Comparison on humus and soil geochemical baselines in Southern

Introduction Statistical methods Results

Low/High Low/High Geological Survey of Finland has carried out geochemical The mean, the median, the maximum, the minimum and the Most of the elements have completely different distribution C content 2,5 C content 48 1.00 > 19% baseline mapping in Southern Finland between 2002-2013, quartiles, and histograms of the 35 elements were analyzed of concentrations in humus and topsoil samples. (Fig. 4 and 5). 2.00 < 19% using topsoil, subsoil and humus samples (Fig.1). Humus sam- both for all humus and topsoil samples, and for the different 2,0 Cd ppm (Humus) Cd ppm (Soil) 38 ples reflect the interplay between atmosphere (especially at- soil parent material separately. For each element, figures com- 1,5 Textbox 200 mospheric deposition), biosphere and lithosphere (Salminen prehensive of histograms, box plots and cumulative probabil- 200 28 150

C (Humus) % 1,0 et al. 2004). ity plots (CP) of the humus and topsoil log-transformed data, Cd (Humus) mg/kg 100 100 18

50 ,5

were made using R studio software (Fig. 3). 50 Frequency Frequency 0 0

8 ,0 −50 −50 0 5000 10000 15000 ,0 ,1 ,2 ,3 ,4 ,5 ,6 −2.5 −2.0 −1.5 −1.0 −0.5 0.0 0.5 −2.0 −1.5 −1.0 −0.5 Al (Humus) mg/kg Cd (Soil) mg/kg 0.005 0.02 0.05 0.2 0.5 1 2 0.01 0.02 0.05 0.1 0.2 0.5 Fig.7: Scatter diagrams of Al Fig.8: Scatter diagram of Cd con- and C in humus samples. centrations in topsoil and humus. Ni ppmNi ppm (Humus) (Humus) Ni ppm (Soil)Ni ppm (Soil) Ni ppm (Humus) Ni ppm (Soil) Ni ppm (Humus) Ni ppm (Soil) 99 Humus In order to explain the anomalous high values in humus, the 90 80 Soil 150 80 Cd (Soil) 150 80

150 geographic distributions of these elements in humus and top- 60 60 80 60 150 100 60 100 20

40 soil were analyzed (Fig. 9) and then compared to the deposi- Probability [%] 100 60 40 5 50 100 40 20 50 tion data obtained by the moss compositions (Rühling 1992, 40 Cd (Humus) Frequency Frequency 20 50 0 0 0.1

20 Page 1 Frequency Frequency Page 1 50 1994; Rühling and Steinnes, 1998; Salminen et al. 2004, 2011). 0 0 20 Frequency Frequency 0.01 0.1 1 0.005 0.020 0.100 0.500 2.000 0 0 Frequency Frequency −20 0 0 −50 0.005 0.02 0.05 0.2 0.5 1 2 High values appear in areas where the anthropogenic impact 0.5 1.0 1.5 2.0 2.5 −0.5−20 0.0 0.5 1.0 1.5 2.0 2.5 −50 −20 −50 0.5 1.0 1.5 2.0 2.5 −20 −0.5 0.0 0.5 1.0 1.5 2.0 2.5 is high, (e.g. Harjavalta) and the more densely populated and −50 2 0.55 10 1.020 501.5 100 2002.0 5002.5 0.2 0.5 1−0.52 0.05 10 0.520 501.0 2001.5 2.0 Fig.2.5 4: CP plot of Cd. 0.5 2 1.0 5 1.510 202.0 50 2.5100 200 500 −0.5 0.00.2 0.50.5 1 1.02 1.55 102.020 2.550 200 industrialized areas, (, the coastline from Porvoo to Fig.1: Humus sampling. 2 5 10 20 50 100 200 500 0.2 0.5 1 2 5 10 20 50 200 2 5 10 20 50 100 200 500 0.2 0.5 1 2 5 10 20 50 200 Helsinki).

Low/High *# C content #*

99 Humus 2.00 *##* HONKAJOKI #* 1.00 #* #* )"") *# MÄNTTÄ-VILPPULA 40 Ni *# PARKAN)" O 15000 90 ") RUOVESI 99 SoilHumus )" Ni (Soil) )" )" #* #* *##* )"*#") Methods )" )" ") )" )" #* )" ) ") *# 99 Humus )" ") *# #* *##* )" )" 99 Humus *# 60 JÄMIJÄRVI *# #* JÄMSÄ 90 Soil *##* #*

Ni (Soil) )" *##* 30 )" )")" 90 Soil )" POMARKKU

90 )" 20 Soil Ni (Soil) )" )" *##* #*)" Ni (Soil) 60 )" *#*# 10000 )")" )" )" *# )"") Probability [%] #* )" )" )")")"*##* )" )" *##*#*#* )"HÄMEENKYRÖ)"*#*# *##* )" 5 *# )" *#)")")" O)"RIVESI / *##* )"") )")"*#)" LAVIA )" *)" )" 60 *# *# )" ##* ##* *#*#*# )" )" 816 sample pairs (humus and topsoil) have been analyzed 60 )" )"**##* )" )" * *# *# *#*# *#*#*#*# )" ") )" )" )" )"") *#*# *#*#*#)")")" ") 20 0 25 50 Y*#LÖJÄRVI )" )""))"") POR)"I )" *#*# )" )"") )" Ni (Humus) )" )" )" ")")"*# )" ") Probability [%] Km ) # ) 20 )")" )" *#*# )")" )"*#*# *#*#)"*#)"#)")" 20 " * 5 #* #* *# # )")")" )" )" *# 20 * ) )" " #" Al (Humus) mg/kg *# *# SAST)"AMALA )" )"))")" *#)" )" )" SYSMÄ in detail (Fig.2). 0.1 )""))" )")" P)")"IR)"KK)"AL)"A*#*# ") ") )" )" Probability [%] LUVIA)"#* ")*# )" Probability [%] Humus (clay) Soil (clay) *#NA*#K*#K"))"ILA#* )")" *# Cr (Humus) mg/kg * )" 5 )" )" )" )")" )")" 5 )" )" 5000 *#*# #* ") *#)")"")")")")" *# *#*#*#*# *#*# *#*#)")")")"))")")"" )")"*# ") Ni (Humus) *# )" 1 10 100 0.2 0.5 2.0 5.0 20.0 100.0 500.0 3 - 6 2 - 3 *#*# )")")" ") )" )")" *# ") )" VE)")"S*#*#I)"*#L)"AH)"TI )")"*#)")" PADASJOKI )" )")"") *#*##* )"#)" )" )")"*#*#*#)" )")")")")" *#*#PÄLKÄNE )"") *#*#K#* O)"*KEMÄKI )" )" )" )"") ") 0.1 EUR")AJOKI )")" )" Ni (Humus) " #* Ni (Humus) ) *# ") 10 6 - 7 3 - 8 )")" )" )"*#*#)"*#)" )"*##* )" )"") 0.2 0.5 1 2 5 10 20 50 200 500 )" )" )"") )" ")" )" )")" )" )" )")" *#)" *#*# #* ) )" )")"A*#*#K)")"AA*##* )")" 0.1 * 0.1 )" )" #*)")"*# #* 7 - 20 8 - 15 EURA *)")"*# *# )")" ASIKKALA MUURAME 1 10 100 0.2 0.5 2.0 5.0 20.0 100.0 500.0 )" #* )" )")"##*)" )" )" #* )" *#*# *#*# )" *# *)")"*##* ") )" " *##**# ") ") )" *##*)" )" )" ") SÄKYLÄ )" ")) )" )")" )" HONKAJOKI 0 )" UR)")"*##*JALA ") #* ") #* MÄNTTÄ-VILPPULA 20 - 29 15 - 50 *##*)" )")" ") ") #* PARKAN")O 1 1 10 10 100 100 0.2 0.5 0.22.0 0.55.0 2.020.0 5.0 100.020.0 500.0100.0 500.0 *# *#)"") )" ") HA)"TT)"ULA )" *# #* )" *##* )" )"#*)"") )""))" )" PYHÄRANTA )" )"") *# )" )"") )" )"") ") RUOVESI 0.2 0.5 1 2 5 10 20 50 200 500 *# ") )" *##* ") )"*##* )" / ") 0 0 10000 20000 30000 40000 50000 50 - 57 ") )")"#* )" )" )") *##* " *# )" SIIKAINEN ") #* #* Humus (till) ) )"") *##* ") )" ") " HOLLOLA ") #* #* )" )")" )" *##* )" )" )" ") ") ") ") ") H*#UMPPILA )" )" ") )" #*") ") ") #* 0.2 0.5 0.21 20.5 51 102 205 5010 20 20050500 200 500 Al (Soil) mg/kg ") )" *##* )" )" )" )" *##* *##* )" #* #*#* ") 2 - 6 )" )"") #* )"") ") JANA*#K)"K)"ALA JÄMIJÄRVI 0 50 100 150 Soil (till) UUSIKAUPUNKI ORIPÄÄ *# )" )" ) )" #* #* JÄMSÄ )" )"") )")" #* )" )" *##* " )"*# )" *# KÄRKÖLÄ #* JUUPAJOKI ") YPÄJÄ *# # ) Cr (Soil) mg/kg )" 6 - 7 0 - 3 ") *#)" ") #* )" ") ")") #* )" )" TAMM)"E*##*LA ") )" *#*# *#*# LUHANKA )" *# ") )" ") POMARKKU VEHMAA PÖYTYÄ )" )" )" H)"AUSJÄRVI *# )" )" *##* *#") *##* ") *#*#)" *#*# ") ") ")#*#*") PUULA )" )" )"") )" *#*# )" ") ") #* ") 7 - 20 3 - 8 *##* )"") )" *##*)"") )"L*#OPP)"I )" #* ") ") ") ") #* ") ") )" )"") )"# )" #* H") ÄMEENKYRÖ ")#* ") #* AURA KOSK)"")I *##* *##* ") )" )" *# * #*")*# #*#* #*") ") #*") ") ORIVESI *# ) )"*#*#*#*# ") #* ") #* ") LAVIA #* ") ") Fig. 3: Histogram, Cp plot and boxplot for log-transformed data for Fig. 5: Scatter diagram of Cr. In Fig.6: Scatter diagram of Al con- )" SOM)"ERO") ") *##* *##* *##* )" )")" )" )"*##*)" ") #* #* )" 20 - 50 8 - 15 ") ) )"#* ") ") ") ") #* ") #* #* #* #*#* ") MASKU )" "") *#*#)" *#)" ") ") #* ") ") MARTTILA )" ") ) #)")" HY#*)"VINKÄÄ ") #* #*#* ") ") *##*)" )" *#*)" )"*#*#*#)" *#)" ") ") YLÖJÄRVI ") *##* *#*# )" ") )" )"") *##*") ") ") ") #*#* ") ") ") KUHMOINEN HARTOLA ) )"") )" )" *##* *##* )"*##* )")"")*#)" ) ") ") ") ")#* ") ") 50 - 191 )" 15 - 50 LIETO *##* KAR)"KKIL)"*#*#A*# #*#*#")#**# ") ") #* #* ") ") ") ")*#*# * *# ") #* ") #* #* #* ") nickel, with similar medians in humus and topsoil. red samples with low organic C. centrations in topsoil and humus. *##* ") *#)")"*# ") *#*# )"*## ")") ") ") ") #* )" )" )")" *#*# *# )"*#)")"##* )" *#*#* ASKOLA #* #* #* SASTA") MAL#*A ") ") ") #*") ") ") *##* *#*#)" )" )" )" * *# )" )")")" *#)"*#)"") ") PI")RKKALA ")K#*ANGASALA SYSMÄ PERTUNMAA ") )" )" #**# )" )" )" )"*#*#)"" # )" )" ") ") ")#* ") ") ") )" 50 - 212 )" *# )")"*# *#*##*)" )"*##*")" )"*#) *#*#*)")")"*#*#*#*#)" LUVIA ") ") ") ") Humus (sand) *# )" )" )")"*#*#)"*# )"*##* *##*)")")" *##*)"*# )" # #* NAK#*KILA #* ") ") #* )"")*# V)"*#IHTI*#)"#* *# )")" *#*#)")" )" )"*##*)"")*#)")" "*#) * ") ") ") ") ") SALO )") *#*#*# )" *##* *##* TUUSULA )"")*#*# )"*#*#)")#*)" ") ") ")") ") #* #* SAUVO *#)")" )"*##**# *#)"*# *#*# )" )" )"*##*")"") * #* #* #*#* ") ") ") ") ") *#*##* )" *#")" )" )")" )")" )" "))")")*# #*#* #* ") ") ") #* ") 1 - 6 *# )" )" #*#*# ))"*# )")")" )" P)"O)"*#RVOO #*#* ") ") ") ") Soil (sand) )"*#") )")"*#)" SIP)"OO )" )"*# )"*#*# #* ") ") #*#* ") ")#*") PADASJOKI )"#* ))" )" )"*#*#"))")" ") ") ") #* ") ") ")L#*E")MP")Ä")")ÄLÄ #*PÄLKÄNE ") )" *# )" )"*#*# ") #* ")#* ") ") #* *# #* *##*)")")"") )"#*)")" )"") *#*#") )"") ") K#*OKEMÄKI ") ") ") ") 6 - 7 0 - 3 ")#* *##* *# *#*# )" )"")") EUR")AJOKI #* LOHJA)" )" )" )"#*)"*##* )" *#*# *#*#)"") *#*# ") ")#*#*") ")#* ") ") ") )")"#*)"#* )" )" ") )" *#*##* )"#* ") ") ") ") #* V") ALKEAKOSKI *##* )" #* *# ") ") ") ") ") ") #* #* #* #*") ") *# ")#* ") #* *# *# )")")" ) )")" )"") ") ") A")#*")K#*AA #* ") 7 - 20 3 - 8 )" *##*)"#* EURA #* ") #* #* ") HEINOLA #*)" )"")ESPOO ") ASIKKALA For some of the elements (Al, Ba, Ca, Fe, K, Mg, Rb, Sr, Ti and SIUNT#)"IO)")" ") ") #* ") #*") ") ") ") * )" )" #* #* #* #* ") ") ") #* *#)"")") )" #* ") ") ") ") #* ") ") *# 20 - 50 *# 8 - 15 ")#* *# ")*##* SÄKYLÄ ") ") UR")JALA )*# #* #* ") )" ")#* #*") ") ") ") ") )" #*)" #* #* ") ") ") *# #* ") #* ")") ") ") ") #*#* ") ") #* ") ") ") ") Zn), the concentrations in humus were positively correlated to *# 50 - 435 *# 15 - 48 PYHÄRANTA #* ") ") ") ") ") #* ") #* ") #* ") ") ") #* ") #* ") ") ") ") HOLLOLA ") ") ") ") HU#*MPPILA ") #* ") ") ") #* ") ") ") ") #* #* ") NASTOLA ") ") ")") ") JANAK#*K")AL")A Page 1 UUSIKAUPUNKI ORIPÄÄ #* ") ") the concentrations in topsoil (Fig. 6). These humus concentra- ") ") IITTI Correlations ") ") ") ") #* ") ")#* #* KÄRKÖLÄ YPÄJÄ #* #* ") ") ") ") ") #* TAMM")EL#*A ") ") #* #* Fig. 9: A dot map for Ni concentrations in humus and topsoil sample pairs. #* ") ") ") ORIMATTILA VEHMAA PÖYTYÄ ") #* ") H")AUSJÄRVI #* ") ") #* ") #* ") #*") #* tions are controlled by the amount of minerogenic matter. ") ") #* Page 1 #* ") ") #* ") ")L#*OPPI") ") AURA ") ") ") #* ") KOSKI") #* #* ") ") R#*")IIHIM#*")#*ÄKI #*SOME") RO #* #* ") ") #* #*") ")#*") KUSTAVI ") ") #* ") ") MASKU ") #*") ") #* #*") PUKKILA MARTTILA ") ") ") HYVINKÄÄ The higher concentrations in humus, depending on the pro- #*") ") #* ") #*#*#* ") #*") The correlation between the element concentrations in hu- ") #* ") ") ") LAPINJÄRVI ") ") #* ") #* #* ") ") ")#* ") #*") LIETO #* KARK")K#*ILA")#* #* #*#*") #* ") #* ")#* #* ") ") #* ")#* ") #* #* PAIMIO ") #* ") ") #* ") #*#* ASKOLA ") #* #*") ") ") ") #* ") ")") ")")") #*")") Conclusions ") ") #* ") PYHTÄÄ portion of the mineral matter in the samples, were thus nega- ") #* ")#*#* ") ") #*#*") #*#*") ") ") mus and topsoil and the content of organic C was evaluated ") ")#* ") #* #*#*") #*#*") ") #*") ") ") #* #* ") ")#* #*") #*") #* ")") #* #*") ")#* ")#*") ")#*") ") ")#* #* Soil parent material SALO ") V#*IH#*TI ") #* #* TUUSULA ")#* #* ") #*") SAUVO #* ")#*#* ") #*") #* ") ") ") ") #*")") ") #*#* #*") ") ") ") ") ")")") #* #* ") ") ")#* ")#* ") ") POR#*VOO #*") ") ")#* SIPOO ") ")#* ") #* ") ") ") #*") ") tively correlated with the contents of organic C in humus (Fig. 7). Clay #* #* ") #* ") by determining the Spearman rank correlation values. Scatter #*")") ") ")")") ") #* ") ")#*") #* #* ") ") ") LOHJA ") #*") ") ") ")#* ") #* #*") #* ") ")") ") ") #* #* ") Glacial till #*#*#* ") ") ") #* #* ") #* ") #*") #* ") ") ") ") #*")#* plots of the element concentrations in humus and in minero- Other elements show a different behavior, that could be ex- There was no correlation between humus and minerogen- ") #* SIUNTIO#*") ") ESPOO Sand #* ") #*#*")") ") #*") #*#*") ")#* ") ")#* 0 50 100 ") #* genic topsoil, and of the content of the element and the con- plained by atmospheric deposition. Evident outliers, with prob- ic topsoil concentrations in Southern Finland. Concentrations #*#* Km tent of organic C, were elaborated where significant Spearman able anthropogenic origin, appeared in the As, Bi, Cd, Co, Cu, in humus layer are more affected by the atmospheric impact Fig.2: Sampling sites in southwestern Finland. values were noticed. Mn, Mo, Ni, Pb, Rb, Th, V and Zn scatter plots (Fig. 8). than by the lithogenic contributes.

Geological Survey of Finland Giulia Minolfi*, Timo Tarvainen and Jaana Jarva Geological Survey of Finland, P.O.Box 96, 02151 ESPOO, Finland * Corresponding author: [email protected]