Dr. Friedrich Locher

[Leonhard Tobler

The influence of carbonate complexes on the solubility of zirconia: new experimental data

New experiments conducted at pH 9 and 298 K clearly indicate that addition of bicarbonate ions in aqueous solutions increases the solubility of both cubic and monoclinic zirconia by several orders of magnitude. In pure water the solubility of zirconia proved to be very low (about 10−10 to 10−8 M), while in the presence of 0.05 M NaHCO3 it increased to 10−6– 10−5 M, indicating the formation of strong carbonate complexes. Due to the limited number of available data and the restricted experimental conditions (fixed pH) it was not possible to identify the stoichiometry of the complex(es). However, up to a total carbonate concentration of 0.05 M, our data are consistent with the formation of a mononuclear tetracarbonate or pentacarbonate complex. At higher carbonate concentrations basic Zr carbonates are possibly formed. The formation constant fitted for the pentacarbonate complex is at the upper limit of a range previously estimated with the help of data on analogous actinide-carbonate complexes. Although our results are not sufficient to determine reliable thermodynamic data for the complexation of Zr with carbonate, they can be used to set limits to the solubility of inert matrix spent fuel in radioactive waste storage environments. Our measurements indicate a Zr solubility in the order of 10−6 to 10−5 M for typical repository conditions, which is still 2–3 orders of magnitude below silica concentrations measured from the dissolution of nuclear waste glasses

Ice-Core Based Assessment of Historical Anthropogenic Heavy Metal (Cd, Cu, Sb, Zn) Emissions in the Soviet Union

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

The onset of Neoglaciation 6000 years ago in western Mongolia revealed by an ice core from the Tsambagarav mountain range

Glacier highstands since the Last Glacial Maximum are well documented for many regions, but little is known about glacier fluctuations and lowstands during the Holocene. This is because the traces of minimum extents are difficult to identify and at many places are still ice covered, limiting the access to sample material. Here we report a new approach to assess minimal glacier extent, using a 72-m long surface-to-bedrock ice core drilled on Khukh Nuru Uul, a glacier in the Tsambagarav mountain range of the Mongolian Altai (4130 m asl, 48°39.338′N, 90°50.826′E). The small ice cap has low ice temperatures and flat bedrock topography at the drill site. This indicates minimal lateral glacier flow and thereby preserved climate signals. The upper two-thirds of the ice core contain 200 years of climate information with annual resolution, whereas the lower third is subject to strong thinning of the annual layers with a basal ice age of approximately 6000 years before present (BP). We interpret the basal ice age as indicative of ice-free conditions in the Tsambagarav mountain range at 4100 m asl prior to 6000 years BP. This age marks the onset of the Neoglaciation and the end of the Holocene Climate Optimum. The ice-free conditions allow for adjusting the Equilibrium Line Altitude (ELA) and derive the glacier extent in the Mongolian Altai during the Holocene Climate Optimum. Based on the ELA-shift, we conclude that most of the glaciers are not remnants of the Last Glacial Maximum but were formed during the second part of the Holocene. The ice core derived accumulation reconstruction suggests important changes in the precipitation pattern over the last 6000 years. During formation of the glacier, more humid conditions than presently prevailed followed by a long dry period from 5000 years BP until 250 years ago. Present conditions are more humid than during the past millennia. This is consistent with precipitation evolution derived from lake sediment studies in the Altai

<SUP>210</SUP>Pb dating of the Miaoergou ice core from the eastern Tien Shan, China

In 2005, two ice cores with lengths of 58.7 and 57.6 m respectively to bedrock were recovered from the Miaoergou flat-topped glacier (43 degrees 03 ' 19 '' N, 94 degrees 19 ' 21 '' E; 4512 m a.s.l.), eastern Tien Shan. Pb-210 dating of one of the ice cores (57.6 m) was performed, and an age of AD 1851 +/- 6 at a depth of 35.2 m w.e. was determined. For the period AD 1851-2005, a mean annual net accumulation of 229 +/- 7 mm w.e. a(-1) was calculated. At the nearby oasis city of Hami (similar to 80 km from the Miaoergou flat-topped glacier) the annual precipitation rate is 38 mm w.e. a(-1), hence glacial meltwater is a major water supply for local residents. The surface activity concentration of Pb-210(ex) was found to be similar to 400 mBq kg(-1), which is higher than observed at other continental sites such as Belukha, Russia, and Tsambagarav, Mongolia, which have surface activity concentrations of 280 mBq kg(-1). The Pb-210 dating agrees well with the chronological sequence deduced from the annual-layer counting resulting from the seasonalities of delta O-18 and trace metals for the period AD 1953-2005, and beta-activity horizons resulting from atmospheric nuclear testing during the period AD 1962-63. We conclude that Pb-210 analysis is a suitable method for obtaining a continuous dating of the Miaoergou ice core for similar to 160 years, which can also be applied to other ice cores recovered from the mountains of western China

A 320 Year Ice-Core Record of Atmospheric Hg Pollution in the Altai, Central Asia

Anthropogenic emissions of the toxic heavy metal mercury (Hg) have substantially increased atmospheric Hg levels during the 20th century compared to preindustrial times. However, on a regional scale, atmospheric Hg concentration or deposition trends vary to such an extent during the industrial period that the consequences of recent Asian emissions on atmospheric Hg levels are still unclear. Here we present a 320 year Hg deposition history for Central Asia, based on a continuous high-resolution ice-core Hg record from the Belukha glacier in the Siberian Altai, covering the time period 1680–2001. Hg concentrations and deposition fluxes start rising above background levels at the beginning of the 19th century due to emissions from gold/silver mining and Hg production. A steep increase occurs after the 1940s culminating during the 1970s, at the same time as the maximum Hg use in consumer products in Europe and North America. After a distinct decrease in the 1980s, Hg levels in the 1990s and beginning of the 2000s return to their maximum values, which we attribute to increased Hg emissions from Asia. Thus, rising Hg emissions from coal combustion and artisanal and small-scale gold mining (ASGM) in Asian countries determine recent atmospheric Hg levels in Central Asia, counteracting emission reductions due to control measures in Europe and North America