Emissions in the Soviet Union - American Chemical Society

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Ice-Core Based Assessment of Historical Anthropogenic Heavy Metal (Cd, Cu, Sb, Zn) Emissions in the Soviet Union Anja Eichler,*,†,‡ Leonhard Tobler,†,‡ Stella Eyrikh,§ Natalia Malygina,§ Tatyana Papina,§ and Margit Schwikowski†,‡,∥ †

Paul Scherrer Institute, CH-5232 Villigen PSI, Switzerland Oeschger Centre for Climate Change Research, University of Bern, 3012 Bern, Switzerland § Institute for Water and Environmental Problems, Siberian Branch of the Russian Academy of Sciences, 656038 Barnaul, Russia ∥ Department of Chemistry und Biochemistry, University of Bern, Freiestrasse 3, 3012 Bern, Switzerland ‡

S Supporting Information *

ABSTRACT: The development of strategies and policies aiming at the reduction of environmental exposure to air pollution requires the assessment of historical emissions. Although anthropogenic emissions from the extended territory of the Soviet Union (SU) considerably influenced concentrations of heavy metals in the Northern Hemisphere, Pb is the only metal with long-term historical emission estimates for this region available, whereas for selected other metals only single values exist. Here we present the first study assessing long-term Cd, Cu, Sb, and Zn emissions in the SU during the period 1935− 1991 based on ice-core concentration records from Belukha glacier in the Siberian Altai and emission data from 12 regions in the SU for the year 1980. We show that Zn primarily emitted from the Zn production in Ust-Kamenogorsk (East Kazakhstan) dominated the SU heavy metal emission. Cd, Sb, Zn (Cu) emissions increased between 1935 and the 1970s (1980s) due to expanded non-ferrous metal production. Emissions of the four metals in the beginning of the 1990s were as low as in the 1950s, which we attribute to the economic downturn in industry, changes in technology for an increasing metal recovery from ores, the replacement of coal and oil by gas, and air pollution control. records from Alpine ice cores15,16 extended our understanding of the response of this region to changing emissions from the strongly populated areas in Western Europe. Air pollution from metallurgical industries and coal combustion in Eastern Europe, e.g., the Soviet Union (SU), Poland, and the Czech Republic, caused widespread damage on the environment and human health (for example, see refs 17 and 18). However, no longterm assessment of heavy metal emissions other than Pb for this region exists so far, except a few heavy metal concentration records with low temporal resolution from sediment and peat bogs in Eastern Europe (see, for example, refs 19 and 20). In these studies actual emissions were not quantified. In this study we present Cd, Cu, Sb, and Zn concentrations for the time period 1680−1991 AD, obtained from an ice core of the Belukha glacier in the Siberian Altai. This region is mainly affected by westerly air masses and thus is located downwind from the major source regions of heavy metal emissions in the SU (see Figure 1). The obtained concentration records are used to assess for the first time historical

1. INTRODUCTION The atmospheric cycle of heavy metals introduced by human activities is much more extended than their natural cycle and has caused related pollution to be a worldwide issue for humans and the environment. Major anthropogenic emission sources are mining, ferrous and non-ferrous metal production, and fossil fuel combustion. Extended research has been performed to study the impact on the environment and human health (for review see, e.g., ref 1), whereas less information is available on heavy metal emission sources and quantities. Such information is needed for the development of strategies and policies aiming at the reduction of environmental exposure to heavy metals.2 Consequently, efforts have been made to assess metal pollution by conducting monitoring programs and compiling emission inventories.3−5 These studies, however, cover only very short time periods from days to single years. Furthermore, a main focus of the performed research is on Pb, after large amounts of this neurotoxic metal had been released into the atmosphere from lead additives in gasoline. Complementary ice cores from Greenland,6−8 the Canadian Arctic,9 Himalayas,10,11 Pamir,12 Tien Shan,13 and Antarctica14 have been used to trace anthropogenic perturbations to the atmosphere from emissions of other heavy metals as Cd, Cu, Sb, and Zn from industrial activities in North America, Asia, and South America during the 20th century. Heavy metal © 2014 American Chemical Society

Received: Revised: Accepted: Published: 2635

October 31, 2013 January 30, 2014 February 10, 2014 February 10, 2014 dx.doi.org/10.1021/es404861n | Environ. Sci. Technol. 2014, 48, 2635−2642

Environmental Science & Technology

Article

Figure 1. (Left) Map of the former Soviet Union22 (pink) together with the location of the Belukha glacier (blue star). Circles indicate the sum of estimated Cd, Cu, Sb, and Zn emissions at 12 regions in the SU for the year 1980 in tons/year (see Table 2). (Right) Frequency plot of seven-day back trajectories for the period 1991−2000 using HYSPLIT and NCEP reanalysis. Back trajectories were run every 6 h.

shown30,31 to be as efficient, but much less time-consuming, compared to the method applied in other studies,7 where the pristine inner part of the ice core was obtained by chiseling off the outer layers using stainless steel scalpels. The decontaminated core sections were transferred into high-density polyethylene containers (HDPE, Nalgene), acidified with hydrochloric acid (HCl, Ultrex II, Baker) to yield a final acid concentration of 0.4%, and subsequently melted at room temperature. We applied HCl instead of the most commonly used HNO37,14 for acidification since the simultaneous analyses of Hg in the same samples required HCl.32 Tests of acidification with HCl and HNO3 showed comparable metal concentrations. Acidification time was at least 24 h before analysis. Concentrations of Cd, Cu, Sb, and Zn were determined by inductively coupled plasma sector field mass spectrometry (ICP-SF-MS) using a Finnigan MAT Element1 (Thermo Finnigan Bremen, Germany).27,33,34 A 100-μL self-aspirating PFA-nebulizer (Elemental Scientific Inc., Omaha, NE, USA) with a cooled Scott-type glass spray chamber together with an autosampler (221 XL, Gilson Inc., Middleton, WI, USA) were used for sample introduction in a laminar flow clean bench (class 100). Linear regression of the external calibration between 1 ng/L and 50000 ng/L was used for quantification. Concentrations were blank-corrected by subtracting the procedural blank and substituted with half the detection limit value if concentrations were below the detection limit.

anthropogenic emissions of Cd, Cu, Sb, and Zn from the territory of the SU during the period 1935−1991.

2. EXPERIMENTAL SECTION 2.1. Sampling Site and Ice-Core Characteristics. In July 2001 a 139-m-long ice core was retrieved from the glacier saddle between the two summits of Belukha, the highest mountain in the Altai region, at the border between Russia, Kazakhstan, China, and Mongolia (49°48′26″N, 86°34′43″E, 4062 m a.s.l.)21 (Figure 1). Ice-core sections (0.7 m long, 7.8 cm diameter) were sealed in polyethylene tubes in the field and transported frozen to the Paul Scherrer Institute (PSI). In this work only the upper part of the ice core (9−113 m) was analyzed, covering the time period 1680−1991. The time scale was derived using a combination of annual layer counting, 210Pb dating, and a nonlinear regression23 through reference horizons related to the maximum of nuclear weapons testing (1963, 3H maximum) and several volcanic eruptions.24−26 The dating uncertainty is ±3 years for the period 1815−1991 and ±5 years between 1680 and 1815. The ice core was already proven to be an invaluable archive of past Eastern European air pollution,26−28 temperature changes in Siberia,24,25 and variations in forest-fire activity and biogenic emissions from Siberian boreal forests.28,29 2.2. Sample Preparation and Analytical Procedures. A total of 484 samples with lengths between 10 and 70 cm were prepared for analyses in the cold room of the PSI at −20 °C.27 Sampling resolution of the continuous record varied from up to six samples per year in the period 1950−1991 to about one sample per year in the period 1680−1700, and 8% of the investigated core interval could not be analyzed due to poor ice quality (small chips). Inner sections of the cores with a cross section of ∼2 cm × 2 cm were cut out using a modified bandsaw setup with stainless steel saw blades and Teflon-covered tabletops and saw guides. To remove possible contamination from the cutting process, ∼0.3 cm of the surface of the firn sections were chiseled with a ceramic knife, whereas ice samples were rinsed with ultra pure water (Milli Q, 18 MΩ cm quality). The applied decontamination was tested and has already been

3. RESULTS AND DISCUSSION 3.1. Data Presentation. Ice-core concentration records of Cd, Cu, Sb, and Zn are presented in Figure 2. As additionally shown in the summary statistics (Table 1), concentrations of the different elements reveal a pronounced variability linked to (a) short-term intra-annual variations, (b) sporadic concentration maxima, and (c) a strong long-term trend: (a) Heavy metal concentrations vary strongly with the season and show differences of about one order of magnitude between summer and winter values. Similar to observed changes in major ions at the Belukha glacier,26 such concentration 2636

dx.doi.org/10.1021/es404861n | Environ. Sci. Technol. 2014, 48, 2635−2642


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China (Taklimakan desert), which are major source regions of mineral dust aerosols.26,37 Accordingly, many of the observed sporadic concentration maxima of the metals can be related to an input of mineral dust aerosols, indicated by high concentrations of typical geogenic tracers (as Al and Fe). However, the mineral dust composition particularly for trace components varies depending on the source region, resulting in different input of Cd, Cu, Sb, and Zn. Frequently, dust input led to pronounced concentration maxima of single elements (e.g., Cd ∼1884/86, Cu ∼1790, Zn ∼1818, Sb ∼1905), while only a few dust events caused similar maxima in the Cd, Cu, Sb, and Zn concentration records (e.g., ∼1774) (see Figure 2). To determine the impact of changing mineral dust input on the heavy metal records, crustal enrichment factors (EFs) were calculated (Supplementary Figure S1) using Ca as a dust tracer and following the conventional equation EF(X) = [X/Ca]sample/ [X/Ca]reference, with the composition of the upper continental crust as reference.38 The geogenic crustal elements Al and Fe could not be used for the EF calculation, since they are affected by anthropogenic sources (as indicated by the high correlation between Al and Cu, Zn, Sb, Cd, period 1935−1991, Supplementary Table S1). In general, heavy metal concentrations and EF records are very similar showing strongly elevated values after ∼1935. However, pronounced concentration maxima from dust input (Cd 1774, 1884/86; Cu ∼1774, 1790; Zn ∼1774, 1818 see above) are still dominant in the EF records. This implicates inhomogeneity of the deposited dust aerosols with varying trace element composition and additional sporadic inputs from other sources than mineral dust. Generally, explosive volcanic eruptions are not a major source for heavy metals in the ice core. Most pronounced maxima in the exSO42‑ concentration record related to the eruptions in 1739, 1783, 1815, and 191224,27 are not accompanied by elevated Cd, Cu, Sb, and Zn concentration maxima. Only the Cd maximum in 1884/86 might be due to a simultaneous input of mineral dust and volcanic emissions following the Krakatao eruption (1883). Sea salt is considered a negligible source of the four metals due to the large distance between the ice core site and the oceans. Biogenic emissions of ammonia and formic acid from Siberian boreal forest increased between 1700 and 1900.28 No corresponding concentration trend is observed for the heavy metals, suggesting that the biogenic contribution is minor. Siberian forest fires peaked in 1770−80 and 1820−30.29 Thus, the exceptional maximum of all elements in 1774 (Figure 2) might be caused by a simultaneous input from mineral dust and forest fires. Therefore we can not exclude a sporadic impact from natural sources other than mineral dust on the heavy metal concentration records. 3.3. Anthropogenic Sources of the Heavy Metals. 3.3.1. Period 1680−1935. Vast polymetallic deposits of late Devonian age containing, e.g., massive sulfide ores of Pb, Cu, Zn, Au, Ag, As, Fe, and Sb are found in the Altai region within

Figure 2. (a) Concentration records of Cd, Cu, Sb, and Zn covering the period 1680−1991. Shown are annual means (black dashed line) and 5-year means (red line).

variations at high-elevation sites are well documented34,35 and attributed to different meteorological conditions within the seasons. While convective transport of pollutions from the boundary layer to the high-altitude sites is favored during the summer months, this process is hindered during the colder seasons due to the higher stability of the atmosphere. (b) Sporadic concentration maxima of the metals can be related to an input of mineral dust aerosols from sedimentary dust areas or to emissions from volcanic events and forest fires (see section 3.2). (c) To infer long-term trends in the concentration records, observed sporadic maxima were removed from the data set. We defined a threshold value using the interquartile range (IQR = Q3 − Q1 where Q1 is the first quartile and Q3 is the third quartile) as a criterion. To account for temporal changes in the threshold value, a running IQR was calculated by moving a window of 15 years through the annual concentration records. Element concentrations above the upper threshold of Q3 + 1.5· IQR were removed from the data set. Five-year averages were calculated from the reduced data set to investigate the longterm trends in the Cd, Cu, Sb, and Zn concentrations records (Figure 2). Concentrations of all four trace metals remained on a low level in the period from 1680 to ∼1935 and are strongly elevated between ∼1935 and 1991. Cd, Sb, and Zn concentrations increased until the 1970s but dropped already at the end of the 1970s. This is different for Cu, decreasing only after the mid-1980s. 3.2. Natural Sources of the Heavy Metals. Natural sources of Cd, Cu, Sb, and Zn include mineral dust and sea salt particles, volcanoes, forest fires, and direct biogenic emissions.36 The study site is located close to the deserts in Kazakhstan and

Table 1. Cd, Cu, Sb, and Zn Detection Limits (DL), Procedure Blanks Determined by Analyzing Ice Prepared from Ultra Pure Water, and the Minimum, Maximum, and Median Values for the Periods 1680−1935 and 1935−1991 (in ng/L) DL Cd Cu Sb Zn

0.3 5.4 0.9 43

procedure blank

min−max (median) 1680−1935

min−max (median) 1935−1991

± ± ± ±

0.15−291 (2.6) 2.7−1230 (44) 0.45−25 (4) 22−5990 (271)

2.9−181 (28) 8−3390 (378) 4.3−121 (26) 220−15600 (1700)

2 37 3 103

1.7 24 2.5 27 2637



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an area of about 500 km length and 60−100 km width.39,40 Mining activities in the Rudny Altai (Russian for “ore Altai”) started already in the Bronze Age, whereas extensive metal mining began in the beginning of the 18th century.41 In the 18th and early 19th centuries, 90% of Russian silver was produced in the Altai. During 1766−1781 Siberian copper coins and between 1781 and 1847 all Russian silver and gold coins were manufactured in this region.42 Although the Altai was one of the major non-ferrous metal producing areas during the 19th century,42 no related increase of the ice-core Cu and Zn concentrations was observed during that time (Figure 2). This is different for Sb and Cd. Sb concentrations increased significantly at the end of the 18th century, whereas Cd concentrations reveal two periods of elevated concentrations at the end of the 18th and beginning of the 19th century. These metals were mainly secondarily emitted during the production of non-ferrous metals, e.g., Pb, Cu, and Zn.43 The intensified mining and related metallurgical processing in the Altai for the production of Russian coins since the time of Catherine the Great left already a clear fingerprint in the ice-core Pb record.27 Pb concentrations increased at the end of the 18th century and continued to rise further at the beginning of the 19th century, parallel with the temporal development of the number of smelters and metallurgical plants in the Altai region. We explain the differences in the temporal evolution of the metal concentrations with differences in the volatility of the emitted compounds from mining and metallurgical processing. The volatility and thus the mobility of the emitted Pb, Cd, and Sb species (e.g., Pb, PbS, PbO, Cd, CdS, Sb2S3, etc.) is higher than that of the released Cu and Zn oxides and sulfides.44 3.3.2. Period 1935−1991. After ∼1935, heavy metal concentrations increased noticeably due to rapid industrialization in the SU following the introduction of the five-year plans. These plans pushed an enormous development in the production of industrial goods including steel, iron, and nonferrous metals. There are almost no SU emission data for the heavy metals Cd, Cu, Sb, and Zn available, and the few data published vary about one order of magnitude depending on the data source, as official statistical data, expert evaluations, or data of emission inventories compiled in the framework of international projects.45,46 For the estimation of the major sources and source regions of the investigated metals in the SU, we used a report of the Norwegian Institute for Air Research (NILU), providing emission data for selected heavy metals from 12 regions in the SU for the year 1980.47 This emission survey was established to obtain a basis for modeling the long-range transport of trace elements to the Arctic. Due to the reluctance of the SU to provide information on the capacity and air pollution of their industries, there might be a number of uncertainties in the survey, and only recently this first report had been partly updated and improved.48 Accordingly to the report, the most significant emissions sources of heavy metals in the SU are Pb and Zn production in the Kuznetsk area (close to the drilling site) and Fergana area (see Figure 1, Table 2). Major single sources of the four metals discussed in the present study are as follows: Cu: The main source of Cu in the SU was copper−nickel production. The largest copper mining and smelting complexes were in Norilsk, the Kola Peninsula, and the Fergana area (Balkhash and Dzhezkazgan plants in Kazakhstan).

Table 2. Emission Estimates of Heavy Metals Cu, Zn, Sb, Cd in the SU for the year 198047 from 12 regions of the SUa

a

Updated values for Kola and Norilsk48 are also given (second values*). The total emissions at the 12 regions and the SU are given in bold, the major single regional sources are in cursive, and the four most dominant regional sources are in red, respectively.

Zn: Lead-zinc and steel-iron production were the major sources of Zn in the SU. More than half of the lead-zinc production in the SU was in the Kuznetsk area including the Altai (Ust-Kamenogorsk, Leninogorsk, Salair). The second largest lead and zinc producing area was the Fergana area (Kentau, Taschkent, Almalyk). Steel and iron manufacturing was concentrated along the Urals (e.g., Serov, Nishni Tagil), Kuznetsk, and Donetsk area. Sb: One of the major Sb sources was secondary emission during copper-nickel and steel-iron production. Coal burning in the Donetsk and Kuznetsk area released also considerable amounts of Sb. Cd: Secondary emission from lead-zinc and copper-nickel production was the main source of Cd in the SU. During the 1970s the SU had the biggest complex of metallurgical industries and was the largest producer of crude steel, lead/zinc, iron ore, and other metals worldwide.49 Starting at the end of the 1970s the SU economy slowed down, strongly affecting also the nonfuel mineral industry. Problems such as rising costs of production and shortages of investment and labor but also increasing depletion of mines and delays in commissioning new mine capacity resulted in a substantially reduced growth or even decline in metal production during the 1980s. The first drop in steel production after World War II was around 1979−83, whereas the growth in non-ferrous metal production slowed down from 5.5%/year (1971−75) to 2.5%/year (1976−80).49 The collapse of the SU economy at the end of the 1980s finally caused a dramatic decrease in metal production (see also Figure 3). Ice-core Cd, Sb, and Zn concentration maxima are in the 1970s, although the Zn, Pb, steel, and Cu production (being the major sources of the three metals) increased until the end of the 1980s (see Figure 3). This is different for Cu, where both 2638



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than half of the Zn in the SU, implemented new filters in 1978.58 c. Implementation of New Facilities and Technologies. In 1955 a new zinc factory started to operate in Ust-Kamenogorsk (Kuznetsk area). A modern technological scheme was introduced, which allowed obtaining refined Zn according to global standards.59 The plant Nadezhda, the youngest metallurgical enterprise of “Norilsk Nickel” (Norilsk area), started working in 1979, producing Cu and Ni concentrates at high technological and environmental standards.60 d. Shifts in the SU Energy Balance. Due to the discovery of large natural gas reserves in the 1970s and 1980s, a dramatic shift in the SU energy mix occurred away from heavy reliance on coal and oil in favor of increased consumption of gas.53 This shift is partly responsible for the drop of the SU stationary emissions from the 1970s on (Figure 3, ref 53) and influenced certainly also heavy metal emissions from the energy sector. 3.4. Estimation of Anthropogenic Cd, Cu, Sb, and Zn Emissions in the SU during the Period 1935−1991. 3.4.1. Method and Validation. The analyses of back trajectories illustrates that the major source region of air pollution arriving at the Belukha site is primarily the territory of the SU except for the eastern-most Siberian parts (Figure 1,27,28). In an earlier study we observed a good agreement between ice-core Pb concentrations and historical Pb emission estimates of the SU during the period 1955−1991.27 Similar long-term estimations do not exist for other heavy metals. As pointed out above, detailed emission histories from different regions in the SU for these metals exist only for the year 1980.47,48 Provided that the relation between metal emission and deposition did not change significantly with time, historical Cd, Cu, Sb, and Zn emissions were calculated from the respective concentration records, applying a two-point linear regression using two assumptions: (1) The concentration averages during the period 1850− 1920 correspond to a SU metal emission of 0 tons/year. (2) Emission values for the year 1980 are in accordance with the SU estimates from the updated NILU report (see Table 2).47,48 For the validation of our method we used the ice-core Pb record. The SU Pb-emission estimate for the year 1980 from the report is 30700 t/year. We performed the two-point linear calibration assigning the 1850−1920 and 1980−1984 Pb concentration averages of 120 ng/L and 1450 ng/L to the emission values of 0 and 30700 t/year, respectively. SU Pbemissions for the period 1950−1991 based on this calibration and the Pb concentration record (Figure 4, ref 27) are in remarkable good correspondence with published longer-term emission estimates.46,61 Thus, even when using the old Pb emission estimate for the single year 1980 together with the icecore Pb concentrations, recent updated Pb emission estimates could be well reproduced. 3.4.2. Estimation of Anthropogenic Cd, Cu, Sb, and Zn Emissions. Pb is transported together with the other heavy metals, which is supported by the highly significant correlations during 1935−1991 (Supplementary Table S1). Based on the common transport and the successful validation of the regression method, historical Cd, Cu, Sb, and Zn emissions were calculated from the respective ice-core concentration records applying the assumptions mentioned above. Emission estimates for the year 1980 are 820, 320, and 20600 t for Cd, Sb, and Zn, respectively. These are updated values (see

Figure 3. SU production of crude steel in million tons (blue, period 1950−91),50 primary smelter zinc in 1000 tons (green, period 1959− 91),51 and primary blister copper in 1000 tons (black, period 1930− 1983,54 period 1983−199151), together with the total SU stationary emissions in million tons (red, period 1976−9052,53).

the production and ice-core concentrations peaked in the 1980s. In addition to the economic downturn in industry, there are various possible causes for the drop of the heavy metal concentrations in the 1970s/1980s: a. Decline in the Average Grade of the Ores. The average grade of Cu and Zn ores has dropped by about 50% since the mid-1960s.49 One measure to sustain Cu production was the increase of the mined ore volume.55 In the early 1980s the SU started to import Cu ore from the Erdenet mine in Mongolia (∼120.000 t/year) and Cu concentrates from Western countries (29.000−32.000 t/year, period 1980−82).55 Nevertheless, overall the Soviet Union was always a net exporter of Cu to the east block countries. In contrast, the SU changed from a net exporter to a net importer for Zn and Zn concentrates in the mid 1970s,49 as a consequence of mine depletion, deteriorating ore quality, and lagging development of new mining capacity. This could be one reason for the decreasing concentrations of Zn and Cd (being a byproduct of zinc smelting and refining43) in the 1970s. b. Air Pollution Control. Overall air pollution from stationary sources in the SU declined about 30% between 1976 and 1991 (see Figure 3 and refs 52 and 53). This is partly a result of an effort of the SU government in the 1970s to improve urban air quality. The SU set temporary emission limits for over 200 chemicals in use in the 1970s.56 In 1981, a new law was introduced, requiring all new enterprises or enterprises that renovate or modernize their production processes to ensure that emissions complied with established norms.53 However, this effort was hampered by a lack of available technology, the reluctance to sacrifice output in favor of pollution control, and the non-strict control of the required implementations. Furthermore, existing SU smelting and mining facilities were not subject to the same law but were expected to control their emissions at least to some extent. Thus, used technology was often out-of-date.55 Little information about new implementations in existing facilities is available. In 1974 the Chimkent lead plant (Fergana area), producing 90% of Pb in the SU, was one of the first among similar enterprises that introduced filters with a jet blowing to clean the vent gases of the smelter shop.57 This reduced the dust content of the air and allowed extraction of some additional amount of valuable metals. Likewise, the zinc factory in Ust-Kamenogorsk (Kuznetsk area), producing more 2639



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Table 3. Estimated Anthropogenic Emissions of Heavy Metals from the Territory of the SU (tons/year); Given Is the ±1σ Range (Gray Area from Figure 5)

Figure 4. Validation of the estimation method for SU heavy metal emissions during the period 1950−1991 based on Pb. Historical Pb emissions were estimated using the ice-core Pb concentrations27 and the SU emission estimate for the year 1980 (30700 t)47 and compared to published values (triangles and diamonds).46,61 Gray bars represent 1σ ranges.

period

Cd

Cu

Sb

Zn

1950−1955 1955−1960 1960−1965 1965−1970 1970−1975 1975−1980 1980−1985 1985−1990 1990−1991

280−530 510−700 500−630 700−880 920−1080 730−870 680−970 540−820 380−630

1060−1720 4140−5900 4160−7320 6530−8250 5600−6900 5300−8600 5160−8840 4890−8220 1730−3000

170−240 130−220 160−210 220−320 370−500 310−380 250−380 270−370 160−240

5200−10650 9800−17900 17300−27200 29600−34700 25300−33700 27290−39900 16000−25600 20800−26900 9980−17100

In general, there is good agreement between the concentration and EF based reconstructions. We attribute discrepancies (e.g., in 1940 and 1955) to an inaccurate dust correction, caused by inhomogeneous dust composition (see section 3.2). In general, Zn predominantly emitted from Zn production in East Kazakhstan dominated the heavy metal emission from non-ferrous metal/iron and steel production during SU times, showing levels in the same order of magnitude as Pb emissions from leaded gasoline (Figures 4 and 5). Due to a combination of changes in technology for an increasing metal recovery from ores, air pollution control, the replacement of coal and oil by gas, and the economic downturn in industry (see above), the emissions of the metals Cd, Cu, Sb, and Zn revealed in the beginning of the 1990s the level of the 1950s.

section 3.3 and Table 2), which are not significantly different from the original NILU report. This is different for Cu, where emissions from the Cu−Ni production at Kola and Norilsk were underestimated in the old report. A mean between the old and updated emission estimates of 7000 t in 1980 was thus used for the Cu regression. The calculated heavy metal emission records together with the 1σ levels for the period 1935−1991 are presented in Figure 5. Values for the validation

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ASSOCIATED CONTENT

S Supporting Information *

Additional figures and a table with correlation analyses, Cd, Cu, Sb, and Zn EF records, and the emission estimates based on the EFs. This material is available free of charge via the Internet at http://pubs.acs.org.

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AUTHOR INFORMATION

Corresponding Author

*Phone: +41 56 310 2077. Fax: +41 56 310 4435. E-mail: anja. [email protected]. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS We thank Patrick Ginot, Beat Rufibach, Susanne Olivier, Martin Lüthi, Henrik Rhyn, Dimitrii N. Kozlov, Sergej Derewstschikow, Vladimir Vashenzev, Andrej Jerjomin, Veronica Morozova, Alexander Chebotkin, and Igor Karakulko for their valuable help during the ice core drilling expedition in the Altai. We thank the three anonymous reviewers for their valuable and constructive comments.

Figure 5. Estimated Cd, Cu, Sb, and Zn emissions in the SU during the period 1935−1991 in tons/year based on ice-core data (5-year averages (black line), ± 1σ range (gray area)) together with published emission estimates (squares).46,62,63

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period 1950−1991 are shown in Table 3. Additional published metal emission estimates for individual years46,62,63 are in fairly good agreement with our estimations for Cu, Zn, and Cd, but less for Sb (Figure 5) keeping in mind the large uncertainties of the published values. To account for a possible bias due to an additional input of the heavy metals with mineral dust, we repeated the calculation of the emission records using EFs (Supplementary Figure S2).

REFERENCES

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