soil acidity indices in east lithuania

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Soil Acidity Indices in East LithuaniaS. Marcinkonis a b , C. A. Booth a , M. A. Fullen c & L. Tripolskaja ba School of Engineering and the Built Environment , University ofWolverhampton , Wolverhampton, United Kingdomb Voke Branch of the Lithuanian Research Center for Agriculture andForestry , Vilnius, Lithuaniac School of Applied Sciences , University of Wolverhampton ,Wolverhampton, United KingdomPublished online: 27 Jun 2011.

To cite this article: S. Marcinkonis , C. A. Booth , M. A. Fullen & L. Tripolskaja (2011) Soil AcidityIndices in East Lithuania, Communications in Soil Science and Plant Analysis, 42:13, 1565-1580, DOI:10.1080/00103624.2011.581720

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Communications in Soil Science and Plant Analysis, 42:1565–1580, 2011Copyright © Taylor & Francis Group, LLCISSN: 0010-3624 print / 1532-2416 onlineDOI: 10.1080/00103624.2011.581720

Soil Acidity Indices in East Lithuania

S. MARCINKONIS,1,2 C. A. BOOTH,1 M. A. FULLEN,3

AND L. TRIPOLSKAJA2

1School of Engineering and the Built Environment, University of Wolverhampton,Wolverhampton, United Kingdom2Voke Branch of the Lithuanian Research Center for Agriculture and Forestry,Vilnius, Lithuania3School of Applied Sciences, University of Wolverhampton, Wolverhampton,United Kingdom

In Lithuania, decades of regular soil liming ceased in 1990. At present, ∼18.7% ofLithuanian agricultural land is acidic and ∼1 million ha are at risk of chemical degra-dation by acidification. Intrasite observations of long-term experiments (monitoredfor >30 years) provide valuable datasets that allow evaluation of current soil con-ditions and enable landscape-scale acidification modelling. Acidic soil properties, soilacidity indices, and their response to liming practices are important issues that mustbe addressed to maintain the ecological functions of these acidifying agricultural land-scapes. An experiment was conducted that involved four liming strategies based on twodirect and two indirect lime requirement (LR) determination methods. These strategiesare common practices, both generally and in the Baltic States. Results indicate the effectof soil liming on soil acidity indices significantly (P < 0.05) differ between the chosenLR determination method and soil acidity gradations.

Keywords Acidity gradations, acidity indices, field experiments

Introduction

In the mid-1960s, ∼41% of Lithuanian soils were acidic [pH in potassium chloride(KCl) ≤ 5.5]. By the 1990s, ∼19% of agricultural lands remained acidic, but this trendis reversing and it is now estimated that ∼1 million ha are undergoing acidification pro-cesses (Mazvila et al. 2004). This is partly a reflection of the climate, as Lithuania has ahumid temperate climate. Furthermore, local arable soil characteristics often promote neg-ative soil calcium (Ca) and magnesium (Mg) balances, with a mean of ∼110 kg ha−1 Caand ∼46 kg ha−1 Mg lost annually by leaching (Marcinkonis 2006). Vos and van der Putten(2004) reported nitrate (NO3)–nitrogen (N) concentrations correlate with Ca concentrationand to a lesser extent with Mg and potassium (K), indicating that these three ion species pri-marily leach in combination with nitrate. Soil liming is widely acknowledged as the mosteffective approach for improving acidic soil properties, preventing associated environmen-tal degradation, and maintaining crop production (Haynes 1984; Smal 1993; Gouldingand Blake 1998; Bolan, Adriano, and Curtin 2003; Lydersen, Löfgren, and Arnesen 2002;

Received to November 2009; accepted 11 February 2011.Address correspondence to Dr. S. Marcinkonis, Voke Branch of the Lithuanian Research

Center for Agriculture and Forestry, Zalioji a.2, Traku Voke, LT-02232, Vilnius, Lithuania. E-mail:[email protected]

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1566 S. Marcinkonis et al.

Matula and Pechova 2002; Hajkowicz and Young 2005). For instance, long-term fieldexperiments in eastern Lithuania have demonstrated that limed soils attain greater cropyields, support more crop varieties, and produce better and higher quality perennial grasses(Eidukevichene et al. 2001; Tripolskaja and Marcinkonis 2005; Tripolskaja, Marcinkonis,and Eidukeviciene 2009).

Soil fertility and the associated economic benefits of liming are emphasized, oftenwithout due attention to its important environmental role, such as liming, which counteractsthe acidifying inputs of sulfur (S) and N compounds from fertilizers and the atmosphere(Lundell, Johannisson, and Hogberg 2001). Moreover, liming can help prevent the uptakeof radionuclides and heavy metals by plants and decrease pollution risk to soils andgroundwater (Goulding and Blake 1998; Eidukeviciene and Vasiliauskiene 2001).

Natural soil acidity strongly influences the decomposition and mineralization oforganic matter in limed soils (Hu, Tang, and Chen 2006). However, liming can enhancenutrient leaching and influence the availability and mobility of plant nutrients for decadesafter application (Curtin and Smillie 1986). There are known linkages between pHand calcium carbonate (CaCO3) supply and soil solution concentrations of arsenic,bromine, molybdenum, sulfur, antimony, selenium, uranium, and tungsten and, to a lesserextent, cobalt, chromium, mercury, magnesium, and strontium (Tyler and Olsson 2001).Furthermore, outflows from limed soils typically contain ∼45% more dissolved organicmatter than nonlimed soils (Karlik 1995).

A historical perspective is helpful when considering agricultural land-use dynamics.Before the 1960s, lime was manually hand-sown because machinery was unavailable, andconsequently, large-scale liming was not feasible. However, as in other Eastern Europeancountries, since the 1960s increased use of mineral fertilizers provided greater crop yieldsbut also brought about unfavorable changes in land use and cropping patterns that promotedacidification (Bouma, Varallyay, and Batjes 1998). Following the introduction of large-scale agricultural machinery (1965–1990) and the adoption of soil liming technologies, thesituation stabilized. Agricultural soils with pH values of <5.5 were regularly limed (a min-imum of three times and 1965–1990), thus decreasing the total acidic soil area from 40.7%to 18.6% of Lithuanian agricultural land (Mazvila, Adomaitis, and Eitminavicius 2004). Inthe 1970–1980s, ≤200,000 ha of acidic soils were limed annually. However, since 1990,liming has virtually ceased. For instance, during the past 15 years just several thousand hahave been limed. Consequently, intensive acidification of formerly limed soils is returningthese soils to their original acidity levels (Mazvila, Adomaitis, and Eitminavicius 2004;Eidukeviciene et al. 2010).

Nowadays, former large-scale agricultural fields have become fragmented because ofrecent land-use changes and the regularity and intensity of liming and fertilizer inputs(Tripolskaja and Marcinkonis 2005). Soils with diverse land use and vegetation cover havevery diverse soil chemical properties, even at relatively small scales. Thus, chemical degra-dation is complex and, moreover, fragmented patterns exist at both regional and nationalscales (Eidukeviciene et al. 2007).

Lithuanian soil acidification is accelerating and, thus, putting many soils at riskof chemical degradation (Mazvila, Adomaitis, and Eitminavicius 2004; Tripolskaja,Marcinkonis, and Eidukeviciene 2009). National cessation of liming agricultural land willdecrease soil pH and increase metal solubility, which could lead to a potential chemi-cal time bomb (Hesterberg, Stigliani, and Imeson 1992). Furthermore, the fragmentationof large-scale agricultural practises and economic restructuring has meant stagnation insoil liming research and concomitantly impaired knowledge of current soil variabilitypatterns.

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Soil Acidity Indices in East Lithuania 1567

Economic changes, together with new environmental regulations, have opened freshdebate on acidic soil use. Many previous soil acidity management strategies do not meetcurrent requirements, in terms of continuous soil acidity regulation, based on complexagronomy, land use, environmental protection principles, and concepts of integrated eval-uations of landscape acidification (Tripolskaja, Marcinkonis, and Eidukeviciene 2009).Selection criteria for lime requirements and optimum lime rate determinations to maxi-mize ecological and economic efficiency are important issues to maintain the ecostabilityand fertility of acidifying soils and, therefore, better models for calculating lime loss andlime requirement are needed (Goulding and Blake 1998).

In a attempt to provide insights into these issues, an experiment was conducted atthe Voke branch of the Lithuanian Institute of Agriculture (2002–2006) that involved fourliming approaches commonly adopted in the Baltic States and elsewhere. Futhermore, soilacidity indices were determined to reveal those parameters most appropriate for soil limingrequirements.

Materials and Methods

Site Description and Previous Site Experiments

The Voke branch of the Lithuanian Research Center for Agriculture and Forestry(N 54◦ 34′ 52′′, E 25◦ 07′ 47′′) is located on the Lentvario-Senuju Traku fluvio-glacialplateau of eastern Lithuania. The climate is continental, with a mean annual precipitationof 677 mm and a mean temperature of 5.7 ◦C.

Experimental field plots (n = 80), each measuring 44 m2 (4 × 11 m), were desig-nated in 1972–1973, and subsequent trials were conducted in accordance with standardapproaches (Tonkunas 1957; Little and Hills 1978). Their establishment was on sandy loam[62–65% sand (0.05–2.0 mm), 33–36% silt (0.002–0.05 mm), 1–2% clay (<0.002 mm)(in soil profile 0–1.30 m, each soil horizon sampled)], carbonaceous fluvio-glacial gravelsoils (effervescence present at 0.60–0.80 m), Haplic Luvisols (LVh) according to theFAO-UNESCO classification (FAO/ISRIC/ISSS 1998). This is the principal regionalarable soil and is typified by low soil organic-matter content (1.6–2.0% humus), initialstrong acidity (pHKCl < 4.5), and low plant-available P and K (100–150 mg kg−1) contents.At the initiation of experiments, lime requirements were calculated and applied accordingto the soil potential acidity (PAC). The primary soil liming (dust limestone agent, with95–98% CaCO3) was conducted in 1972 and 1973. This treatment was repeated (cycles of5–10 years) at various treatment rates. Liming efficiency was tested in crop rotations with50% cereals. Mean mineral fertilizer rates were N 30–60; phosphorus pentoxide (P2O5)30–60; and potassium oxide (K2O) 60 kg ha−1 active matter.

Current Site Experiments

The field site was originally designed in 1972. However, in 1996, to minimize the effectof soil transport between plots, buffer borders were widened 1 m (to 5 m in total). Newexperimental field plots (n = 48), each measuring 30 m2 (3 × 10 m), were created in2002. Treatments were grouped into a two-factorial experimental arrangement, whereby12 treatments were randomly arranged into three acidity levels (factor A) and lime ratesdetermined by four lime requirement (LR) methods (factor B) (Figure 1). The methodswere (i) to neutralize mobile Al (LR-MAL); (ii) to neutralize part of potential acidityaccording to Nebolsin (LR-N); (iii) to neutralize part of potential acidity according to a

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Figure 1. Experimental design.

modified Adams–Evans method (LR-AE); and (iv) to lime according to base saturation(LR-BS) (Table 1). Replications were distributed between four randomized blocks andtested at three acidity levels.

Neutralization liming to target potential acidity levels (at optimum pH) was proposed(Neboljsin and Neboljsina 1997), and the modified classical Adam–Evans method was

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Tabl

e1

Met

hods

oflim

ere

quir

emen

tdet

erm

inat

ion

Met

hod

and

intr

oduc

tion

Det

erm

inat

ion

equa

tion

Neu

tral

izin

gm

obil

eA

l(L

R-M

AL

).R

esul

tsof

expe

rim

ents

expl

orin

gth

ero

leof

mob

ileal

umin

umin

soil

acid

ityen

cour

age

deve

lopm

ento

fne

wso

illim

ing

conc

epts

.The

yar

eba

sed

onpr

esum

ptio

nsth

atth

eam

ount

oflim

ing

mat

eria

lsto

neut

raliz

em

obile

Ale

xtra

cted

inne

utra

lunb

uffe

red

solu

tions

,lik

eK

Cl,

shou

ldbe

appl

ied.

LR

-MA

L=

MA

L×5

×10×

3×10

6

109

=M

AL

×0.

15w

here

MA

Lis

mob

ileal

umin

um(m

eqkg

−1),

5is

CaC

O3

tone

utra

lize

1m

eqkg

−1in

soil,

109

isco

effic

ient

totr

ansf

erm

gto

t,an

d3

×106

ism

ass

ofar

able

laye

r(k

gha

−1).

Neu

tral

izin

gpa

rtof

pote

ntia

laci

dity

acco

rdin

gto

Neb

oljs

in(L

R-N

).Ty

peof

crop

rota

tion,

hydr

olog

ical

cond

ition

s,so

ilte

xtur

e,bu

lkde

nsity

,thi

ckne

ssof

the

arab

lela

yer,

soil

orga

nic

mat

ter

(SO

M),

amou

ntof

avai

labl

eP 2

O5,a

ndse

vera

lph

ytot

oxic

elem

ents

(Al,

Mn,

and

Fe)

are

estim

ated

inca

lcul

atio

ns.C

alcu

late

dlim

era

tere

quir

edto

neut

raliz

epa

rtof

harm

fulp

oten

tials

oila

cidi

ty.T

his

part

isca

lcul

ated

asdi

ffer

ence

betw

een

pote

ntia

laci

dity

atop

timal

pHle

vela

ndat

actu

alpH

leve

l.

LR

-N=

( lnpH

optim

al−

lnpH

actu

al

) ×M

hw

here

Mis

the

free

coef

ficie

nt(M

=5

bKd)

,b

isth

eco

effic

ient

ofre

gres

sion

,K

isth

eco

effic

ient

ofco

rrec

tion,

5is

the

tran

sfor

mat

ion

coef

ficie

ntfr

omm

eqto

tC

aCO

3,a

ndh

isth

ede

pth

ofth

ear

able

laye

r(m

).

Neu

tral

izin

gpa

rtof

pote

ntia

laci

dity

acco

rdin

gto

mod

ified

Ada

ms–

Eva

nsm

etho

d(L

R-A

E).

From

four

lime

requ

irem

entd

eter

min

atio

nm

etho

dsus

edin

the

Uni

ted

Stat

es(W

oodr

uff

1948

,Sho

emak

er,M

cLea

n,an

dPr

att(

SMP)

1961

,Meh

lich

1976

,Ada

ms

and

Eva

ns19

62),

the

last

one

ism

osts

uita

ble

for

low

sorp

tion

soils

with

pHle

vel≤

6.5.

Thi

sm

etho

dof

LR

dete

rmin

atio

nis

base

don

empi

rica

lrel

atio

nshi

psbe

twee

npH

and

acid

ifyi

ngca

tions

inso

ilso

rptio

nca

paci

ty.T

hem

etho

dis

desc

ribe

dby

Ada

ms

and

Eva

ns(1

962)

.We

mod

ify

the

dete

rmin

atio

nof

lime

rate

acco

rdin

gto

actu

alva

lues

ofto

talc

atio

nex

chan

geca

paci

ty(T

CE

C)

and

pote

ntia

laci

dity

.The

pote

ntia

laci

dity

atop

timal

pHle

veli

sde

term

ined

byre

gres

sion

equa

tions

base

don

our

earl

ier

expe

rim

enta

lres

ults

from

the

sam

esi

te.

1.T

heac

idsa

tura

tion

atth

eor

igin

also

ilpH

(X1)

and

atth

eta

rget

pH(X

2)

com

bine

dw

ithC

EC

are

used

toca

lcul

ate

the

amou

ntof

the

pote

ntia

laci

dity

(�PA

C)

that

isto

bene

utra

lized

�PA

C=

T×

(X1−

X2).

2.L

R-A

E=

�PA

C×

0.15

whe

re0.

15is

the

CaC

O3

tone

utra

lize

1m

eqkg

−1in

soil.

(Con

tinu

ed)

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Tabl

e1

(Con

tinue

d)

Met

hod

and

intr

oduc

tion

Det

erm

inat

ion

equa

tion

Neu

tral

izin

gso

ilac

idit

yac

cord

ing

toba

sesa

tura

tion

(LR

-BS)

.R

ate

oflim

ing

mat

eria

lsho

uld

assu

resa

tisfa

ctor

yle

velo

fso

ilba

sesa

tura

tion.

Acc

ordi

ngto

requ

irem

ents

inL

ithua

nia

soil

shou

ldbe

limed

ifba

sesa

tura

tion

leve

lis<

70%

.A

chie

ving

ahi

gher

leve

lof

soil

base

satu

ratio

nis

ofte

nir

ratio

nal.

LR

-BS

=[ A

B(B

S_re

quir

edB

S_in

itial

−1] ×

0.15

)w

here

AB

is

the

amou

ntof

abso

rbed

base

s(m

eqkg

−1),

BS_

initi

alis

the

initi

alle

velo

fso

ilB

S%,

BS_

requ

ired

isth

ere

quir

edle

velo

fso

ilB

S%,

0.15

isth

eC

aCO

3to

neut

raliz

e1

meq

kg−1

inso

il.

1570

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Table 2Scheme of soil acidity ranges

Acidity Mobile Al Potential acidity Baselevels pHKCl (mg kg−1) (meq kg−1) saturation (%)

1 <4.5 >50 >40 <552 4.5–5.0 10–50 30–40 55–703 >5.0 <10 <30 >70

used. Both methods are indirect methods of determining LR. Quantities of lime required,to neutralize mobile Al (MAL) and achieve the required base saturation (BS) level, wereselected as direct LR measurements.

Soil acidity properties are presented, where soil acidity levels are indicated by pHKCl,mobile Al (MAL), potential acidity (PAC), and base saturation (BS) (Table 2). The firstlevel indicates the initial soil acidity state (or soil acidity restoration limits). The third levelindicates the sustainable soil acidity management level on light-textured Luvisols (sandsand loamy sands). The second level presents transitional soils between the previous two.The physical amounts of applied dust limestone are also reported (Table 3).

Before field cultivation and sowing ammonium nitrate, superphosphate and potas-sium chloride were sown according to crop requirements. Crop rotation and fertilizationprotocols are presented (Table 4).

Sample Collection and Laboratory Analyses

Soil samples were taken from the arable layer (0–20 cm deep) of all the plots at thebeginning (spring 2002) and end (autumn 2006) of the field experiment. Soil pH wasestimated potentiometrically after equilibration with 1 N potassium chloride (KCl) solution.Mobile aluminium (Al) was determined by the Sokolov method (Yagodin, Derjugin, andZhukov 1987), after extraction with 1.0 N KCl solution. A suitable aliquot was titratedwith 0.01 N sodium hydroxide (NaOH) using phenolphthalein as the indicator for thedetermination of exchangeable acidity (EAC). In a second aliquot, the acidity from H+ ionswas determined by the same titration, after precipitation of aluminum (Al3+) ions with 3.5%

Table 3Physical amount of required liming materials in active matter and as

percentage of LR-MAL

Soil acidity graduations

Level 1 Level 2 Level 3Applied LRdeterminationmethod t ha−1 % t ha−1 % t ha−1 %

LR-MAL 1.0 100 0.5 100 0.10 100LR-N 4.7 470 4.8 960 3.70 3700LR-AE 2.2 220 1.7 340 0.60 600LR-BS 1.7 170 1.5 300 0.00 0

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Table 4Crops and their fertilization protocols

Crops N (kg ha−1) P2O5 (kg ha−1) K2O (kg ha−1)

1. Buckwheat (Fagopyrum esculentum) 15 30 302. Spring wheat with red clover undersow

(Triticum aestivum with Trifoliumpratense)

60 30 40

3. Red clover (Trifolium pratense) 0 30 604. Winter triticale (Triticosecale) 90 30 355. Spring rape (Brassica napus) 100 45 55Total 265 165 200

sodium fluoride (NaF). The quantity of mobile Al was calculated as the difference betweenthe first and second titrations. The sum of absorbed bases (AB) was determined by theKappen–Hilkovitz method. Soil (20 g) was extracted with 100 ml 0.1 N hydrochloric acid(HCl) solution for 1 h and titrated with 0.1 N NaOH solution until a solution, containingphenolphthalein, developed a weak red color. To determine potential acidity (PAC), usingKappen (GOST 26212-91), soil samples were treated with 1.0 N Na acetate (CH3COONa3H2O) solution. As before, the formed filtrate was titrated with 0.1 N NaOH until a solution,containing phenolphthalein, developed a weak red color or until pH 8.2 was reached. Totalcation exchange capacity (TCEC) was then computed from both the potential acidity andsum of absorbed base values, and the base saturation was expressed as a percentage of TCEC.

Data Analysis

All data were collated and statistically processed using the descriptive statistic tools, treatedby employing the Fisher’s criteria (F) and LSD (least significant difference) (Little andHills 1978), and the effects of liming and soil acidity levels on soil acidity indices wereanalyzed by correlation–regression methods.

Results

Changes in Soil Acidity Indices

Initial soil pH data (1972–1973) before regular liming was low (4.2–4.4). At the estab-lishment of this experiment (2002), pH in some treatments was notably higher (4.5–6.3)depending on liming intensity.

Soil acidity data [in the fifth year (2006) after liming] show significant differencesbetween factor A and B gradations, plus interactions among these factors (Table 5).

Among factors A only LR-N and LR-BS were insignificant (0.03 pH). In the fifth yearafter liming, primary soil acidity level was a factor affecting soil pH. Interactions amongthese factors showed distinct differences between the same LR determination combinationsat the second and third acidity levels. Such differences exist between the first and secondacidity levels for LR-N and LR-AE, where liming is based on indirect LR determinationmethods.

Evaluation of results, on the basis of applied LR methods (factor A), indicate soillimed according to mobile Al was most acidic, with greater mobile Al concentration and

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Tabl

e5

Eff

ecto

fap

plie

dlim

ere

quir

emen

tmet

hods

and

soil

acid

ityle

vels

onso

ilac

idity

prop

ertie

s

EA

CPA

CM

AL

AB

TC

EC

BS

Tre

atm

ents

pH(m

eqkg

−1)

(meq

kg−1

)(m

eqkg

−1)

(meq

kg−1

)(m

eqkg

−1)

(%)

Fact

orA

(LR

dete

rmin

atio

nm

etho

d)L

R-M

AL

4.50

3.47

38.3

2.48

32.0

70.3

44.4

LR

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higher exchangeable and potential acidity. Soil pH, amount of absorbed bases, potentialsorption, and base saturation were significantly lower (P < 0.05; n = 48). Properties ofsoil limed according to LR-AE and LR-BS took the medium position between LR-MALand LR-N where acidity was lowest. LR-AE and LR-BS treatments of factor A comparedto each other significantly differ (P < 0.05; n = 48) in only pH (0.13 pH), potential acid-ity (3.5 meq kg−1), and amount of absorbed bases (3.8 meq kg−1). Soil limed accordingto LR-N exhibited the lowest acidity indicated by pH, EAC, and MAL but not for soilsorption-related properties: potential acidity, amount of absorbed bases, potential sorption,and base saturation properties.

Significant differences (P < 0.05; n = 48) in soil acidity properties exist betweenvarious soil acidity levels (factor B). The most acidic soils (2002) continued to remain themost acidic (acidity level 1) at the end of study (2006) with significantly greater values ofmobile Al, exchangeable and potential acidity, lower pH values, amount of absorbed bases,and base saturation. Acidity levels 2 and 3 significantly (P < 0.05; n = 48) varied for all soilproperties. Lowest (2006) mobile Al, exchangeable and potential acidity values, greatestpH, amount of absorbed bases, sorption capacity, and base saturation values continued tobe in the least acidic soil.

Results of factors A × B interaction reveal specific soil processes. Interactionof LR-MAL and soil acidity level 1 resulted in the greatest mobile Al concentration(4.5 meq kg−1) and soil exchangeable acidity: the soil is continuing to acidify. Interactionof LR-MAL and acidity level 3 led to decreases in these parameters and lower soil pH (–0.16),which demonstrates LR-MAL is adequate to regulate soil acidity at low acidity levels.

Soil affected by LR-N at soil acidity (1) had significantly (P < 0.05; n = 48) lowerpH, AB, and BS% properties and greater PAC compared to the same limed soils at aciditylevels 2 and 3. No significant differences were found between soil acidity levels 2 and 3.Soil TCEC varied in a similar range (69.9–73.5 meq kg−1) at all treatments limed by LR-N.LR-AE demonstrated significant differences (P < 0.05; n = 48) in each soil acidity levelfor pH, PAC, AB, and BS% soil properties compared to LR-AE limed soils. EAC and MALhad significantly greater concentrations at soil acidity level 1 compared to levels 2 and 3,indicating greater soil toxicity for plants (≥1 meq kg−1 MAL).

The LR-BS at soil acidity level 3 significantly decreased exchangeable and potentialacidity and Al concentrations, with increased pH, absorbed and base saturation, and alsostimulated an enlarged soil sorption capacity. On initially lower acidity soil (2002), LR-BSapplications increased pH, amount of absorbed bases, sorption capacity, base saturation,and potential acidity compare to initial values. The LR-BS liming based method failed toincrease BS% level to the planned <70.

In summary, LR-BS × soil acidity level 3 had the greatest neutralizing influence (alltested properties), while LR-MAL × soil acidity level 1 led to the most acidic soil proper-ties and poorest sorption. Furthermore, soil liming according to various LR methods, andthe various soil acidity levels, failed to saturate the soil sorption complex, except LR-AEand LR-BS at soil acidity level 3.

Changes of Relationships between Soil Acidity Indices

Soil pH variation after liming shows buffering capacity depends on the soil acidificationrate (Hsu et al. 2004). In our study, to determine the effect of liming and soil acidity levelson soil acidity indices, correlation–regression analyses were applied. According to resultsbefore liming, significantly strong, negative correlations (r = −0.85 to −0.96; P < 0.05;n = 48) exist between soil pH and EAC, PAC, MAL, and TCEC saturation with Al

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Table 6Correlation matrix between soil acidity indices (n = 48) before the establishment of

the experiment (Voke 2002)

EAC MAL PAC AB TCEC BSpHKCl (meq) (meq) (meq) (meq) (meq) (%)

EAC (meq) −0.85MAL (meq) −0.85 0.98PAC (meq) −0.96 0.91 0.90AB (meq) 0.50 −0.42 −0.45 −0.50TCEC (meq) −0.54 0.52 0.49 0.55 0.46BS (meq) 0.65 −0.61 −0.61 −0.68 0.88 0.20Al saturation (%) −0.75 0.90 0.93 0.81 −0.60 0.25 −0.70

saturation (%) (Table 6). EAC exhibits a significantly strong correlation with MAL andPAC (r = 0.91–0.99; P < 0.05; n = 48). Base saturation correlates with the sum of AB(r = 0.88; n = 48, P < 0.05), but not with TCEC (r = 0.20; n = 48, P < 0.05), and mod-erate correlations (r = 0.50–0.65; P < 0.05; n = 48) exist between pH and soil sorptionproperties (AB, TCEC, and BS%).

In the fifth experimental year, after liming, there were notably stronger correla-tions between properties (Table 7), with only EAC and TCEC exhibiting weak kinships(r = 0.49; P < 0.05; n = 48) with other properties. Correlation of TCEC tended to beopposite compared to determinations before liming, excluding only the AB parameter. Asan effect of liming, soil TCEC became strongly correlated with AB (r = 0.91; P < 0.001,n = 48). Soil pH remained strongly correlated with the acidic part of soil sorption (EAC andPAC), while correlation with the alkaline part increased significantly (P < 0.05; n = 48)and those were reflected in the larger and opposite correlation of TCEC. This illustratesthat liming alters soil physicochemical conditions in several ways: increasing Ca solutionconcentrations, soil cation exchange surfaces, and soil solution ionic strength (Curtin andSmillie 1995; Vidal et al. 2003).

Strong and stable (before liming and after 5 years) correlations exist between MALand EAC (r = 0.98–0.99; P < 0.05, n = 48). Critical level for Al mobility is at pH 5.5,

Table 7Correlation matrix between soil acidity indices (n = 48) in the fifth year of

experiments (Voke 2006)

EAC MAL PAC AB TCEC BSpHKCl (meq) (meq) (meq) (meq) (meq) (%)

EAC (meq) −0.75MAL (meq) −0.74 0.99PAC (meq) −0.97 0.79 0.77AB (meq) 0.93 −0.70 −0.70 −0.90TCEC (meq) 0.72 −0.49 −0.51 −0.64 0.91BS (%) 0.95 −0.81 −0.81 −0.95 0.97 0.80Al saturation (%) −0.68 0.97 0.98 0.72 −0.69 −0.54 −0.79

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and EAC is dominated by H+ at the higher pH range. EAC at pH < 5.5 accordswith the MAL correlation, which indicates Al ions partly increase in EAC when thesoil acidifies. Our data shows the main part of EAC at ≥1 meq kg−1 level consists ofAl3+ ions. MAL is a critical issue in combination with depressed pH at >10 mg kg−1

(or >1 meq kg−1), and such conditions can be attributed to the suppression of the plantrhizosphere, including a reduction in root length. The Al3+ ions remains a part of EACeven at low levels of EAC (Figure 2). Structure of EAC shows Al+ is the most dynamicparameter, with the variation being 46–83% of EAC. Correlation of Al + (y) to H + (x)is significant (r = 0.84; P < 0.001, n = 48) and follows the linear regression equation:y = 2.4475 x − 0.0273.

Figure 2. Structural composition of exchangeable acidity.

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Discussion

The Lithuanian agricultural soil survey has an archive of pH data (1961–1965) and suchintrasite data of long-term experiments (>30 monitoring years) offers a valuable resourceof continuous soil acidity information. Linking scales permits evaluation of the cur-rent state of soils and, furthermore, the potential modelling of landscape scale changes.Recently Lithuanian territorial regularities in acidic horizon thickness were determinedby cartographical analysis, and factors influencing effective soil acidification managementhave been reported by Eidukeviciene et al. (2010).

Long-term experiments carried out in various regions of Lithuania agree with resultsfrom other countries that show the efficiency of primary liming depends on both the limingmaterial (amount, compounds, texture) and soil properties (soil genesis and initial hydro-chemical properties) (Ahern and Weinand 1995; Eidukevichene et al. 2001, Marcinkonisand Tripolskaja 2001; Palaveev and Totev 1983; Wiklander 1979). Secondary and con-tinued liming can be less economically effective but do influence soil properties. Theystabilize soil acidification processes and improve soil physicochemical and biological prop-erties. A major problem in the Baltic region is associated with the inherently low naturalbuffering capacity of soils.

Soil liming has been demonstrated to both increase soil TCEC and change relation-ships between other soil acidity indices. Our data proves soil pH does not fully reflectactual soil acidity levels; rather that it is the H+ concentration in soil solution. The mainpart of EAC (≤83%) was determined by Al3+ ions. The effect of soil liming varies fora wide range of soil pH relationships with other soil acidity indices. It substantially sup-ports propositions that allow acidity acceleration to initial levels (pH < 4.5) and requirehigh lime application rates to stabilize soil pH at this acidity level, where the greatest limedemands are calculated by the Nebolsin LR determination method. In contrast, stabiliza-tion of other parameters (EAC, MAL, BS%) requires significantly (P < 0.05) lower limerates but it is tolerable to use lower lime applications determined by other systems.

At the landscape level, the influence of land cover is important for both the concentra-tion and speciation of Al (Cory 2006). Our data, from a flat agricultural landscape, showsMAL has moderate to strong correlation with soil sorption properties (AB, PAC, TCEC)but also demonstrates that within one liming period the relationship can turn from positiveto negative (as in the case of TCEC). Several works have related soil buffering proper-ties (sorption) to soil pH and have suggested that soil pH (based on pH-dependent CECcurve calculations) is the only measurement necessary for calculating future lime require-ments (Matula and Pechova 2002; Lemire, Taillon, and Hendershot 2006). Van Breemenet al. (Van Breemen, Mulder, and Driscoll 1983; Van Breemen, Driscoll, and Mulder 1984)emphasized the importance of capacity factors and defined soil acidification as the decreasein acid neutralizing capacity (ANC). It has been reported that the restoration of soil acid-ity depends on the initial liming rate and lime material type (Bernotas, Ozeraitiene, andKoncius 2005). The correlation matrix of our soil acidity indices datasets indicates distinctchanges in the relationships after liming, which suggests the LR determination methods,based on soil acidity indices relationships (indirect methods), are less suitable for soils withirregular or no liming, representing soils with high variation of soil acidity indices.

Conclusions

This work clarifies the advantages of soil liming and the problems of liming cessationand highlights soil parameters that can be used to identify soil acidity and to enable cal-culation of the lime requirement of previously regularly limed soils based on regional

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approaches. The use of acid-tolerant plants is another strategy potentially capable of man-aging soil acidity problems, analogous to chemical time bomb hazards. Our experimentalresults explore many applied systems in terms of effects on soil properties and reveal thatsoil acidity indices significantly differ between specific LR determination methods andsoil acidity gradations, as well as interactions between these factors. In doing so, it isclearly indicates that relations between soil pH and soil sorption properties are not stable.Changeability is high and hardly predictable for PAC, AB, and TCEC, but it is rather stablefor BS% (r = 0.70–0.79). Although applied liming has changed the strength and directionof correlations between tested soil acidity indices, a strong and stable relation betweenEAC and MAL exists. Therefore, before selection of LR determination methods, the soilacidity level should be more precisely defined. This includes routine soil pH testing anddetermination of EAC or MAL parameters as reliable means of LR prediction. This workhas also revealed that historical soil acidity records provide a useful prognosis of soil acid-ification correction, for both indicating restoration ranges and acidification acceleration.However, further monitoring and additional investigation of soil parameters will enablemore detailed evaluation of liming effects on the environment (GHG emission from soils)and more accurate calculation of lime requirements for agrochemical restoration, plus theintroduction of appropriate and practical measures to avoid related problems.

Acknowledgments

All authors thank the seniors researchers, J. Savickas and Vl. Ignotas, who were the pio-neering scientists on soil liming in Lithuania. Financial support from the Research Councilof Lithuania (COST Action ES0805) is gratefully acknowledged. The first author grate-fully acknowledges receipt of a Lady Wulfrun Visiting Research Fellowship from theformer School of Engineering and the Built Environment (now STech) at the Universityof Wolverhampton, United Kingdom.

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soil acidity indices in east lithuania

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