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
Mar 28, 2015
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.