Harald Biester

Binding and mobility of mercury in soils contaminated by emissions from chlor-alkali plants

Chlor-alkali plants are known to be an important source of Hg emissions to the atmosphere and related contamination of soils in their vicinity. In the present study, the results of Hg speciation and mobility of Hg in soils affected by Hg emissions from three chlor-alkali plants are compared. Solid phase mercury speciation analyses was carried out using a mercury-thermo-desorption technique with the aim of distinguishing elemental Hg [Hg(0)] from Hg(II)-binding forms. Mercury species in soil leachates were distinguished using an operationally defined method, which is based on the reactivity of soluble Hg compounds. Results show that the Hg(0) emitted from the plants could not be detected in any of the investigated soils. This indicates quantitative re-emission or oxidation of this Hg species in the atmosphere or soils. In most soils Hg was predominately bound to organic matter. Only in sandy soils deficient in organic matter was Hg, to a larger extent, sorbed onto mineral soil components. Leachable Hg in most soils occurred as non-reactive, soluble organic Hg complexes such as fulvic acid-bound Hg, and reach their highest values (90 microg kg(-1)) in soils rich in organic matter. Concentrations of reactive, soluble Hg compounds were highest in sandy soils where the content of organic matter was low. Leachability of Hg was found to be inhibited in soils with a high content of clayey soil components. The distribution of Hg in soil profiles suggests that migration of Hg to deeper soil layers (approx. 20 cm) is most effective if Hg is bound to soluble organic complexes, whereas reactive Hg or weak Hg complexes are effectively retained in the uppermost soil layer (5 cm) through sorption on mineral surfaces.

Investigation of the light-enhanced emission of mercury from naturally enriched substrates

Incident radiation has been reported to facilitate mercury release from soils. In this study the influence of light on mercury emissions from substrates amended with pure synthetic mercury species, and from naturally and anthropogenically mercury-enriched substrates were investigated using laboratory experiments and in situ flux measurements. Light-enhanced emissions were found to occur from substrates amended with HgS, and from elemental mercury (Hg 0 ) and HgCl2 amended iron oxide and organic containing substrates. The magnitude of light-enhanced emissions for natural substrates ranged from 1.5 to 116 times that occurring in the dark at the same substrate temperature. Substrates containing corderoite, metacinnabar and ‘‘matrix bound mercury’’ (that bound to organic or inorganic phases) exhibited a higher degree of light-enhanced emissions relative to that containing predominantly cinnabar. Calculated activation energies for both laboratory and field data indicate that photo-reduction is a process associated with the light-enhanced emissions. Activation energies, derived using in situ mercury fluxes and soil temperatures, indicated that photo-reduction was a dominant process facilitating release of Hg from substrates with sunrise. Activation energies, calculated using daytime data, were less than those calculated for sunrise. This is hypothesized to be due to a pool of Hg 0 being developed with photo-reduction at first light that is released as soil temperatures and convective heat transfer increase during the day. This study demonstrated that light energy is the more dominant process controlling mercury emissions from naturally enriched substrates than soil temperature. r 2002 Elsevier Science Ltd. All rights reserved.

Mercury speciation in tailings of the Idrija mercury mine

Abstract Five hundred years of mercury (Hg) mining activity in Idrija, Slovenia caused widespread Hg contamination. Besides Hg emissions from the ore smelter, tailings have been found to be the major source of river sediment contamination. In the present study, solid phase binding forms and the aqueous mobility of Hg have been investigated in tailings of the Idrija Hg mine by means of a pyrolysis technique and aqueous Hg speciation. Results show that Hg binding forms differ with the age of the tailings due to the processing of different ores with different roasting techniques. In older tailings, the predominant Hg species is cinnabar (HgS), due to incomplete roasting, whereas in tailings of the 20th century the amount of cinnabar in the material decreased due to a higher efficiency of the roasting process and the increasing use of ores bearing native Hg. In younger tailings, metallic Hg (Hg 0 ) sorbed to mineral matrix components such as dolomite and Fe-oxyhydroxides became the predominant Hg binding form in addition to unbound Hg 0 and traces of HgO. Leaching tests show that in younger tailings high amounts of soluble Hg exist in reactive form. In older tailings most of the soluble Hg occurs bound to soluble complexes. It might be assumed that in the long term, matrix-bound Hg 0 could be bound to humic acids derived from soils covering the tailings. This means that, despite the lower total Hg concentrations found in the younger tailings, the long-term risk potential of its mobile matrix-bound Hg 0 is higher than that of older tailings bearing mostly immobile cinnabar.

Iron traps terrestrially derived dissolved organic matter at redox interfaces

Reactive iron and organic carbon are intimately associated in soils and sediments. However, to date, the organic compounds involved are uncharacterized on the molecular level. At redox interfaces in peatlands, where the biogeochemical cycles of iron and dissolved organic matter (DOM) are coupled, this issue can readily be studied. We found that precipitation of iron hydroxides at the oxic surface layer of two rewetted fens removed a large fraction of DOM via coagulation. On aeration of anoxic fen pore waters, >90% of dissolved iron and 27 ± 7% (mean ± SD) of dissolved organic carbon were rapidly (within 24 h) removed. Using ultra-high-resolution MS, we show that vascular plant-derived aromatic and pyrogenic compounds were preferentially retained, whereas the majority of carboxyl-rich aliphatic acids remained in solution. We propose that redox interfaces, which are ubiquitous in marine and terrestrial settings, are selective yet intermediate barriers that limit the flux of land-derived DOM to oceanic waters.

Over three millennia of mercury pollution in the Peruvian Andes

We present unambiguous records of preindustrial atmospheric mercury (Hg) pollution, derived from lake-sediment cores collected near Huancavelica, Peru, the largest Hg deposit in the New World. Intensive Hg mining first began ca. 1400 BC, predating the emergence of complex Andean societies, and signifying that the region served as a locus for early Hg extraction. The earliest mining targeted cinnabar (HgS) for the production of vermillion. Pre-Colonial Hg burdens peak ca. 500 BC and ca. 1450 AD, corresponding to the heights of the Chavín and Inca states, respectively. During the Inca, Colonial, and industrial intervals, Hg pollution became regional, as evidenced by a third lake record ≈225 km distant from Huancavelica. Measurements of sediment-Hg speciation reveal that cinnabar dust was initially the dominant Hg species deposited, and significant increases in deposition were limited to the local environment. After conquest by the Inca (ca. 1450 AD), smelting was adopted at the mine and Hg pollution became more widely circulated, with the deposition of matrix-bound phases of Hg predominating over cinnabar dust. Our results demonstrate the existence of a major Hg mining industry at Huancavelica spanning the past 3,500 years, and place recent Hg enrichment in the Andes in a broader historical context.

Estimating distribution and retention of mercury in three different soils contaminated by emissions from chlor-alkali plants: part I

Mercury emissions from chlor-alkali plants have been past and present sources of soil contamination with Hg. Here we calculate net mercury (Hg) deposition to soils in the vicinity (100-1000-m downwind) of three-chlor alkali plants. Calculations were based on spatial distribution patterns of Hg concentrations in soils, which were extrapolated by kriging. Moreover, we investigated to what extent Hg deposition depends on the elevation of receptors and canopy throughfall. Mercury concentrations in soil exceed background values up to a factor of 56 and show enrichment factors between 2 and 5.8 calculated from the median Hg concentration. Net deposition rates range between 2356 and 8952 microg m(-2) year(-1), which is up to 224-fold the background values. Net deposition of Hg to soils at the three sites varies between 1.2 and 2.4% of total emitted Hg. Highest deposition rates were found at sites with extended elevated or forested areas. Here, Hg concentrations in soils increased by a factor of up to 7.3 in elevated (+180 m) forest areas compared to non-elevated grassland soils.

Holocene peat and lake sediment tephra record from the southernmost Chilean Andes (53-55°S)

Se han estudiado testigos de tefras y sedimentos de la peninsula Munoz Gamero con el seno Skyring y con el proposito de mejorar la tefrocronologia local. Nuevas edades 14C junto con tasas de crecimiento de las turbas y de sedimentacion, proporcionan nuevas marcas para la edad de las tefras. La capa mas gruesa de tefra (5-15 cm) se origino en una erupcion del volcan del monte Burney, a los 4,254±120 anos calibrados AP. Las isopacas de esta erupcion indican una deposicion de ca. 2,5 a 3 km3 de tefra, principalmente en el area andina forestada, al sureste del volcan. El monte Burney tuvo otra gran erupcion pliniana entre 9,009±17 y 9,175±110 anos cal. AP, y cuatro erupciones menores durante el Holoceno. Se observan, tambien, en algunos testigos tefras de las grandes erupciones de los volcanes Reclus (>15,384±578 cal. anos AP), Hudson (entre 7,707±185 y 7,795±131 cal. anos AP) y Aguilera (<3,596±230 cal. anos AP) como lo indican las composiciones caracteristicas de los vidrios de tefra, los cuales difieren entre los diferentes centros volcanicos. Se establecio una perdida significativa de los elementos alcalinos durante la alteracion del vidrio volcanico en las capas de tefra, especialmente en los testigos de suelos acidos. lo que podria ser un factor importante en el suministro de nutrientes para las plantas.

An analytical protocol for the determination of total mercury concentrations in solid peat samples

Traditional peat sample preparation methods such as drying at high temperatures and milling may be unsuitable for Hg concentration determination in peats due to the possible presence of volatile Hg species, which could be lost during drying. Here, the effects of sample preparation and natural variation on measured Hg concentrations are investigated. Slight increases in mercury concentrations were observed in samples dried at room temperature and at 30 degrees C (6.7 and 2.48 ng kg(-1) h(-1), respectively), and slight decreases were observed in samples dried at 60, 90 and 105 degrees C (2.36, 3.12 and 8.52 ng kg(-1) h(-1), respectively). Fertilising the peat slightly increased Hg loss (3.08 ng kg(-1) h(-1) in NPK-fertilised peat compared to 0.28 ng kg(-1) h(-1) in unfertilised peat, when averaged over all temperatures used). Homogenising samples by grinding in a machine also caused a loss of Hg. A comparison of two Hg profiles from an Arctic peat core, measured in frozen samples and in air-dried samples, revealed that no Hg losses occurred upon air-drying. A comparison of Hg concentrations in several plant species that make up peat, showed that some species (Pinus mugo, Sphagnum recurvum and Pseudevernia furfuracea) are particularly efficient Hg retainers. The disproportionally high Hg concentrations in these species can cause considerable variation in Hg concentrations within a peat slice. The variation of water content (1.6% throughout 17-cm core, 0.97% in a 10 x 10 cm slice), bulk density (40% throughout 17-cm core, 15.6% in a 10 x 10 cm slice) and Hg concentration (20% in a 10 x 10 cm slice) in ombrotrophic peat were quantified in order to determine their relative importance as sources of analytical error. Experiments were carried out to determine a suitable peat analysis program using the Leco AMA 254, capable of determining mercury concentrations in solid samples. Finally, an analytical protocol for the determination of Hg concentrations in solid peat samples is proposed. This method allows correction for variation in factors such as vegetation type, bulk density, water content and Hg concentration in individual peat slices. Several subsamples from each peat slice are air dried, combined and measured for Hg using the AMA254, using a program of 30 s (drying), 125 s (decomposition) and 45 s (waiting). Bulk density and water content measurements are performed on every slice using separate subsamples.

Use and Legacy of Mercury in the Andes

Both cinnabar (HgS) and metallic mercury (Hg(0)) were important resources throughout Andean prehistory. Cinnabar was used for millennia to make vermillion, a red pigment that was highly valued in pre-Hispanic Peru; metallic Hg(0) has been used since the mid-16th century to conduct mercury amalgamation, an efficient process of extracting precious metals from ores. However, little is known about which cinnabar deposits were exploited by pre-Hispanic cultures, and the environmental consequences of Hg mining and amalgamation remain enigmatic. Here we use Hg isotopes to source archeological cinnabar and to fingerprint Hg pollution preserved in lake sediment cores from Peru and the Galápagos Islands. Both pre-Inca (pre-1400 AD) and Colonial (1532-1821 AD) archeological artifacts contain cinnabar that matches isotopically with cinnabar ores from Huancavelica, Peru, the largest cinnabar-bearing district in Central and South America. In contrast, the Inca (1400-1532 AD) artifacts sampled are characterized by a unique Hg isotopic composition. In addition, preindustrial (i.e., pre-1900 AD) Hg pollution preserved in lake sediments matches closely the isotopic composition of cinnabar from the Peruvian Andes. Industrial-era Hg pollution, in contrast, is distinct isotopically from preindustrial emissions, suggesting that pre- and postindustrial Hg emissions may be distinguished isotopically in lake sediment cores.

Millennium-scale volcanic impact on a superhumid and pristine ecosystem

Ecosystems damaged by distal volcanic ash and sulfur deposition usually recover within decades. However, sediment, stalagmite, and pollen records from the southernmost Andes indicate a 2000 yr impact on forest and aquatic ecosystems after deposition of a thin tephra layer. SO 2 released from altering pumice produced intense soil and lake acidification in a >150,000 km 2 area. Acidification led to nutrient leaching and affected soil microorganisms, causing plant decay and increased soil erosion in an area larger than 8000 km 2 . We conclude that weakly buffered soils in humid environments are extremely vulnerable to volcanic and anthropogenic acidification, causing long-lasting ecosystem damage and perturbations of paleoclimate proxy records.