPTION - DESOPRTION OF ZINC
In most of the recent zinc studies emphasis was laid on introduction of adsorption desorption techniques to reveal mode of sorptive processes, test sorption models and especially the mechanisms of Zn sorption. BR'I.)MMER (1981), analysing Zn solubility and adsorption isotherms, concludes, that the solubility of Zn in soils depends more on ad- and desorption, than on precipitation and redissolution. He further demonstrates, in confirmation of older findings by ELGABALI (1950), a special sorptive affinity of Zn towards Feoxides and clay silicates. Also SINGH et al. (1977) questioned prevalence of adsorption or precipitation. They
118
SCHARPENSEEL, EICHWALD, HAUPENTHAL & NEUE
found agreement with Langmuirian equations and a predominant correlation between adsorbing power and CEC. Other authors, using the Langmuirian approach, were BAR-YOSEF (1979), partitioning Zn between solid and liquid phases under variable pH, and DIXIT et al. (1980). The latter studied adsorption-desorption in algerian vertisols, splitting the retained Zn into one rate, adsorbed by ion exchange and another rate at lower concentration, held by "specific" adsorption mechanisms. KALBASI et al. (1978), testing Zn sorption by Fe and AI, recognized specific Zn sorption related to exchange against 1 H ÷ and nonspecific Zn sporption to involve another anion such as CL-, and to release 1 H ÷ for each mol of Zn 2+ getting adsorbed. According to KUO et al. (1980) Zn adsorption in acid soils, pH below the zero point of the net charge, increases with rising pH, whereby Cu interfered with the sorption of Zn. The dependence of Zn adsorption on the cation costume of the exchange sites was investigated by SHUKLA et al. (1980). The values of standard free energy of adsorption and blocking of Zn adsorption increased in the sequence Ca >/Mg > K > Na. They further explain Zn adsorption data by Freundlich and Langmuir isotherms, which they split into three concentration ranges with different bonding energies for the adsorbed Zn. A distinction between higher Zn adsorption by constant and lower adsorption by variable charge colloids was observed by SAEED & FOX (1979). In this work Zn concentrations > 0.01 ppm followed the Freundlich isotherm. Suitability of the Freundlich isotherm for description of Zn-adsorption was also confirmed by KUO & MIKKELSEN (1979), who calculated the required activation energy for Znadsorption and concluded, that Zn-adsorption is based more on chemisorption than on electrostatic attraction to the colloidal surfaces.
3.
SITE OF THE EXPERIMENT, SOIL CATENA
From soil and cropping experiments VAN BREEMEN et al. (1980) and VAN BREMEN & CASTRO (1980) concluded, that Zn deficiency of rice in the lower part of the Tiaong area, Quezon Province, Philippines, experimental region of this report as well, is due to lack of soil aeration throughout the year, and levels of organic matter are highly correlated with the disorder, while pH, calcium carbonate content and dissolved bicarbonate had little effect. In addition to above studies soil analytical and radiometric investigations were carried out in two experimental lots in the highest (H) and lowest (L) positions of the rice soil toposequence of Tiaong, as indicated in Fig. 1. The area is situated in the pediment of Mount Banahaw, consisting of strongly weathered pleistocene volcanic ashes, muds and lapillis. Soils range from Hydraquent in the lower part (L) to Tropaquent in the higher part (H). Beyond the artesian well, outside the rice land in the coconut grove are Tropaquepts. This kind of shallow terraced rice land at the fringe of a mountain slope with downslope partly perched artesian water and vertical seapage down in the rice fields is typic for many sites, especially in highly volcanic countries like the Philippines and parts of Indonesia. The dramatic increase of Zn deficiency downslope, within just 2 m of altitude difference, is a phenomenon, enforcing new systems of land use like a mixed rice land and fish pond pattern, unless we discover the cause and find straight means of land rehabilitation. Below the toposequence follows a permanently wet, humus rich, partly halfbog like soil with Phragmites australis and Hygrophila angustifolia as predominating plant species. Beyond (H) better drained Tropaquets with coconut and banana groves extend to the hilltop.
RADIOMETRIC STUDIES ON Zn DEFICIENT RICE SOIL CATENA
119
NE
SW
Meters above se~ level Coconuts,bor~rv~
rs~ieO
45-1
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44-
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77
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A-Horizon with high content or organic matter A-horizon, puddled Mineral weathering horizon Gley-hodzon Gley-horizon, oxidized Gley-horizon, reduced
(11;~) k-k
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(1i~) ~1 GrC O0 IOY5/I suL- suT k-k'
"[" k k' uL suL uT suT
Ivery mo~t
contentoffreecarbonates, high content of frae carbonates, medium content of frae carbonates, low silty loam sandy sdty loam silty clay sandy silty clay
Fig. 1: NE-SW cross section and soil profiles of the Tiaong toposequence
4.
MATERIALS AND METHODS
The total element analysis by X-ray fluorescence, the 65Zn adsorption-desorption and distibution measurements in the soil were carried out by standard methods. 1 The air dried soil samples from five horizons each of the (L) and (H) profiles were analysed for pH, CEC, available P, organic C and total N. The same was repeated with freeze dried samples. 2 For clay mineral analysis the fraction < 2/zm was used, after destruction and removal of allophanes by 0.1 NaOH (HASHIMOTO & JACKSON 1960) 3 All element analysis was done by X-ray fluorescence; Zn was analysed by atomic absorption spectrometry in dithionite, oxalate (SCHWERTMANN 1964) and DTPA extracts (LINDSAY & NORVELL 1978). 4 65Zn movement was studied by autoradiographity of soil columns, taken from the field. In the bunded experimental lots, Tiaong site (fig. 1), plastic rings were inserted in the highest (H) and the lowest (L) areas (fig. 2). The large rings, 35 cm wide, were pressed down into the hard pan and were used to study Zn uptake in the rice plants under different regimes
-
120
SCHARPENSEEL, EICHWALD, HAUPENTHAL & NEUE
A
0.5 mc~Zn applied in the center
Q
o,o, ~
0 4 mc 6SZnin I portion mixed with upper 5crn soil (,q,Omg Zn)
0
0 • Upper
Q
0
© 0 ©
0 I-
195 m dlstonce
oreo
I Lower OrSO
Fig. 2: Experimental scheme ofhSZn-fieldexperiment in Tiaong
of Zn application. After harvesting, the rings were dug out, naturally dried for about 1 year and rewetted again in order to study a possible remobilization of fixed Zn due to intermittant drying of the soil, i.e., to assess the effect of drainage to alleviate Zn deficiency. The smaller rings (25 cm wide) were inserted 10 cm deep into the flooded soil to study vertical and lateral transport ofhSZn. 65Zn labelled ZnSO4 was applied to the upper three cm of the soil; 65Zn radioactivities per g ofsoil were measured in 10 g samples from cores, taken in different depth and lateral distances from the center by means ofa PiJrkhauer soil auger 3, 6 and 9 weeks after 65Zn administration. 5 Adsorption/desorption studies were based on 0.5 ml of fresh soil from different horizons at (L) and (H) sites. Soil samples were stored in screw cup centrifuge tubes under N2 gas immediately after sampling. For the adsorption studies the soil was mixed with 25 ml of aquaeus solution, representing 5 different 65Zn concentration levels and agitated over 48 hours. After spinning down the soil, always 10 ml of the supernatant were tested against a 65Zn-], standard in a well type scintillation counter, based on a TI activated NaJ borehole cristal detector. Desorption was undertaken accordingly by shaking the soil with the respective desorbing agent, such as 0.05 M DTPAand 0.1 N HCI solution. The insoluble remainder of the 65Zn after desorption is measured as a 250 mg aliquod of the previously air dried soil in aquaeus suspension.
5.
RESULTS AND DISCUSSION
Table 1, 2 and 3 summarize the results of general soil analysis of the individual soil horizons at the two sites. Carbon and nitrogen are highest in (L), total and available Zn levels, measured by atomic absorption, in (H). Analysis was carried out in parallel with air dried as well as with directly nitrogen protected and then freeze dried soil samples. Differences in
RADIOMETRIC STUDIES ON Zn DEFICIENT RICE SOIL CATENA
121
Tab. 1: TIAONGSOILSL AND H, AIR DRIED.
~ (%) pH 1:1 w/v H20 EC mmhos w/v H20 Carbonate (%) Sol. Cations meq/lO0 g ads Exch. cations
No.
Moisture
1:1 Na K Na K Mg
maq/100 g ads
Ca
TEB meq/100 g ads CEC meq/lO0 g ads S a t u r a t i o n (%) Avail, P Bray ppm ads Olsen Total N % ods Or S. C % ods C/N ratio Total element P (major) ppm K ods Hg Total element (m/~or) ppm ods
Particle size anal. microns
Cu Mn Zn Fe (%) % Clay % Silt % Sand
A v a i l . Zn Bray (ppm)
L 0-3
L L L L 3-23 23-43 43-63 63-83
H 0-3
H H H 3-18 18-33 33-53
H 53-73
8.6 7.9 0.30
8.2 8.0 7.9 8.0 0.27 "0.19
9.2 7.7 0.24
9.1 7.8 0.22
10.4 7.6 0.19
1.0 1.0 37.7 57.1
8.1 8.1 0.14
8.8 8.1 0.i1
8.9 7.8 0.18
9.0 7.8 0.13
0.9 0.9 33.2 65.5
0.8 0.8 28.3 66.7
0.6 0.7 23.9 56.3
0.6 1.1 22.7 37.7
0.7 0.6 34.3 54.0
0.8 0.6 33.5 64.2
0.8 0.6 33.7 54.6
0.7 0.6 29.7 32.4
0.5 1.0 23.3 22.6
96.8 100.5 32.6 33.0
96.6 33.4
81.5 33.7
62.1 44.7
89.6 36.7
99.1 34.3
89.7 37.1
63.4 47.1
47.4 43.1
21 22 23 23 13 12 11 9 8 .576 .541 .428 .253 .081 .309 .301 .281 .178 6.51 5.43 3.98 1,94 0.60 3.47 3.16 2.91 2.36 11.30 10.04 9.30 7,67 7.41 11.23 10.50 10.36 13.26 1473 1377 1338 1271 839 902 907 917 853 •
8567 43 2.57 5.7 70.7 23.6 .54
8945 10037 44 48 2.87 3.02 7.5 68.7 23.8
30.2 49.2 20.6
.43
.65
6425 57 3.44 24.4 50.1 25.5 1.62
1904 55 6.03 18.5 63.4 18,1 3.78
1627 60 3.39 36.7 50.7 12.6 1.51
1443 58 3.40 36.0 49.3 14.7 1.51
1408 66 3.72 37.3 48.8 13.9 1.73
713 64 3.89 40.2 47.5 12.3 4.97
9 .152 0.78 5.13 679
678 57 6.71 36.2 50.8 13.0 3.46
ads - air dried soil; ods -- oven dried soil results were moderate and confined to criteria, influenced by pH and Eh, such as available nutrients. In the fraction < 2/.zm, smectite was the only clay mineral, discemable by X-ray diffraction. The fraction < 0.2 ~m apparently contains some vermiculite. X-ray fluorescence measurements of elements beyond atom number 9, that exceeded a concentration of 1 ppm, are summarized in table 2 and 3. The Tiaong soil accordingly is siallitic, carbonaceous with high excess of Ca over Mg, deviating in this criteria from PONNAMPERUMA's clich6 of preconditions for Zn deficiency (1979). In most Zn-deficient soils, especially those of ultrabasic parent material, Mg exceeds in fact Ca. The differences between the high and low site ((H) and (L)) are summarized in table 4. Concentrations ofSi, AI, K, Ti, Na. Zr, Rb and Zn are higher in (H), whereas Ca, Mg, Mn and P are superior in (L). Extractions by ammonium oxalate (pH 3.2) and dithionite (pH 7.3) release between 11 and 13% of the total Zn, by neutralized DTPA3-4% (table 5). Combustion of soil organic matter at lowest possible temperature does not influence the contents of extractable Zn distinctly. Evidently, it can be at most a smaller part of the total Zn in the soil, which is present in organically complexed form. Further, 1.5-8 ppm Zn, ca. 2.5-25% of total soil-Zn are pedogen only, the majority being lithogen and insoluble.
122
SCHARPENSEEL, EICHWALD,HAUPENTHAL& NEUE
Tab. 2: QUANTITATIVE ANALYSIS BY X-RAY FLUORESCENCE, TIAONG, LOWER SITE Element concentrations in %
HOR. om
ELEM Si Ca A I Fe Mn K Ti P Mg Na Rb Sr Zr Pb Zn Ni Cu Cr
Co Ba
J
0- 3
3 - 23
23 - 43
43- 63
63- 83
ELEMENT-CONCENTRATIONS 22,6150
23,3300
23,8050
25,6410
30,3610
14,7070
14,4200
13.2180
11.1680
4.2190
2,7800
2,7680
3,3350
3,7040
6,1940
3.6510 1,7254
3,7360 1,8372
4.0590 1,8629
4.3180 1,6323
5.2640 0,1875
0,3030
0,2900
0.3370
0.3600
0.3800
0,3400
0,3480
0,3690
0,3980
0.4230
0.1978 2.2751
0.2015 2.1493
0,1908 1.8903
0.2021 1.8333
0.1248 ].6366
0,7973
0.7484
0.8540
0.8291
1.2289
0,0014 0,0832
0,0013 0,0788
0,0008 0,0716
0,0018 0,0615
0.0016 0,0643
0,0111 0,0014 0.0035 0,0024
0,0110 0,0017 0.0038 0,0023
0,0106 0,0015 0.0039 0,0024
0,0105 0,0018 0.0045 0,0026
0,0129 0,0018 0,0060 0,0023
0.0030 0.0012
0,0041 0.0020
0.0034 0.0020
0,0044 0.0033
0,0041 0.0029
0.0fl04
0.0004
0.0006
0.0008
0,0013
n.n~nR
0.04]7
0.0433
0.0438
0,n587
I
RADIOMETRICSTUDIESON Zn DEFICIENTRICE SOIL CATENA
123
Tab. 3: QUANTITATIVE ANALYSIS BY X-RAY FLUORESCENCE, TIAONG, HIGHER SITE Element concentrations in %
HOR. cm
0- 3
3 - 18
18- 33
33 - 53
ELEM. ELEMENT-CONCENTRATIONS Si 26,3990 26.3780 26.4q~n ~R.R74N Ca 7,3250 7,2700 7,2980 3,0930 AI 6,5380 6,5090 6,4800 8,0590 Fe 4,3690 4,3750 4,3620 5,2320 MR 0,2185 0,2199 0,2095 0,0617 K 0,4250 0,4100 0,4190 0,4320 Ti 0,4560 0;4520 0,4520 0,4750 P 0,1214 0,1230 0,1193 0,0927 Mg 1,4379 1 4250 1,4403 1,2286 Na 1,0955 1,1441 1,1486 1,2193 ,Rb 0,0034 0,0033 0,0032 0,0030 Sr 0,0865 0,0871 0,0866 0,0728 Zr 0,0146 0,0146 0,0145 0,0155 Pb 0,0021 0,0021 0,0024 0,0022 Zn 0,0061 0,0060 0,0060 0,0066 Ni 0,0029 0,0026 0,0027 0,0029 Cu 0,0050 0,0047 0,0047 0,0051
53 - 73
?R.n~n 2,6860 8,7470 6,0620 0,0629 0,3940 0,4750 0,0809 1,1376' 1,2033 0,0022 0,0719 0,0156 0,0022 0,0059 0,0025 0,0051
C r
0,0035
0,0018
0,0035
0,0057
0,0025
Co
0,0009
0,0009
0,0009
0,0012
0,0017
Ba
0.0435
0,0422
0,0425
0,0449
0,0503
124
SCHARPENSEEL,EICHWALD,HAUPENTHAL& NEUE
DIFFERENCESBETWEEN HIGHER CATENA MEMBER (H) (TROPAQUENT) AND LOWER CATENA MEMBER (L) (HYDRAQUENT)OF TIAONG CATENA Tab. 4:
ELEMENT
CONCENTRATION
MEAN CONCENTRATION DIFFERENCES (WEIGHT - %)
RELATIV (%)
OH>L OL>H
SI
H > L
3,40
14
[]
AL
H > L
2,50
40
[]
FE
H z L
0,40
9
CA
H < L
6,80
105
0
K
H > L
0,06
14
[]
-MN
H < L
0~80
570
0
TI
H> L
0,09
27
[]
NA
H > L
0,26
22
[]
'MG
H< L
1,000
72
O
P
H< L
0,080
71
O
ZR
H> L
0,002
25
D
SR
H_L
0,009
10
RB ZN
H>L
0,001
I00
[]
H>L
0,0020
47
[]
Co
H>L
0,0013
34
[]
NI
H>L
0,0003
12
Co
H>L
0,0004
57
D []
CR
H>L
0,0008
31
D
BA
H>L
0,0034
D
5.1. TRANSLOCATION, ADSORPTION, DESORPTION STUDIES UNDER USE OF 6sZN Table 6 shows, that the vertical and lateral translocation are much more pronounced at (H) than at (L). Deeper vertical 6SZn translocation was also confirmed by autoradiography of soil cores. After drying the cores, replanting in this reoxidized material showed much less severe Zn deficiency than before in the rice field. The adsorption isotherms (see also MAYER 1978, KIEKENS 1975) of Zn in the Tiaong soil follow the Freundlich relation.
RADIOMETRIC
STUDIES ON Zn DEFICIENT RICE SOIL CATENA
125
Tab. 5: Zn-CONCENTRATIONS IN OXALATE-, DITHIONITE- and DTPA-EXTRACTS OF LOWER AND HIGHER TIAONG SITE SOILS, BEFORE AND AFTER COMBUSTION AT 550* C LOWER SAMPLES
I
TIAONG
SITE SOILS and HIGHER TIANG
WITHOUT COMBUSTION C*/o
SITE SOILS NITH COMBUSTION
Oxalate extract ppm Zn]DTPA extract ppm Zn Oxalate extract ppm Zn ~Dithlonite ppm Zn
DTPA pprn Zn
L 0-3
!
6.51
8.0
2.7
8.0
8.3
2.7
L 3-23
i
5.43
6.5
1.55
6.5
6.1
1.6
L 23 - 43
3.98
6.5
2.50
6.5
6.7
2,5
L 43 - 63
1.94
6.5
1.60
6.5
6.9
2,6
L 63 - 83 j
0.60
7.5
1.45
7.5
7.9
1,5
H 0-3
3.47
1.75
7.8
7.2
1.8
IH 3 - 18
3.16
8.0
1.70
8.0
8.2
1.7
H 18-33
2.91
7.5
1.50
7.5
[
7.2
1.5
H 33 - 53
2.36
6.5
1.55
6.5
ii
7.1
1.6
,H 53 - 73
0.78
6.0
1.80
6.0
~
6.8
1.8
10.0 (?)
i I
X
=
K • C 1/n
m
C = concentration of Zn in solution X = concentration of Zn in the soil m K = Freundlich constant 1/n = slope of isotherm Table 7 and 8 as well as fig. 3 show the results of adsorption of Zn out ofaquaeus solution as well as ofdesorption by 0.05 M DTPA and 0.1 M HC1 extraction. Evidently, adsorption is stronger by the fresh soil samples of the Hydraquent (L) compared with the higher Tropaquent (H). K values are in general very high, indicating very strong, tight adsorption of Zn by the Tiaong soil, expectably, considering the extreme Zn deficiency especially in (L). K values for the DTPA extracts are low, which means, that DTPA chelate is easily desorbing most of the zinc, while the much higher K values of the HCI fraction express tight bonding of the zinc, that remains adsorbed after the DTPA elution. This is also demonstrated by tables 9 and 10. The rather low differences of soluble zinc in different extractants (DTPA, dithionite, oxalate) between normal samples and the same samples after previous combustion (table 5) created concern, whether Zn could really be preferably bound by the organic matter, as high correlation factors suggest in the work of VAN BREEMEN et al. in Tiaong (1980). Additional partial correlation, applied to those data make the highly significant negative correlation
126
SCHARPENSEEL, EICHWALD, HAUPENTHAL & NEUE
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RADIOMETRIC STUDIES ON Zn DEFICIENT RICE SOIL CATENA
×
Hg"g
127
soTl
10000
,0
1000 s 0 /
100 ®
?/
•
10
6
+
+
S
I
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I
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.0001
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C o = Adsorptlon + = De~orptlon * = Desorption
location pro?11e depth materlal
: : : :
by by
Fig. 3:
~g/ml
0.05 m DTPR 0.1 m HCI
T1aong~ Quezon, Tropaquent ? r e s h ~oil 0 - 3 cm
K Ads DTPR HCI
=
35966.9 4.7 1749.2
Ph111pplnes
1/n 0.7947 0.3672 1.0161
Zn-Adsorption-Desorption according to Freundlich x / m -
r 0.999 0. 720 0. 902
K • C 1/n
solutlon
128
SCHARPENSEEL,EICHWALD,HAUPENTHAL& NEUE
Tab. 7: Zn-ADSORFrION-DESORPTIONACCORDINGTOFREUNDLICH(x/m-K. Cl/n Location: Tiaong, Quezon, Philippines; profile: Tropaquent; material: fresh soil 0-3 cm
Ads DTPA HC1
K 35966.9 4.7 1749.2
1/n 0.7947 0.3672 1.0161
r 0.999 0.720 0.902
3-18 cm
Ads DTPA HC1
37183.2 6.3 165.9
0.7938 0.6281 0.6170
0.996 0.927 0.951
18-33 cm
Ads DTPA HCI
40967,0 6.4 55.8
0.7998 0.4607 0.4803
0.992 0.925 0.759
33-53 cm
Ads DTPA HC1
50792.4 10.5 201.4
0.8311 0.6001 0.6307
0.998 0.958 0.805
53-73 cm
Ads DTPA HCI
38946.2 10.6 564.0
0.8140 0.7250 0.7929
0.998 0.997 0.981
Tab. 8: Zn-ADSORPTION-DESORPTIONACCORDINGTO FREUNDLICH (x/m - k. Cl/n) Location: Tiaong, Quezon, Philippines; profile: Hydraquent; material: fresh soil 0-3 cm
Ads DTPA HC1
K 40272.6 7.6 1126.8
1/n 0.8039 0.7587 1.1300
r 0.994 0.986 0.852
3-23 cm
Ads DTPA HCI
40505.5 8.4 898377.3
0.8062 0.8768 2.3561
0.998 0.999 0.885
23-43 cm
Ads DTPA HCI
69819.0 3.9 23.8
0.8644 0.5317 0.4867
0.999 0.866 0.451
43-63 cm
Ads DTPA HCI
84839.1 7.9 7395.9
0.8853 0.8597 1.4767
0.998 0.995 0.966
63-83 cm
Ads DTPA HCI
54190.8 11.1 6383.0
0.8456 0.8567 1.3872
0.998 0.987 0.918
between Zn and organic carbon disappear, when Mg and also HCO-3 are set constant. This would suggest interference of Mg with the highly significant correlation between Zn and organic carbon and a truly existing strong correlation between Zn deficiency and Mg, perhaps by isomorphic exchange of Zn against Mg into the trioctahedric clay minerals. Recent studies by MURTHY & SCHOEN (1980), using Cu-acetate as well as electro ultrafiltration (EUF) extraction techniques, also suggested, that 25 to 50% of the Zn in soils
RADIOMETRIC STUDIES ON Zn DEFICIENT RICE SOIL CATENA
129
Tab. 9: SUMMARYOF RESULTS EXPRESSED IN PERCENTOF INPUT (EXPERIMENTWITH FRESH UNDRIED SOIL), HIGHER AREA, TIAONG, QUEZON, PHILIPPINES (TROPAQUENT) Sample no.
Depth (cm)
51+ 52 53+ 54 55+ 56 57+ 58 59+ 60 61+ 62 63+ 64 65~ 66 67+ 68 69÷ 70 71+ 72 73+ 74 75+ 76 77+ 78 79+ 80 81+ 82 83+ 84 85+ 86 87+ 88 89+ 90 91+ 92 93+ 94 95+ 96 97+ ~8 99+100
O- 3 3-18 18-33 33-53 53-73 O- 3 3-18 18-33 33-53 53-73 0- 3 3-18 18-33 33-53 53-73 0- 3 3-18 18-33 33-53 53-73 0- 3 3-18 19-33 33-53 53-73
Input pc /Jg Zn
5.0 5.0 5.0 5.0 5.0 1.0 1.0 1.0 1.0 1.0 0.2 0.2 0.2 0.2 0.2 0.04 0.04 0.04 0.04 0.04 0.008 0.008 0.008 0.008 0.008
500 500 500 500 500 100 100 100 100 100 20 20 20 20 20 4 4 4 4 4 0.8 0.8 0.8 0.8 0.8
Left In solution, unadsorbed (%) 0.087 0.096 0.092 0.064 0.081 0.038 0.033 0.033 0.043 0.051 0.031 0.025 0.018 0.025 0.030 0.021 0.018 0.017 0.018 0.020 0.015 0.018 0.020 0.020 0.021
Desorption by 0.SM Desorption .Remained DTPA by .1 N HCI adsorbed (%) (%) to soi| 99.56 98.01 98.69 96.71 93.22 92.36 93.85 94.74 89.99 89.99 80.49 76.48 78.26 71.87 81.08 78.37 78.37 74.91 67.48 74.25 77.97 84.08 67.03 69.39 71.86
0.41 0.41 0.48 0.56 0.58 0.35 0.31 0.40 0.46 0.40 0.49 0.58 0.35 0.38 0.40 0.48 0.48 1.39 0.41 0.59 2.42 0.18 1.68 3.18 0.74
4.19 4.44 4.75 6.80 7.66 5.30 5.53 5.97 9.50 9.64 6.24 6.10 7.19 7.59 14.07 9.97 6.15 8.50 11.60 15.20 10.03 9.83 15.56 20.90 30.56
Sum o1 all % of input 104.25'I 102.96 / 103.97 p ~103.37% 104.13| 101.54.1 98.051 99.72 1 101.14 ~-¢ 99.81%
10o.07| 100.08 J 87.251
83.18/ 85.81 ~ ¢ 86.33% 79.87] 95.583 88.84"I 85.02| 84.82 i' ~ 85.72% 79.B7| 90.06J 90.431 94.11 ] 84~9 ~"~ 93.10% 93.49| 103.18,1
0.935 ~K).037
2.078.98 ~b83.16
18.11 ~b0.72
242.55 ¢9.70
2,340.57 ~93.62
Total (hydraquent + tropaquent) Average (hydraquent and tropaquent)
1.793 0.036
4,274.19 86.48
64.52 1.29
397.93 7.96
4,738.43 94.76%
Percent of total input
0.037
1.36
8.40
100.00
90.21
may exist in weak organic bonds, the major part - being mainly responsible for the nutrition of the rice plant - in a complexed pool. From the analytical and radiometrical results the following conclusions can be derived for the Tiaong catena: 1 Soil analysis reveals higher Zn concentration in (H), while higher C-contents, supposed to correlate strongest with Zn deficiency, are in (L). 2 Freeze drying of the highly reduced rice soil samples, expected to be indispensable for correct analytical results, is no real breakthrough compared to air dried samples, except for some criteria of analysis, influenced directly by pH and Eh. 3 In the clay mineral fraction smectites dominate, i.e. soils are low in variable charge colloids, which adsorb Zn less strongly (SAEED & FOX 1979). 4 X-ray fluorescence indicates in (H) superior contents of all heavy metals except for Mn, which is much higher in (L) and could bloc the Fe reduction and availability. C and Mg, suspected to be responsible for Zn deficiency, are higher in (L). 5 By DTPA, oxalate and dithionite extraction collected Zn fractions are small, compared to the insoluble Zn fraction. Apparently, most Zn is still protected in pyrogenic primary minerals. Also the gain of Zn by previous combustion is very modest, which makes it questionable, whether correlation between Zn and C (soil organic matter) is really the decisive condition for the observed Zn deficiency.
130
SCHARPENSEEL, EICHWALD,HAUPENTHAL& NEUE
Tab. 10: SUMMARYOFRESULTS EXPRESSED IN PERCENTOFINPUT(EXPERIMENTWITH FRESH UNDRIED SOIL), LOWERAREA, TIAONG, QUEZON, PHILIPPINES (HYDRAQUENT) Sample no.
1+ 2 3+ 4 5+ 6 7+ 8 9 + 10 11 + 12 13+ 14 15+ 16 17 + 18 19 + 20 21 + 22 23 + 24 25 + 26 27 + 28 29 + 30 31 + 32 33 + 34 35 + 36 37 + 38 39 + 40 41 + 42 43 + 44 45 + 46 47 + 48 49 + 50
Depth (cm)
0- 3 3-23 23-43 43-63 63-83 O- 3 3--23 23-43 43-63 63-83 O- 3 3-23 23-43 43-63 63-83 0- 3 3-23 23-43 43-63 63-83 O- 3 3-23 23--43 43--63 63--83
input pc /Jg Zn
5.0 5.0 5.0 5.0 5.0 1.0 1.0 1.0 1.0 1.0 0.2 0.2 0.2 0.2 0.2 0.04 0.04 0.04 0.04 0.04 0.008 0.008 0.008 0.008 0.008
500 500 500 600 500 100 100 100 100 100 20 20 20 20 20 4 4 4 4 4 0.8 0.8 0.8 0.8 0.8
Left in .so ution, unadsorbed
Desorption by 0.5M OTPA
(%)
(%1
Desorption
Remained
by 1 N HCI (%)
adsorbed to soil
0.094 0.084 0.066 0.053 0.068 0.033 0.038 0.033 0.028 0.040 0.023 0.025 0.026 0.026 0.028 0.018 0.020 0.021 0.021 0.023 0.020 0.017 0.020 0.023 0.021
.
96.14 100.32 99.34 91.05 86.29 92.58 90.50 92.28 92.21 92.06 84.61 87.38 86.99 87.12 83.69 79.12 85.30 92.07 89.26 75.74 84.40 84.64 82.17 80.44 81.43
0.51 0.49 0.41 0.36 0.41 0 40 Q.33 0.35 0.36 0.36 0.54 0.54 0.59 0.58 0.54 1.50 1.68 1.50 1.65 1.27 6.75 7.49 6.19 5.06 6.55
2.94 2.51 3.08 3.12 3.30 3.68 3.17 3.83 4.64 6.01 3.51 3.98 4.52 6.50 8.48 2.51 2.46 4.03 3.86 8.76 5.06 14.25 22.59 9.47 19.12
0.858 0.034
2,195.21 ~ 87.81
46.41 ~ 1.86
156.38 <~6.21
Sum of all % of input
98.68 103.32 102.88 94.58 90.07 96.69 94.04 96.49 97.24 98.47 88.661 91.93 92.13 94.23 92.74
97.90%
96.58%
91.94%
83.15] 89.46|
97.62 ~,~ 913.16% 94.79| 85.79 , I 96.23 I
106.:19|
110.97 ~¢ 103.14% 94.99 | 107.12 J 2,397.86 ~ 95.91
6 Adsorption/desorption isotherms with 65Zn have very high K values, signifying generally low Zn solubility. Beyond this, the K values in the more Zn deficient Hydraquent at lower catena level are superior to those of the less Zn deficient Tropaquent at higher catena level. Again, the K values of desorption by DTPA extracts are low, indicating strong chelate solubility of the adsorbed Zn. High K-values of the following HC1 extract shows tight binding forces of the Zn remainder. 7 By partial correlation Mg rather than C correlates with Zn deficiency. This would fit to the widespread experience, that most Zn deficient soils have an inverted Ca/Mg ratio < 1. Isomorphic interchange between Zn and Mg is favoured by their almost identical ion radius (see Zn, Mg study by ZUNINO et al. 1979). This also corresponds with electro ultra filtration (EUF) analysis by MURTHY & SCHOEN (1980), showing, that only the smaller part of Zn in soils exists in weak organic bonds. 8 After removal and drying of the 65Zn treated soil cores replanting was accompanied by much less severe Zn deficiency. Thus, soil drainage and at last shorttime reoxidation seems to be prime condition to overcome lethal Zn deficiency on the lower catena level; by lowering the pH and organic matter content, by oxidizing the iron and improve anion, especially phosphate sorption (see MANDAL & HALDAR 1980). Use of the excess water for fish ponding at lowest level with N-collecting Azolla anabeana for rice green manuring as well as for fish feed, seems the best solution.
RADIOMETRICSTUDIESON Zn DEFICIENTRICE SOIL CATENA
131
REFERENCES
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MIKKELSEN, D.S. & KUO, S. (1977): Zinc fertilization and behavior in flooded soils. Proc. Seminar on Nutrients in Rice Culture, Taipei. Commonwealth Bureau of Soils Spec. Publ. 5, 59 p. MITCHELL, K.L. (1955): Trace elements. In: Chemistry of Soil, Reinhold, N.Y., 263. MURTHY, A.S.P. & SCHOEN, H.G. (1980): A comparative study of the soil zinc fractions, determined by chemical methods and Electro Ultraftltration (EUF) and their relations to zinc content in rice. Terminal report, submitted to IRRI. NAYYAR, V.K. & TAKKAR, P.N. (1980): Evaluation of various zinc sources for rice grown on alkali soil. Z. Pfanzenem~ihr. Bodenkunde 143, 5. OSMAN, A.Z., WASSIF, M.M., EL KADI, M.A. & ABDEL SALAM, M.A. (1980): Effect of carbonate in clay fraction on fixation ofzinc. Z. Pflanzenemiihr. Bodenkunde 143, 524-529. PONNAMPERUMA, F.N. (1979): Characterization. Ann. Progr. Rev., IRRI. REHM, G.W., WlESE, ILA. & HERGERT, G.W. (1980): Response of corn to zinc source and rate of zinc band applied with either orthophosphate or polyphosphate. Soil Sci. 129, 36-44. SAEED, M. & FOX, R.L. (1979): Influence of phosphate fertilization on zinc adsorption by tropical soil. Soil Sci. Soc. Am. J. 43, 683-685. SCHWERTMANN, U. (1964): Differenzierung der Eisenoxide des Bodens durch photochemische Extraktion mit saurer Ammonium Oxalat L6sung. Z. Pflanzenem~ihr. Bodenkunde 105, 194. SHUKLA, U.C. & MITrAL, S.B. (1979): Characterization of Zn adsorption in some soils of India. Soil Sci. Soc. Am. J. 43, 905-908. SHUKLA, U.C., MITrAL, S.B. & GUPTA, R.K. (1980): Zinc adsorption in some soils as affected by exchangeable cations. Soil Sci. 129, 366-370. SINGH, BIJAY& SEKHON, G.S. (1975): The effect of soil properties on adsorption and desorption of Zn by soils. Meal. Fac. Landbouww. Rijksuniv. Gent 40, 1481-1492. SINGH, B. & SEKHON, G.S. (1977): The effect of soil properties on adsorption and desorption of zinc by alkaline soils. Soil Sci. 124, 366-369. SWAINE, D.J. (1955): The trace element content of soils. Commenwealth Bur. of Soil Sci. Techn. Comm. 48, 157. THENG, B.K.G. & SCHARPENSEEL, H.W. (1976): The adsorption of 14C-labelled humic acid by montmorillonite. Proc. of the Int. Clay Conf., Appl. Publ. Ltd. Wilmette, Illinois 60091, USA, 643-653. TIWARI, K.N., PATHAK, A.N. & UPADHYAY, R.L. (1976): Studies on Fe and Zn nutrition office at varying moisture regimes in a black clay soil of Uttah Pradesh. J. Indian Soc. Soil Sci., 24, 3, 303-307. TRIER, K. & BERGMANN, W. (1974): Ergebnisse zur wechselseitigen Beeinflussung der Zink und Phosphors~iureem~ihrung von Mais (Zea Mays L.). Arch. Acker u. Pflanzenbau u. Bodenkunde 18, 65-75. VAN BREEMEN, N., QUIJANO, C.C. & LE NGOC SEN (1980): Variation in zinc deficiency in rice along a toposequence of soils in Tiaong, Quezon Province, Philippines. I. Soil conditions and hydrology. Plant and Soil. VAN BREEMEN, N. & CASTRO, ILU. (1980): Variation in zinc deficiency in rice along a toposequence of soils in Tiaong, Quezon Province, Philippines. III Cropping experiment, Plant and Soil. WALLACE, A., MUELLER, R.T. & ALEXANDER, G.V. (1978): Influence of Phosphorus on zinc, iron, manganese and copper uptake by plant. Soil Sci. 126, 336-341. ZUNINO, H., AGUILERA, M., CAIOZZI, M., PEIRANO, P., BORIE, F. & MARTIN, I.P. (1979): Metal binding organic macromolecules in soil: 3. Competition of Mg(II) and Zn(II) for binding sites in humic and fulvic type model polymers. Soil Sci. 128, 257-266.
Addresses of authors: Prof. Dr. H.W. Scharpenseel, E. Eichwald, Ordinariat f'tirBodenkunde der Universit~t Hamburg von Melle Park 10, D-2000 Hamburg 13 Dr. Ch. Haupenthal, from April 1983 Ciba-Geigy Company, Basel, Switzerland Dr. H.U. Neue, IRRI, Department of Soil Chemistry, P.O. Box 933, Manila, Philippines
Vol. 10, 115-132
Braunschweig 1983
ZINC DEFICIENCY IN A SOIL TOPOSEQUENCE, GROWN TO RICE, AT TIAONG, QUEZON PROVINCE, PHILIPPINES H.W. Scharpenseel, E. Eichwald, Ch. Haupenthai, H.U. Neue, Hamburg ABSTRACT After scrutiny of the pertinent literature analytical and tracer experiments with 65Zn along a toposequence office paddies in Tiaong, Quezon Province, Philippines are described. The higher catena member is moderately Zn deficient, the lower member extremely Zn deficient. Soil analysis reveals Tiaong soil to be slightly alkaline, smectitic, strongly humic, of high CEC and base saturation, of low plant available Zn (Bray method). The higher catena member (H) leads in Si, Al, K, Na, Zn, Cu, Ni, Co, Cr, Ba, the lower member (L) in C, Ca, Mg, Mn, P. The very high deficiency in (L) corresponds with higher humus-, Ca-, Mg, and P concentrations, all potential agents to Zn fixation. Clay minerals are higher in less deficient (H). This, and studies of VAN BREMEN et al. (1980) would point to strong Zn organic fixation. However, DTPA-, dithionite- and oxalate-extracts represent only 2.5-25% pedogenlc zinc, the rest is lithogenic and insoluble. Previous combustion scarcely increases these rates• This points against Zn organic linkages as predominating Zn fixation mechanism. Partial correlation, applied to VAN BREMEN's data also annihilates the high correlation between zinc and organic maAter, which is replaced by strong Zn-Mg and Zn-bicarbonate correlations. Field tests with °°ZnSO4 in plastic tubes of 35 and 25 cm diameter,inserted in the rice fields, showed, that mobility, i.e. lateral and vertical translocation of the zinc was much more pronounced at (H) than at(L). After air drying the removed soil cores replanting was accompanied by much less Zn deficiency than in loco in the rice field• Drainage and at least temporary oxidation seems to be the primary requirement for soil rehabilitation. Adsorption - desorption isotherms followed the Freundlich relation. K-values were very high, especially in (L), indicating strong adsorption of Zn. K-values of the DTPA desorption extracts were quite low, representative for easy desorption by chelate solution, whereas the 0.1 M HC1 extract after DTPA elution had again high K-values as a sign of strong adsorption of the non DTPA extractable Zn. For rehabilitation mixed rice - fish farming with fishponds in the lowest points of the relief seems to be best with propagation ofazolla as N-green manure for the rice and feed for the fish. 1. INTRODUCTION Zinc is in soils, grown to rice, next to N the second most important element. Along with the pH value of submerged rice soils near neutrality and with a syndrom of other factors, such as overwetting and extreme reduction, which consumes protons and lifts up the pH, and with lithogenic inhefitage ofMg > Ca, it is estimated, that about 50% ofaU paddy rice soils are Zn-deficient or depleted to the extent, that the rice plant responds favorably upon Zn application. The strong Zn deficiency of the rice soil toposequence at Tiaong, Quezon Province, Philippines, varies greatly in effect with just slight differences of altitude and slope position. By means of analysis and tracer work with Zn it is tried, to expose the differences between an upper Zn deficient catena member, where rice grows fairly well after seedling dipping in ZnO suspension and a just 2 m lower catena member, where Zn deficiency is lethal to the plant despite of Zn treatment. •
65
•
116 2.
2.1.
SCHARPENSEEL,EICHWALD,HAUPENTHAL& NEUE LITERATURE REVIEW
OCCURRENCE IN SOIL
Zinc contents are about 60 ppm in felsic, 130 ppm in mafic rocks, 10 to 300 ppm in soils and 15 to 60 ppm in plant dry matter (MITCHELL 1955, SWAINE 1955). The soil solution contains 1-80 ppb of Zn and up to several, hundred ppb of Zn in submerged rice soils (MIKKELSEN & KUO 1977). Zn concentrations below 1 ppm in a 0,05 N HCI extract express Zn-deficiency (PONNAMPERUMA 1979); 0.05 M cu-acetate and EUF (electro ultra filtration) extracts have been likewise tested (MURTHY 1980). Other inorganic or chelate extractants are compared by HAQ et al. (1980) as well as HAVLIN et al. (1981). Numerous factors influence Zn availability and fixation. Zn mobility and plant uptake of Zn depends partly of the form of Zn in the soil, especially on soil pH (GERTH et al. 1981, HERMS & BR'IJMMER 1980). Zinc may be present as ZnCO3, ZnS, Zns(CO3)2(OH)6 (KALBASI 1975), adsorbed at Fe and Al oxides as aquo and hydroxo complexes (KIEKENS 1975), eventually as ZnFe204 with Ferrihydrit (BAR-YOSEF et al. 1980), Zn-phosphate and adsorbed or isomorl?.hically exchanged f.ex. in trioctahedric Mg-smectites. Contrary to BRUMMER (198 I), who expected in soils with neutral to alkaline pH rather formation of Zn-silicates than precipitation of ZnCO3, OSMAN et al. (1980) noticed in calcareous soils of Egypt stronger Zn fixation as ZnCO3 than by silicate clays. Zinc can be fixed by adsorption at negative charge points of the soil humic matter as well as by incorporation into clay-Zn-organic matter complexes. Zinc surpasses Ca and Mg in forming clay-metal-humic acid complexes (TIWARI et al. 1976). Zn humic coils are too big (3-8 nm) to allow a full intercalation between smectite layers, but they could penetrate between oriented clay domains in a swollen soil, such as in submerged soil of neutral pH (AYLMORE & QUIRK 1959, 1960, GILES et al. 1974).The polarizing power of Zn for water molecules and the electrostatic energy of interaction between exchangeable Zn and a water molecule in the primary hydration shell of montmorillonite suggest, that the contribution of clay-Zn- organic matter complexes to the total of Zn fixation might be considerable (ELGABALI 1950, MACKENZIE 1964, THENG & SCHARPENSEEL 1976, VAN BREEMEN et al. 1980, ZUNINO et al. 1979). Abasic study by ZUNINO et al. (1979), regarding sorption points and competition between Zn and Mg for binding sites in humic and fulvic polymers, indicates, that Zn is mostly favoured by the terminal groups. Also McBRIDE et al. (1979) exclude simple precipitation as Zn-hydroxide or -carbonate to be an important mechanism of zinc fixation in soils of a pH level below 7.0, while at high pH > 7.5 they regard increase in Zn solubility as result of organic complex formation. They consider nucleation of Zn on clay minerals or interaction with hydrated oxide surfaces important in the moderately acidic pH-range. Similarly, HERMS et al. (1980), studying the influence of organic matter on Zn solubility in soils, observed decreasing Zn solubility after organic matter application within a range from pH 4-6, while between pH 7 and 8 Zn solubility increased. VAN BREEMEN (1980) observed in connection with a soil, near to the experimental site of this report, highest correlation between Zn deficiency and soil organic matter. In important studies of chemical equilibria in soils LINDSAY (1979) expresses the solubility isotherm for Zn in soils as soil Zn + 2H + ~- Zn2; log Zn 2+ = 5.80 - 2 pH. Provided Zn concentrations are high enough, the increase of Zn-solubility with pH equals -2
RADIOMETRICSTUDIESON Zn DEFICIENTRICESOILCATENA
117
at pH 7 and up; at acidic pH it can change to 0 till -1. A basic study, aimed to elucidate and model the Zn 2+ transport as well as possible improvement of the Zn 2+ transport to the plant root was carried out by BAR YOSEF et al. (1980).
2.2.
CONDITIONS FOR Zn DEFICIENCY
PONNAMPERUMA (1979), after defining about 30 Zn deficient areas in the Philippines with pH values of the soils between 5.2 and 8.2, has layed down a combination of soil conditions, framing most of the Zn deficient soils: Perennial wetness - low reliefposition artesian water condition - interflow/upweUing - pH > 7 - calcareous soil - Mg > Ca organic matter > 3% - available Zn in 0.05 N HCI extract < 1 ppm - Aquent/Aquept/hydric Hemist Suborder or Great Soil Group. Besides of the mainly geomorphological syndrom of preconditions for Zn deficiency specific lithological and chemical factors can contribute. Alcali soils, being inherently liable to Zn fLxation (SINGH & SEKHON 1977, KUO & MIKKELSEN 1979), were subjected to Zn adsorption studies. Among various sources of Zn for alleviation of the deficiency, ZnSO4 ranked first (NAYYAR & TAKKAR 1980). Also the possible Zn fLxing interaction with P-fertilization required elucidation," While studies with corn (REHM et al. 1980, MANDAL & HALDAR 1980, FRIESEN et al. 1980, TRIER & BERGMANN 1974) did not reveal any depression of Zn availability, soybeans and bushbeans, grown in nutrient solution (SAEED & FOX 1979), responded pH dependent with higher Zn uptake upon P application at lower pH, with Zn stress after P application at high pH. Hawaiian soils, high in colloids of variable charge, decreased in Zn availability, whereas those with predominantly constant charge colloids released Zn upon P application (WALLACE et al. 1978). In the rice field, P application was depressing Zn availability, more with regard to the native Zn in the soil than to the newly applied Zn (MANDAL & HALDAR 1980). Decrease of Zn concentration in aquaeus extracts of non calcareous soil was lower after phosphate plus ZnSO4 treatment than after ZnSO4 application only (KALBASI et al. 1978). Other authors observed in Vertisols, grown to rice, mutual antagonism between Zn and Fe. While Fe was highest under water lagged conditions, Zn concentration climaxed at field capacity (TIWARI et al. 1976). FRANCK & FINCK (1980) determined yield related Znrequirements for oats and wheat by means of hydroculture and statistic evaluation of data collective, derived from field experiments. -
2.3.
ADSORPTION - DESOPRTION OF ZINC
In most of the recent zinc studies emphasis was laid on introduction of adsorption desorption techniques to reveal mode of sorptive processes, test sorption models and especially the mechanisms of Zn sorption. BR'I.)MMER (1981), analysing Zn solubility and adsorption isotherms, concludes, that the solubility of Zn in soils depends more on ad- and desorption, than on precipitation and redissolution. He further demonstrates, in confirmation of older findings by ELGABALI (1950), a special sorptive affinity of Zn towards Feoxides and clay silicates. Also SINGH et al. (1977) questioned prevalence of adsorption or precipitation. They
118
SCHARPENSEEL, EICHWALD, HAUPENTHAL & NEUE
found agreement with Langmuirian equations and a predominant correlation between adsorbing power and CEC. Other authors, using the Langmuirian approach, were BAR-YOSEF (1979), partitioning Zn between solid and liquid phases under variable pH, and DIXIT et al. (1980). The latter studied adsorption-desorption in algerian vertisols, splitting the retained Zn into one rate, adsorbed by ion exchange and another rate at lower concentration, held by "specific" adsorption mechanisms. KALBASI et al. (1978), testing Zn sorption by Fe and AI, recognized specific Zn sorption related to exchange against 1 H ÷ and nonspecific Zn sporption to involve another anion such as CL-, and to release 1 H ÷ for each mol of Zn 2+ getting adsorbed. According to KUO et al. (1980) Zn adsorption in acid soils, pH below the zero point of the net charge, increases with rising pH, whereby Cu interfered with the sorption of Zn. The dependence of Zn adsorption on the cation costume of the exchange sites was investigated by SHUKLA et al. (1980). The values of standard free energy of adsorption and blocking of Zn adsorption increased in the sequence Ca >/Mg > K > Na. They further explain Zn adsorption data by Freundlich and Langmuir isotherms, which they split into three concentration ranges with different bonding energies for the adsorbed Zn. A distinction between higher Zn adsorption by constant and lower adsorption by variable charge colloids was observed by SAEED & FOX (1979). In this work Zn concentrations > 0.01 ppm followed the Freundlich isotherm. Suitability of the Freundlich isotherm for description of Zn-adsorption was also confirmed by KUO & MIKKELSEN (1979), who calculated the required activation energy for Znadsorption and concluded, that Zn-adsorption is based more on chemisorption than on electrostatic attraction to the colloidal surfaces.
3.
SITE OF THE EXPERIMENT, SOIL CATENA
From soil and cropping experiments VAN BREEMEN et al. (1980) and VAN BREMEN & CASTRO (1980) concluded, that Zn deficiency of rice in the lower part of the Tiaong area, Quezon Province, Philippines, experimental region of this report as well, is due to lack of soil aeration throughout the year, and levels of organic matter are highly correlated with the disorder, while pH, calcium carbonate content and dissolved bicarbonate had little effect. In addition to above studies soil analytical and radiometric investigations were carried out in two experimental lots in the highest (H) and lowest (L) positions of the rice soil toposequence of Tiaong, as indicated in Fig. 1. The area is situated in the pediment of Mount Banahaw, consisting of strongly weathered pleistocene volcanic ashes, muds and lapillis. Soils range from Hydraquent in the lower part (L) to Tropaquent in the higher part (H). Beyond the artesian well, outside the rice land in the coconut grove are Tropaquepts. This kind of shallow terraced rice land at the fringe of a mountain slope with downslope partly perched artesian water and vertical seapage down in the rice fields is typic for many sites, especially in highly volcanic countries like the Philippines and parts of Indonesia. The dramatic increase of Zn deficiency downslope, within just 2 m of altitude difference, is a phenomenon, enforcing new systems of land use like a mixed rice land and fish pond pattern, unless we discover the cause and find straight means of land rehabilitation. Below the toposequence follows a permanently wet, humus rich, partly halfbog like soil with Phragmites australis and Hygrophila angustifolia as predominating plant species. Beyond (H) better drained Tropaquets with coconut and banana groves extend to the hilltop.
RADIOMETRIC STUDIES ON Zn DEFICIENT RICE SOIL CATENA
119
NE
SW
Meters above se~ level Coconuts,bor~rv~
rs~ieO
45-1
'•••IQ
44-
Artes4on I well
4342Pl
RICE land
exp~lrnent
J
;
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I i=
I t
19sin
IP3
i p4
i•L•,,re
H~
I
I
I
I [~
Apu
17/I uL,k'
54
uL,k
167
AGr
GrC
77
75GY 4/I
AG 25Y 2/I .IL-.uT
52
9.5Y4/I
25Y 3/I LIL-uT k
63
Gr 154
GrG
uLIk
69
IOY4/I SuL,k'
~C
GoGI
• 100
O0
Apu B G GO Gr
3/2 uL,~ 3I
AGr
A h"
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ApuZ IOYR E/I
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~
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E/I .ILtk
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Li I
Apu~
IOYR
Ah
Lower area experiment
Ico
A-Horizon with high content or organic matter A-horizon, puddled Mineral weathering horizon Gley-hodzon Gley-horizon, oxidized Gley-horizon, reduced
(11;~) k-k
)1
GC [OGY4/I -3/I suL~k'
DO
GaG r Gley-horizon, preferentially reduced GrG o Gley-horizon, preferentially oxidized C parent material
(1i~) ~1 GrC O0 IOY5/I suL- suT k-k'
"[" k k' uL suL uT suT
Ivery mo~t
contentoffreecarbonates, high content of frae carbonates, medium content of frae carbonates, low silty loam sandy sdty loam silty clay sandy silty clay
Fig. 1: NE-SW cross section and soil profiles of the Tiaong toposequence
4.
MATERIALS AND METHODS
The total element analysis by X-ray fluorescence, the 65Zn adsorption-desorption and distibution measurements in the soil were carried out by standard methods. 1 The air dried soil samples from five horizons each of the (L) and (H) profiles were analysed for pH, CEC, available P, organic C and total N. The same was repeated with freeze dried samples. 2 For clay mineral analysis the fraction < 2/zm was used, after destruction and removal of allophanes by 0.1 NaOH (HASHIMOTO & JACKSON 1960) 3 All element analysis was done by X-ray fluorescence; Zn was analysed by atomic absorption spectrometry in dithionite, oxalate (SCHWERTMANN 1964) and DTPA extracts (LINDSAY & NORVELL 1978). 4 65Zn movement was studied by autoradiographity of soil columns, taken from the field. In the bunded experimental lots, Tiaong site (fig. 1), plastic rings were inserted in the highest (H) and the lowest (L) areas (fig. 2). The large rings, 35 cm wide, were pressed down into the hard pan and were used to study Zn uptake in the rice plants under different regimes
-
120
SCHARPENSEEL, EICHWALD, HAUPENTHAL & NEUE
A
0.5 mc~Zn applied in the center
Q
o,o, ~
0 4 mc 6SZnin I portion mixed with upper 5crn soil (,q,Omg Zn)
0
0 • Upper
Q
0
© 0 ©
0 I-
195 m dlstonce
oreo
I Lower OrSO
Fig. 2: Experimental scheme ofhSZn-fieldexperiment in Tiaong
of Zn application. After harvesting, the rings were dug out, naturally dried for about 1 year and rewetted again in order to study a possible remobilization of fixed Zn due to intermittant drying of the soil, i.e., to assess the effect of drainage to alleviate Zn deficiency. The smaller rings (25 cm wide) were inserted 10 cm deep into the flooded soil to study vertical and lateral transport ofhSZn. 65Zn labelled ZnSO4 was applied to the upper three cm of the soil; 65Zn radioactivities per g ofsoil were measured in 10 g samples from cores, taken in different depth and lateral distances from the center by means ofa PiJrkhauer soil auger 3, 6 and 9 weeks after 65Zn administration. 5 Adsorption/desorption studies were based on 0.5 ml of fresh soil from different horizons at (L) and (H) sites. Soil samples were stored in screw cup centrifuge tubes under N2 gas immediately after sampling. For the adsorption studies the soil was mixed with 25 ml of aquaeus solution, representing 5 different 65Zn concentration levels and agitated over 48 hours. After spinning down the soil, always 10 ml of the supernatant were tested against a 65Zn-], standard in a well type scintillation counter, based on a TI activated NaJ borehole cristal detector. Desorption was undertaken accordingly by shaking the soil with the respective desorbing agent, such as 0.05 M DTPAand 0.1 N HCI solution. The insoluble remainder of the 65Zn after desorption is measured as a 250 mg aliquod of the previously air dried soil in aquaeus suspension.
5.
RESULTS AND DISCUSSION
Table 1, 2 and 3 summarize the results of general soil analysis of the individual soil horizons at the two sites. Carbon and nitrogen are highest in (L), total and available Zn levels, measured by atomic absorption, in (H). Analysis was carried out in parallel with air dried as well as with directly nitrogen protected and then freeze dried soil samples. Differences in
RADIOMETRIC STUDIES ON Zn DEFICIENT RICE SOIL CATENA
121
Tab. 1: TIAONGSOILSL AND H, AIR DRIED.
~ (%) pH 1:1 w/v H20 EC mmhos w/v H20 Carbonate (%) Sol. Cations meq/lO0 g ads Exch. cations
No.
Moisture
1:1 Na K Na K Mg
maq/100 g ads
Ca
TEB meq/100 g ads CEC meq/lO0 g ads S a t u r a t i o n (%) Avail, P Bray ppm ads Olsen Total N % ods Or S. C % ods C/N ratio Total element P (major) ppm K ods Hg Total element (m/~or) ppm ods
Particle size anal. microns
Cu Mn Zn Fe (%) % Clay % Silt % Sand
A v a i l . Zn Bray (ppm)
L 0-3
L L L L 3-23 23-43 43-63 63-83
H 0-3
H H H 3-18 18-33 33-53
H 53-73
8.6 7.9 0.30
8.2 8.0 7.9 8.0 0.27 "0.19
9.2 7.7 0.24
9.1 7.8 0.22
10.4 7.6 0.19
1.0 1.0 37.7 57.1
8.1 8.1 0.14
8.8 8.1 0.i1
8.9 7.8 0.18
9.0 7.8 0.13
0.9 0.9 33.2 65.5
0.8 0.8 28.3 66.7
0.6 0.7 23.9 56.3
0.6 1.1 22.7 37.7
0.7 0.6 34.3 54.0
0.8 0.6 33.5 64.2
0.8 0.6 33.7 54.6
0.7 0.6 29.7 32.4
0.5 1.0 23.3 22.6
96.8 100.5 32.6 33.0
96.6 33.4
81.5 33.7
62.1 44.7
89.6 36.7
99.1 34.3
89.7 37.1
63.4 47.1
47.4 43.1
21 22 23 23 13 12 11 9 8 .576 .541 .428 .253 .081 .309 .301 .281 .178 6.51 5.43 3.98 1,94 0.60 3.47 3.16 2.91 2.36 11.30 10.04 9.30 7,67 7.41 11.23 10.50 10.36 13.26 1473 1377 1338 1271 839 902 907 917 853 •
8567 43 2.57 5.7 70.7 23.6 .54
8945 10037 44 48 2.87 3.02 7.5 68.7 23.8
30.2 49.2 20.6
.43
.65
6425 57 3.44 24.4 50.1 25.5 1.62
1904 55 6.03 18.5 63.4 18,1 3.78
1627 60 3.39 36.7 50.7 12.6 1.51
1443 58 3.40 36.0 49.3 14.7 1.51
1408 66 3.72 37.3 48.8 13.9 1.73
713 64 3.89 40.2 47.5 12.3 4.97
9 .152 0.78 5.13 679
678 57 6.71 36.2 50.8 13.0 3.46
ads - air dried soil; ods -- oven dried soil results were moderate and confined to criteria, influenced by pH and Eh, such as available nutrients. In the fraction < 2/.zm, smectite was the only clay mineral, discemable by X-ray diffraction. The fraction < 0.2 ~m apparently contains some vermiculite. X-ray fluorescence measurements of elements beyond atom number 9, that exceeded a concentration of 1 ppm, are summarized in table 2 and 3. The Tiaong soil accordingly is siallitic, carbonaceous with high excess of Ca over Mg, deviating in this criteria from PONNAMPERUMA's clich6 of preconditions for Zn deficiency (1979). In most Zn-deficient soils, especially those of ultrabasic parent material, Mg exceeds in fact Ca. The differences between the high and low site ((H) and (L)) are summarized in table 4. Concentrations ofSi, AI, K, Ti, Na. Zr, Rb and Zn are higher in (H), whereas Ca, Mg, Mn and P are superior in (L). Extractions by ammonium oxalate (pH 3.2) and dithionite (pH 7.3) release between 11 and 13% of the total Zn, by neutralized DTPA3-4% (table 5). Combustion of soil organic matter at lowest possible temperature does not influence the contents of extractable Zn distinctly. Evidently, it can be at most a smaller part of the total Zn in the soil, which is present in organically complexed form. Further, 1.5-8 ppm Zn, ca. 2.5-25% of total soil-Zn are pedogen only, the majority being lithogen and insoluble.
122
SCHARPENSEEL, EICHWALD,HAUPENTHAL& NEUE
Tab. 2: QUANTITATIVE ANALYSIS BY X-RAY FLUORESCENCE, TIAONG, LOWER SITE Element concentrations in %
HOR. om
ELEM Si Ca A I Fe Mn K Ti P Mg Na Rb Sr Zr Pb Zn Ni Cu Cr
Co Ba
J
0- 3
3 - 23
23 - 43
43- 63
63- 83
ELEMENT-CONCENTRATIONS 22,6150
23,3300
23,8050
25,6410
30,3610
14,7070
14,4200
13.2180
11.1680
4.2190
2,7800
2,7680
3,3350
3,7040
6,1940
3.6510 1,7254
3,7360 1,8372
4.0590 1,8629
4.3180 1,6323
5.2640 0,1875
0,3030
0,2900
0.3370
0.3600
0.3800
0,3400
0,3480
0,3690
0,3980
0.4230
0.1978 2.2751
0.2015 2.1493
0,1908 1.8903
0.2021 1.8333
0.1248 ].6366
0,7973
0.7484
0.8540
0.8291
1.2289
0,0014 0,0832
0,0013 0,0788
0,0008 0,0716
0,0018 0,0615
0.0016 0,0643
0,0111 0,0014 0.0035 0,0024
0,0110 0,0017 0.0038 0,0023
0,0106 0,0015 0.0039 0,0024
0,0105 0,0018 0.0045 0,0026
0,0129 0,0018 0,0060 0,0023
0.0030 0.0012
0,0041 0.0020
0.0034 0.0020
0,0044 0.0033
0,0041 0.0029
0.0fl04
0.0004
0.0006
0.0008
0,0013
n.n~nR
0.04]7
0.0433
0.0438
0,n587
I
RADIOMETRICSTUDIESON Zn DEFICIENTRICE SOIL CATENA
123
Tab. 3: QUANTITATIVE ANALYSIS BY X-RAY FLUORESCENCE, TIAONG, HIGHER SITE Element concentrations in %
HOR. cm
0- 3
3 - 18
18- 33
33 - 53
ELEM. ELEMENT-CONCENTRATIONS Si 26,3990 26.3780 26.4q~n ~R.R74N Ca 7,3250 7,2700 7,2980 3,0930 AI 6,5380 6,5090 6,4800 8,0590 Fe 4,3690 4,3750 4,3620 5,2320 MR 0,2185 0,2199 0,2095 0,0617 K 0,4250 0,4100 0,4190 0,4320 Ti 0,4560 0;4520 0,4520 0,4750 P 0,1214 0,1230 0,1193 0,0927 Mg 1,4379 1 4250 1,4403 1,2286 Na 1,0955 1,1441 1,1486 1,2193 ,Rb 0,0034 0,0033 0,0032 0,0030 Sr 0,0865 0,0871 0,0866 0,0728 Zr 0,0146 0,0146 0,0145 0,0155 Pb 0,0021 0,0021 0,0024 0,0022 Zn 0,0061 0,0060 0,0060 0,0066 Ni 0,0029 0,0026 0,0027 0,0029 Cu 0,0050 0,0047 0,0047 0,0051
53 - 73
?R.n~n 2,6860 8,7470 6,0620 0,0629 0,3940 0,4750 0,0809 1,1376' 1,2033 0,0022 0,0719 0,0156 0,0022 0,0059 0,0025 0,0051
C r
0,0035
0,0018
0,0035
0,0057
0,0025
Co
0,0009
0,0009
0,0009
0,0012
0,0017
Ba
0.0435
0,0422
0,0425
0,0449
0,0503
124
SCHARPENSEEL,EICHWALD,HAUPENTHAL& NEUE
DIFFERENCESBETWEEN HIGHER CATENA MEMBER (H) (TROPAQUENT) AND LOWER CATENA MEMBER (L) (HYDRAQUENT)OF TIAONG CATENA Tab. 4:
ELEMENT
CONCENTRATION
MEAN CONCENTRATION DIFFERENCES (WEIGHT - %)
RELATIV (%)
OH>L OL>H
SI
H > L
3,40
14
[]
AL
H > L
2,50
40
[]
FE
H z L
0,40
9
CA
H < L
6,80
105
0
K
H > L
0,06
14
[]
-MN
H < L
0~80
570
0
TI
H> L
0,09
27
[]
NA
H > L
0,26
22
[]
'MG
H< L
1,000
72
O
P
H< L
0,080
71
O
ZR
H> L
0,002
25
D
SR
H_L
0,009
10
RB ZN
H>L
0,001
I00
[]
H>L
0,0020
47
[]
Co
H>L
0,0013
34
[]
NI
H>L
0,0003
12
Co
H>L
0,0004
57
D []
CR
H>L
0,0008
31
D
BA
H>L
0,0034
D
5.1. TRANSLOCATION, ADSORPTION, DESORPTION STUDIES UNDER USE OF 6sZN Table 6 shows, that the vertical and lateral translocation are much more pronounced at (H) than at (L). Deeper vertical 6SZn translocation was also confirmed by autoradiography of soil cores. After drying the cores, replanting in this reoxidized material showed much less severe Zn deficiency than before in the rice field. The adsorption isotherms (see also MAYER 1978, KIEKENS 1975) of Zn in the Tiaong soil follow the Freundlich relation.
RADIOMETRIC
STUDIES ON Zn DEFICIENT RICE SOIL CATENA
125
Tab. 5: Zn-CONCENTRATIONS IN OXALATE-, DITHIONITE- and DTPA-EXTRACTS OF LOWER AND HIGHER TIAONG SITE SOILS, BEFORE AND AFTER COMBUSTION AT 550* C LOWER SAMPLES
I
TIAONG
SITE SOILS and HIGHER TIANG
WITHOUT COMBUSTION C*/o
SITE SOILS NITH COMBUSTION
Oxalate extract ppm Zn]DTPA extract ppm Zn Oxalate extract ppm Zn ~Dithlonite ppm Zn
DTPA pprn Zn
L 0-3
!
6.51
8.0
2.7
8.0
8.3
2.7
L 3-23
i
5.43
6.5
1.55
6.5
6.1
1.6
L 23 - 43
3.98
6.5
2.50
6.5
6.7
2,5
L 43 - 63
1.94
6.5
1.60
6.5
6.9
2,6
L 63 - 83 j
0.60
7.5
1.45
7.5
7.9
1,5
H 0-3
3.47
1.75
7.8
7.2
1.8
IH 3 - 18
3.16
8.0
1.70
8.0
8.2
1.7
H 18-33
2.91
7.5
1.50
7.5
[
7.2
1.5
H 33 - 53
2.36
6.5
1.55
6.5
ii
7.1
1.6
,H 53 - 73
0.78
6.0
1.80
6.0
~
6.8
1.8
10.0 (?)
i I
X
=
K • C 1/n
m
C = concentration of Zn in solution X = concentration of Zn in the soil m K = Freundlich constant 1/n = slope of isotherm Table 7 and 8 as well as fig. 3 show the results of adsorption of Zn out ofaquaeus solution as well as ofdesorption by 0.05 M DTPA and 0.1 M HC1 extraction. Evidently, adsorption is stronger by the fresh soil samples of the Hydraquent (L) compared with the higher Tropaquent (H). K values are in general very high, indicating very strong, tight adsorption of Zn by the Tiaong soil, expectably, considering the extreme Zn deficiency especially in (L). K values for the DTPA extracts are low, which means, that DTPA chelate is easily desorbing most of the zinc, while the much higher K values of the HCI fraction express tight bonding of the zinc, that remains adsorbed after the DTPA elution. This is also demonstrated by tables 9 and 10. The rather low differences of soluble zinc in different extractants (DTPA, dithionite, oxalate) between normal samples and the same samples after previous combustion (table 5) created concern, whether Zn could really be preferably bound by the organic matter, as high correlation factors suggest in the work of VAN BREEMEN et al. in Tiaong (1980). Additional partial correlation, applied to those data make the highly significant negative correlation
126
SCHARPENSEEL, EICHWALD, HAUPENTHAL & NEUE
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RADIOMETRIC STUDIES ON Zn DEFICIENT RICE SOIL CATENA
×
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127
soTl
10000
,0
1000 s 0 /
100 ®
?/
•
10
6
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S
I
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C o = Adsorptlon + = De~orptlon * = Desorption
location pro?11e depth materlal
: : : :
by by
Fig. 3:
~g/ml
0.05 m DTPR 0.1 m HCI
T1aong~ Quezon, Tropaquent ? r e s h ~oil 0 - 3 cm
K Ads DTPR HCI
=
35966.9 4.7 1749.2
Ph111pplnes
1/n 0.7947 0.3672 1.0161
Zn-Adsorption-Desorption according to Freundlich x / m -
r 0.999 0. 720 0. 902
K • C 1/n
solutlon
128
SCHARPENSEEL,EICHWALD,HAUPENTHAL& NEUE
Tab. 7: Zn-ADSORFrION-DESORPTIONACCORDINGTOFREUNDLICH(x/m-K. Cl/n Location: Tiaong, Quezon, Philippines; profile: Tropaquent; material: fresh soil 0-3 cm
Ads DTPA HC1
K 35966.9 4.7 1749.2
1/n 0.7947 0.3672 1.0161
r 0.999 0.720 0.902
3-18 cm
Ads DTPA HC1
37183.2 6.3 165.9
0.7938 0.6281 0.6170
0.996 0.927 0.951
18-33 cm
Ads DTPA HCI
40967,0 6.4 55.8
0.7998 0.4607 0.4803
0.992 0.925 0.759
33-53 cm
Ads DTPA HC1
50792.4 10.5 201.4
0.8311 0.6001 0.6307
0.998 0.958 0.805
53-73 cm
Ads DTPA HCI
38946.2 10.6 564.0
0.8140 0.7250 0.7929
0.998 0.997 0.981
Tab. 8: Zn-ADSORPTION-DESORPTIONACCORDINGTO FREUNDLICH (x/m - k. Cl/n) Location: Tiaong, Quezon, Philippines; profile: Hydraquent; material: fresh soil 0-3 cm
Ads DTPA HC1
K 40272.6 7.6 1126.8
1/n 0.8039 0.7587 1.1300
r 0.994 0.986 0.852
3-23 cm
Ads DTPA HCI
40505.5 8.4 898377.3
0.8062 0.8768 2.3561
0.998 0.999 0.885
23-43 cm
Ads DTPA HCI
69819.0 3.9 23.8
0.8644 0.5317 0.4867
0.999 0.866 0.451
43-63 cm
Ads DTPA HCI
84839.1 7.9 7395.9
0.8853 0.8597 1.4767
0.998 0.995 0.966
63-83 cm
Ads DTPA HCI
54190.8 11.1 6383.0
0.8456 0.8567 1.3872
0.998 0.987 0.918
between Zn and organic carbon disappear, when Mg and also HCO-3 are set constant. This would suggest interference of Mg with the highly significant correlation between Zn and organic carbon and a truly existing strong correlation between Zn deficiency and Mg, perhaps by isomorphic exchange of Zn against Mg into the trioctahedric clay minerals. Recent studies by MURTHY & SCHOEN (1980), using Cu-acetate as well as electro ultrafiltration (EUF) extraction techniques, also suggested, that 25 to 50% of the Zn in soils
RADIOMETRIC STUDIES ON Zn DEFICIENT RICE SOIL CATENA
129
Tab. 9: SUMMARYOF RESULTS EXPRESSED IN PERCENTOF INPUT (EXPERIMENTWITH FRESH UNDRIED SOIL), HIGHER AREA, TIAONG, QUEZON, PHILIPPINES (TROPAQUENT) Sample no.
Depth (cm)
51+ 52 53+ 54 55+ 56 57+ 58 59+ 60 61+ 62 63+ 64 65~ 66 67+ 68 69÷ 70 71+ 72 73+ 74 75+ 76 77+ 78 79+ 80 81+ 82 83+ 84 85+ 86 87+ 88 89+ 90 91+ 92 93+ 94 95+ 96 97+ ~8 99+100
O- 3 3-18 18-33 33-53 53-73 O- 3 3-18 18-33 33-53 53-73 0- 3 3-18 18-33 33-53 53-73 0- 3 3-18 18-33 33-53 53-73 0- 3 3-18 19-33 33-53 53-73
Input pc /Jg Zn
5.0 5.0 5.0 5.0 5.0 1.0 1.0 1.0 1.0 1.0 0.2 0.2 0.2 0.2 0.2 0.04 0.04 0.04 0.04 0.04 0.008 0.008 0.008 0.008 0.008
500 500 500 500 500 100 100 100 100 100 20 20 20 20 20 4 4 4 4 4 0.8 0.8 0.8 0.8 0.8
Left In solution, unadsorbed (%) 0.087 0.096 0.092 0.064 0.081 0.038 0.033 0.033 0.043 0.051 0.031 0.025 0.018 0.025 0.030 0.021 0.018 0.017 0.018 0.020 0.015 0.018 0.020 0.020 0.021
Desorption by 0.SM Desorption .Remained DTPA by .1 N HCI adsorbed (%) (%) to soi| 99.56 98.01 98.69 96.71 93.22 92.36 93.85 94.74 89.99 89.99 80.49 76.48 78.26 71.87 81.08 78.37 78.37 74.91 67.48 74.25 77.97 84.08 67.03 69.39 71.86
0.41 0.41 0.48 0.56 0.58 0.35 0.31 0.40 0.46 0.40 0.49 0.58 0.35 0.38 0.40 0.48 0.48 1.39 0.41 0.59 2.42 0.18 1.68 3.18 0.74
4.19 4.44 4.75 6.80 7.66 5.30 5.53 5.97 9.50 9.64 6.24 6.10 7.19 7.59 14.07 9.97 6.15 8.50 11.60 15.20 10.03 9.83 15.56 20.90 30.56
Sum o1 all % of input 104.25'I 102.96 / 103.97 p ~103.37% 104.13| 101.54.1 98.051 99.72 1 101.14 ~-¢ 99.81%
10o.07| 100.08 J 87.251
83.18/ 85.81 ~ ¢ 86.33% 79.87] 95.583 88.84"I 85.02| 84.82 i' ~ 85.72% 79.B7| 90.06J 90.431 94.11 ] 84~9 ~"~ 93.10% 93.49| 103.18,1
0.935 ~K).037
2.078.98 ~b83.16
18.11 ~b0.72
242.55 ¢9.70
2,340.57 ~93.62
Total (hydraquent + tropaquent) Average (hydraquent and tropaquent)
1.793 0.036
4,274.19 86.48
64.52 1.29
397.93 7.96
4,738.43 94.76%
Percent of total input
0.037
1.36
8.40
100.00
90.21
may exist in weak organic bonds, the major part - being mainly responsible for the nutrition of the rice plant - in a complexed pool. From the analytical and radiometrical results the following conclusions can be derived for the Tiaong catena: 1 Soil analysis reveals higher Zn concentration in (H), while higher C-contents, supposed to correlate strongest with Zn deficiency, are in (L). 2 Freeze drying of the highly reduced rice soil samples, expected to be indispensable for correct analytical results, is no real breakthrough compared to air dried samples, except for some criteria of analysis, influenced directly by pH and Eh. 3 In the clay mineral fraction smectites dominate, i.e. soils are low in variable charge colloids, which adsorb Zn less strongly (SAEED & FOX 1979). 4 X-ray fluorescence indicates in (H) superior contents of all heavy metals except for Mn, which is much higher in (L) and could bloc the Fe reduction and availability. C and Mg, suspected to be responsible for Zn deficiency, are higher in (L). 5 By DTPA, oxalate and dithionite extraction collected Zn fractions are small, compared to the insoluble Zn fraction. Apparently, most Zn is still protected in pyrogenic primary minerals. Also the gain of Zn by previous combustion is very modest, which makes it questionable, whether correlation between Zn and C (soil organic matter) is really the decisive condition for the observed Zn deficiency.
130
SCHARPENSEEL, EICHWALD,HAUPENTHAL& NEUE
Tab. 10: SUMMARYOFRESULTS EXPRESSED IN PERCENTOFINPUT(EXPERIMENTWITH FRESH UNDRIED SOIL), LOWERAREA, TIAONG, QUEZON, PHILIPPINES (HYDRAQUENT) Sample no.
1+ 2 3+ 4 5+ 6 7+ 8 9 + 10 11 + 12 13+ 14 15+ 16 17 + 18 19 + 20 21 + 22 23 + 24 25 + 26 27 + 28 29 + 30 31 + 32 33 + 34 35 + 36 37 + 38 39 + 40 41 + 42 43 + 44 45 + 46 47 + 48 49 + 50
Depth (cm)
0- 3 3-23 23-43 43-63 63-83 O- 3 3--23 23-43 43-63 63-83 O- 3 3-23 23-43 43-63 63-83 0- 3 3-23 23-43 43-63 63-83 O- 3 3-23 23--43 43--63 63--83
input pc /Jg Zn
5.0 5.0 5.0 5.0 5.0 1.0 1.0 1.0 1.0 1.0 0.2 0.2 0.2 0.2 0.2 0.04 0.04 0.04 0.04 0.04 0.008 0.008 0.008 0.008 0.008
500 500 500 600 500 100 100 100 100 100 20 20 20 20 20 4 4 4 4 4 0.8 0.8 0.8 0.8 0.8
Left in .so ution, unadsorbed
Desorption by 0.5M OTPA
(%)
(%1
Desorption
Remained
by 1 N HCI (%)
adsorbed to soil
0.094 0.084 0.066 0.053 0.068 0.033 0.038 0.033 0.028 0.040 0.023 0.025 0.026 0.026 0.028 0.018 0.020 0.021 0.021 0.023 0.020 0.017 0.020 0.023 0.021
.
96.14 100.32 99.34 91.05 86.29 92.58 90.50 92.28 92.21 92.06 84.61 87.38 86.99 87.12 83.69 79.12 85.30 92.07 89.26 75.74 84.40 84.64 82.17 80.44 81.43
0.51 0.49 0.41 0.36 0.41 0 40 Q.33 0.35 0.36 0.36 0.54 0.54 0.59 0.58 0.54 1.50 1.68 1.50 1.65 1.27 6.75 7.49 6.19 5.06 6.55
2.94 2.51 3.08 3.12 3.30 3.68 3.17 3.83 4.64 6.01 3.51 3.98 4.52 6.50 8.48 2.51 2.46 4.03 3.86 8.76 5.06 14.25 22.59 9.47 19.12
0.858 0.034
2,195.21 ~ 87.81
46.41 ~ 1.86
156.38 <~6.21
Sum of all % of input
98.68 103.32 102.88 94.58 90.07 96.69 94.04 96.49 97.24 98.47 88.661 91.93 92.13 94.23 92.74
97.90%
96.58%
91.94%
83.15] 89.46|
97.62 ~,~ 913.16% 94.79| 85.79 , I 96.23 I
106.:19|
110.97 ~¢ 103.14% 94.99 | 107.12 J 2,397.86 ~ 95.91
6 Adsorption/desorption isotherms with 65Zn have very high K values, signifying generally low Zn solubility. Beyond this, the K values in the more Zn deficient Hydraquent at lower catena level are superior to those of the less Zn deficient Tropaquent at higher catena level. Again, the K values of desorption by DTPA extracts are low, indicating strong chelate solubility of the adsorbed Zn. High K-values of the following HC1 extract shows tight binding forces of the Zn remainder. 7 By partial correlation Mg rather than C correlates with Zn deficiency. This would fit to the widespread experience, that most Zn deficient soils have an inverted Ca/Mg ratio < 1. Isomorphic interchange between Zn and Mg is favoured by their almost identical ion radius (see Zn, Mg study by ZUNINO et al. 1979). This also corresponds with electro ultra filtration (EUF) analysis by MURTHY & SCHOEN (1980), showing, that only the smaller part of Zn in soils exists in weak organic bonds. 8 After removal and drying of the 65Zn treated soil cores replanting was accompanied by much less severe Zn deficiency. Thus, soil drainage and at last shorttime reoxidation seems to be prime condition to overcome lethal Zn deficiency on the lower catena level; by lowering the pH and organic matter content, by oxidizing the iron and improve anion, especially phosphate sorption (see MANDAL & HALDAR 1980). Use of the excess water for fish ponding at lowest level with N-collecting Azolla anabeana for rice green manuring as well as for fish feed, seems the best solution.
RADIOMETRICSTUDIESON Zn DEFICIENTRICE SOIL CATENA
131
REFERENCES
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Addresses of authors: Prof. Dr. H.W. Scharpenseel, E. Eichwald, Ordinariat f'tirBodenkunde der Universit~t Hamburg von Melle Park 10, D-2000 Hamburg 13 Dr. Ch. Haupenthal, from April 1983 Ciba-Geigy Company, Basel, Switzerland Dr. H.U. Neue, IRRI, Department of Soil Chemistry, P.O. Box 933, Manila, Philippines