5500 YEARS OF LEAD DEPOSITION RECORDED IN STAROSELSKII MOCH, AN OMBROTROPHIC

PEAT BOG IN NW RUSSIA

Tatiana Pampura1, E. Novenko2, S. Dril3, O. Zarubina3, T. Vladimirova3, M. Meili4
1Instituteof Physicochemical and Biological Problems in Soil Science RAS, Pushchino, Russia
2M.V. Lomonosov Moscow State University, Geographical department, Moscow, Russia
3A.P. Vinogradov Institute of Geochemistry RAS, Irkutsk, Russia
4Stockholm University, Department of Environmental Science and Analytical Chemistry (ACES), Stockholm, Sweden

pampura@mail.ru

INTRODUCTION Ombrotrophic peat is widely used as an archive for reconstructing atmospheric deposition of Pb and other elements. Profiles dated
with 210Pb and 137Cs and covering the past 100-150 years allow tracing of changes in Pb sources and deposition fluxes, reflecting industrial activity and
also consequences of the introduction and ban of leaded gasoline over the past decades. Recent changes can be related to pre-industrial changes
recorded in deep peat layers dated with 14C. Application of Pb isotope geochemistry facilitates the identification of Pb sources and their changes over
time. However, no such documentation is available for the vast territory of Russia. The aim of this study was the reconstruction of the natural and
56.47588°N, 33.04627°E
anthropogenic Pb deposition history over several millennia, based on a combination of elemental concentrations and isotopic ratios in dated
ombrotrophic peat.

STUDY AREA Peat cores were collected in the ombrotrophic peat bog Staroselskii Moch located in the Central Forest State Natural Biosphere Reserve,
Tver region, NW Russia (56.47588°N, 33.04627°E) in August 2013: three 5.5 m cores covering almost 9000 years and a 64 cm surface monolith were taken
using a Russian and a Wardenaar corer, respectively. The lower margin of ombrotrophic peat was determined at 4.0 m (5500 years).

METHODS Peat cores and monolith were sliced into 2-cm sections, and bulk density and loss on ignition (550, 900°C) were determined. The upper part
of the peat was dated from profile of unsupported 210Pb (t 1/2 22.3 yr) determined by alpha spectrometry (Flett Research Ltd., Canada). Two dating models
(linear regression model LRM and constant rate of supply model CRS, Appleby, 2001) provided very similar results, and also showed good agreement
with 137Cs profiles determined by gamma spectrometry (Stockholm University) revealing a distinct peak from the Chernobyl fallout in 1986. The lower
part of the core was dated using 14C (Institute of Geography RAS, Moscow). After ashing (550 °C), samples were totally digested in concentrated HF,
HNO3 and HCl at 120 °C, dried, and diluted in 3% HNO3 for determination of element concentrations and Pb isotopes by ICP-MS (NexION 300D, Institute of
Geochemistry RAS, Irkutsk).
206 Pb/ 207 Pb
1820 AD Age, yr 602
BP AD Bulk density, g cm-3 Ash, %
1 10 100 1000 100000.0 0.1 0.2 0.3 0.4 0.50 1 10 0.001 100 0.1 10 1000 0.01
100000 0.1 1 10 100 10001.12 1.17 1.22 1.27 1.32
0 0 0 0 0 0
1979
1953
50 1936
50 50 50 50 50
1820 AD

445 100
AD 100 445501
AD
100 100 100 100
1416
1592AD
1415 AD
150 150 Core SM1 150 150 150 150
183 AD Core SM 154
183 AD
Core SM1а Peat
Pb-210 (CRS) Core SM 200 Monolith
200 602 AD 200 200 Ti200
ppm 200
1949 BC Monolith 1949 BC
Cs-137, Chernobyl
Depth, cm

250 250 250 250 250 250

1986 Local brown coal
2311 BC Li ppm 2311 BC Pb ppm
C-14, Cal yr BP
300 300 300 300 300 300

PB-210 (LRM) Pb/Ti*1000 Russian gasoline

350 350 350 350 Sc350
ppm 350
OMBROTROPHIC PEAT 3822 BC 1995 г (Mukai et
3822 BC al, 2001)
400 400 400 400 400 Pb/Sc 400
TRANSITIONAL PEAT K ppm Preanthopogenic
450 450 450 450 450 450 deposition
Pb/Ash
MINEROTROPHIC PEAT 6098 BC
6098 BC
500 500 500 500 500 500
Pb/Li
GYTTJA 7779 BC
7779 BC
550 550 550 550 550 550

Pre-anthropogenic atmospheric deposition

Fig. 1. Characteristics of peat profile

Results
Deep layers in the ombrotrophic (atmospherically fed) peat represent background conditions 2700-5700 yr ago with respect to ash, Pb atmospheric
deposition flux and isotopic composition: 1.47 ± 0.51 Ash %, 0.013 ± 0.011 Pb mg m-2 yr-1, 206Pb/207Pb background = 1.197 ± 0.006, 208Pb/206Pb =
2.080 ± 0.006.
Already about 2000 years ago, Pb concentrations started to grow and isotopic composition started to shift towards less radiogenic ore-Pb (Fig 1).
Deposition of Pb reached a maximum of about 17 mg m-2 yr-1 in the 1930s, exceeding the background level about 1200 times. Despite a pronounced
Nelidovo, Tver region, Russia, mine №3
decrease in Pb deposition since the 1970s, the modern deposition (0.7 mg m-2 yr-1) still exceeds the background value about 50 times (Fig 2a).
56.24788°N, 32.78986°E
Shift of isotopic ratios with time towards the less radiogenic values confirms the dominating role of ore-derived Pb in anthropogenic deposition. Slagheaps
Fractions of natural (background) and anthropogenic (ore/gasoline) Pb in deposition were calculated using a mixing model based on 206Pb/207Pb
ratios. Results show that the fraction of ore/gasoline-Pb reached a maximum of 80% in the last decade of the XX century, while in the modern
deposition the fraction is about 70%. However, the uncertainty of such calculations is considerable (standard error about 20%) (Fig. 2b). SOURCES OF Pb in ombrotrophic peat

Anthropogenic
100.00 1000.000 1. Brown coal excavated from local mines in 1948-1996 yr, the
a 1975
Peat, Pb mg/m2/yr slagheaps still remain at a distance of about 40 km. Мaximum coal
10.00
production was >1 000 000 t in 1975, totally > 30 000 000 t
Pb мг/м2/г
1936 100.000
206Pb/207Pb coal = 1.285 ± 0.063, 208Pb/206Pb = 1.954 ± 0.095
Model deposition, Pb
1.00 mg/m2/yr, EMEP
10.000 2. Leaded gasoline used in Russia from the 1930s until 2003. The
0.10
Anthropogenic emission isotopic composition of gasoline Pb agrees well with the average
of Pb, Former USSR, isotopic composition of the main Pb-ore deposits in Russia and
1.000
0.01 1000 t/yr (Pacyna and the former USSR (Mukai et al., 2001, Haak et al., 2000) and
Pacyna, 2000)
Pb mg/m2/yr, Sweden,
average Russian aerosols in 1990-1999 (Mukai et al. 2001):
0.00 0.100 biomonitiring (from
Hansson et al., 2015) 206Pb/207Pb gasoline = 1.151 ± 0.009 (used for mixing model),
-6500-6000-5500-5000-4500-4000-3500-3000-2500-2000-1500-1000 -500 0 500 1000 1500 2000 2500 1820 1840 1860 1880 1900 1920 1940 1960 1980 2000 2020
208Pb/206Pb gasoline = 2.115 ± 0.007 (Mukai et al., 2001).

120 120 1990

b 100
206Pb/207Pb ore = 1.161 ± 0.060,
Fraction of Pb-ore (=Pb-
100 208Pb/206Pb ore = 2.103 ± 0.069 (based on Mukai et al., 2001,
80 gasoline), %
Fraction of Pb-ore 60 Haak et al., 2003).
(=Pb-gasoline), % 80 Period of coal mining 206Pb/207Pb aerosols = 1.140 ± 0.020,
40
20 208Pb/206Pb aerosols= 2.122 ± 0.019 (based on Mukai et al., 2001).
60
0 Period of leaded
-20 40
gasoline Natural
-40
The Second World War
Geogenic Pb in dry and wet deposition. Isotopic composition of
-60 20 pre-anthropogenic Pb deposition determined as an average for
-80 deep layers of ombrotrophic peat (207-365 cm, 2700-5700 yr BP)
-100 0
-6500-6000-5500-5000-4500-4000-3500-3000-2500-2000-1500-1000 -500 0 500 1000 1500 2000 2500 1820 1840 1860 1880 1900 1920 1940 1960 1980 2000 2020 206Pb/207Pb background = 1.197 ± 0.006 (used for mixing
Year BC(-) /AD Year
model)
208Pb/206Pb background = 2.080 ± 0.006
MINEROTROPHIC PEAT OMBROTROPHIC PEAT

Fig. 2. History of Pb deposition (a) and fraction of anthropogenic ore(gasoline)-derived Pb in atmospheric deposition (b). Dates are
calculated using CRS model (Pb-210) above the depth of 64 cm, and linear regression model based on C-14 dates (calibrated yr BP) Conclusion
below 64 cm. Our study demonstrated a predominance of anthropogenic Pb
in modern deposits of lead in NW Russia, even after the
Our data on Pb deposition agree well with Pb deposition, modeled for our sampling site by MSC EAST EMEP
significant reduction of Pb (deposition) emissions during the
http://www.msceast.org/index.php/reports (1990-2012), and with Pb deposition data for southern Sweden, based on herbaria mosses (1870-1960)
past decades.
and on forest moss biomonitoring program (data from IVL.se,1975-2005) (cited from Hansson et al., 2015) (Fig. 2a).

Supported by a grant of the Russian Foundation for Basic Research № 13-05-00958а 8th International Conference on Heavy Metals in the Environment 12 to 15 September 2016 Ghent, Belgium