Applied Geochemistry (v.54, #C)

The phase behavior of CO2–CH4–H2S–brine systems is of importance for geological storage of greenhouse gases, sour gas disposal and enhanced oil recovery (EOR). In such projects, reservoir simulations play a major role in assisting decision makings, while modeling the phase behavior of the relevant CO2–CH4–H2S–brine system is a key part of the simulation. There is a need for an equation of state (EOS) for such system which is accurate, with wide application range (pressure, temperature and aqueous salinity), computationally efficient and easy for implementation in a reservoir simulator.In this study, an improved cubic EOS model of the system CO2–CH4–H2S–brine is developed based on the modifications of the binary interaction parameters in Peng–Robinson EOS, which is widely implemented in reservoir simulators. Thus the new model is suited for numerical implementation in reservoir simulators.The available experimental data of pure gas brine equilibrium and gas mixture solubility in water/brine are carefully reviewed and compared with the new model. From the comparison, the new model can accurately reproduce (1) the CO2–brine mutual solubility data at temperature from 0 °C to 250 °C, pressure from 1 bar to 1000 bar and NaCl molality (mole number in 1 kg water, molal is used for short) from 0 to 6 molal, (2) CH4–brine mutual solubility data at temperature from 0 °C to 250 °C, pressure from 1 bar to 2000 bar and NaCl molality from 0 to 6 molal, (3) H2S–brine mutual solubility data at temperature from 0 °C to 250 °C, pressure from 1 bar to 200 bar and NaCl molality from 0 to 6 molal, and (4) has good accuracy for gas mixture solubility in brine.

A mass-flow event triggered by the 1996 flood in the Saguenay region buried the mercury-contaminated indigenous sediments at the head of the Saguenay Fjord under up to 50 cm of postglacial deltaic sediments. The vertical distributions of total mercury and methyl-mercury in the sediments and pore waters were measured in box cores recovered from the Saguenay Fjord within and outside the affected area prior to and on six consecutive years after the flood. The total solid mercury (THgs) profiles show that remobilization was limited and most of the mercury remobilized from the contaminated, indigenous sediments was trapped below or slightly above the former sediment–water interface by authigenic acid-volatile sulfides (AVS). Nonetheless, a small fraction of the remobilized mercury diffused into the flood layer, some of it was methylated and/or scavenged by organic matter and AVS. Elevated solid-phase methyl-mercury concentrations, [MeHgs], at depth in the sediment are correlated to peak AVS and THgs but, in the absence of elevated dissolved methyl-mercury concentrations, [MeHgd], the higher [MeHgs] may reflect an earlier episode of Hg methylation, the product of which was scavenged by the AVS and buried. Throughout the sediment cores, sediment–water partitioning of MeHg and Hg(II) appears to be controlled in great part by the AVS and residual organic matter content of the sediment.

Biogenic nano-magnetite and nano-zero valent iron treatment of alkaline Cr(VI) leachate and chromite ore processing residue by Mathew P. Watts; Victoria S. Coker; Stephen A. Parry; Richard A.D. Pattrick; Russell A.P. Thomas; Robert Kalin; Jonathan R. Lloyd (27-42).
Highly reactive nano-scale biogenic magnetite (BnM), synthesized by the Fe(III)-reducing bacterium Geobacter sulfurreducens, was tested for the potential to remediate alkaline Cr(VI) contaminated waters associated with chromite ore processing residue (COPR). The performance of this biomaterial, targeting aqueous Cr(VI) removal, was compared to a synthetic alternative, nano-scale zero valent iron (nZVI). Samples of highly contaminated alkaline groundwater and COPR solid waste were obtained from a contaminated site in Glasgow, UK. During batch reactivity tests, Cr(VI) removal from groundwater was inhibited by ∼25% (BnM) and ∼50% (nZVI) when compared to the treatment of less chemically complex model pH 12 Cr(VI) solutions. In both the model Cr(VI) solutions and contaminated groundwater experiments the surface of the nanoparticles became passivated, preventing complete coupling of their available electrons to Cr(VI) reduction. To investigate this process, the surfaces of the reacted samples were analyzed by TEM-EDX, XAS and XPS, confirming Cr(VI) reduction to the less soluble Cr(III) on the nanoparticle surface. In groundwater reacted samples the presence of Ca, Si and S was also noted on the surface of the nanoparticles, and is likely responsible for earlier onset of passivation. Treatment of the solid COPR material in contact with water, by addition of increasing weight % of the nanoparticles, resulted in a decrease in aqueous Cr(VI) concentrations to below detection limits, via the addition of ⩾5% w/w BnM or ⩾1% w/w nZVI. XANES analysis of the Cr K edge, showed that the % Cr(VI) in the COPR dropped from 26% to a minimum of 4–7% by the addition of 5% w/w BnM or 2% w/w nZVI, with higher additions unable to reduce the remaining Cr(VI). The treated materials exhibited minimal re-mobilization of soluble Cr(VI) by re-equilibration with atmospheric oxygen, with the bulk of the Cr remaining in the solid fraction. Both nanoparticles exhibited a considerable capacity for the remediation of COPR related Cr(VI) contamination, with the synthetic nZVI demonstrating greater reactivity than the BnM. However, the biosynthesized BnM was also capable of significant Cr(VI) reduction and demonstrated a greater efficiency for the coupling of its electrons towards Cr(VI) reduction than the nZVI.

Characterization of natural organic matter in bentonite clays for potential use in deep geological repositories for used nuclear fuel by Michaela H.M. Marshall; Jennifer R. McKelvie; André J. Simpson; Myrna J. Simpson (43-53).
The Nuclear Waste Management Organization (NWMO) is developing a Deep Geological Repository (DGR) to contain and isolate used nuclear fuel in a suitable rock formation at a depth of approximately 500 m. The design concept employs a multibarrier system, including the use of copper-coated used fuel containers, surrounded by a low-permeability, swelling clay buffer material within a low permeability, stable host rock environment. The natural organic matter (NOM) composition of the bentonite clays being considered for the buffer material is largely uncharacterized at the molecular-level. To gain a better understanding of the NOM in target clays from Wyoming and Saskatchewan, molecular-level methods (biomarker analysis, solid-state 13C NMR and solution-state 1H nuclear magnetic resonance (NMR)) were used to elucidate the structure and sources of NOM. Organic carbon content in three commercially available bentonites analyzed was low (0.11–0.41%). The aliphatic lipid distribution of the clay samples analyzed showed a predominance of higher concentration of lipids from vascular plants and low concentrations of lipids consistent with microbial origin. The lignin phenol vanillyl acid to aldehyde ratio (Ad/Al) for the National sample indicated an advanced state of lignin oxidation and NOM diagenesis. The 13C NMR spectra were dominated by signals in the aromatic and aliphatic regions. The ratio of alkyl/O-alkyl carbon ranged from 7.6 to 9.7, indicating that the NOM has undergone advanced diagenetic alteration. The absence lignin-derived phenols commonly observed in CuO oxidation extracts from contemporary soils and sediments as well as the lack of amino acids suggests that the material corresponding to the aromatic signal is not composed of lignin or proteins but may be derived from another source such as black carbon or some other non-extractable aromatic-rich NOM. The aliphatic signal appears to correspond to long-chain compounds with little side branching based on the results of the one-dimensional (1D) and two-dimensional (2D) solution-state 1H NMR analyses. Overall, the organic geochemical analyses suggest that the NOM is composed mainly of plant-derived waxes and highly aromatic carbon with low contributions from small molecules. The compounds identified by the molecular-level analysis of NOM in the clay samples are hypothesized to be recalcitrant but future studies should examine if these compounds may serve as a microbial substrate to further test the observations of this study. Furthermore, our study suggests that the NOM has undergone diagenesis and that marine NOM signatures are no longer recognizable or detectable. As such, future work may also examine the diagenesis of these deposits to further understand the NOM geochemistry and paleoenvironmental conditions in bentonite deposits.

Dissolution of arkose in dilute acetic acid solution under conditions relevant to burial diagenesis by Leilei Yang; Tianfu Xu; Mingcong Wei; Guanhong Feng; Fugang Wang; Kairan Wang (65-73).
The organic acid produced during diagenesis can cause mineral dissolution, leading to the formation of secondary porosity zones. Arkose dissolution in organic acid solution is important in the evolution of reservoir quality, and is influenced by various factors. To investigate the effects of acetic acid on arkose dissolution under different burial diagenetic conditions, seven batch experiments were conducted over a wide range of reaction conditions. Medium-grained lithic arkose from Songliao Basin, northeastern China, was selected for the study. Four primary factors were considered: temperature (80 °C, 120 °C, and 160 °C), pH (2.5, 4.0, and 5.5), initial water/rock mass ratio (10:1 and 15:1) and grain size (1–3 mm, 3–5 mm). Each experiment was performed for 312 h and sampled six times in parallel. Results indicate that these four factors have significant effects on arkose dissolution. In a certain temperature range, feldspar dissolution increased, but declined when the temperature exceeded a certain value. Different minerals/elements were affected differently by temperature. Silicon was the element most sensitive to temperature. Under acidic conditions, the dissolution rates of most minerals increased as the pH decreased. Grain size and water/rock mass ratio affected the degree of reaction in the early period and then the form of mineral transformation in the late period. The experimental results are generally consistent with previous field research outcomes. Understanding the factors that control sandstone dissolution under organic acid conditions will allow the easier detection of secondary porosity zones, which may improve the precision of oil exploration.

Biogeochemical weathering of serpentinites: An examination of incipient dissolution affecting serpentine soil formation by Julie L. Baumeister; Elisabeth M. Hausrath; Amanda A. Olsen; Oliver Tschauner; Christopher T. Adcock; Rodney V. Metcalf (74-84).
Serpentinite rocks, high in Mg and trace elements including Ni, Cr, Cd, Co, Cu, and Mn and low in nutrients such as Ca, K, and P, form serpentine soils with similar chemical properties resulting in chemically extreme environments for the biota that grow upon them. The impact of parent material on soil characteristics is most important in young soils, and therefore the incipient weathering of serpentinite rock likely has a strong effect on the development of serpentine soils and ecosystems. Additionally, porosity generation is a crucial process in converting rock into a soil that can support vegetation. Here, the important factors affecting the incipient weathering of serpentinite rock are examined at two sites in the Klamath Mountains, California. Serpentinite-derived soils and serpentinite rock cores were collected in depth profiles from each sampling location. Mineral dissolution in weathered serpentinite samples, determined by scanning electron microscopy, energy dispersive spectrometry, electron microprobe analyses, and synchrotron microXRD, is consistent with the order, from most weathered to least weathered: Fe-rich pyroxene > antigorite > Mg-rich lizardite > Al-rich lizardite. These results suggest that the initial porosity formation within serpentinite rock, impacting the formation of serpentine soil on which vegetation can exist, is strongly affected both by the presence of non-serpentine primary minerals as well as the composition of the serpentine minerals. In particular, the presence of ferrous Fe appears to contribute to greater dissolution, whereas the presence of Al within the parent rock appears to contribute to greater stability. Iron-oxidizing bacteria present at the soil–rock interface have been shown in previous studies to contribute to the transition from rock to soil, and soils and rock cores in this study were therefore tested for iron-oxidizing bacteria. The detection of biological iron oxidation in this study indicates that the early alteration of these Fe-rich minerals may be mediated by iron-oxidizing bacteria. These findings help provide insight into the incipient processes affecting serpentinite rock weathering, important to the development of extreme serpentine soils and the biota that grow on them.

Elucidating the formation of terra fuscas using Sr–Nd–Pb isotopes and rare earth elements by Christophe Hissler; Peter Stille; Jérôme Juilleret; Jean François Iffly; Thierry Perrone; Gilles Morvan (85-99).
Carbonate weathering mantles, like terra fusca, are common in Europe but their formation and evolution is still badly understood. We propose to combine geological, mineralogical and pedological knowledge with trace element and isotope data of a weathering mantle as a novel approach to understand the evolution of terra fuscas. Sr–Nd–Pb isotopes and rare earth element (REE) contents were analyzed in a cambisol developing on a typical terra fusca on top of a condensed Bajocian limestone-marl succession from the eastern side of the Paris Basin. The isotope data, REE distribution patterns and mass balance calculations suggest that the cambisol mirrors the trace element enrichments present in this carbonate lithology, which are exceptionally high compared to global average carbonate. The deeper soil horizons are strongly enriched not only in REE (ΣREE: 2640 ppm) but also in redox-sensitive elements such as Fe (44 wt.%), V (1000 ppm), Cr (700 ppm), Zn (550 ppm), As (260 ppm), Co (45 ppm) and Cd (2.4 ppm). The trace element distribution patterns of the carbonate bedrock are similar to those of the soil suggesting their close genetic relationships. Sr–Nd–Pb isotope data allow to identify four principal components in the soil: a silicate-rich pool close to the surface, a leachable REE enriched pool at the bottom of the soil profile, the limestone on which the weathering profile developed and an anthropogenic, atmosphere-derived component detected in the soil leachates of the uppermost soil horizon. The leachable phases are mainly secondary carbonate-bearing REE phases such as bastnaesite ((X) Ca(CO3)2F) (for X: Ce, La and Nd). The isotope data and trace element distribution patterns indicate that at least four geological and environmental events impacted the chemical and isotopical compositions of the soil system: 1. An oxygen-deficient diagenetic or hydrothermal event caused trace metal enrichments in the Bajocian limestone-marls. 2. Carbonate dissolution caused the enrichment of detrital silicate phases and authigenic REE-bearing residual phases – e.g. marine authigenic fluorapatites and bastnaesite – in the newly formed condensed horizons. 3. Dissolution/precipitation of metastable bastnaesite phases and downward migration of the REE during soil formation. 4. Overprinting of the chemical and isotopical compositions of the uppermost soil horizon by recent atmospheric depositions.

Rare earth elements as a tool for studying the formation of cemented layers in an area affected by acid mine drainage by Anja Grawunder; Martin Lonschinski; Dirk Merten; Georg Büchel (100-110).
In a profile with two cemented layers sampled in an area affected by acid mine drainage, both have rare earth element (REE) signatures with positive Ce anomalies in the Post Archean Australian Shale-normalised patterns. Both cemented layers have higher contents of environmentally relevant metals (Cd, Co, Cu, Fe, Mn, U, and Zn) than the over- and underlying unconsolidated Quaternary sediments and are depleted of Al, Ca, K, and Mg. The cemented layers are enriched in middle and heavy REE, but only the bulk pattern of the lower cemented layer reveals a positive Ce anomaly. For the upper cemented layer, this positive Ce anomaly was only determined by spatially resolved laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) studies only for segments with a high abundance of Mn, occurring as Mn phases as proven by energy dispersive X-ray spectroscopy. The Mn phases are formed secondarily to the ferric cement and are especially enriched in Ce and Co. The Ce anomaly of the lower cemented layer most probably is inherited from groundwater to the ferric cement, whereas the Ce anomaly of the upper cemented layer is the result of preferential scavenging of Ce onto the Mn phases compared to other REE.

Reply to the comment on the paper “Stable isotope fractionation of chlorine during the precipitation of single chloride minerals” by Chong-guang Luo; Ying-kai Xiao; Han-jie Wen; Hai-zhou Ma; Yun-qi Ma; Yan-ling Zhang; Mao-yong He (117-118).