Pierre D. Glynn

Reaction paths and equilibrium end-points in solid-solution aqueous-solution systems

Equations are presented describing equilibrium in binary solid-solution aqueous-solution (SSAS) systems after a dissolution, precipitation, or recrystallization process, as a function of the composition and relative proportion of the initial phases. Equilibrium phase diagrams incorporating the concept of stoichiometric saturation are used to interpret possible reaction paths and to demonstrate relations between stoichiometric saturation, primary saturation, and thermodynamic equilibrium states. The concept of stoichiometric saturation is found useful in interpreting and putting limits on dissolution pathways, but there currently is no basis for possible application of this concept to the prediction and/ or understanding of precipitation processes. Previously published dissolution experiments for (Ba, Sr)SO4 and (Sr, Ca)CO3orth. solids are interpreted using equilibrium phase diagrams. These studies show that stoichiometric saturation can control, or at least influence, initial congruent dissolution pathways. The results for (Sr, Ca)CO3orth. solids reveal that stoichiometric saturation can also control the initial stages of incongruent dissolution, despite the intrinsic instability of some of the initial solids. In contrast, recrystallisation experiments in the highly soluble KCl-KBr-H2O system demonstrate equilibrium. The excess free energy of mixing calculated for K(Cl, Br) solids is closely modeled by the relation GE = χKBrχKClRT[a0 + a1(2χKBr−1)], where a0 is 1.40 ± 0.02, a1, is −0.08 ± 0.03 at 25°C, and χKBr and χKCl are the mole fractions of KBr and KCl in the solids. The phase diagram constructed using this fit reveals an alyotropic maximum located at χKBr = 0.676 and at a total solubility product, ΣΠ = [K+]([Cl−] + [Br−]) = 15.35.

Methane production and consumption monitored by stable H and C isotope ratios at a crude oil spill site, Bemidji, Minnesota

Abstract Stable isotopic ratios of C and H in dissolved CH4 and C in dissolved inorganic C in the ground water of a crude-oil spill near Bemidji, Minnesota, support the concept of CH4 production by acetate fermentation with a contemporaneous increase in HCO3− concentration. Methane concentrations in the saturated zone decrease from 20.6 mg L−1 to less than 0.001 mg L−1 along the investigated flow path. Dissolved N2 and Ar concentrations in the ground water below the oil plume are 25 times lower than background; this suggests that gas exsolution is removing dissolved CH4 (along with other dissolved gases) from the ground water. Oxidation of dissolved CH4 along the flow path seems to be minimal because no measurable change in isotopic composition of CH4 occurs with distance from the oil body. However, CH4 is partly oxidized to CO2 as it diffuses upward from the ground water through a 5- to 7-m thick unsaturated zone; theδ13C of the remaining CH4 increases, theδ13C of the CO2 decreases, and the partial pressure of CO2 increases. Calculations of C fluxes in the saturated and unsaturated zones originating from the degradation of the oil plume lead to a minimum estimated life expectancy of 110 years. This is a minimum estimate because the degradation of the oil body should slow down with time as its more volatile and reactive components are leached out and preferentially oxidized. The calculated life expectancy is an order of magnitude estimate because of the uncertainty in the average linear ground-water velocities and because of the factor of 2 uncertainty in the calculation of the effective CO2 diffusion coefficient.

MBSSAS: a code for the computation of Margules parameters and equilibrium relations in binary solid-solution aqueous-solution systems

Abstract The computer code MBSSAS uses two-parameter Margules-type excess-free-energy of mixing equations to calculate thermodynamic equilibrium, pure-phase saturation, and stoichiometric saturation states in binary solid-solution aqueous-solution (SSAS) systems. Lippmann phase diagrams, Roozeboom diagrams, and distribution-coefficient diagrams can be constructed from the output data files, and also can be displayed by MBSSAS (on IBM-PC compatible computers). MBSSAS also will calculate accessory information, such as the location of miscibility gaps, spinodal gaps, critical-mixing points, alyotropic extrema, Henrys law solid-phase activity coefficients, and limiting distribution coefficients. Alternatively, MBSSAS can use such information (instead of the Margules, Guggenheim, or Thompson and Waldbaum excess-free-energy parameters) to calculate the appropriate excess-free-energy of mixing equation for any given SSAS system.

Dissolution of aragonite-strontianite solid solutions in nonstoichiometric Sr (HCO3)2−Ca (HCO3)2−CO2-H2O solutions

Synthetic strontianite-aragonite solid-solution minerals were dissolved in CO2-saturated non-stoichiometric solutions of Sr(HCO3)2 and Ca(HCO3)2 at 25°C. The results show that none of the dissolution reactions reach thermodynamic equilibrium. Congruent dissolution in Ca(HCO3)2 solutions either attains or closely approaches stoichiometric saturation with respect to the dissolving solid. In Sr(HCO3)2 solutions the reactions usually become incongruent, precipitating a Sr-rich phase before reaching stoichiometric saturation. Dissolution of mechanical mixtures of solids approaches stoichiometric saturation with respect to the least stable solid in the mixture. Surface uptake from subsaturated bulk solutions was observed in the initial minutes of dissolution. This surficial phase is 0–10 atomic layers thick in Sr(HCO3)2 solutions and 0–4 layers thick in Ca(HCO3)2 solutions, and subsequently dissolves and/or recrystallizes, usually within 6 min of reaction. The initial transient surface precipitation (recrystallization) process is followed by congruent dissolution of the original solid which proceeds to stoichiometric saturation, or until the precipitation of a more stable Sr-rich solid. The compositions of secondary precipitates do not correspond to thermodynamic equilibrium or stoichiometric saturation states. X-ray photoelectron spectroscopy (XPS) measurements indicate the formation of solid solutions on surfaces of aragonite and strontianite single crystals immersed in Sr(HCO3)2 and Ca(HCO3)2 solutions, respectively. In Sr(HCO3)2 solutions, the XPS signal from the outer ~ 60 A on aragonite indicates a composition of 16 mol% SrCO3 after only 2 min of contact, and 14–18 mol% SrCO3 after 3 weeks of contact. The strontianite surface averages approximately 22 mol% CaCO3 after 2 min of contact with Ca(HCO3)2 solution, and is 34–39 mol% CaCO3 after 3 weeks of contact. XPS analysis suggests the surface composition is zoned with somewhat greater enrichment in the outer ~25 A (as much as 26 mol% SrCO3 on aragonite and 44 mol% CaCO3 on strontianite). The results indicate rapid formation of a solid-solution surface phase from subsaturated aqueous solutions. The surface phase continually adjusts in composition in response to changes in composition of the bulk fluid as net dissolution proceeds. Dissolution rates of the endmembers are greatly reduced in nonstoichiometric solutions relative to dissolution rates observed in stoichiometric solutions. All solids dissolve more slowly in solutions spiked with the least soluble component ((Sr(HCO3)2)) than in solutions spiked with the more soluble component (Ca(HCO3)2), an effect that becomes increasingly significant as stoichiometric saturation is approached. It is proposed that the formation of a non-stoichiometric surface reactive zone significantly decreases dissolution rates.

Kinetic dissolution of carbonates and Mn oxides in acidic water: measurement of in situ field rates and reactive transport modeling

Abstract The kinetics of carbonate and Mn oxide dissolution under acidic conditions were examined through the in situ exposure of pure phase samples to acidic ground water in Pinal Creek Basin, Arizona. The average long-term calculated in situ dissolution rates for calcite and dolomite were 1.65×10 −7 and 3.64×10 −10 mmol/(cm 2 s), respectively, which were about 3 orders of magnitude slower than rates derived in laboratory experiments by other investigators. Application of both in situ and lab-derived calcite and dolomite dissolution rates to equilibrium reactive transport simulations of a column experiment did not improve the fit to measured outflow chemistry: at the spatial and temporal scales of the column experiment, the use of an equilibrium model adequately simulated carbonate dissolution in the column. Pyrolusite (MnO 2 ) exposed to acidic ground water for 595 days increased slightly in weight despite thermodynamic conditions that favored dissolution. This result might be related to a recent finding by another investigator that the reductive dissolution of pyrolusite is accompanied by the precipitation of a mixed Mn–Fe oxide species. In PHREEQC reactive transport simulations, the incorporation of Mn kinetics improved the fit between observed and simulated behavior at the column and field scales, although the column-fitted rate for Mn-oxide dissolution was about 4 orders of magnitude greater than the field-fitted rate. Remaining differences between observed and simulated contaminant transport trends at the Pinal Creek site were likely related to factors other than the Mn oxide dissolution rate, such as the concentration of Fe oxide surface sites available for adsorption, the effects of competition among dissolved species for available surface sites, or reactions not included in the model.

Reactive transport of metal contaminants in alluvium—model comparison and column simulation

Abstract A comparative assessment of two reactive-transport models, PHREEQC and HYDROGEOCHEM (HGC), was done to determine the suitability of each for simulating the movement of acidic contamination in alluvium. For simulations that accounted for aqueous complexation, precipitation and dissolution, the breakthrough and rinseout curves generated by each model were similar. The differences in simulated equilibrium concentrations between models were minor and were related to (1) different units in model output, (2) different activity coefficients, and (3) ionic-strength calculations. When adsorption processes were added to the models, the rinseout pH simulated by PHREEQC using the diffuse double-layer adsorption model rose to a pH of 6 after pore volume 15, about 1 pore volume later than the pH simulated by HGC using the constant-capacitance model. In PHREEQC simulation of a laboratory column experiment, the inability of the model to match measured outflow concentrations of selected constituents was related to the evident lack of local geochemical equilibrium in the column. The difference in timing and size of measured and simulated breakthrough of selected constituents indicated that the redox and adsorption reactions in the column occurred slowly when compared with the modeled reactions. MINTEQA2 and PHREEQC simulations of the column experiment indicated that the number of surface sites that took part in adsorption reactions was less than that estimated from the measured concentration of Fe hydroxide in the alluvium.

From data to decisions: Processing information, biases, and beliefs for improved management of natural resources and environments

Our different kinds of minds and types of thinking affect the ways we decide, take action, and cooperate (or not). Derived from these types of minds, innate biases, beliefs, heuristics, and values (BBHV) influence behaviors, often beneficially, when individuals or small groups face immediate, local, acute situations that they and their ancestors faced repeatedly in the past. BBHV, though, need to be recognized and possibly countered or used when facing new, complex issues or situations especially if they need to be managed for the benefit of a wider community, for the longer-term and the larger-scale. Taking BBHV into account, we explain and provide a cyclic science-infused adaptive framework for (1) gaining knowledge of complex systems and (2) improving their management. We explore how this process and framework could improve the governance of science and policy for different types of systems and issues, providing examples in the area of natural resources, hazards, and the environment. Lastly, we suggest that an “Open Traceable Accountable Policy” initiative that followed our suggested adaptive framework could beneficially complement recent Open Data/Model science initiatives. Plain Language Summary Our review paper suggests that society can improve the management of natural resources and environments by (1) recognizing the sources of human decisions and thinking and understanding their role in the scientific progression to knowledge; (2) considering innate human needs and biases, beliefs, heuristics, and values that may need to be countered or embraced; and (3) creating science and policy governance that is inclusive, integrated, considerate of diversity, explicit, and accountable. The paper presents a science-infused adaptive framework for such governance, and discusses the types of issues and systems that it would be best suited to address.

Integrated Environmental Modelling: Human decisions, human challenges

Abstract Integrated Environmental Modelling (IEM) is an invaluable tool for understanding the complex, dynamic ecosystems that house our natural resources and control our environments. Human behaviour affects the ways in which the science of IEM is assembled and used for meaningful societal applications. In particular, human biases and heuristics reflect adaptation and experiential learning to issues with frequent, sharply distinguished, feedbacks. Unfortunately, human behaviour is not adapted to the more diffusely experienced problems that IEM typically seeks to address. Twelve biases are identified that affect IEM (and science in general). These biases are supported by personal observations and by the findings of behavioural scientists. A process for critical analysis is proposed that addresses some human challenges of IEM and solicits explicit description of (1) represented processes and information, (2) unrepresented processes and information, and (3) accounting for, and cognizance of, potential human biases. Several other suggestions are also made that generally complement maintaining attitudes of watchful humility, open-mindedness, honesty and transparent accountability. These suggestions include (1) creating a new area of study in the behavioural biogeosciences, (2) using structured processes for engaging the modelling and stakeholder communities in IEM, and (3) using ‘red teams’ to increase resilience of IEM constructs and use.

Purpose, processes, partnerships, and products: four Ps to advance participatory socio‐environmental modeling

Including stakeholders in environmental model building and analysis is an increasingly popular approach to understanding ecological change. This is because stakeholders often hold valuable knowledge about socio-environmental dynamics and collaborative forms of modeling produce important boundary objects used to collectively reason about environmental problems. Although the number of participatory modeling (PM) case studies and the number of researchers adopting these approaches has grown in recent years, the lack of standardized reporting and limited reproducibility have prevented PMs establishment and advancement as a cohesive field of study. We suggest a four-dimensional framework (4P) that includes reporting on dimensions of (1) the Purpose for selecting a PM approach (the why); (2) the Process by which the public was involved in model building or evaluation (the how); (3) the Partnerships formed (the who); and (4) the Products that resulted from these efforts (the what). We highlight four case studies that use common PM software-based approaches (fuzzy cognitive mapping, agent-based modeling, system dynamics, and participatory geospatial modeling) to understand human-environment interactions and the consequences of ecological changes, including bushmeat hunting in Tanzania and Cameroon, agricultural production and deforestation in Zambia, and groundwater management in India. We demonstrate how standardizing communication about PM case studies can lead to innovation and new insights about model-based reasoning in support of ecological policy development. We suggest that our 4P framework and reporting approach provides a way for new hypotheses to be identified and tested in the growing field of PM.

Modeling groundwater flow and quality

In most areas, rocks in the subsurface are saturated with water at relatively shallow depths. The top of the saturated zone—the water table—typically occurs anywhere from just below land surface to hundreds of feet below the land surface. Groundwater generally fills all pore spaces below the water table and is part of a continuous dynamic flow system, in which the fluid is moving at velocities ranging from feet per millennia to feet per day (Fig. 33.1). While the water is in close contact with the surfaces of various minerals in the rock material, geochemical interactions between the water and the rock can affect the chemical quality of the water, including pH, dissolved solids composition, and trace-elements content. Thus, flowing groundwater is a major mechanism for the transport of chemicals from buried rocks to the accessible environment, as well as a major pathway from rocks to human exposure and consumption. Because the mineral composition of rocks is highly variable, as is the solubility of various minerals, the human-health effects of groundwater consumption will be highly variable.