Applied Geochemistry (v.15, #5)

Teflon strips were used in-situ in the bottom sediments at two sites in the Swan River Estuary to collect diagenetic Fe–Mn oxyhydroxides and monitor monthly changes in their morphology and trace element geochemistry. This study demonstrates that substantial concentrations of trace elements accumulate at the redox front during the formation of diagenetic Fe–Mn oxyhydroxides. It is likely that the Fe–Mn oxyhydroxides initially nucleate and grow on the Teflon strips via bacterial activity. Trace element geochemistry of the diagenetic Fe–Mn oxyhydroxides is influenced by changes in the supply of trace elements from either the bottom sediments and/or water column or changes in the physico-chemical status of bottom and porewaters. If sufficient diagenetic Fe–Mn oxyhydroxides are preserved in the upper layer(s) of the bottom sediment it is possible that diagenetic (secondary) trace element enrichment profiles may be produced which modify the historical input of natural or anthropogenic trace element sources. Alternatively, partial or complete dissolution of the diagenetic Fe–Mn oxyhydroxides in response to temporal changes in the redox status of the bottom sediment may lead to a substantial underestimate of trace element fluxes in historical bottom sediment profiles. This study highlights that considerable care must be taken when interpreting short- to long-term geochemical profiles in bottom sediments due to the possible occurrence of rapid, seasonally mediated diagenetic processes.

Heavy metal distribution in sediment profiles of the Pearl River estuary, South China by Xiangdong Li; Onyx W.H. Wai; Y.S. Li; Barry J. Coles; Michael H. Ramsey; Iain Thornton (567-581).
The Pearl River estuary is created by the inflow of freshwater from the largest river system that drains into the South China Sea. In recent years, massive economic growth and development in the region has led to excessive release of waste into the environment. The accumulation of contaminants in sediments is likely to pose serious environmental problems in surrounding areas. The study of sediment profiles can provide much information on the metal contamination history and long term potential environmental impacts. In this project, 21 core samples (up to 3.65 m deep) were collected in the Pearl River estuary. About 15 subsamples from each core were analysed for moisture content, total organic matter (L.O.I.), particle size and heavy metal and major element concentrations. The results show that Pb and Zn contents are elevated in the sediments at most of the sampling sites. Compared with historical monitoring results, the sediment metal contents have increased over the last 20 a, particularly for Pb. The west side of the Pearl River estuary tends to be more contaminated than the east side due to the contaminants inputs from the major tributaries and different sedimentation conditions. There are close associations between Fe, Co, Ni and Cu concentrations in the sediments. Zinc and Pb contents in the sediment profiles reflect a combination of the natural geochemical background, anthropogenic influences and the mixing effects within the estuary. The distribution of Pb in the sediments shows strong influences of atmospheric inputs, probably from the coal burning activities in the region.

14C dating of Gorleben groundwater by G. Buckau; R. Artinger; S. Geyer; M. Wolf; P. Fritz; J.I. Kim (583-597).
Previous attempts to apply 14C for dating of groundwater in the Gorleben aquifer system has given results with conflicting 3H and stable isotope data and hydrological estimates. 14C model ages of 1–10 ka have been found for 3H containing recharge water, up to 31 ka for groundwater with Holocene stable isotope signatures and 6–10 ka for groundwater at 35 m depth. In this paper it is shown, that the reasons are assumption of to high 14C concentration in recharge groundwater and not correcting for the influence of 14C dilution by dissolved inorganic C (DIC) from microbiologically mediated mineralization of organic components in deep sediments. To overcome these difficulties a new approach is applied evaluating the site-specific 14C source term (including the influence of nuclear atmospheric testing), and the already previously used overall dilution of DIC. Closed system conditions are assumed and no isotopic fractionation is considered. For most of the groundwaters, the 14C ages achieved by the present method are in agreement with 3H, stable isotopes and hydrological estimates. It is shown that down to approximately 140 m depth no 14C decay can be detected. Situations are also discussed, either where the 14C method is not applicable (shallow peat-bog like groundwater) or does not yield reliable groundwater ages (brines at <200 m depth).

The effects of agriculture on the isotope geochemistry of Sr were investigated in two small watersheds in the Atlantic coastal plain of Maryland. Stratified shallow oxic groundwaters in both watersheds contained a retrievable record of increasing recharge rates of chemicals including NO3 , Cl, Mg, Ca and Sr that were correlated with increasing fertilizer use between about 1940 and 1990. The component of Sr associated with recent agricultural recharge was relatively radiogenic (87Sr/86Sr=0.715) and it was overwhelming with respect to Sr acquired naturally by water–rock interactions in the oxidized, non-calcareous portion of the saturated zone. Agricultural groundwaters that penetrated relatively unoxidized calcareous glauconitic sediments at depth acquired an additional component of Sr from dissolution of early Tertiary marine CaCO3 (87Sr/86Sr=0.708) while undergoing O2 reduction and denitrification. Ground-water discharge contained mixtures of waters of various ages and redox states. Two streams draining the area are considered to have higher 87Sr/86Sr ratios and NO3 concentrations than they would in the absence of agriculture; however, the streams have consistently different 87Sr/86Sr ratios and NO3 concentrations because the average depth to calcareous reducing (denitrifying) sediments in the local groundwater flow system was different in the two watersheds. The results of this study indicate that agriculture can alter significantly the isotope geochemistry of Sr in aquifers and streams and that the effects could vary depending on the types, sources and amounts of fertilizers added, the history of fertilizer use and groundwater residence times.

The present study presents a multivariate procedure to reveal light hydrocarbon components which significantly distinguish between source rock thermal extracts. The two source rocks included in this study are the marine shales of the Late Jurassic Spekk Formation and the coals and paralic shales of the Early Jurassic Åre Formation offshore Mid-Norway.Because of the large number of components in the C4–C13 hydrocarbon fraction of source rock extracts a multivariate approach was required. The procedure consists of three distinct steps: (1) Principal component analysis of the whole data set for detection of non-significant individual components. This reduced the number of individual components from 46 to 22. (2) Separate principal component analysis of the two source rocks (Åre and Spekk) to detect outliers. (3) Principal component modelling of each of the two source rocks after deletion of outliers and non-discriminating variables to detect those hydrocarbon components which are most significant and robust for the separation of the two source rocks.The resulting model shows that there is a definitive compositional difference between the source rocks investigated.

Stream waters and sediments draining a gossan tailings pile at the Murray Brook massive sulphide deposit were collected to investigate Au mobility. Weathering of the massive sulphides at Murray Brook during the Late Tertiary period resulted in the concentration of Au in the gossan cap overlying the supergene Cu and unoxidized massive sulphide zones of the deposit. The gossan was mined between 1989 and 1992, and Au and Ag were extracted using a cyanide vat leach process. Although stream sediments prior to mining had Au<5 ppb (the detection limit), sediments collected in 1997 had Au contents ranging up to 256 ppm with values up to 6 ppm more than 3 km downstream from the deposit. Dissolved Au contents were similarly anomalous, up to 19 μg/L and in excess of 3 μg/L 3 km downstream. The elevated Au contents in the waters and sediments are interpreted to reflect complexation of Au (as Au(CN)2 ) by cyanide hosted within the gossan tailings pile. Precipitation recharges through the tailings pile with groundwater flow exiting to Gossan Creek. Degradation of cyanide along the flow path and within Gossan Creek allows colloidal Au to form via reduction of Au(I) by Fe2+, consistent with SEM observations of Au as <1 μm subrounded particles. In the surface waters, the majority of the Au must be in a form <0.45 μm in size to account for the similarity in Au contents between the <0.45 μm and unfiltered samples. The very elevated stream sediment Au values close to the headwaters of Gossan Creek near the tailings indicate that upon exiting to the surface environment, Au(CN)2 complexes are rapidly destroyed and Au removed from solution. However, the high Au<0.004 μm/Autotal in the headwaters and the extended Au dispersion in Gossan Creek waters and sediments suggest that Au(CN)2 complexes persist for the full length of Gossan Creek. The decrease in aqueous Au which is less than 0.004 μm indicates that Au is converted from a complexed form to a colloidal form with increasing distance downstream, consistent with dissolved NO3 contents which decrease from 5210 μg/L near the headwaters to 1350 μg/L at the lower end of the stream.

The problem of a geochemical baseline in areas differing in basic geology was studied by comparing the results of regional geochemical mapping programmes undertaken in Finland and Lithuania using different sample media and a variety of analytical methods. The authors discuss issues relevant to the definition of a geochemical baseline.Most of the differences in geochemical baselines between Lithuania and Finland are due to the dissimilarities in basic geology, which in Lithuania is controlled by Palaeozoic and Mesozoic sedimentary rocks, but in Finland by Archaean and Proterozoic metamorphic and intrusive rocks. Other important factors are the geological processes that after the last glaciation created the present surficial materials. In Finland, for instance, the abundances of potentially harmful elements derived from crystalline bedrock tend to be higher than in Lithuania. However, in both countries element concentrations are higher in finely-grained marine and lacustrine sediments than in glacial till, and they are also higher in the finer grain size fractions than in the coarser fractions of till samples. Only a small proportion of the total heavy metal concentrations is bioavailable. Thus the baseline concentrations depend not only on the basic geology, but also on sample material collected, its grain size and the extraction method.

A process model of natural attenuation in drainage from a historic mining district by Amy C Berger; Craig M Bethke; James L Krumhansl (655-666).
A process model was used to better understand the controls on the chemical evolution of drainage in a historic mining district. At the Pecos Mine Operable Unit, New Mexico, drainage near the waste rock pile is acidic (pH varies from 3.0–5.0) and carries high concentrations of Zn, Al, Cu and Pb. As drainage flows toward the Pecos River, pH increases to greater than 7 and heavy metal content decreases. A process model of natural attenuation in this drainage shows the main controls on pH are reaction with a local bedrock that contains limestone, and concurrent mixing with tributary streams. Models that account for both calcite dissolution and mixing reproduce the observed decrease in aqueous metal concentrations with increasing pH. Contaminant concentrations attenuate primarily via two distinct pathways: Al, Cu, Fe and Pb precipitate directly from solution, whereas Zn, Mg, Mn and SO4 concentrations decrease primarily through dilution. Additionally, Pb adsorbs to precipitating hydroxide surfaces.

Interstitial water from the Boom clay Formation around the HADES (high activity disposal experimental site, an underground research facility belonging to the Nuclear research centre, SCK·CEN, at Mol-Dessel, Belgium.) underground research facility at Mol, Belgium, and waters sampled at different locations in the Rupelian aquifer, underlying the clay formation, have been studied. The Boom clay is a Tertiary mudrock containing about 55 % clay and the Rupelian aquifer is located in a silty layer. Special care was taken to adapt or improve measurement, sampling, conservation and analysis methods to get a reliable regional and local database, for the purpose of testing a general model describing the regulation and acquisition of the composition of these fluids. The isotopic and chemical composition of the waters allows them to be assigned to a common origin, namely mixing between a marine endmember and the clay interstitial water, followed by reequilibration with the host rock through dissolution–precipitation reactions involving identified secondary minerals. Oxidation–reduction state and trace element behavior are also discussed and the limits of the model are outlined.

Differential diagenesis of strontium in archaeological human dental tissues by Paul Budd; Janet Montgomery; Barbara Barreiro; Richard G. Thomas (687-694).
The investigation of prehistoric human migration from the measurement of Sr-isotope ratios within preserved tissue is critically dependent on the preservation of biogenic Sr. A number of recent studies have involved isotope ratio measurements on samples of archaeological tooth and bone, but doubt remains as to the extent of diagenesis in various skeletal tissues and the effectiveness of procedures designed to decontaminate them. The authors have compared Sr abundance and isotope ratios in enamel and dentine from archaeological teeth in order to assess the integrity of the biogenic Sr signal preserved within the respective tissues. It is concluded that enamel appears, in most cases, to be a reliable reservoir of biogenic Sr, but that dentine, and by implication bone, is not. The diagenesis of dentine is highly variable even between burials within a single site. For the majority of teeth, dentine diagenesis was not simply by addition of soil-derived Sr, but involved substantial, sometimes complete, turnover of the original biogenic material. It is suggested that, for most of the samples investigated, current decontamination techniques may not have been effective in isolating biogenic Sr from dentine. Similar considerations are likely to apply to archaeological and fossil bone, but the possibility arises to use dentine and enamel measurements to assess the effectiveness of decontamination procedures which may then be used for bone.