ANTONI SZAFRANEK
PHOSPHATE SORPTION IN RELATION
TO EXTRACTABLE IRON AND ALUMINIUM
IN RUSTY SOILS
Department o f Soil Science and Soil Conservation, Warsaw University o f Technology
INTRODUCTION
A bout 29% o f Polish soils are com posed o f rusty soils. Rusty soils have been recognized and described by many authors [Kuźnicki et al. 1978a, b, B iałou sz 1978, Kuźnicki et al. 1979, Bednarek 1991, Janowska 1994, K onecka-B etley, Janowska 1996, Czępińska-K am ińska 1992]. These soils tend to be infertile, acidic with lim ited holding capacity, and dry. In som e countries (U S A ) such soils w ere cropped for a short time and then abandoned for crop production. In Poland these soils are cropped for many years and m ost o f them can not be abandoned for crop production for many reasons. In som e regions o f Poland soils o f w eak ryeland and very w eak ryeland utility com plexes cover more than 40% o f arable land. A significant decline in soil quality has occurred in these soils during the last 2 0 years. One o f the main soil degradation processes observed in Polish soils is their acidification. A cidification has widespread impact on soil quality. Soil acidifica tion causes an increase in harmful elem ents, such like aluminium, soil im p ove rishment by leaching base cations, causing a deficiency in nutrient elem ents.T he influence o f acidification on biological soil properties has been measured in several studies [Ronse et al. 1988]. Soil acidification causes am ong other things an increase in sorption or im m obilisation o f phosphorus. Phosphorus is one o f the m ost important plant nutrients and o f concern from the environm ental point o f view as w ell. Phosphorus is generally considered as the lim iting nutrient respon sible for eutrophization in ground waters, lakes and reservoirs [M oore, M iller
1994]. Yuan and Lavkulich [1994] reported that in many acidic soils, the oxides, hydroxyoxides, and oxyhydroxides o f Fe and A1 predominantly influence p hos phate sorption. The relationship between different forms o f A1 and Fe and P is important in soil m an agem en t.
The objective o f the study was to measure the effects o f different forms o f A1 and Fe and other soils com ponents on P sorption in rusty soils o f w eak ryeland
and very weak ryeland utility com plexes developed from sand, situated in the region o f K ałuszyn Upland (W ysoczyzna K ałuszyńska).
MATERIALS AND METHODS
Fifteen soil sam ples were taken in 1994 from 5 pedons to investigate their physical, chem ical and water properties. All pedons were classified as rusty soils w ith Ap, B v and B vC horizons re sp e ctiv ely [System atics o f Polish S oils 1989]. T he upper horizons are represented by com posite sam ples taken from many fields, representing the sam e soil unit. The soil material was air dried and passed through a 1 mm sieve. In all sam ples their granulometric com position, pH, exchangeable and hydrolitic acidity, exchangeable cations, cation exchange capacity, organic carbon content were determined. Soil pH was determined using a 1 : 2.5 soil - water ratio and a 1 : 2.5 1 M KC1 ratio, total С was determined by the Tiurin’s m ethod, particle-size distribution was determined by Cassagrande method, ex changeable cations were extracted by 1M amm onium acetate (N H4O A c) at pH 7.0 and determined by A AS; A l, Fe, Ca, M g, К soluble in 20% HC1 were determined by ICP; the total content o f Al, Fe, Ca, M g, К was determined by ICP after dissolution in HF [Jackson 1982]. For determining P retention - the N ew Zealand technique was em ployed [U S D A 1992]. A 5 g soil sample was shaken in 1000 ppm P solution for 24 h. The mixture was then centrifuged at 2000 rpm for 15 min. An aliquot o f supernatants was transferred to a colorim etric tube to which vanadom olybdate acid reagent was added. The percent transmittance o f the solution w as determined using colorim eter. The N ew Zealand P retention is reported as percent P retained. Alum inium and iron were determined in sodium dithionite-citrate (A ld and Fed), ammonium oxalate (A l0 and Fe0) and sodium pyrophosphate extracts (A lp and F eP) respectively and measured by FA A S [U S D A
1992], correlation between Al and Fe fraction and P sorption was calculated.
RESULTS AND DISCUSSION
A ll pedons were classified as rusty soils with Ap, B v and B vC horizons (Table 1). Rusty soils tested are strongly acidified. The acidity decreased with depth o f the profiles. T hese soils are characteristic o f a high exchangeable acidity, with alum inium playing the m ost important role. The content o f organic carbon in upper horizons is comparable with that in utility com plexes and it decreased with depth. The soils developed from sand and they contain 3-3 .5 % o f clay in Ap horizons and 1-3.5% in B v and BvC horizons. The content o f basic cations is very low w hich influences the saturation degree with base cations.
Iron and aluminium distribution
The present paper has been aimed at explaining the role o f different forms o f iron and aluminium in phosphorus sorption. Extractable iron and aluminium were determined using sodium pyrophosphate, amonium oxalate and dithionite-citrate extractens. The data are presented in Table 2. A lso, total content o f iron and aluminium as well as the content o f their 20% HC1 soluble forms are included.
T A B L E 1. S elected properties o f sam p les studied
Pro S o il H ori D epth pH С C lay Alexch. S V P sorp
file s A U C * * zon s [cm] KC1 tion
N o [%] [cm ol • k g '1] [%] [%] 5 w eak A p 0 - 2 4 3 .9 0 1.09 3.5 1.51 0 .4 8 9.3 9.5 ryeland B v 2 4 - 5 0 4 .5 5 0 .1 5 3.5 0 .7 8 0 .2 5 10.5 23.1 (6) B vC 5 0 - 7 2 4 .6 0 0 .0 6 3.5 0.61 0 .1 5 10.3 21.1 6 w eak A p 0 - 2 7 4 .2 4 0 .9 4 3 1.01 0 .6 2 15.4 12.8 ryeland A p B v 2 7 ^ 2 4 .5 0 0 .33 3 2 .3 5 0 .2 9 12.1 19.1 (6) B v 4 2 - 6 5 5.35 0 .1 8 1 0 .0 8 0 .7 6 14.6 14.5 19 w eak A p 0 -2 1 4 .0 6 1.04 3.5 1.08 0 .7 6 14.9 11.2 ryeland B v 2 1 - 5 5 3.98 0 .2 4 3.5 0 .7 8 0 .1 5 6.3 16.5 (6 ) B v C 5 5 - 7 0 4 .0 0 0 .1 8 3 0.91 0 .2 2 12.8 16.5 10 very w eak A p 0 - 2 2 4 .0 6 1.07 3 0 .8 5 0 .8 2 18.6 11.0 ryeland B v 2 2 - 4 4 4 .0 7 0 .1 9 3 0 .7 0 0 .1 9 8.1 15.5 (7) B v C 4 4 - 7 5 4 .1 8 0 .1 2 2 0 .3 9 0 .0 8 5 .2 13.3 12 very w eak A p 0 - 3 0 4 .0 6 0 .8 5 3 0 .8 7 0 .5 4 14.1 11.1 ryeland B v 3 0 - 4 5 4 .1 9 0 .1 6 2 0 .6 5 0 .1 8 9.5 13.0 (7) B vC 4 5 - 7 0 4 .2 6 0 .1 2 2 0 .43 0 .1 8 12.4 12.0
**A U C - Agriculture U tility C om plexes; S - sum o f bases; V - degree o f saturation with bases.
It was observed that in m ost cases the amount o f pyrophosphate soluble iron (Fep ) was the low est in all horizons but the dithionite-citrate soluble iron (Fed) the highest. The Fed content was the highest in Ap horizons and the low est in B vC horizons. Taking into consideration F eP and Fe0 it was observed, that only in Ap and B vC horizons amonium oxalate extracted more iron. The Fe0 average con cen tration in B v horizons is sim iliar to F ep concentration.
O nly in one case, in B v horizon, the Fe released decreasing order was as follow s: Fed > Fe0 > F e p.
Taking into consideration the content o f Al in horizons o f all pedons it is worth to note that aluminium is more m obile than Fe and it is displaced from Ap into B v horizons [K uźnicki,Skłodow ski 1970;M okm a 1991;E vans 1988;B ednarek 1991; Pokojska 1979]. In all cases the greatest concentration o f A lp and A l0 was observed in B v horizons. A l0 as w ell as A lp peaked in B v horizons but then declined in B vC horizons. In most cases the differences between pyrophosphate and oxalate extractable Al in Ap as w ell as in B v and BvC horizons are relatively sm all. It m eans that am ong different fractions there dominates pyrophosphate Al bounded to the humus com plexes o f soil [Evans 1988]. Dithionite-citrate is not the best extrahent for crystalline forms and extracted less Al in regards to oxalate and pyrophosphate [M olina et al. 1991; M elke 1997; Mokma, Buurman 1982]. In som e cases, the A ld concentrations were low er than AI0 concentrations.
The highest amount o f forms soluble in 20% HC1 and determined in HF occurred in B v horizons and declined in B vC horizons. More than 20% in average o f total Fe (Fet ) and 26% o f soluble in 20% HC1 Fe (FeHC1) in Ap horizons occur in pyrophosphate forms which means that they are bound into humus com plexes (Table 3). Sodium pyrophosphate as w ell as ammonium oxalate extracted small amount o f aluminium. Only a little more than 9% o f total aluminum (A lt) occur
T A B L E 2. Iron and alum inium distribution in p ed on s [m g • k g '] Pro file s N o H ori zo n s F e P * 4 A 1p 4 A ld A1t Fer c HCl A ^HC1 5 A p 611 8 3 0 1099 1031 8 8 0 77 9 3 5 0 4 10366 2 2 7 7 3 6 5 8 B v 4 1 8 231 376 2 2 1 0 1705 1317 3 9 8 7 13837 2 7 7 0 7 0 7 8 B vC 3 4 0 2 1 0 401 1312 1222 85 2 2941 10725 1805 4 0 0 9 6 A p 4 3 7 4 7 7 571 959 1004 659 1967 8 1 4 9 1360 2521 B v 661 52 2 677 1703 1616 1015 2 6 4 7 10811 1761 4 2 7 5 B v C 961 941 1052 1001 991 889 2 8 1 7 9 4 9 0 1910 2 5 6 0 19 A p 6 1 7 1083 1311 803 1054 671 3 4 6 4 10542 2 9 2 5 3 6 0 0 B v 8 9 2 1203 1341 1243 1665 1140 4 2 1 3 1 3 040 3 4 0 0 2 5 5 0 B v C 2 5 0 3 6 0 7 2 6 551 1322 601 3 1 0 7 11023 2 6 5 0 3 6 5 0 10 A p 703 898 1311 65 2 773 58 4 2 6 1 0 7 5 2 9 2 4 5 0 2 5 2 5 B v 9 1 2 851 1327 1092 1442 1090 3 2 0 9 8 7 2 4 3 0 0 0 3 9 0 0 B v C 3 7 0 3 9 0 738 731 951 701 2 4 0 4 8 5 1 4 1900 2 5 5 0 12 A p 52 7 7 1 2 1097 667 812 5 6 4 2 7 0 9 8 4 2 8 2 2 5 0 2 1 7 5 B v 521 461 1002 972 9 5 2 927 2 4 0 5 8 1 1 6 2 3 5 0 3 2 5 0 B v C 2 8 0 3 6 0 7 0 0 581 84 0 5 5 0 2 5 0 4 90 1 3 2 0 0 0 2 4 5 0 A ll A p 57 9 8 0 0 1078 822 90 4 651 2851 9 003 2 2 5 2 2 8 9 6 p e B v 681 6 5 4 945 1444 1476 1098 3 2 9 2 10906 2 6 5 6 4211 don s B v C 4 4 0 4 5 2 723 835 1065 719 2 7 5 4 9 753 20 5 3 3 0 4 4 S o il A p 555 7 9 7 9 9 4 931 979 703 2 9 7 8 96 8 5 2 1 8 7 3 2 6 0 A U C B v 65 7 6 5 2 798 1719 1662 1157 3 6 1 6 12563 2 6 4 4 4 6 3 4 (6) B v C 5 1 7 5 0 4 7 2 6 955 1178 781 2 9 5 5 10413 2 1 2 2 3 4 0 6 S o il A p 615 805 1204 66 0 7 9 2 57 4 2 6 6 0 7 9 7 9 2 3 5 0 2 3 5 0 A U C B v 71 7 6 5 6 1165 1032 1197 1009 2 8 0 7 8 4 2 0 26 7 5 35 7 5 (7) B vC 325 375 719 656 896 62 6 2 4 5 4 8 7 6 4 1950 2 5 0 0
Fcr Alt - analyzed by HF digestion; FeHCI Al 11C, - soluble in 20% HC1; p - pyrophosphate extract; о - am monium oxalate cxtract; d - dithionite-citrate extract.
in Ap horizons in humus com plexes. Am m onium oxalate extracted a small amount o f amorphous aluminium. Bv horizons contain about 4% more aluminium which is either organically bound or occurs in amorphous forms. Fep averaged 25.7% o f F eH C 1 in Ap horizons, 25.6% in Bv and 21.4% in B vC respectively. This order seem s sim iliar to that for Fe0 and Fed. The data show us once again that the different extractable forms o f iron after weathering o f parent material do not m ove d ow n ward and remain in the horizons. Quite different situation is observed in relation to aluminium. A lp averaged 28.4% in Ap horizons and respectively 34.3% in Bv and 27.4% in BvC. Taking into consideration A l0, only significant difference occurs between Ap and Bv horizons.
Phosphorus sorption
M ost o f rusty soils used in agricultural production are characteristic o f very low levels o f available phosphorus. Recent research conducted on rusty soils situated
T A B L E 3. Iron and alum inium extractable / F e,A l total and Fe, A l so lu b le in 20% HC1 ratios C o m p lex H orizon s F e p /F e t F e p/ F e HCl F e 0/F e t F e 0/F e HCi F e d /F e t ' F e d/F e HC1 A lp/A lt А 1 р/ А 1 НС1 A l0/A lt A 1 o/ A 1 HCI A V A it A 1 c / A l HCI A ll ped on s A p A p B v , B v B v C 2 0.3 2 5 .7 28.1 3 5.5 3 7.8 4 7 .9 9.1 2 8 .4 10.0 3 1 .2 7 .2 22.5 2 0 .7 2 5 .6 19.9 2 4 .6 28 .7 3 5 .6 13.2 34.3 13.5 35.1 10.1 26.1 16.0 2 1 .4 16.4 2 2 .0 2 6 .2 3 5 .2 8 .6 2 7 .4 10.9 3 5 .0 7.4 2 3 .6 W eak A p 18.6 2 6 .8 3 3 .4 9 .6 10.1 7.3 ryeland 2 5 .4 3 6 .4 4 5 .4 2 8 .6 3 0 .0 2 1 .6 co m p lex A p B v , B v 18.2 18.0 22.1 13.7 13.2 9.2 2 4 .9 2 4 .7 3 0 .2 37.1 3 5 .9 2 5 .0 B v C 17.5 17.1 2 4 .6 9 .2 11.3 7.5 2 4 .4 2 3.8 34 .2 2 8 .0 3 4 .6 2 2 .9 V ery A p 23.1 30.3 4 5 .3 8.3 9.9 7.2 w eak 2 6 .2 34.3 5 1 .2 28.1 3 3 .7 2 4 .4 ryeland B v 2 5.5 23 .4 4 1 .5 12.3 14.2 12.0 c o m p lex 2 6 .8 24.5 4 3 .6 2 8 .9 3 3 .5 2 8 .2 B vC 13.2 15.3 29.3 7.5 10.2 7.1 16.7 19.2 3 6 .9 2 6 .2 3 5.8 2 5 .0
in the region o f K ałuszyn Upland shows moderate content o f available phosphorus. In 6 Agriculture Utility C om plexes ( 6 A U C ) the content o f available phosphorus averaged from about 12 mg P205 per 100 g o f soil in Ap horizons down to 8 mg in subsoil. It is interesting to add that the content o f available phosphorus for 7 A U C in Ap horizons was higher and averaged about 15 mg in Ap horizon and about 11 m g in B v horizons. To investigate the capacity for binding phosphate the N ew Zealand technique described above was used. Precipitation or phosphorus sorption o f Al and Fe is recognized as an important reaction leading to phosphate retention by acid soils [Gebhardt, Colem an 1974]. The effect o f different forms o f Fe and Al oxides on phosphorus sorption o f rusty soils was investigated. A ccording to the N ew Zealand method, phosphorus retention is determined as percent o f phosphorus retained by soil. The data characterizing phosphorus sorption o f rusty soils are presented in Table 4.
The low est phosphorus sorption was observed in Ap horizons and it accounted to about 11%. This means that about 11 % on average o f 1000 mg • kg- 1 P solution has been sorbed by the soil in Ap horizons or about 15.5% in average in B vC horizons. The low est phosphorus sorption in Ap horizons has been caused by the migration o f aluminium, into deeper horizons as w ell as plow ing, the latter had resulted in m ixing o f the A horizon with those o f E and Bv. M ost o f Polish podzols were developed under forest vegetation and later cleared for cropping. Sim iliar results for phosphorus sorption have been obtained from the M ichigan spodosols. N o more significant differences were observed between similar soils and respec tive horizons. The highest amount o f phosphorus sorbed was observed in Bv horizons. The phosphorus sorption is higher in pedons representing weak ryeland com plex and it increases with the increasing in iron and aluminium content (Table
T A B L E 4. P hosp horus sorption in Agricultural U tility C o m p le x e s (A U C ) [%]
H orizons R yeland utility com plexes Average
W eak ryeland (6) Very weak (7) 6 A U C
7 A U C
All pedons Profil 5 Profil 6 Profil 19 Profil 10 Profil 12
Ap 9.5 12.8 11.5 11.0 11.1 11.2 11.0 11.2
Bv 23.1 19.1 16.5 15.5 13.0 19.6 14.3 17.4
BvC 21.1 14.5 16.5 13.3 12.0 17.4 12.7 15.5
5). T he retention o f phosphorus by soils correlated with several properties, e.g. extractable A1 and Fe, Fet A lt, F eHC1, A1H C 1 c o n te n t.
T able 5 show s that A l0 correlated best with the sorption o f phosphorus; then cam e A lp and Alp+Fe„ ( r - 0.61) (data not included). In som e cases iron correlated very strongly with phosphorus sorption. Both total and soluble in 20% HC1 A1 correlated very w ell with phosphorus sorption. It is interesting that also m agne- zium (data not included) correlated very highly with phosphorus sorption.
In many acid soils, the oxides, hydroxides, and oxyhydroxyoxides o f alum i nium predominantly influence phosphate sorption [Yuan, Lavkulich 1994; Zawar tka, H uszcza-C iołkow ska 1989] and the relationship between P sorption may be important from the point o f view o f soil managem ent [Yuan, Lavkulich 1994]. The A l-organic matter com plexes have a significant sorption capacity. A ny change in organic matter dynam ics resulting from either environmental factors or mana gem ent practices (acid rain, lim ing or fertilization) will affect P sorption capacity and behavior o f Al, controlling thus the availability o f P. It is difficult to say which form o f iron or aluminum influences P sorption. The low pH values measured in KC1 (pH < 4 .0) in all investigated profiles indicate that organically bound Al is responsible for the P sorption [ Evans 1988]. The effect o f A lcxch on P sorption was considered as w ell, but it was found to be negatively correlated with P sorption. The amount o f Al exchangeable o f rusty soils was rather small compared with other AI fractions and it decreased with the depth, show ing the highest values in Ap horizons. Am m onium oxalate extracted a little more or quite the sam e amount o f aluminium and iron as w ell. The (A1H-A l p) content is rather sm all, what means that P sorption can be related first o f all to A lp but in a small degree to amorphous material as w ell. Those cations realesed during weathering processes can form organo m etalic com plexes binding soluble forms o f phosphorus [M okma, Buur- man 1982; M okma 1991; Evans 1988]. On the the other hand, som e organic acids that form stable com plexes with Al should, theoretically, increase P desorption [Fox et al. 1990]. The relationship between organically com plexed fraction parameters may be important in soil management, since the organically com plexed
T A B E L A 5. C orrelation cocl'ficicn ts (/•) betw een P retention and content o f differen t form s o f Fe and Al Item F C P * 4 F‘ d A 1 P A1o A 1 c F e t F e HCl A1t A I HC1 P sorption A ll pedon s - 0 .1 1 - 0 .4 6 - 0 .6 0 0.78 0 .8 2 0 .7 0 0 .3 6 0 .0 8 0 .6 8 0 .7 2 6 -S o il A U C - 0 .3 0 - 0 .6 4 - 0 .6 8 0 .7 2 0 .7 8 0 .6 6 0 .1 7 0.03 0 .6 0 0 .6 5 7 -S o ilA U C 0 .4 5 0.01 0.13 0 .8 4 0 .95 0 .9 0 0.55 0 .5 4 0 .4 4 0 .88
fraction is sen sitive to m anagem ent practices change [Yuan, Lavkulich 1994]. Y uan and Lavkulich [ 1994] have tested tw o European m odels that relate P sorption capacity to oxides o f Al and Fe. They tested Borggaard’s m odel w ho found that P sorption m axim um was significantly correlated with poorly crystalline Fe and Al oxides and w ell-crystallized Fe oxides. They were also testing another m odel, proposed by van der Z ee and van Riem sdijk, describing P sorption capacity as function o f amorphous Fe and Al (Fe0+ A l0). According to Yuan and Lavkulich [1994] this kind o f m odels is very useful in monitoring soil and environm ental quality for sustainable d ev elo p m en t.
CONCLUSIONS
1. D ifferent extractable forms o f iron after weathering o f parent material do not m ove downward and remain in the original horizons. Quite different situation is observed in relation to aluminium
2. A lum inium is more m obile than Fe and it is displaced from Ap into B v horizons. 3. The low est P sorption was observed in Ap horizons and it accounts about 11%. 4. The phosphorus sorption is higher in pedons representing weak ryeland com plex and it increased with increasing the content o f different forms o f iron and aluminium.
5. A ny change in organic matter dynam ics resulting from either environmental factors or managem ent practices (lim ing or fertilization) w ill affect P sorption capacity and the reaction with Al w ould lead to lim ited P availability.
6 . T he soil property best correlated with P sorption for all pedons is A l0 fo llo w ed by Alp.
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A. Szafranek
SORPCJA FOSFORANÓW W GLEBACH RDZAWYCH
W RELACJI DO EKSTAHOWANEGO GLINU I ŻELAZA
Zakład Gleboznawstwa i Ochrony Gruntów Politechniki Warszawskiej
STRESZCZENIE
Jednym z głów nych procesów zachodzących w polskich glebach jest zakw a szenie. Zakw aszenie oddziałuje m iędzy innymi na wzrost zawartości w glebie różnych form żelaza i glinu, które m ogą w pływ ać na w ielk ość sorpcji dostarczo nego do gleby fosforu. C elem badań było określenie w pływ u różnych form żelaza i glinu na sorpcję fosforu w glebach rdzawych w ytw orzonych z piasków zalicza nych do kom pleksu żytniego słabego oraz bardzo słabego p ołożonych na W yso- czyżn ie Kałuszyńskiej. Zaobserwowano, że w e w szystkich poziom ach najmniej żelaza zostało wekstrahowane za pom ocą pirofosforanu sodu, natomiast najwięcej w wyniku zastosow ania cytrynianu sodu z ditionitem. Stwierdzono, że glin jest bardziej m obilny i przem ieszcza się do p oziom ów Bv. N ajw iększa koncentracja A lp i A l0 w ystąpiła w poziom ach Bv. Najmniej fosforu, średnio 11 %, zasorbowały poziom y Ap. W poziom ach B v i BvC gleb zaliczanych do kom pleksu żytniego słabego sorpcja fosforu była w iększa. Jest to zw iązane głów n ie z w ięk sza zawar tością różnych form glinu. W ielkość sorpcji w p oszczególnych poziom ach g en e tycznych najlepiej była skorelowana z zawartością glinu - A l0, a następnie A lp. W e w szystkich przypadkach zawartość różnych form żelaza była ujem nie skore lowana z w ielk ością sorpcji. Zarówno glin rozpuszczalny w 20% HC1, jak i całkow ita je g o ilość były w ysoko skorelowane z sorpcją fosforu.
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