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ROCZNIKI GLEBOZNAWCZE (SOIL SCIENCE ANNUAL) SUI’i’L. 'Г. X U V . WARSZAWA 1044: 63-70

D A N U T A CZĘPIŃSKA-KAM 1ŃSKA

T H E EFFEC T O F T H E PO D ZO LIZA TIO N PRO CESS

ON TH E PRO FILE D ISTRIBU TIO N

O F M IN ER A L CO M PO U N D S OF PH O SPH O R U S

D epartm ent o f S oil S c ien ce , W arsaw Agricultural U n iversity

INTRODUCTION

The amount and distribution of different forms of phosphorus are of diag­ nostic importance for the evaluation of the direction and intensity of soil- forming processes. These processes modify the distribution of phosphorus along the soil profile by modifying the bedrock substrate.

Many authors have observed an eluvial-i lluvial translocation of phosphorus (total) and some of its fractions as a consequence of the process of podzolization [Brogowski, Okołowicz 1986; Konecka-Betley et al. 1985; Pokojska 1979; Rześniowiecka-Sulimierska et al. 1983].

The fractions of mineral compounds were usually reported as treated together, or only some of them were extracted.

In this paper results are presented of an investigations on distribution of mineral fractions of phosphorus compounds as found in podzols profiles. The purpose of this work is to specify more exactly the role of compounds of the process of podzolization.

METHODS

The following characteristics were determined in the sampled soils: - mechanical composition - with use of a Casagrande-Prószyński modifi­ cation of the Bouyoucos method;

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64

£>. Czępińska-Kamińska

- p H - by means of the electrometric method, using a combined electrode. The figures free aluminium amount and free iron amount are cited from an earlier paper of the author [Czępińska-Kamińska 1986].

Total phosphorus content (Pi) was determined in fusion with Ыа2СОз. The fractionation of inorganic compounds of phosphorus was done according to the method proposed by Changs and Jackson [ 1957]. Seven different fractions were identified:

1) L-P - soluble compounds of phosphorus (labile compounds), 2) Al-P - non-occluded aluminium phosphates,

3) F e-P - non-occluded iron phosphates, 4) Ca-P - calcium phosphates,

5) Fe-Po - occluded iron phosphates, 6) Al-Ро - occluded aluminium phosphates,

7) Al, Fe-P - mixed aluminium-iron phosphates of the barrandite type. The sum of all the fractions identified was treated as the total amount of mineral phosphorus (P min). Phosphorus contained in organic compounds (Porg) was counted as:

Porg — P \ — P min

An index of translocation ( V) was counted for all fractions, according to the formula:

the amount of given fraction at horizon Bh the amount of given fraction at horizon Ees

Coefficients of correlation were determined for the relationship between free forms of iron and aluminium on one hand, and the amount of non-occluded aluminium and iron phosphates, on the other.

G EN ERA L DESCRIPTION OF THE SOILS

The soils investigated in this work are from the Kampinos National Park. Profile No 1 was situated in the deflation bowl while profile No 2 - o n a lowland part of the southern strip of dunes originated from sands of Otwock Terrace in the Vistula Valley. The Park itself is situated in the Warsaw Basin. The mean annual precipitation amounts to less than 500 mm, and the mean annual temperature is 7.5°C.

The profile structure of the soil studied has the sequence of genetic horizons typical for podzols:

Profile 1 :

О (from 0 to 7 cm) - AEes (from 7 to 20 cm) - Ees (20-35 cm) - Bh (35-40 cm) - Bhl'e (40^19 cm) - С (49-100 cm) - Cgg (100 cm and more).

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Mineral compounds ofphosphorus

65

Profile 2:

О (from 0 to 8 cm) - OA (8-17 cm) - Ees (17-28 cm) - Bh (28-34 cm) - Bhfe ( 3 4 ^ 0 cm) - С - (40-70 cm) - Cgg (70 cm and more).

The studied soils originated from loose sands and weakly loamy sands containing significant amounts of silt fraction in the upper horizons of profile 2; in profile 1 silt fraction was thinly stratified within the bedrock (Table 1).

Upper horizons of the soils are very acidic. The acidicity is slightly less evident in the bedrock.

The amount of organic carbon, being high in the thick horizons of ectohu- mus, decreases rapidly in the eluvial horizons Ees, and it increases slightly in the illuvial horizon В (Table 1).

T A B L E 1. S om e physico-chem ical properties o f so ils

G en etic Sam pling Per cent o f particle o f mm in diameter С org. pH

horizon depth [cm] 1-0.1 0 .1 -0 .0 2 <0.02 <0.002 [%] H 20 IM KC1 Profile No 1 Ol 0 - 2 n.d. n.d. n.d. n.d. 42.79 4 .7 4.0 O f 2 - 6 n.d. n.d. n.d. n.d. 31.62 4 .0 3.1 Oh 6 - 7 n.d. n.d. n.d. n.d n d . 3.8 2.9 A E es 7 - 2 0 90 6 4 2 3.01 3.5 2.7 Ees 2 5 -3 0 84 9 7 2 0.45 3 .9 3.1 Bh 3 5 —40 87 6 7 2 1.96 4.3 3.9 B hfe 4 0 ^ 9 90 6 4 2 0.60 4.6 4.3 С 5 5 -6 5 81 15 4 2 n.d. 4.8 4.5 С 7 5 -8 0 27 6 0 13 2 n.d. 4 .4 3.9 C g g 1 1 5 -1 2 5 81 15 4 2 n.d. 4.8 4.5 Profile No 2 01 0 - 2 n.d. n.d. n.d. n.d. 34.86 4.5 3.8 O f 2 - 8 n.d. n.d. n.d. n.d. 36.94 4.2 3.5 O hA 8 - 1 7 70 20 10 5 8.17 3.5 2.6 Ees 1 7 -2 8 74 18 8 3 0.32 4.1 3.2 Bh 2 8 -3 4 63 26 11 7 4.00 3.7 3.3 B hfe 3 4 -4 0 55 37 8 5 3.05 4.1 3.7 С 5 5 -6 5 93 5 2 2 n.d. 4.9 4.5 1 2 0 -1 3 0 98 1 1 0 n.d. 5.9 5.3

n.d. - not determ ined.

TH E FORMS OF PHOSPHORUS COM POUNDS

In both soils investigated, it has been found a significant differentiation of total amount of phosphorus between particular genetic horizons. The amount of phosphorus (total) is smaller in the ectohumus subhorizons O: from 98 mg P/100 g of soil in subhorizon Ol to 64 mg P/100 g of soil in subhorizon Oh (Table 2). In the mineral part of the profiles (Figures 1 and 2) smallest amount of phosphorus were found in the bedrock (14-20 mg P/100 g of soil), similar amounts of P occur in the accumulation-eluvial horizons AEes and eluvial horizons Ees (18—21 mg P/100 gsoil), and biggest amounts of P were found in the illuvial horizons Bh and Bhfe (51-120 mg P/100 g of soil). In horizons: A, E and В from 1/3 to 1/2 of total phosphorus amount can be attributed to organic

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D. Сzępińska-Kamińska

T A B L E 2. A m ount o f P in the raw humus subhorizons Profile No S u b ­ horizon Total P [in mg P /100 g o f soil]________

compounds, whereas in the bedrock the appropriate figure is merely 8-12% (Table 3). The amount and distribution of inorganic compounds of phosphorus as related to total amount of the element’s content is therefore smaller in soil horizons, and bigger in bedrock (Table 3).

The following fractions: L-P, Fe-P, Ca-P, Al-Ро and Al, Fe-P contain small amounts of phosphorus, in most horizons less than 1 mg P/100 g of soil. The

above-listed fractions contain relative­ ly high portions of phosphorus in hori­ zons Bh, with an exception of fraction Ca-P, the latter contains the maximum portion of phosphorus in the bedrock (Figures I and 2).

The prevailing part of mineral pho­ sphorus is stored in two fractions: the non-occluded aluminium phosphates Al-P (0, 40-64-37 mg P/100 g of soil) and occluded iron phosphates Fe-Po (7.40-12.42 mg P/100 g of soil). Frac­ tion Fe-Po prevails'in horizons A, E and C, while phosphates contained in fraction Al-P dominated in horizon B.

The composition of mineral compounds of phosphorus is diversified in particular genetic horizons of the studied podzolic soils. In accumulation- and eluvial-horizons, particular fractions can be ordered as follows:

Fe-Po> Al-Po> Fe-P> Al-P >A1, Fe-P> Ca-P> L-P. In the case of illuvial horizons the situation is: Al-P> Fe-Po> L-P> Fe-P> Al-Po> Al, Fe-P= Ca-P, and the bedrock:

Fe-Po> Al-P> Ca-P> Fe-P > Al-Po> L-P> Al, Fe-P. 98

90 64 96 84

T A B L E 3. The share o f phosphorus o f particular fraction in relation to total P Sam pl­ G enetic Total P Per cent in relation to total P

ing depth [cm ]

horizon in mg P per 100 g o f soil

L-P A l-P Fe-P Ca-P Fe-Po AJ-Po AI, Fe-P P . min Porg.

Profile No 1 1 0 -1 7 A E es 18.5 2.0 4.6 4.9 3.0 40 .0 5.9 3.6 64.1 35.9 2 5 -3 5 Ees 20 .0 1.2 2.5 1.2 0.7 45.9 1.9 1.0 54.5 45.5 3 5 - 4 0 Bh 120.0 1.5 53.6 1.2 0.7 8.7 0.6 0.5 66.9 33.1 40—49 В life 70.0 0.3 38.6 1.5 0.7 17.7 0.3 0.9 60.1 39.9 5 5 -6 5 С 20.0 0.6 42.9 2.7 1.1 41.6 1.1 1.3 91.2 8 . 8 7 5 - 8 0 С 14.0 1.2 4.4 7.8 3.1 71.2 1.5 1.1 90.4 9.6 1 1 5 -1 2 5 c ’g g 20.0 1.3 16.5 1.9 14.0 55.1 1.3 1.7 91.5 8.5 Profile No 2 8 - 1 7 Oh A 29.0 1.2 7.7 2.9 2.2 29.5 3.6 2.3 49.6 50 .4 1 7 -1 8 Ees 21.0 1.0 1.9 1.2 0.7 34.6 6.4 1.3 47.2 52.8 2 8 -3 4 Bh 105.0 1.0 52.7 1.1 0.6 8.8 2.2 0.3 66.8 33 .2 3 4 - 4 0 B hfe 5 1.0 0.5 34.7 1.1 0.3 23.0 0.9 0.3 60.8 39 .2 5 5 -6 5 С 16.0 1.2 15.9 1.6 5.1 56.6 7.2 0.68 8 8.2 11.8 1 2 0 -1 3 0 17.0 1.5 11.5 3.3 10.6 55.6 5.0 0.3 87.8 12.2

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Muterai compounds о/ phosphorus

67

P r o file 1

Fig. I. Profile No I -d istribution o f phosphorus fraction

The pattern of distribution of all forms phosphorus can be attributed to the eluvial-illuvial differentiation. Horizons Ees contain several times less phos­ phorus than horizons Bh. The difference is even more evident in the case of mineral compounds. The translocation index is about 7 for mineral compounds,

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Z). Czępińska-Kamińska

T A B L E 4. Translocation index o f phosphorus fractions

Phosphorus Profile No Phosphorus Profile No

fractions________ 1_________ 2______ fractions_________ 1_________2_ U p г в 17) ai-P o To ГУ A l-P 128.7 138.4 A l,Fe-P 3.1 1.3 Fe-P 5.6 4.5 P min 7.3 7.1 C a-P 5.2 4 .0 Porg. 4.4 3.1 Fe-P o 1.1 1.3 Pt 6.0 5.0

DISCUSSION

The pattern of the inorganic phosphorus distribution along the profile is a combined result of the proportion between particular fractions. The advanced process of podzolization has led to an eluvial-illuvial differentiation of content of all the phosphorus fractions determined. The importance of particular fractions in this process is also different.

The labile phosphorus, appearing as a consequence of mineralization of plant tissues and humus and weathering of minerals, may either be bonded by iron, aluminium and calcium [Hsu 1964; Pena, Torrent 1984; Wójcik 1990] or absorbed by plants. Therefore, the role of this form of phosphorus is less significant in the process of podzolization.

Calcium phosphates are of little significance in the studied podzolic soils. The very acidic reaction favours primary appatites dissolving and limits the secondary bonding of phosphorus ions by calcium. A significant portion of fraction Ca-P (10-14% of P total) occurs only in the bedrock.

The prevailing part of inorganic phosphorus is contained in the compounds ofironandalum inium .This is in agreement with Pokojska’s findings [Pokojska 1979]. In general, the occluded forms previal in iron phosphates, but in aluminium phosphates the non-occluded.

The trans location of phosphorus in the process of podzolization takes place in 3-element complexes: “organo acid - metal (A1 or Fe) - phosphate” [eg. Levesque 1969; Sinha 1971; Fokin, Argunowa 1974; Pokojska 1979]. The lability of phosphorus depends mainly on the solubility of the metal-organic complexes.

In the podzols studied, the highest portion of phosphorus migration from horizons O, A and Ees to horizons Bh and Bhfe, can most probably be attributed to the “fulvie acid - A1 - phosphate” complexes. The complexes of iron are less significant in the process.

The average index of translocation equals to 135 for Al-P and 5.0 for Fe-P. In the illuvial horizons, the free forms of aluminium overweight the free forms of iron. In organic compounds, fulvic acids dominate [Czępińska-Kamińska 1986]. There is also a high correlation between the amount of free forms of iron

and is only half that for or­ ganic compounds (Table 4). Within mineral compo­ unds, the n o n -occlu d ed phosphates were subject to a more intensive transloca­ tion and especially the alu­ minium phosphates (V » 130).

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Mineral compounds о/ phosphorus

69

T A B L E 5. Correlation coefficien ts betw een free Fe and free AJ content and the Fe-P and A l-P content and aluminium on one hand, and the amount of fractions Fe-P and Al-P, on the other (Table 5).

The portion of Fe-Po in phosphorus (total) is the highest as compared with other fractions. The weak within-profile differentiation of the fraction is result of a low solubility of the frac­

tion’s compounds. The high load­ ings of occluded iron phosphates in the bedrock horizons would suggest that some of them might have been carried together with the depositing mineral substrate. Therefore, those phosphates can be considered allogenic [Day et

al. 1987], while some have originated as a result of transformation of soil phosphates in genetic horizons in situ. Occluded phosphates are, according to ideas often emphasized in literature, the final result of phosphorus transforma­ tion in the long-term soil-forming processes [Walker, Syers 1976].

(x) (y) Correlation co efficien ts

Free Al content A l-P content 0.8210**

Free Fe content Fe-P content 0.8008**

n=12

(x ) - independent variable, (y ) - dependent variable, n - number o f data

CONCLUSIONS

The present study allows to draw the following conclusions:

1. The process of podzolization leads to a within-profile differentiation in amount of all fractions of phosphorus; as a result, eluvial horizons with little phosphorus and more rich illuvial ones appear.

2. The fraction of non-occluded aluminium phosphates plays the most important role in phosphorus translocation in the course of podzolization process. Least important is the fraction of occluded iron phosphates.

3. The amount of phosphorus contained in non-occluded aluminium phos­ phates is correlated with the amount of free aluminium, while the amount of non-occluded iron phosphates is correlated with the amount of free iron.

REFERENCES

BROGOW SKI Z., OKOŁOW ICZ M., 1986: R ozm ieszczenie zw iązków fosforu w glebie kopalnej, wytw orzonej z holoceńskich piasków w ydm ow ych. [Distribution o f phosphorus com pounds in fossil soil developed from holocene dune sands]. (W:) W pływ działalności człow ieka na środow isko gleb ow e Kam pinoskiego Parku Narodow ego (1 9 8 4 -1 9 8 5 ). W yd. SG G W -A R , W ar­ szawa: 1 7 9 -1 8 7 .

C H A N G S.C., JACKSON M.L., 1957: Fractionation o f soil phosphorus. S oil Sei. 84, 2: 1 3 3 -1 4 4 . C Z Ę PIŃ SK A -K A M IŃ SK A D., 1986: Z ależność między rzeźbą terenu a typami gleb obszarów

w yd m ow ych Puszczy Kampinoskiej. [Relationship between the area relief and soil types o f dune areas o f the Kampinos Primaeval Forest]. (W:) W pływ działalności człow ieka na środow isko gleb ow e K am pinoskiego Parku Narodow ego ( 1984-1985). W yd. SG G W -A R , Warszawa: 5 -7 1 . D A Y L .D .,COLLINS M.B., W ASHER N.E., 1987: Landscape position and particle size effects on

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D. Czępińska -Kam ins ка

FOKIN A .D ., A R G U N O W A W. A .,1974: Issledowanije migracii fosfora w podzolistoj p oczw ie. [A study o f phosphorus migration in podsolic soil]. P oczw ow iedien ije 4: 8 5 -9 3 .

HSU IU I., 1964: Adsorption o f phosphate by aluminium and iron in soils. S o il Sc. S o c.A m c r. Proc. 28: 4 7 4 -4 7 8 .

K O N E C K A -B E Ï'LEY K., BROGOWSKI Z., OKOŁOWICZ M., 1985: R ozm ieszczenie zw iązk ów fosforu w kopalnych glebach wytw orzonych z późnoplejstoceńskich piasków w ydm ow ych w C ięciw ie. [Distribution o f phosphorus com pounds in fossil soils developed from late pleistocene dune sands at C ięciw a]. Rocz. G lebozn. 36, 2: 7 5 -8 4 .

LEV ESQ U E M., 1969: Characterization o f model and soil organic matter-metal-phosphate com ple-. xes. C a n . ./. S o il Sc. 49, 3: 3 6 5 -3 7 3 .

PEN A F., TO RR EN T J., 1984: Relationship between phosphate sorption and iron oxides in A lfisola from a river terrace sequences o f Mediterranean Spain. G eoderm a 33, 4: 2 8 3 -2 9 6 .

PO K O JSK A I J., 1979: Geochem ical studies on podzolization. Part III. Phosphorus in podzolization. Rocz. G lebozn. 30, 2 : 1 5 3 -1 6 1 .

R ZEŚ N IO W IECKA-S U LI MIE RS К A G., CIEŚLA W., KOPER J., 1983: Badania nad glebow ym fosforem organicznym. Cz. I. Fosfor organiczny na tle zawartości C, N i S w niektórych glebach uprawnych i leśnych. [Investigations on soil organie phosphorus. Part I. Organie phosphorus and C, N and S content in som e arable and forest soils]. Rocz. Glebozn. 34, 3: 6 3 -7 4 .

S IN H A M .K ., 1971 : O rgano-m etalic phosphates. I. Interaction o f phosphorus com pounds with hum ic substances. II. Physico-chem ical characteristics o f humic and ful v ie metal phosphates. P lan t and S o il 35: 4 7 1 -4 8 3 .

W ALK ER T.W ., SY E R S J.K., 1976: The fate o f phosphorus during pedogenesis. G eoderm a 15: 1-19.

WÓJCIK J., 1990: Starzenie się fosforanów naw ozow ych w różnych glebach. [A geing o f fertilizer phosphate in different soils]. Rocz. Glebozn. 41, 1/2: 9 3 -1 1 5 .

D . C zęp ińsk a-K am ińska

WPŁYW PROCESU BIELICOWANIA NA PROFILOWE ROZMIESZCZENIE MINERALNYCH ZWIĄZKÓW FOSFORU

Katedra G lebozn aw stw a SG G W w W arszaw ie

STRESZCZENIE

W pracy przedstawiono wyniki badań nad rozm ieszczeniem mineralnych zw iązk ów fosforu w y ­ dzielonych metodą Changa i Jacksona w profilach bielic w ytw orzonych z piasków tarasu otw ockiego w Kampinoskim Parku Narodowym . Stw ierdzono, że proces bielicowania prowadzi do zróżnicow a­ nia w profilu zawartości fosforu wszystkich badanych frakcji, w wyniku czego tworzą się uboższe w ten składnik poziom y eluw ialne i w zbogacone iluwialne. Analiza w skaźników przem ieszczania w skazuje, ż e największą rolę w migracji fosforu w procesie bielicowania odgrywają nie okludowane fosforany glinu, a najmniejszą - okludowane fosforany żelaza. Ilości fosforu zw iązanego w nie okludow anych fosforanach glinu są istotnie skorelowane z zawartością w olnego glinu, a ilości nie okludow anych fosforanów żelaza z zawartością w olnego żelaza.

D r hab. Danuta Czepińska -Kamińska D epartm ent o f Soil Science

Warsaw A gricultural University-SGG W 02-528 Warszawa, Rakowiecka 26/30, Poland

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