Applied Geochemistry (v.16, #1)
Hydrogeochemistry and stable isotopes of thermal springs: earthquake-related chemical changes along Belice Fault (Western Sicily) by R Favara; F Grassa; S Inguaggiato; M Valenza (1-17).
Three geothermal systems, Montevago, Castellammare-Alcamo and Sciacca, are located along the main seismogenetic structures in Western Sicily. Concentrations of dissolved species including the gases CO2, N2, He and the results of stable isotope measurements δ 18O, δD and δ 13CTDIC in water samples collected from six thermal springs and 28 cold discharges were used to characterise their feeder aquifers and to reveal the relationships between water chemistry and regional seismicity. The Sciacca thermal springs differ chemically and isotopically from those of Montevago and the Castellammare-Alcamo areas. The inferred deep end-members of the thermal waters of Montevago and Castellammare-Alcamo are almost similar, suggesting that both systems are fed by carbonate waters and selenite waters. A slight contribution (1–3%) of seawater, during groundwater ascent it is also present. The Sciacca thermal springs are fed by a deep reservoir comprising a mixture of 50% carbonate water and 50% seawater. During ascent towards the surface, these waters interact with NaCl-rich evaporite layers. By combination of published and present data significant temporal variations of temperature and some chemical parameters in the thermal waters of Western Sicily have been recorded. These variations were mostly between 1966 and 1969. Although the data are discontinuous it is still possible to reveal a direct link between physico–chemical changes in the Acqua Pia and Terme Selinuntine springs and the 1968 Belice Valley earthquake. Within the studied springs, two kinds of geochemical behaviour have been recognised. The chemistry of the Montevago thermal springs was permanently changed in response to changes in the groundwater system. Water temperature and dissolved SO4, Cl, Na, and TDS showed minimum values before the earthquake and maximum values after the event. Almost constant values substantially higher than before, were recorded after the seismic event. Conversely, the temporal variations observed in the waters of the Terme Selinuntine spring, from 1965 to 1991, exhibit a transient increase most probably caused by a temporary contribution of deep CO2-rich fluids caused by the strain release during the 1968 earthquake.
Geochemistry of thirteen Voronin Trough cores, Kara Sea, European Arctic: Hg and As contaminants at a 1965 timeline by Frederic R Siegel; Jennifer J Galasso; Joseph H Kravitz (19-34).
The potentially toxic elements Hg and As are found at high concentrations in surface/near-surface sediments from Arctic ocean cores collected from the Voronin Trough, Kara Sea, during 1965. The levels reach 2045 ppb for Hg and 270 ppm for As. Manganese high values (up to 1.27%) are also found in the cores’ surface/near-surface sections. Other heavy metals tracked by the Arctic Monitoring and Assessment Program (e.g., Cu, Ni, Pb, Sb, Ti, Zn) have baseline concentrations in the cores. The cores average >57% clay-size and >35% silt-size in their textural composition. The elevated contents may result from anthropogenic input for Hg and As with diagenesis adding to the As concentration. Possible sources for these elements are emissions and effluents from industry such as mining and smelting operations, and burning of fossil fuels in Siberia and the Urals. When discharged into the Kara Sea from Siberian catchments, the As and Hg likely attach to charged particulate surfaces of Fe oxy/hydroxides (for As) and particulate organic matter or clay minerals (for Hg). These are transported, entrained in ocean currents or adhered to pack ice, to the Voronin Trough where they deposit according to size and specific gravity.
Brines in the Carboniferous Sydney Coalfield, Atlantic Canada by A.T Martel; M.R Gibling; M Nguyen (35-55).
Formation waters within Upper Carboniferous sandstones in the sub-sea Prince and Phalen coal mines, Nova Scotia, originated as residual evaporative fluids, probably during the precipitation of Windsor Group (Lower Carboniferous) salts which underlie the coal measures. Salinity varies from 7800 to 176,000 mg/l, and the waters are Na–Ca–Cl brines enriched in Ca, Sr and Br and depleted in Na, K, Mg and SO4 relative to the seawater evaporation curve. Br:Cl and Na:Cl ratios suggest that the brine composition corresponds to an evaporation ratio of as much as 30. The brines lie close to the meteoric line on H/O isotopic plots but with a compositional range of δ18O from −4.18 to −6.99 and of δD from −42.4 to −23.5, distant from modern meteoric or ocean water. Mine water composition contrasts with that of nearby salt-spring brines, which are inferred to have originated through dissolution of Windsor Group evaporites by modern meteoric waters. However, a contribution to the mine waters from halite dissolution and from Br in organic matter cannot be ruled out. Present concentrations of several elements in the brines can be explained by water–rock interaction. The original Windsor brines probably moved up into the overlying coal-measure sandstones along faults, prior to the Late Triassic. The high salinity and irregular salinity distribution in the Phalen sandstones suggests that the brines have undergone only modest dilution and are virtually immobile. In contrast, Prince waters show a progressive increase in salinity with depth and are inferred to have mixed with surface waters. Basinal brines from which these modern formation fluids were derived may have been important agents in base-metal and Ba mineralisation from the mid-Carboniferous onwards, as saline fluid inclusions are common in Zn–Pb sulphide deposits in the region.
U-series disequilibrium study on a gaseous discharge area (Solforata of Pomezia, Alban Hills, Italy): implications for volcanic and geochemical risk by M Voltaggio; G.A Di Lisa; S Voltaggio (57-72).
The age and environmental impact of the gaseous discharge at Solforata of Pomezia (Alban Hills, Italy) has been investigated by the application of U-series disequilibrium methods. Chronological data of sulphide mineralization and of a phreatomagmatic deposit close to Solforata fit with a temporal window (26–47 ka BP) of intense volcanic activity which occurred during the final hydromagmatic phase (180–11 ka BP) of the Alban Hills volcano. Radon measurements have allowed an estimation of fluxes of the main gases presently released at Solforata. A model combining Darcy’s law and modified Stoker–Krüger equations has been used in order to predict the upper limit of the gas pressure (19 atmospheres) at the base of the volcanic succession and of the rising time (35 days) of the gas through the volcanic pile. Geochronological and geochemical constraints, obtained by U-series disequilibrium methods, have proved useful in comparing the volcanic and geochemical risks in this area. The comparison shows that, under normal conditions of gas dispersion, the geochemical risk associated with Rn and H2S exposure is high and it must be tackled immediately with particular surveillance and intervention methods.
A 120 year record of changes in nitrogen and carbon cycling in Lake Alexandrina, South Australia: C:N, δ 15N and δ 13C in sediments by A.L Herczeg; A.K Smith; J.C Dighton (73-84).
Variations in δ 15N and δ 13C and C:N ratios of organic matter in sediment cores in Lake Alexandrina, South Australia show that there have been modifications of N and C sources due to land use changes, water diversions and irrigation since European settlement of the surrounding basin in the middle 1800s. δ 15Norg and δ 13Corg concentrations from three short sediment cores range from 1.8 to 3.9‰ and −26.7 to −21.1‰, respectively. All cores showed a ∼2‰ increase in δ 15N over the top 100 mm with little variation below about 150 mm. δ 13C values increased by about ∼3‰ from the base of the sediment cores to a maximum of ∼−21‰ at 150 mm depth, before decreasing by ∼5‰ to ∼–27‰ over the top 100 mm. C:N mass ratios <11 suggest that organic matter preserved in the sediment is composed primarily of aquatic plant material, with terrestrial plants contributing <10%. Excess 210Pb and 137Cs dating indicate a sediment accumulation rate of 3±1 mm a−1 suggesting the enrichment in 15N began in the 1950s and the δ 13C maxima corresponds to approximately 1940. The increase in δ 15N concentration over the past 30–50 a is attributed to the increasing agricultural expansion and development in the lower catchment, particularly intensive grazing of cattle for dairying. The authors suggest that there has been an increased flux of 15N-enriched inorganic N (derived from mineralized animal waste and sewage) to the river and lake over the past 30–40 a, which in turn is incorporated into the aquatic plants. The variation in δ 13C reflects a change from terrestrial dominated input of inorganic C to increasingly marine dominated sources after water diversions commenced in the late 1800s. Once barrages were completed at the outlet of the lake in 1939 (to prevent seawater intrusion), the aquatic plants in the lake reverted to assimilation of dissolved inorganic C derived from oxidation of terrestrial organic matter.
Adsorption of radioelements on mixtures of minerals — experimental study by P Jacquier; P Meier; J Ly (85-93).
An experimental study has been undertaken concerning the adsorption of radioelements on mixtures of minerals. The question is whether the adsorption of trace elements by rocks and soils can be easily predicted from the properties of the constituent minerals. The goal of these experiments was the comparison between the measurements of distribution coefficients of some radioelements for pure minerals and for binary mixtures according to the Doehlert’s uniform shell designs and to test an additive law of combination of Kd. The results showed that when one of the constituents acts as a dilutant in the mixture, i.e. it presents a very low adsorption capacity with respect to some trace element, then the relations of additivity of Kd are fulfilled. Otherwise, these relations are not satisfied and this is probably caused, in the present cases, by interactions from solubilized species.
Comparative study of sterols in shelf and slope sediments off northeastern Taiwan by Woei-Lih Jeng; Chih-An Huh (95-108).
Bottom sediments and suspended matter from the shelf and slope areas off northeastern Taiwan were analyzed for sterol, n-alkanol and n-alkane compositions. The Σ(algal sterols/cholesterol) ratios (mean±1σ) were 1.00±0.31 (n=7) for the shelf sediments, 3.29±0.61 (n=7) for the slope sediments, and 1.54±0.19 (n=3) for the suspended matter. The much higher proportion of cholesterol in the shelf sediments is most likely derived from mollusks in the relict sediments. An additional sterol source for the shelf sediments probably is suspended matter in the water column although the shelf has no apparent sedimentation. Results from phytol and n-alkanols suggest recent inputs of lipids from the water column to the shelf. The stanol/stenol ratios are lower for the older shelf sediments than for the younger slope sediments.
Radium geochemistry of ground waters in Paleozoic carbonate aquifers, midcontinent, USA † † This manuscript has been created by the University of Chicago as Operator of Argonne National Laboratory under Contract No. W-31-109-ENG-38 with the U.S. Department of Energy by N.C Sturchio; J.L Banner; C.M Binz; L.B Heraty; M Musgrove (109-122).
The purpose of this study was to elucidate the processes controlling the distribution and behavior of the longer-lived Ra isotopes in continuous Paleozoic carbonate aquifers of parts of Missouri, Kansas, and Oklahoma. Activities of (228Ra) and (226Ra) were analyzed in fresh and saline ground waters, brines, and rocks. The fluids have a wide salinity range (200–250,000 mg l−1 total dissolved solids). The (226Ra) activity ranges from 0.66–7660 dpm kg−1 and correlates with salinity and other alkaline earth element (Ca, Sr, and Ba) concentrations. The range of (228Ra:226Ra) ratios in the fluids (0.06–1.48) is similar to that in the aquifer rocks (0.21–1.53). The relatively low mean fluid (228Ra:226Ra) ratio (0.30) reflects the low Th:U ratio of the predominant carbonate aquifer rock. Radium occurs mostly (≥77%) as Ra2+ species in the fluids. Salinity-dependent sorption–desorption processes (with log K values from 100–104 and negatively correlated with salinity), involving Th-enriched surface coatings on aquifer flow channels, can explain the rapid solid–fluid transfer of Ra isotopes in the system and the correlation of Ra with salinity.
Relationships between geochemistry of basal till and chemistry of surface soil at forested sites in Finland by Anne-Maj Lahdenperä; Pekka Tamminen; Timo Tarvainen (123-136).
Concentrations of several elements extractable with BaCl2 and acid ammonium acetate (pH 4.65) were measured in the organic and 4 mineral soil layers on the national forest inventory plots of the Finnish Forest Research Institute. The soil data also includes total concentrations of elements in the organic layer and site and soil physical characteristics. Data were compared with the aqua regia extractable element concentrations measured in the nationwide regional till geochemical mapping carried out by the Geological Survey of Finland.Correlations between concentrations in surface soil and underlying basal till were generally highest for K, Mg, Mn, P and Zn; in the organic layer and till they were highest for Cr and Cu. The strength of these correlations did not increase regularly from surface to deeper soil layers. All soil base cations with the exception of Ca, which is of relatively low solubility, were well correlated. The elements Zn, K, P, Al and Mn in till were the most reliable indicators of surface soil chemistry.Fuzzy clustering showed that the correlation between element concentrations in basal till and the two uppermost layers of mineral soil was better within areas of distinct till geochemistry, such as the schist belts in southwestern Finland, the Lake Ladoga–Bothnian Bay zone and the Kuusamo schist belt.Surface soil chemical variables were clearly better in discriminating fertility classes of forest sites than were element concentrations in basal till. The independent ability of till geochemistry to distinguish these productivity classes and to explain surface soil fertility was nevertheless demonstrated.