Granitic Site in the Czech Republic and Paired-Catchments

Possibilities

Pavel Kram, Jakub Hruska, Tomas Navratil, Filip Oulehle, Daniela Fottova and Martin Novak

Czech Geological Survey, Prague

GEOMON Network of Fourteen Forest Catchments in Central Europe (Coordinated by Daniela Fottova, Czech Geological Survey, Prague, since 1994)

GER

POL

SVK

AUT

GER

CZE

Lysina

Hydrochemical monitoring: since 1988Hydrologic monitoring: since 1989In the GEOMON network (Daniela Fottová et al.): since 1994In the ICP-IM network (Sirpa Kleemola et al.): since 2002

Topographic situation 1989

ROAD

ROAD

Different stages of surface runoff and water color at 90O V-notch weir of LYS

DOC, H+

DOC, H+

Baseflow

Flood

Throughfall Collectors in Even-Aged Norway Spruce Plantation at LYS

Photo: Galina Koptsik, 2005

Shallow Root System at LYS

photo Hofmeister 2003, published Hofmeister et al. 2008

0.5 m2 Soil Pit at LYS – Podzol on Leucogranite

Photo: Skorepa J (2006)Technique: Huntington TG, Ryan DF, Hamburg SP (1988) SSSAJ 52: 1162-1167

MAGIC Model Simulation of Annual Mean Base Saturation of Lumped 90 cm of Soil at Lysina

0

5

10

15

20

25

30

1840 1860 1880 1900 1920 1940 1960 1980 2000 2020 2040

Year

Soi

l bas

e sa

tura

tion

(%)

Data 1993 a 2004

MAGIC - hindcast

MAGIC - forecast

Hruska and Kram (2007)

SAFE Model Simulation of Annual Mean Base Saturation of Five Soil Horizons at Lysina

0%

10%

20%

30%

40%

50%

60%

70%

80%

1900 1925 1950 1975 2000 2025 2050 2075 2100Rok

Baz

ická

sat

ura

ce

L+F

H

EE

B

C

Navratil et al. (2007)

POL

SVKAUT

GER

CZE

.

Lithology Gradient in the Czech GEOMON Network and in the American Critical Zone Exploration Network

LYS:Leucogranite vs. PLB:Ultramafic Serpentine

GEOMON

in paired catchment-level observatories

Granite vs. Mafic Basalt

Brantley et al. 2006, 2008

Leucogranite versus serpentine (Lysina vs. Pluhuv Bor)

Mg

MgAcid rock

Ultramafic rock

Sandy soil

Silty soil

Bedrock composition (mass %)

CaO

MgO

Na2O

K2O

Al2O3

SiO2

Pluhuv Bor-serpentinite Lysina-leucogranite

0.05 0.5

36.1 0.1

0.02 2.9

0.02 4.4

1.0 14.0

40.7 72.9

original data: serpentinite: Kram et al., 2007, leucogranite: Fiala F. et al., 1961

Soil Base saturation in 1993

0 20 40 60 80 100 120

C

B

E,A

H

L+F

%

LysinaPluhuv Bor

Kram et al. (1997)

Mean Acid Neutralizing Capacity of Streamwater (1994-2005)

ANC

Navratil et al. (2006)

Real Life

Lysina

Pluhuv Bor

1992-1994 Kram et al., 2000

3 ueq/l Ni++

Black Brook

Studeny Vrch

Nad Zelenym

Na Zelenem

Zizkuv Vrch

Za Rozcestim

Koule A

Kozi Hrbety

Koule B

Spicak

Pila

Zadni Domky

Ovcak

Lesny Bublak

Na Sykoraku

Stara Dira

Cisarsky Les

Vlci Kamen

Pistov

Betlemsky Les

Pluhuv Bor

Lysina

0 10 20 Kilometers

hranice CHKO Slavkovský Leshranice zájmových povodí

N

Pøehled poloh studovaných povodí

Podklad tvoøí výøez barevné RGB kompozicesatelitního snímku Landsat 7 ETM+ v pravých barvách (Red = TM3, Green = TM2, Blue = TM1)

Mariánské Láznì

Sokolov

Karlovy Vary

Input digital space data: satelite image LANDSAT ETM+

Malenovsky, Kram, Cudlin, 2004

21 “mono-rock” “mineral soil“ catchmens of the Slavkov Forest underlain by 5 geochemically contrasting environments (leucograniteleucogranite/granite/gneiss+mica schist/

amphibolite+neovolcanites/serpentine) studied in 2001-2003

+ 2 “organic soil“ catchments studied in 1992-2007

Mean concentrations of magnesium in stream waters at 11 catchments on 3 bedrocks

Mg

0 3 6 9 12 15 18

Na zeleném - A

Pístov - A

Nad zeleným - A

Žižkův vrch - A

Vlčí kámen - S

Císařský les - S

Pluhův bor - S

Špičák - L

Ovčák - L

Velký Bublák - L

Lysina - L

mg/l

leucogranite

serpentine

amphibolite

V-notch weir for continuous measurements of surface water runoff from the Pluhuv Bor watershed

Conclusions • Quantification of lithologic controls on regolith,

mineral soil and organic soil in (2+21) forest catchments (in monolithologic and tree monoculture environment of central Europe)

• Selected paired monolithologic catchments include end-members of ecosystem sensitivity to acidification

• Comparison of spatial scales of chemical weathering from laboratory microscale, soil profiles to small catchments

More information about the Czech catchments: Hofmeister J, Oulehle F, Kram P, Hruska J (2008) Loss of nutrients caused by litter raking as compared with an

effect of acid deposition. Biogeochemistry 88: 139-151.

Hruska J, Johnson CE, Kram P (1996) The role of organic solutes in the chemistry of acid-impacted bog waters of the western Czech Republic. Water Resources Research 32: 2841-2851.

Hruska J, Kram P (2003) Modelling of long-term changes of streamwater chemistry in two catchments with contrasting vulnerability to acidification. Hydrology and Earth System Sciences 7: 525-539.

Kram P, Hruska J, Wenner BS, Driscoll CT, Johnson CE (1997) The biogeochemistry of basic cations in two forest catchments with contrasting lithology in the Czech Republic. Biogeochemistry 37: 173-202.

Krám P (2006) Chemical composition of runoff from eleven forested and geochemically contrasting catchments underlain by leucogranite, serpentinite and amphibolite (in Czech, English Abstract). Geoscience Research Reports, Czech Geological Survey, Prague,182-186.

Kram P, Oulehle F, Stedra V, Hruska J, Shanley JB, Minocha R, Traister E (2008) Geoecology of a forest watershed underlain by serpentine in Central Europe. Northeastern Naturalist, in review.

Navratil T, Kurz D, Kram P, Hofmeister J, Hruska J (2007) Acidification and recovery of soil at a heavily impacted forest catchment (Lysina, Czech Republic) – SAFE modeling and field results. Ecological Modeling 205: 464-474.

Novak M, Kirchner JW, Fottova D., Prechova E, Jackova I, Kram P, Hruska J (2005) Isotopic evidence for processes of sulfur retention/release in 13 forested catchments spanning a strong pollution gradient (Czech Republic, Central Europe). Global Biogeochemical Cycles 19: Art.No.GB4012, 1-14.

Oulehle F, McDowell WH, Aitkenhead-Peterson JA, Kram P, Hruska J, Navratil T, Buzek F, Fottova D (2008) Long-term trends in stream nitrate concentrations and losses across watersheds undergoing recovery from acidification in the Czech Republic. Ecosystems 11: 410-425.

MAGIC Model Simulation of Annual Mean Streamwater Acid Neutralizing Capacity (ANC) at Lysina

-250

-200

-150

-100

-50

0

50

100

150

1840 1860 1880 1900 1920 1940 1960 1980 2000 2020 2040

Year

m eq/

L

Data 1990-2006

MAGIC - hindcast

MAGIC - forecast

Hruska and Kram (2007)

MAGIC Model Simulation of Annual Mean

Streamwater Sulfate Concentration at LYS and PLB

0

200

400

600

800

1000

1200

1850 1870 1890 1910 1930 1950 1970 1990 2010 2030

Year

eq/L

Data Lysina, 1990-2006

Data Pluhuv Bor, 1992-2006

MAGIC Model - Lysina

MAGIC Model - Pluhuv Bor

Hruska and Kram (2007)

MAGIC Model Simulation of Annual Mean Soil Base Saturation at LYS and PLB

0

5

10

15

20

25

30

1840 1860 1880 1900 1920 1940 1960 1980 2000 2020 2040

Year

Soi

l bas

e sa

tura

tion

(%)

Data 1993 a 2004

MAGIC - hindcast

MAGIC - forecast

PLB: PLB: decline of base saturation from 95% to 88%

LYS

Hruska and Kram (2007)

0.5 m2 soil pit at PLB – Eutric Inceptisol

Photo July 1993Technique: Huntington TG, Ryan DF, Hamburg SP (1988) SSSAJ 52: 1162-1167

Zero-tension lysimeters for sampling of soil water at Pluhuv Bor

Photo July 1993

metabasics

granite

leukogranite

volcanics

gneiss

sediments

serpentinite

mica-schist

Mean concentrations of the nutrient potassium and potentially toxic nickel in stream waters at 11 catchments on 3 bedrocks

K

0,0 0,3 0,6 0,9 1,2

Na zeleném - A

Pístov - A

Nad zeleným - A

Žižkův vrch - A

Vlčí kámen - S

Císařský les - S

Pluhův bor - S

Špičák - L

Ovčák - L

Velký Bublák - L

Lysina - L

mg/l

Ni

0 20 40 60 80 100 120

Na zeleném - A

Pístov - A

Nad zeleným - A

Žižkův vrch - A

Vlčí kámen - S

Císařský les - S

Pluhův bor - S

Špičák - L

Ovčák - L

Velký Bublák - L

Lysina - L

ug/l

Mean concentrations of the nutrient divalent base cations in stream waters at 11 catchments on 3 bedrocks

Mg

0 3 6 9 12 15 18

Na zeleném - A

Pístov - A

Nad zeleným - A

Žižkův vrch - A

Vlčí kámen - S

Císařský les - S

Pluhův bor - S

Špičák - L

Ovčák - L

Velký Bublák - L

Lysina - L

mg/l

Ca

0 3 6 9 12 15 18 21

Na zeleném - A

Pístov - A

Nad zeleným - A

Žižkův vrch - A

Vlčí kámen - S

Císařský les - S

Pluhův bor - S

Špičák - L

Ovčák - L

Velký Bublák - L

Lysina - L

mg/l

Outline

Location of fourteen catchments Methods of water and soil sampling and

chemical analyses “Long-term“ monitoring results

(deposition, soil, streamwater) MAGIC and SAFE modeling results

(streamwater, soil) Short Conclusions

Water Sampling at Lysina (LYS) (for example)

November 1989/1991- October 2007 (18 water years)

Bulk precipitation (open area), throughfall (below spruce)

monthly sampling

Soil water (organic horizon, upper mineral soil, about -15 cm)

at least monthly sampling (zero-tension lysimeters)

Soil water (lower mineral soil, -80 cm)

monthly sampling (tension lysimeters, only 1992-1996)

Shallow ground water (well with overflow, -150 cm) piezometers (max -470 cm)

monthly sampling (CGS) (BU – only Aug-Nov 2000)

Stream water continuous measurements of discharge (V-notch weir, water-level recorder), water temperature (weekly), at least weekly sampling

Water Analyses at LYS

November 1989- October 2007 (18 water years)

pH, Gran alkalinity (measured), ANC (calculated), SiO2

anions: SO42-, Cl-, NO3

-, F- major cations: NH4

+, Ca2+, Mg2+, Na+, K+, Al, Fe, Mn, Zn

Regular sampling (CGS)

As, Cd, Pb Regular (CGS)

Be,Cu Irregular, regular until 2005 (CGS)

Ni Irregular, regular since March 1997 (CGS)

Cr, Co, Mo, Li Rare (CGS)

DOC, DON Irregular (SU, SLU), regular since March 1999 (UNH, CGS)

Almonomeric, Alorganic, Alinorganic Irregular (CGS, SU, ASCR, CGS)

Isotopes of O, S, Sr, Ca Irregular (CGS, USGS)

Analyte Extraction Equipment

pH H2O, 0.1M CaCl2 Potentiometric, GCE

Exchangeable Ca2+,Mg2+, Na+, K+

1M NH4Cl, Mechanical VacuumExtractor

AAS (Atomic Absorp.Spectrophotometry)

ExchangeableAcidity, Al3+; (H+)

1M KCl, Mechanical VacuumExtractor

Titration

Extractable Al3+,Fe3+

0.2M Acid-Oxalate, MechanicalVacuum Extractor;0.1M Na-Pyrophosphate,Reciprocating Shaker, Centrifuge

DCP (Direct-CurrentPlasma EmissionSpectroscopy)

Extractable NO3 -,

SO42-, Cl-

H2O, 0.016M Na-Phosphate,Reciprocating Shaker, Centrifuge

Ion ExchangeChromatography

Extractable F- H2O, 0.016M Na-Phosphate,Reciprocatig Shaker, Centrifuge

Potentiometric

LOI; (SOM) Combustion Muffle Furnace

Total C, N, H, S Combustion Elemental Analyzer

Selected Soil Analyses at LYS (sampling in 1993, analyzed at Syracuse University)

Selected Soil Analyses (cont.) at LYS

Analyte Extraction Equipment

SiO2, Al2O3, Fe2O3, FeO, MnO,CaO, MgO, Na2O, K2O, Li2O,P2O5, CO2, C, F, H2O

CGU CGU

Mineralogy CGU X-Ray Diffraction

Grain Size GravimetricSedimentation,Pipetting,Centrifuging, WetSieving

Analyte Extraction Equipment

Total Ca, Mg, Na,K, Al, Fe, Mn, Zn,Ni

Conc. HNO3 + 30% H2O2,10% HCl + 10% HNO3,Combustion

InductivelyCoupled PlasmaSpectrophot.

Total C, N, H, S Combustion Elem. Analyzer

Results of the Mann-Kendall Test* of the Mean Annual Atmospheric

Deposition Fluxes to the GEOMON Catchments in 1994-2005

Compound Bulk Precipitation: Sen-slope

Spruce Throughfall: Sen-slope

Precipitation (mm yr-1)

(-10) (not significant)

(-5) (not significant)

Sulfur (kg ha-1yr-1)

-0.9 p<0.001

-2.2 p<0.001

Inorganic Nitrogen (kg ha-1yr-1)

-0.5 p<0.01

(+0.02) (not significant)

Hydrogen Ions (kg ha-1yr-1)

-0.02 p<0.05

-0.07 p<0.001

*Libiseller C. (2004) MULTMK/PARTMK – A program for the computation of Multivariate and Partial Mann-Kendall Test. Linkoping University, Sweden.

Kram et al. (2006)

Mean Streamwater Export of Nitrate in 1994-2005 vs. Organic Soil C/N Mass Ratio at fourteen GEOMON Catchments

UDL

MOD

UHL

SALLYS

LESPOM

LIZ

JEZ

CERLKV

PLB

SPAANE

forest floor C/N

15 20 25 30 35 40

mea

n N

-NO

3 ex

po

rt (

kg h

a-1

yr-1

)

0

5

10

15

20

Oulehle et al. (2008)

MAGIC Model Simulation of Annual Mean Soil Base Saturation at other GEOMON Catchments

0

10

20

30

40

50

60

70

1850 1870 1890 1910 1930 1950 1970 1990 2010 2030

ANE

CER

JEZ

LES

LIZ

MOD

POL

SAL

SPA

UDL

UHL

Hruska and Kram (2004)

Conclusions

CZ = Critical Zone

CZ = Czech Republic

More information about biogeochemical models MAGIC Cosby BJ,

Hornberger GM, Galloway JN, Wright RF (1985): Time scales of catchment acidification. Environmental Science and Technology 19: 1144-1149. Cosby BJ, Ferrier RC, Jenkins A, Wright RF (2001): Modelling the effects of acid deposition: refinements, adjustments and inclusion of nitrogen dynamics in the MAGIC model. Hydrology and Earth System Sciences 5: 499-517.

SAFEWarfvinge P, Falkengren-Grerup U, Sverdrup H, Andersen B (1993): Modeling long-term supply in acidified forests stands. Environmental Pollution 80: 209-221.Martinson L, Alveteg M, Warfvinge P (2003): Parametrization and evaluation of sulfate adsorption in a dynamic soil chemistry model. Environmental Pollution 124: 119-125.

Results of the Mann-Kendall Test of the Mean Annual Stream Runoff Fluxes from the GEOMON Catchments in 1994-2005

Catchment Inorganic N:

(kg ha-1yr-1)

Sen-slope

Sulfur:

(kg ha-1yr-1)

Sen-slope

CER NS -1.9

LIZ -0.1 NS

LKV NS -3.2

LYS -0.1 -1.0

MOD -0.9 -1.4

PLB NS -2.3

POM -0.3 -1.7

UHL -0.5 NS

ANE,JEZ,LES,SAL,SPA,UDL NS NS

NS: not significant, P>0.05

Oulehle et al. (2008)

Results of the Mann-Kendall Test of the Mean Annual Streamwater Concentration in the GEOMON Catchments in 1994-2005

Catchment Inorganic N: (ueq L-1yr-1) Sulfur: (ueq L-1yr-1) Sen-slope

ANE -2.2 +24.8

CER NS -6.7

JEZ -2.4 -33.6

LIZ -2.1 NS

LYS -0.4 -17.3

MOD -2.5 -1.9

PLB NS -37.0

POM -6.2 -28.9

SPA -0.1 -4.4

UDL -4.2 -1.5

UHL -3.3 NS

LES, LKV, SAL NS NS

NS: not significant, P>0.05Oulehle et al. (2008)

Mean Calcium and Magnesium Concentration in Streamwater (1994-2005)

Ca

Mg

Very different proportions of Mg fluxes in throughfall at sites with Mg-poor (LYS) and Mg-rich (PLB) substrate in 1992-2002

internal

dry dep.

wet dep.

Lysina

Pluhuv Bor

Decline of internal cycling and dry deposion fluxes of base cations in throughfall in 1994-2002. The pattern of internal cycling follows the large increase of throughfall pH. However the wet deposition fluxes remain stable. Dry deposition flux of base cations

was larger than the wet deposition flux in the middle of 1990s, but not later.

Lysina Pluhuv Bor

0

20

40

60

80

100

120

1994 1995 1996 1997 1998 1999 2000 2001 2002m

eq/m

2/yr BC int

BC dry

BC wet

0

20

40

60

80

100

120

1994 1995 1996 1997 1998 1999 2000 2001 2002

meq

/m2/

yr

BC int

BC dry

BC wet

Monthly Mean Water Fluxes

0 10 20 30 40 50 60 70 80 90

100

mm

/mo

nth

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

Runoff LYS PLB, precip ML (1992-2006)

0

500

1000

1500

2000

2500

3000

3500

0 200 400 600 800 1000 1200

Pluhuv Bor, 1991-2002

ALK 91-94ALK 95-98ALK 99-02

Alk

alin

ity, u

eq/L

Sulfate, ueq/L

Sulfate vs. alkalinity in streamwater, data are split into three time periods

Shanley et al., 2004

b baseflow

highflow

Serpentinite Tremolitic shale

Actinolitic shale

Amphibolite

median

mass %

median

mass %

median

mass %

median

mass %

Base cations (impotrant nutrients for forest ecosystem):

MgO 36.1 24.2 15.2 8.0

CaO 0.05 8.4 9.8 8.8

K2O 0.02 0.02 0.16 0.23

Na2O 0.02 0.08 2.1 4.5

Potentially toxic metals:

Ni 0.20 0.12 0.03 0.01

Cr 0.25 0.22 0.04 0.01

Al2O3 1.0 3.1 13.5 16.4

Kram et al., 2007

Real Life

H+

Ca++

Na+

H+

Ca++K+Na+

Mg++

Lysina

Pluhuv Bor

1992-1994 Kram et al., 2000

3 ueq/l Ni++

More information about the GEOMON catchments: Fottova D, Skorepova I (1998) Changes in mass element fluxes and their importance for

critical loads: GEOMON network, Czech Republic. Water, Air, and Soil Pollution 105: 365-376.

Hofmeister J, Oulehle F, Kram P, Hruska J (2008) Loss of nutrients caused by litter raking as compared with an effect of acid deposition. Biogeochemistry 88: 139-151.

Hruska J, Kram P (2003) Modelling of long-term changes of streamwater chemistry in two catchments with contrasting vulnerability to acidification. Hydrology and Earth System Sciences 7: 525-539.

Kram P, Hruska J, Wenner BS, Driscoll CT, Johnson CE (1997) The biogeochemistry of basic cations in two forest catchments with contrasting lithology in the Czech Republic. Biogeochemistry 37: 173-202.

Navratil T, Kurz D, Kram P, Hofmeister J, Hruska J (2007) Acidification and recovery of soil at a heavily impacted forest catchment (Lysina, Czech Republic) – SAFE modeling and field results. Ecological Modeling 205: 464-474.

Novak M, Kirchner JW, Fottova D., Prechova E, Jackova I, Kram P, Hruska J (2005) Isotopic evidence for processes of sulfur retention/release in 13 forested catchments spanning a strong pollution gradient (Czech Republic, Central Europe). Global Biogeochemical Cycles 19: Art.No.GB4012, 1-14.

Oulehle F, McDowell WH, Aitkenhead-Peterson JA, Kram P, Hruska J, Navratil T, Buzek F, Fottova D (2008) Long-term trends in stream nitrate concentrations and losses across watersheds undergoing recovery from acidification in the Czech Republic. Ecosystems 11: 410-425.