Applied Geochemistry (v.16, #6)

Use of solid phase characterisation and chemical modelling for assessing the behaviour of arsenic in contaminated soils by D.G Lumsdon; J.C.L Meeussen; E Paterson; L.M Garden; P Anderson (571-581).
A soil, containing waste material from an industrially contaminated site, was found to be heavily contaminated with several heavy metals and As. A risk assessment for As leaching from this material has been carried out in several stages, collation and examination of historical records, solid-phase characterization and chemical modelling. The historical record indicates that the most probable source of As was arsenopyrite. However, the solid phase characterization of the soil, using X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy-dispersive microanalysis (EDAX), did not yield any direct evidence for pyritic phases, although there was clear evidence of known pyrite-weathering products, such as jarosite. The relative stability of pyrite and arsenopyrite have been modelled for the range of acidity and redox potentials likely to be encountered on the site. For adsorption modelling, a surface complexation model was used to predict arsenate desorption as a function of pH. It was assumed that the principal reactive adsorbent for As was hydrous ferric oxide (HFO) and this assumption was supported by the results of direct and indirect measurements and by the mineral stability calculations. This approach was successful at predicting the increased mobility of As at increasingly alkaline conditions. The modelling predictions were supported by results from batch equilibration experiments. Thus, it was possible to link direct observations of mineralogy, mineral stability calculations and adsorption models in order to predict the mobility of As. The success of this approach was dependent on identifying the reactive phase in this particular soil and having the appropriate data required for the adsorption modelling.

Temporal variability of nitrate concentration in a schist aquifer and transfer to surface waters by Hélène Pauwels; Patrick Lachassagne; Paul Bordenave; Jean-Claude Foucher; Anne Martelat (583-596).
Nitrate concentrations monitored for 2.5 a in the stream water and groundwater of a small catchment, 86.5% of which is devoted to intensive agriculture, show temporal variations with a maximum during winter (as much as 200 mg l−1 in groundwater and 100 mg l−1 in stream water) and a minimum at the end of summer/beginning of autumn. Variations were also observed in the stream water and shallow groundwater after rainfall. The processes involved to explain these variations, determined mainly from NO3 Cl, SO4 2−, piezometric and streamflow data, are: (a) variability of the relative contributions to stream water and shallow groundwater by upward fluxes of deeper groundwater which, as demonstrated previously, is denitrified mainly as a result of reaction with pyrite. (b) Denitrification of shallow groundwater during summer with organic matter acting as the electron donor. (c) Dilution by rain water. Nitrate concentrations in both stream water and shallow groundwater depend on the amount of precipitation, with an increased contribution from deep denitrified groundwater during dry periods. The temporal variations in NO3 concentration observed several metres below the water table are related to the preferential and rapid movement of NO3 -polluted water through fractures and large fissures, which has been estimated at 1 m day−1. Nitrate pollution in the catchment, because of the interaction with pyrite, also increases the net chemical weathering rate to values exceeding the world average.

Most current investigations of sites contaminated with heavy metals (e.g. Pb, Zn, Cu) emphasise the importance of determining the amounts of physical and chemical forms of metals rather than just the total amounts present. Chemical extraction techniques used for this purpose are inevitably operationally defined. A more direct approach to the identification of crystalline forms can be made by mineralogical techniques such as X-ray powder diffraction (XRPD), but quantitative determination of a particular form is not often attempted. Recent advances in methods of analysis and sample preparation for XRPD mean that it is now a relatively simple matter to obtain quantitative XRPD data. Here, it is applied to the quantitative determination of the forms of Pb in different size-fractions of stream sediment samples from Leadhills/Wanlockhead, SW Scotland, an historic Pb mining area. Comparison of the XRPD analyses with determinations of Pb by atomic absorption spectrophotometry demonstrates that a large proportion of the Pb present in the stream sediments is in the form of cerussite (PbCO3). Furthermore, the cerussite tends to be concentrated in the silt fraction and is even a minor component of the clay-size fraction. However, quantitative analysis of fractions <6 μm indicates that cerussite alone cannot account for all the Pb in this size range. Indirectly, this result suggests that Pb adsorbed to clay minerals, organic matter and/or amorphous Fe and Mn oxides may be proportionally more important for the <6 μm materials. Sediment in this size range, however, typically accounts for no more than 1% by weight of the total stream bed sediment samples collected in the study area. In relation to its size distribution, the mobility of Pb within the wider environment is most likely to occur principally through physical transport of fine particles.

Generally, the history of past sub-surface fluid movements is difficult to reconstruct. However, the composition of oil-field waters characterizes the origins and mixing processes that allow such a reconstruction. We have investigated present-day formation waters from Brent Group sedimentary rocks of the Oseberg Field in order to assess both their geochemical variations, and their origin(s). Water samples (sampled at the separator) produced from immediately above the oil–water contact and from the aquifer (water-saturated zone below the oil–water contact) were taken from 11 wells across the field. In addition, 3 trace water samples were extracted from oil produced from higher up in the oil column. The water samples were analysed for their chemical components and isotopic compositions. Conservative tracers such as Cl, Br, δD, and δ18O were used to evaluate the origin of the waters. All formation waters can be characterised as Na–Cl-brines. The separator samples are of aquifer origin, indicating that aquifer water, drawn up by the pressure reduction near the well, is produced from the lower few tens of metres of the oil-zone. By defining plausible endmembers, the waters can be described as mixtures of seawater (60–90%), meteoric water (10–30%), evaporated seawater (primary brines) (3–5%), and possibly waters which have dissolved evaporites (secondary brines). Alternatively, using multidimensional scaling, the waters can be described as mixtures of only 3 endmembers without presupposing their compositions. In fact, they are seawater, very dilute brine, and a secondary brine (confirming the power of this approach). Meteoric water was introduced into the reservoir during the end-Brent and early-Cretaceous periods of emergence and erosion, and partially replaced the marine pore fluids. Lateral chemical variations across the Oseberg Field are extremely small. The waters from closer to the erosion surfaces show slightly stronger meteoric water isotopic signatures. The primary and secondary brines are believed to come from Permian and Triassic evaporitic rocks in the deeply buried Viking Graben to the west, and to have been modified by water–rock interactions along their migration path. These primary basinal brines have not been detected in the oil–zone waters, suggesting that the brines entered the reservoir after the main phase of oil-migration. There are indications that these external fluids were introduced into the reservoir along faults. Present-day aquifer waters are mixtures of waters from different origins and hardly vary at a field-scale. They are different in composition to the water trapped in the present oil-zone. One of the oil-zone samples is a very dilute brine. It is thought to represent a simple mixture of seawater and meteoric water. Due to oil-emplacement, this geochemical signature was preserved in the waters trapped within the oil-zone. Another oil-zone water shows a very similar chemical signature to the aquifer waters, but the chlorine isotopic signature is similar to that of the dilute oil-zone water. This water is interpreted to represent a palaeo-aquifer water. That is, it was within the aquifer zone in the past, but was trapped by subsequent emplacement of more oil. These vertical differences can be explained by two features: (i) emergence of the Brent Group sedimentary rocks in the Early Cretaceous allowed ingress of meteoric water; (ii) subsequent rapid burial of Viking Graben rocks caused migration of petroleum and aqueous fluids into the adjacent, less deeply buried Oseberg Field.

Water inflows in the Gotthard Highway Tunnel and in the Gotthard Exploration Tunnel are meteoric waters infiltrating at different elevations, on both sides of an important orographic divide. Limited interaction of meteoric waters with gneissic rocks produces Ca–HCO3 and Na–Ca–HCO3 waters, whereas prolonged interaction of meteoric waters with the same rocks generates Na–HCO3 to Na–SO4 waters. Waters circulating in Triassic carbonate-evaporite rocks have a Ca–SO4 composition. Calcium-Na–SO4 waters are also present. They can be produced through interaction of either Na–HCO3 waters with anhydrite or Ca–SO4 waters with a local gneissic rock, as suggested by reaction path modeling. An analogous simulation indicates that Na–HCO3 waters are generated through interaction of Ca–HCO3 waters with a local gneissic rock. The two main SO4-sources present in the Alps are leaching of upper Triassic sulfate minerals and oxidative dissolution of sulfide minerals of crystalline rocks. Values of δ34SSO4 < ∼+9‰ are due to oxidative dissolution of sulfide minerals, whereas δ34SSO4 >∼+9‰ are controlled either by bacterial SO4 reduction or leaching of upper Triassic sulfate minerals. Most waters have temperatures similar to the expected values for a geothermal gradient of 22°C/km and are close to thermal equilibrium with rocks. However relatively large, descending flows of cold waters and ascending flows of warm waters are present in both tunnels and determine substantial cooling and heating, respectively, of the interacting rocks. The most import upflow zone of warm, Na-rich waters is below Guspisbach, in the Gotthard Highway Tunnel, at 6.2–9.0 km from the southern portal. These warm waters have equilibrium temperatures of 65–75°C and therefore constitute an important low-enthalpy geothermal resource.

Two different mathematical techniques have been used to analyse data obtained from a set of experiments in which a range of radiotracers were sorbed onto two contrasting lake sediments. The advantages and disadvantages of the two techniques have been evaluated. Both approaches to the analysis were capable of providing rate parameters which can be used to determine the mobility and rate of removal of trace species from the water column. However, the values of the parameters were often different, depending upon which approach was used and, in some cases, even the number of sorption processes identified was method dependent.