Geochemical and Biogeochemical Reaction Modeling

An indispensable primer and reference textbook, the third edition of Geochemical and Biogeochemical Reaction Modeling carries the reader from the field's origins and theoretical underpinnings through to a collection of fully worked examples. A clear exposition of the underlying equations and calculation techniques is balanced by real-world example calculations. The book depicts geochemical reaction modeling as a vibrant field of study applicable to a wide spectrum of issues of scientific, practical, and societal concern. The new edition offers a thorough description of surface complexation modeling, including two- and three-layer methods; broader treatment of kinetic rate laws; the effect of stagnant zones on transport; and techniques for determining gas partial pressures. This handbook demystifies and makes broadly accessible an elegant technique for portraying chemical processes in the geosphere. It will again prove to be invaluable for geochemists, environmental scientists and engineers, aqueous and surface chemists, microbiologists, university teachers, and government regulators.

Comparison of Porosity Change Due to Geochemical Reaction between Samples from High CO2 Field and Depleted Field

When developing a high CO2 field, oil and gas companies must consider the best and most economical carbon capture and storage (CCS) plan. After considering the distance of the storage site and storage capacity, PETRONAS has identified 2 carbonate fields, known as X Field and N Field in East Malaysia as the potential CO2 storage site. Interestingly, both fields are different, as X field is a high CO2 green field, while N field is a depleted gas field. The research team’s initial hypothesis is that N Field would have more severe geochemical reaction between CO2, brine and carbonates compared to X Field, since X field is already saturated with CO2. In order to test the hypothesis, samples from these two fields were selected to undergo static batch reaction analysis, and changes in porosity were determined using Digital Core Analysis (DCA). Both X and N fields are carbonate gas fields, with aquifer zone located below gas zones. The aquifer zones are the preferable CO2 injection zone because the deeper the zone, the longer it will take for the plume migration to happen. For static batch reaction analysis, samples each field were selected from the aquifer zone. After Routine Core Analysis (RCA) and Quality Control (QC), the samples were scanned under the high resolution microCT scan, before they were saturated into the respective synthetic brine. After saturation is completed, both brine and samples were placed inside a batch reactor, where the reactor’s pressure and temperature are set according to the field’s pressure and temperature. Once stabilized, the supercritical CO2 is injected into the brine, and was left for 45 days with constant observation. After aging with supercritical CO2, the samples were then scanned under microCT scan once again, using the same resolution, before being analysed via image processing software. Using registration algorithm software, both pre and post CO2 aging images were overlapped and subtracted digitally. The difference images were analyzed to determine the change in porosity. Samples from X Field has around 1% p.u. increase in porosity, while samples from N field shows increment of 2% p.u. porosity. While N field (depleted field) has higher reaction compared to X field (high CO2) field as per hypothesis, the difference is very minimal, which is much less than expected. The usage of DCA in the analysis enabled the team to determine minute changes that were happening during CO2 batch reaction. Without DCA, the 1% changes usually regarded as equipment’s error margin. The next step would be modelling, where the lab results will be upscaling into field scale, for modelled longer period of time. Hence, although the porosity changes between X and N field are very small under laboratory condition, it can have greater impact in field scale.

The Hydrogeochemical Characteristics of Groundwater Subjected to Seawater Intrusion in the Archipelago, Korea

The effect of seawater on the groundwater in archipelago of South Korea where it has rarely been investigated was analyzed by examining the hydrogeochemical characteristics. A total of 74 groundwater samples were classified by water quality type and Cl−/HCO3− molar ratio. First, 36 samples of the Ca–Cl type and 32 samples of the Na–Cl type (accounting for 91.9% of the total) were considered to have been influenced by seawater. When the samples had been classified based on the Cl−/HCO3− molar ratio, the samples with a Cl−/HCO3− molar ratio of 2.8 or higher (indicating that seawater had highly influenced the groundwater) accounted for 40 out of 74 samples. This confirms that the groundwater in the study area had been affected by seawater. When quantitatively determining the influence of seawater on the groundwater, the seawater mixing ratios using either Cl or Br ion were found to be almost the same. In the case of Cl ion, the mixing ratio was in the range of 0–10.4% (average of 1.0%), while when using Br ion, the mixing ratio was in the range of 0–7.6% (average of 0.6%). From a principal component analysis, it can be seen that the influence of seawater occupied the first component of 54.1% and it is evident that the samples with a large mixing ratio of seawater were from regions where seawater has a large influence. The ion-exchange reaction was proceeded by calculating the ionic delta value to indicate the seawater intrusion and cation exchange, and specific trends of the ions participating in the geochemical reaction related to the seawater mixing ratio are reported herein. It was found that the ionic delta value of each ion had a mixing ratio and specific tendency according to the change in mixing ratio before the constant value of the seawater mixing ratio saturated with Na2+. Our results show that it can be possible to grasp the contribution of the geochemical reactions of each ion to the seawater mixing ratio.

Chemo-Mechanical Interactions in the Ettringite Induced Expansion of Sulfate-Bearing Soils

Expansive sulfate-bearing soils are frequently encountered in transportation and construction practices. These soils are often treated with a lime or cement stabilizer to improve the relevant qualities. However, the reaction between sulfate and alumina in soils and calcium of lime or cement can lead to the formation of ettringite, an expansive sulfate mineral resulting in soil swelling or heaving. The underlying mechanisms often involve intricate interactions between chemical processes and mechanical responses. The present study explores a chemo–mechanical approach in an attempt to quantify several mechanisms potentially responsible for the volume expansion, including the geochemical formation of ettringite, crystallization pressure, and osmosis-induced swelling. The geochemical reaction leading to ettringite formation is examined with a specific focus on the circumstances under which it may lead to volume change. The crystallization pressure developed during the ettringite formation may also play a significant role in the soil expansion and is investigated in the present study based on thermodynamic formulations, and the resulting volume expansion is simulated. The osmosis-induced swelling is studied within the context of the chemo–mechanical framework, and its kinetics is also explored. Numerical simulations are performed in the present study to examine different scenarios driven by distinct predominant mechanisms. In particular, the interplay between ettringite formation and osmosis swelling as interpreted from some recently-reported experimental studies shows that these mechanisms can all contribute to the observed expansion processes, and overall, the modeling results are consistent with the experimental findings.

The Interpretation of Biogeochemical Growths on Gold Coins from the SS Central America Shipwreck: Applications for Biogeochemistry and Geoarchaeology

Black crusts that formed on gold coins recovered from the 1857 shipwreck of the SS Central America played a key role in their preservation in a near original state. Within a few years of the sinking, the significant quantities of iron and steel on the shipwreck produced laminar geochemical precipitates of fine-grained iron minerals on the coins. This coating served to armor the coins from future chemical or biological attacks. Once coated, the coins were colonized by at least two distinct populations of gold-tolerant bacteria that precipitated abundant nanoparticulate gold in the black crust material and produced biomineralized bacteria in a web-like mat. Above this middle layer of black crust, the outer layer consisted of a geochemical reaction front of euhedral crystals of iron sulfate and iron oxy-hydroxide species, formed by the interaction of seawater with the chemical wastes of the bacterial mat. Understanding this process has application for assessing the diverse and extreme conditions under which nano-particulate gold may form through biological processes, as well as understanding the conditions that contribute to the preservation or degradation of marine archaeological materials.