Applied Geochemistry (v.21, #3)

Water leaching of cesium from selected cesium mineral analogues by Zdenek Klika; Zdenek Weiss; Marcello Mellini; Milan Drábek (405-418).
Recently, a new mica phase Cs-tetra-ferri-annite has been synthesized and studied. This phase has been investigated because its high structural stability and assumed associated low leachability for Cs suggest that it may be a suitable waste form for immobilization of Cs. Further, synthesis, under hydrothermal conditions, is possible under conditions typical of an industrial-scale immobilization plant. Consequently, cesium-tetra-ferri-annite can be considered as a waste form for the fixation of Cs from solid radioactive waste. In this study, Cs immobilization in Cs-tetra-ferri-annite and CsAlSiO4, as well as sorption onto montmorillonite and zeolite 13X, have been studied. Experiments were carried out to determine the influence of pH, temperature, time and leaching technique on the extent of release of Cs from these solids. These leaching studies have confirmed the limited leachability of Cs-tetra-ferri-annite, which was found to be more stable than CsAlSiO4 by a factor of 3.7 at ambient temperature and near-neutral pH. These waste forms have also been found to be more effective in retaining Cs than Cs-montmorillonite and Cs-zeolite 13X. The relative release of Cs from all of the studied phases exhibits a similar trend with pH, temperature, time and techniques of leaching used in this study. For these phases, the leachability of Cs increases with acidity (pH 3) or alkalinity (pH 11) of the leachates as well as with increasing temperature and time of leaching. For CsAlSiO4, the Cs-leachability was most strongly affected by increasing temperature. Cesium releases from this phase increased by a factor of about 6 when the temperature was raised from 20 to 100 °C. This increase with temperature was 3–6 times higher than that measured for the other phases. Under the present leaching conditions, Cs is released more than the matrix elements. Elements present in tetrahedral positions of CsAlSiO4, Cs-montmorillonite and Cs-zeolite 13X leach much easier than elements in octahedral positions.

Application of Sr isotopes to geochemical mapping and provenance analysis: The case of Aichi Prefecture, central Japan by Yoshihiro Asahara; Hiroko Ishiguro; Tsuyoshi Tanaka; Koshi Yamamoto; Koichi Mimura; Masayo Minami; Hidekazu Yoshida (419-436).
Geochemical maps expressing areal distributions of chemical elements in the earth’s land surface have been published in several countries in relation to various global environment issues. The authors have applied a radiogenic isotope ratio, 87Sr/86Sr, to geochemical mapping in order to understand the geological origin, transportation and dispersion system of chemical elements in the earth’s land surface. The Sr isotope ratio is a useful tracer for distinguishing the geological origin of surficial deposits, especially in areas where surface exposure of bedrocks is low, because it is not significantly altered by the processes of weathering and transportation. Most bedrocks in the Japanese islands are covered by plants, soils and urban areas. In this study, 142 of 1219 stream sediments (<180 μm) collected from the northeastern part of Aichi Prefecture, in the central part of Japan (75 km × 30 km), were analyzed. Their Sr isotope ratios range from 0.7086 to 0.7315 with an average of 0.7129, except for one sample. This average is higher than the mean of the upper crust of the Japan Arc (the Japanese Island Crustal Composite, JICC), 0.7077. This difference can be attributed to the below-average presence of young volcanic rocks, generally having lower 87Sr/86Sr values, and the above-average presence of granitic rocks, in the study area compared with the surface exposure of the Japan Arc. The first factor controlling the distribution of Sr isotope ratios is the bedrock distributed around the sampling points. Regional variation in the 87Sr/86Sr value shows that it is higher in the western and southeastern parts, where sedimentary rocks and metamorphic rocks are distributed, and that it is lower mainly in the central part, where granitic rocks are distributed. The 87Rb/86Sr–87Sr/86Sr plot for stream sediments more clearly reveals the differences and similarities of bedrocks. In some locations, the distribution of Sr isotope ratios does not correspond to that of bedrocks on the geological map. One reason is the existence of unmapped bedrock, for example, small intrusive masses of granite. The other is fluvial transportation and dispersion. The distribution of the isotope ratios suggests that some stream sediments include surficial deposits from a few km upstream. Application of the Sr isotope ratio to geochemical mapping is useful for revealing both the distribution of unexposed bedrocks and the transportation of surficial deposits. Information on unexposed bedrocks will be expected to contribute to the improvement of geological mapping.

Precipitation of secondary Fe(III) minerals from acid mine drainage by Jörgen Jönsson; Julia Jönsson; Lars Lövgren (437-445).
Oxidation of FeS2 in mine waste releases SO 4 2 - , Fe(II) and H+, resulting in acid mine drainage (AMD). Subsequent oxidation and precipitation of Fe produces different Fe(III) phases where the mineralogical composition depends on pH and the ambient concentrations of metal ions and complexing ligands. The oxidation and precipitation of Fe in AMD has been studied under various conditions with the intent of understanding the role these processes play in the natural attenuation of metal contaminants in the AMD. The combined process of Fe oxidation and precipitation in AMD from the Kristineberg mine, northern Sweden, has been investigated with pH-stat experiments at pH 5.5 and 7 at 10 and 25 °C. The precipitates formed have been characterised in terms of mineralogy and surface area. Similar phases formed at both temperatures, while the oxidation and precipitation occurred more readily at the higher temperature and higher pH. At pH 7, mainly lepidocrocite (γ-FeOOH) was precipitated while at a lower pH of 5.5, a mixture of schwertmannite, goethite, ferrihydrite and lepidocrocite formed. The ambient Zn(II) concentration was immediately reduced to acceptable levels (according to Swedish EPA) at pH 7 whereas a 2–3 weeks ageing period was necessary to achieve the same effect at pH 5.5. The presence of natural organic matter (NOM) reduced the attenuating effect at pH 5.5 after ageing but increased it slightly at pH 7. Addition of Zn(II) at pH 8 resulted in a mixed Fe(III)–Zn(II) precipitate of unknown composition with some Zn(II) adsorbed at the surface. The Fe(III) precipitates formed are potentially useful for the natural attenuation of metal contaminants in AMD although based on these investigations, the degree of success depends upon pH and NOM concentration.

Effects of humus on the environmental activity of mineral-bound Hg: Influence on Hg volatility by Yao Aijun; Qing Changle; Mu Shusen; Eric J. Reardon (446-454).
The effects of three humus fractions (fulvic acid, brown humic acid and grey humic acid) on the volatility of five types of mineral-bound Hg were investigated. Fulvic acid was found to strongly promote the volatilization of Hg bound by Fe2O3, MnO2 and kaolinite, but suppressed the volatilization of Hg bound by bentonite and CaCO3. Brown humic acid was found to enhance the volatilization of Hg bound from all the tested minerals, except for Fe2O3. Grey humic acid had the weakest effect in promoting or suppressing Hg volatilization. The influence of the various humus fractions on the volatilization of mineral-bound Hg is closely related to the complexing capacity and complex stability of the particular humus material. The higher the complexing capacity and the lower the complex stability, the more prominent is the humus material in promoting Hg volatility. The Hg sorption capacity and sorption strength of the minerals, as well as their Hg speciation characteristics, limit the effect that humus has to volatilize Hg.

The origin and heterogeneity of oilfield formation water in the Lower Triassic Sherwood Sandstone at Wytch Farm in the Wessex Basin, UK, have been investigated using production data, detailed water geochemistry and O, S and H stable isotope data. The formation waters are highly saline, NaCl-type brines with TDS values of up to 230,000 mg/L. There is a general decrease in salinity from the flanks of the field to the crest with Cl decreasing from about 136,000 to 109,000 mg/L. The Cl/Br ratio of the water shows that salinity was largely derived from the dissolution of Upper Triassic continental evaporites found off-structure to the west and north of the field. The water in the field had a meteoric source although variation in δ 2H values suggests that there may be meteoric waters of different ages in the oilfield, reflecting recharge under different palaeoclimatic conditions. At the crest of the field, aqueous SO 4 2 - resulted from dissolution of anhydrite in the reservoir. In contrast, in other parts of the field there is an indication that some of the dissolved SO 4 2 - was derived from oxidation of pyrite at some point on the recharge path of meteoric water to the field. There were two meteoric influx events bringing different Cl concentrations and different δ 2H values. The first was probably before the Eocene oil influx and could have occurred in the Lower Cretaceous or early Tertiary. The second meteoric influx event probably occurred after or during oil migration into the Wytch Farm structure since the second meteoric water is found at the flanks of the field adjacent to the regions where salt is found in the stratigraphy. The preservation of heterogeneities in oilfield formation water compositions suggests that there has been little aqueous fluid movement or diffusive flux for over 40 million years. Mass flux has been restricted by density stratification within the aquifer and the very low effective permeability for the aqueous phase in the oil-filled reservoir.

Many mining-impacted streams in western Montana with pH near or above neutrality display large (up to 500%) diel cycles in dissolved Zn concentrations. The streams in question typically contain boulders coated with a thin biofilm, as well as black mineral crusts composed of hydrous Mn–Zn oxides. Laboratory mesocosm experiments simulating diel behavior in High Ore Creek (one of the Montana streams with particularly high Zn concentrations) show that the Zn cycles are not caused by 24-h changes in streamflow or hyporheic exchange, but rather to reversible in-stream processes that are driven by the solar cycle and its attendant influence on pH and water temperature (T). Laboratory experiments using natural Mn–Zn precipitates from the creek show that the mobilities of Zn and Mn increase nearly an order of magnitude for each unit decrease in pH, and decrease 2.4-fold for an increase in T from 5 to 20 °C. The response of dissolved metal concentration to small changes in either pH or T was rapid and reversible, and dissolved Zn concentrations were roughly an order of magnitude higher than Mn. These observations are best explained by sorption of Zn2+ and Mn2+ onto the secondary Mn–Zn oxide surfaces. From the T-dependence of residual metal concentrations in solution, approximate adsorption enthalpies of +50 kJ/mol (Zn) and +46 kJ/mol (Mn) were obtained, which are within the range of enthalpy values reported in the literature for sorption of divalent metal cations onto hydrous metal oxides. Using the derived pH- and T-dependencies from the experiments, good agreement is shown between predicted and observed diel Zn cycles for several historical data sets collected from High Ore Creek.

Geochemical mapping in northern Honshu, Japan by Masumi Ujiie-Mikoshiba; Noboru Imai; Shigeru Terashima; Yoshiko Tachibana; Takashi Okai (492-514).
Geochemical mapping of northern Honshu in the Northeast Japan Arc was carried out using stream sediments at a sampling density of one sample per 130 km2. More than 50 elements were determined in 395 stream sediment samples (<0.18 mm fraction). In geochemical maps, areas with especially low concentrations of large ion lithophile elements (LILE), Be and Li widely overlap with the distribution of Quaternary volcanic rocks along the volcanic front. The areas rich in mafic elements are associated with mafic rocks in many cases. On a regional scale, Ni, Cr and Cu contents are higher in the eastern Paleozoic–Mesozoic basement zone, Pb and Tl tend to be higher on the western zones, and Zn and Cd are high in the western back-arc zone. The areas especially rich in Cu, Zn, Cd, Pb, Bi and Tl coincide with the distribution of large mineral deposits. High concentrations related to Kuroko, hydrothermal-vein, and skarn-type deposits are recognized. High values of As and Sb are related to active geothermal areas near volcanoes and ore deposits. Chemical variations of K, Ce, Th and Sn in the stream sediments are concordant with chemical variations in major rocks. The median and mean concentrations for the stream sediments in northern Honshu, showing arc signatures, are lower in Rb, Cs, Th, Li, K, Be, Ta, LREE, Ni, Hg and Sn, and higher in Sc, Ca and Cd relative to the whole area of Japan, largely because of the contribution of Cenozoic island-arc volcanic rocks that are generally poor in incompatible elements. The averaged chemical compositions of the stream sediments for the geologic zones show systematic variations of many elements. The contrasting variations of LREE and Th contents, which are lower in the zones of Cenozoic rocks relative to the zones of pre-Neogene basements, reflect the regional variations in the main rocks, and also reflect the change of geological settings of the studied area from the continental margin to an island arc during the Cenozoic.

Mercury in the Lot–Garonne River system (France): Sources, fluxes and anthropogenic component by J. Schäfer; G. Blanc; S. Audry; D. Cossa; C. Bossy (515-527).
Dissolved and particulate Hg fluxes in the Lot–Garonne–Gironde fluvial-estuarine system were obtained from observation of daily discharge and suspended particulate matter (SPM) concentrations. In addition to the measurements of the total dissolved (<0.45 μm) and particulate Hg (>0.45 μm), called HgTD and HgTP respectively, the dissolved inorganic Hg species (HgRD) were determined monthly. Geochemical background values for HgTP in sediments and SPM were similar to crustal values and to typical concentrations in SPM of non-contaminated river systems, respectively. The Riou Mort watershed already known as the origin of important historical polymetallic (e.g., Cd, Zn) pollution was identified as an important Hg point source. In the downstream Lot River, Hg concentrations were clearly higher than those in other moderately contaminated systems. The mean relative contribution of HgRD to HgTD in the Lot River and in the Garonne River was close to 25% and 50%, respectively, and showed no correlation with water discharge or SPM concentration. Depending on the origin and nature of SPM, HgTP concentrations were correlated or not with particulate organic C (POC). Maximum HgTP concentrations were measured in samples containing low POC concentrations and were attributed to sediment resuspension. In contrast, high POC concentrations (6–17%) during algal blooms were associated with low/moderate HgTP concentrations (<0.5 mg kg−1) at different sites, suggesting that Hg concentrations in fluvial phytoplankton may be limited by bioavailability of dissolved Hg and/or physiologically controlled Hg accumulation. Mercury was mostly (up to 98%) transported in the particulate phase with estimated annual Hg fluxes at the outlet of the Lot River system ranging from 35 to 530 kg a−1 for the past decade. The minimum anthropogenic component (58–84% of total Hg fluxes) could not be explained by present Riou Mort point source contributions, suggesting important Hg release from contaminated sediment as a major source and from downstream point sources (e.g., coal-fired power plants and/or metal processing industries). HgTP concentrations and fluxes were strongly related to hydrologic variations and were clearly increased by riverbed dredging during lock construction. Therefore, the estimated Hg stocks in the Lot River sediment (5–13 tons) represent an important potential Hg source for the downstream fluvial-estuarine system.

Geochemical patterns of arsenic-enriched ground water in fractured, crystalline bedrock, Northport, Maine, USA by Gail Lipfert; Andrew S. Reeve; William C. Sidle; Robert Marvinney (528-545).
High mean As concentrations of up to 26.6 μmol/L (1990 μg/L) occur in ground water collected from a fractured-bedrock system composed of sulfidic schist with granitic to dioritic intrusions. Sulfides in the bedrock are the primary source of the As in the ground water, but the presence of arsenopyrite in rock core retrieved from a borehole with As concentrations in the ground water barely above the detection limit of 2.0 μmol/L, shows that there are complicating factors. Chemical analyses of water from 35 bedrock wells throughout a small watershed reveal spatial clustering of wells with high As concentrations. Stiff diagrams and box plots distinguish three distinct types; calcium-bicarbonate-dominated water with low As concentrations (CaHCO3 type), sodium-bicarbonate-dominated water with moderately high As concentrations (NaHCO3 type), and calcium-bicarbonate-dominated water with very high As concentrations (High-As type). It is proposed that differences in recharge area and ground-water evolution, and possible bedrock composition difference are responsible for the chemical distinctions within the watershed. Lack of correlation of As concentrations with pH indicates that desorption of As is an insignificant control on As concentration. Correlations of As concentrations with Fe and redox parameters indicates that reductive dissolution of Fe(III) oxyhydroxides may play a role in the occurrence of high As concentrations in the NaHCO3 and High-As type water. The oxidation of sulfide minerals occurs within the ground-water system and is ultimately responsible for the existence of As in the ground water, but there is no correlation between As and SO4 concentrations, probably due to precipitation of Fe(III) oxyhydroxides and adsorption of As under oxidizing conditions.