Applied Geochemistry (v.23, #1)

The use of covers with capillary barrier effects (CCBEs) for reducing acid mine drainage (AMD) from sulphidic mine tailings is simulated using the MIN3P finite volume model for coupled groundwater flow, O2 diffusion and multi-component reactive transport. The model is applied to simulate five pilot-scale in situ test cells containing reactive tailings from the Manitou mine site, Val d’Or, Que., Canada. Four of the cells were constructed with CCBEs over the tailings, while the fifth tailings cell was left uncovered. Observed and simulated discharge from the base of each cell showed that the capillary barrier covers significantly reduced sulphide oxidation and AMD. Compared to acidic discharge from the uncovered cell, discharge from the four CCBE-covered cells had neutral pH levels and 1–7 orders of magnitude lower concentrations of SO4, Fe, Zn, Cu and Al. The simulations showed that the moisture retaining layer of the CCBEs reduced AMD by inhibiting O2 diffusion into the underlying reactive wastes. Provided the moisture-retention layer of the CCBE remains close to saturation, its thickness had a relatively minor effect. Under such near-saturated conditions, O2 availability is limited by its diffusion rate through the bulk porous medium and not by the diffusion rate through the oxidized grain shells. The model is providing important new insights for comparing design alternatives for reducing or controlling AMD.

Ombrotrophic bogs are useful records of the impact of historical human activity on heavy metal contamination. Several studies concerning the trace element record (mainly Pb and Hg) in these particular environments have been carried out in recent years, although the role of humic substances has often not been considered. In particular, of the components of peat organic matter, fulvic acids and low molecular weight compounds are generally responsible for the mobility of trace elements through the profile, while humic acids (HAs) are involved in the formation of more stable organo-mineral complexes. In order to study the parallel distribution of As, Cr, Ni, Rb, Ti and Zr in bulk peat and the corresponding HAs, a peat core (10 × 10 × 81 cm) was collected from Etang de la Gruère (Switzerland) and cut into 27 slices of 3 cm. The samples were freeze-dried and milled very finely, and HAs extracted from each sample. Both peat and HAs were analyzed using an energy-dispersive miniprobe X-ray fluorescence multielement analyser (EMMA-XRF). Of the considered elements, Ni showed a great affinity for the humic acid component, while Cr was concentrated mainly into humic material from the deeper layers. On the other hand, Ti, Zr and Rb seemed to reflect the variation in mineral material both in peat and HA samples, while the As content of both materials reflected the environmental conditions characterizing the bog.

The effect of organics on lead sorption onto Apatite II™ by W.A. Martin; S.L. Larson; D.R. Felt; J. Wright; C.S. Griggs; M. Thompson; J.L. Conca; C.C. Nestler (34-43).
Training activities at firing ranges, both civilian and military, deliver large quantities of Pb bullets into range soils where the physical and geochemical properties of the soil can influence Pb transport. Some best management practices (BMPs) developed for range managers include the addition of phosphate amendments, such as apatite, to immobilize Pb and other metals associated with firing ranges. In this study, the effect of the organic matter content of apatite II™ on its metal sorption properties was investigated. Batch and column experiments were conducted using mechanically, enzymatically, and thermally-treated forms of Apatite II™ to sorb soluble Pb. In batch experiments, mechanically and enzymatically-treated Apatite II™ reduced soluble Pb concentrations from 29% to 96%, depending on the age of the Apatite source. Thermally-treated Apatite II™ consistently reduced soluble Pb concentrations in solution by more than 90%, regardless of aging. The mechanically and enzymatically-treated Apatite II™ produced significantly higher dissolved organic carbon (DOC) and biochemical oxygen demand (BOD) concentrations while undergoing aging. This contrasts with the thermally-treated Apatite II™ that produced very low to non-detectable levels of DOC and BOD while aging. To determine the effects of thermal treatment on performance efficiencies, studies were performed using 500 mg L−1 Pb solutions in columns packed with Apatite II™ that had been preheated at various temperatures for 2 h. The column study showed Pb loading of the Apatite II™ at different thermal treatments that ranged from 10.5% to 16.8% Pb by weight of substrate. The Pb loading capacity (by weight of substrate) increased as the treatment temperature of the Apatite II™ increased.

Fe and Mn levels regulated by agricultural activities in alluvial groundwaters underneath a flooded paddy field by Kangjoo Kim; Hyun-Jung Kim; Byoung-Young Choi; Seok-Hwi Kim; Ki-hoon Park; Eungyu Park; Dong-Chan Koh; Seong-Taek Yun (44-57).
Iron and Mn concentrations in fresh groundwaters of alluvial aquifers are generally high in reducing conditions reflecting low SO4 concentrations. The mass balance and isotopic approaches of this study demonstrate that reduction of SO4, supplied from agricultural activities such as fertilization and irrigation, is important in lowering Fe and Mn levels in alluvial groundwaters underneath a paddy field. This study was performed to investigate the processes regulating Fe and Mn levels in groundwaters of a point bar area, which has been intensively used for flood cultivation. Four multilevel-groundwater samplers were installed to examine the relationship between geology and the vertical changes in water chemistry. The results show that Fe and Mn levels are regulated by the presence of NO3 at shallow depths and by SO4 reduction at the greater depths. Isotopic and mass balance analyses revealed that NO3 and SO4 in groundwater are mostly supplied from the paddy field, suggesting that the Fe-and Mn-rich zone of the study area is confined by the agricultural activities. For this reason, the geologic conditions controlling the infiltration of agrochemicals are also important for the occurrence of Fe/Mn-rich groundwaters in the paddy field area.

Intensive monitoring of the Cuise Sands Aquifer in a small agricultural catchment (3 km2, where agricultural practices are well documented) over nearly 5 a showed significant disparities for major element concentrations, Sr concentrations, isotopic compositions and 3H values, depending on the groundwater sampling locations. Lower 87Sr/86Sr values (0.7079–0.7085) associated with low NO 3 - concentrations, low Mg/Sr molar ratios (<100) and low 3H values are attributed to natural end-members. Groundwater with higher 87Sr/86Sr values (>0.7085) and higher Mg/Sr molar ratios (>250) suggest a contribution of Sr from anthropogenic sources. Strontium isotopes coupled with Mg/Sr and Ca/Sr ratios of groundwater in this catchment successfully demonstrated the capacity to trace fertilizer contributions, which significantly modify the natural Sr isotopic signature of groundwater. The specific geochemical signature of groundwater revealed by Sr isotopes, in addition to major and trace element concentrations (in particular Mg/Sr and Ca/Sr molar ratios), demonstrated the partial isolation of groundwater bodies in this catchment. Compartmentalisation of the aquifer is compatible with fault distribution as defined by geological and geophysical investigations. Thus, the Sr isotopic tool coupled with Mg/Sr and Ca/Sr ratios has been applied with success to trace water pathways and recharge and to provide scenarios for the hydrological functioning of the system.

A major challenge for mineral explorers is to efficiently detect mineralisation beneath the weathered cover that extends across the landscape. Determination of the elemental composition of plants (biogeochemical exploration) can aid in the detection of buried ore deposits due to their root penetration through the weathered cover. At the coyote prospect in Western Australia a range of plant species were sampled traversing a buried Au orebody. Here it is shown that the soft spinifex (Triodia pungens) accumulated important pathfinder elements related to the mineralisation, which produced a multi-element surficial expression of the underlying ore deposit. Spinifex grasses are one of the most widespread grasses over the Australian continent and have vertical root systems that can extend for many 10s of metres through sedimentary cover and interact with buried mineral deposits and alteration zones in the underlying substrate. Spinifex biogeochemistry therefore has potential to be a low cost, low environmental impact, sampling medium for mineral exploration programs across large parts of arid Australia. The examination of similar grasses from other semi-arid and arid regions from around the world therefore also warrants further investigation.

Elevated As concentrations in groundwater in the eastern United States have been recognized predominantly in the accretionary geologic terranes of northern New England. A retrospective examination of more than 18,000 existing groundwater samples from the Pennsylvania Department of Environmental Protection (PA DEP) Drinking Water and Sampling Information System database indicates that elevated groundwater As concentrations occur throughout the northern half of the Piedmont Province of Pennsylvania. Chemical analyses of 53 samples collected in 2005 from drinking water wells in this area all had detectable As, and 23% of these samples contained elevated (>133 nmol/L or >10 μg/L) concentrations of As. Elevated concentrations of As in the groundwater samples were most common in the Mesozoic sedimentary strata composed of sandstone and red mudstone with interbedded gray shale, and gray to black siltstone and shale. Arsenic was typically not elevated in groundwater of diabase intrusions of the Newark Basin or in crystalline and calcareous aquifers to the north of the Newark Basin. Geochemical parameters such as pH and oxidation–reduction potential can indicate mobility mechanisms of As in some regions. In this area, measured groundwater conditions were predominantly oxidizing (Eh > +50 mV), and more than 85% of samples contained arsenate as the dominant As species. Variations in pH were strongly correlated to the As concentration, with highest As concentrations observed at pH values greater than 6.4. The original source of As is most likely the black and gray shales that contain some arsenian pyrite with groundwater concentrations likely to be controlled by adsorption/desorption reactions with Fe oxides in the red mudstone aquifer materials.