Rolf S. Arvidson

Rolf S. Arvidson
Universität Bremen | Uni Bremen · MARUM - Center for Marine Environmental Sciences

PhD

About

131
Publications
16,400
Reads
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4,204
Citations
Additional affiliations
September 2012 - March 2018
MARUM Center for Marine Environmental Sciences
Position
  • Senior Researcher
October 1999 - November 2012
Rice University
Position
  • Senior Researcher
August 1989 - January 1998
University of Hawaiʻi at Mānoa
Position
  • Research Assistant
Education
August 1989 - January 1998
University of Hawaiʻi at Mānoa
Field of study
  • Oceanography
August 1986 - December 1990
University of Iowa
Field of study
  • Geology
August 1977 - March 1980

Publications

Publications (131)
Article
Intrinsic heterogeneities of crystals almost always impose challenges on the investigation of dissolution kinetics. In the case of the incomplete solid solution series of alkali feldspars, additional complexity to the wide range in chemical composition and crystallographic characteristics is introduced in the form of chemical differentiation at low...
Article
In a unique “perspectives” format that examines both past and future, we appraise the field of crystal dissolution kinetics, showing how the last century's strong progress in experimental discovery has both driven, and been driven by, the tandem evolution of basic theory. To provide context for examining the current state-of-the-art in this critica...
Article
Full-text available
This brief paper presents a rare dataset: a set of quantitative, topographic measurements of a dissolving calcite crystal over a relatively large and fixed field of view (~400 μm2) and long total reaction time (>6h). Using a vertical scanning interferometer and patented fluid flow cell, surface height maps of a dissolving calcite crystal were produ...
Article
Full-text available
Recent advances in bridging kinetics and thermodynamics of mineral dissolution have opened new horizons in our understanding of the role of dissolution in cement hydration. Indeed most hydration kinetic regimes of alite can be rationally envisioned from a dissolution perspective. This short note reviews some key findings on dissolution mechanisms a...
Conference Paper
Full-text available
Recent research on carbonate mineral surface reactivity has demonstrated fundamental variability of dissolution rates and the heterogeneous distribution of the reaction over the mineral surface. These findings have raised major concerns over the use of a 'mean rate' and the derived 'rate constant' for predicting the long term stability of minerals...
Article
Crystal size is an important parameter for many geochemical processes, and is often observed to have a significant influence on crystal dissolution rate. Although size versus solubility relationships are often cast in thermodynamic terms (the critical radius), the mechanistic basis for size versus dissolution rate is not understood in any detail. H...
Conference Paper
Full-text available
Carbonate-water systems attract a significant interest from the scientific community with regard to the problems of diagenesis, geochemical carbon cycle, sequestering of CO2 and toxic metals. The complex interplay between carbonate mineral dissolution, precipitation, and solvent composition governs the evolution of the rock-fluid system. The reliab...
Conference Paper
Kinetics of mineral dissolution in natural environments are controlled by a vast variety of factors, chemical compo-sition and crystal structure, surface site reactivity, fluid com-position and presence of inhibiting/catalyzing species. Previous attempts to express overall mineral dissolution rates as functions of ionic “activity” and “reactive sur...
Article
We compare the canonical treatment of calcite’s dissolution rate from the literature in a closed system, particle batch reactor, with the alternative approach suggested by Truesdale (Aquat Geochem, 2015). We show that the decay of rate over time can be understood in terms of the evolution and distribution of reactive sites on the surface of these p...
Data
Full-text available
The onset of pelagic sedimentation attending the radiation of pelagic calcifiers during the Mesozoic was an important divide in Earth history, shifting the locus of sig-nificant carbonate sedimentation from the shallow shelf environments of the Paleozoic to the deep sea. This shift would have impacted the CO 2 cycle, given that decarbonation of sub...
Article
We apply common image enhancement principles and sub-pixel sample positioning to achieve a significant enhancement in the spatial resolution of a vertical scanning interferometer. We illustrate the potential of this new method using a standard atomic force microscope calibration grid and other materials having motifs of known lateral and vertical d...
Article
Full-text available
Real-time microscopic observations of reacting mineral surfaces have provided a significant advance in the understanding of mineral dissolution and growth. The kinetics of surfaces are often dominated by the distribution of defects, e.g., screw dislocations, that provide a critical means of sustaining step movement and kink creation that are fundam...
Data
We explore the relationship between atmospheric O2 and CO2 evolution and seawater chemistry, with particular focus on the CO2-carbonic acid system and ocean ventilation, over the Phanerozoic Eon using a coupled biogeochemical Earth system model (MAGic). This model describes the biogeochemical cycles involving the major components of seawater (Ca, M...
Article
Plasmon resonance is expected to occur in metallic and doped semiconducting carbon nanotubes in the terahertz frequency range, but its convincing identification has so far been elusive. The origin of the terahertz conductivity peak commonly observed for carbon nanotube ensembles remains controversial. Here we present results of optical, terahertz,...
Article
Full-text available
Many areas of science and industry require a fundamental understanding of crystal dissolution. Examples are diverse and include chemical weathering, pharmaceutical delivery, and the response of marine carbonates to CO2 increases. Understanding these processes ultimately demands knowledge of reaction dynamics. Techniques allowing high-resolution obs...
Article
Full-text available
We report the observation of strong third harmonic generation from a macroscopic array of aligned ultralong single-wall carbon nanotubes (SWCNTs) with intense midinfrared radiation. Through power-dependent experiments, we determined the absolute value of the third-order nonlinear optical susceptibility, $\chi^{(3)}$, of our SWCNT film to be 5.53 $\...
Article
There is increasing divergence in approaches describing the geochemical kinetics of mineral surface reactions. The first approach, for which there is long-standing traditional support and a large number of observational data, assumes that the most systems are essentially deterministic, i.e., imposing a given set of initial conditions or a perturbat...
Article
Colloid-surface interactions are mainly governed by electrostatic and van der Waals interactions. Nevertheless, surface topography variations on the micrometer and nanometer scale are able to alter significantly the local interaction potential. The resulting variations in the interaction energy at small separation distances may change the general i...
Article
Recent studies by [1] have demonstrated that intrinsic rate variations in mineral dissolution are common and of up to 2.5 orders of magnitude. As a major consequence, we have abandoned the concept of simple closed-form rate equations. Instead, we have intro- duced the concept of rate spectra. Such rate spectra are the direct result of the fact that...
Article
The large discrepancy between field and laboratory measurements of mineral reaction rates is a long-standing problem in earth sciences, often attributed to factors extrinsic to the mineral itself. Nevertheless, differences in reaction rate are also observed within laboratory measurements, raising the possibility of intrinsic variations as well. Cri...
Article
The micas are a unique class of minerals because of their layered structure. A frequent question arising in mica dissolution studies is whether this layered structure radically changes the dissolution mechanism. We address this question here, using data from VSI and AFM experiments involving muscovite to evaluate crystallographic controls on mica d...
Patent
An apparatus has a data acquisition device, an environmental cell in a spatial registration relative to the data acquisition device, the environmental cell being configured to support a sample, and a fluid management system configured to initiate and discontinue exposure of the sample to a reaction fluid while the spatial registration is maintained...
Conference Paper
Full-text available
Glauconite is an iron-rich, mica-type clay-sized mineral that forms as a rule in marine environments via successive diagenetic processes. It is commonly accepted that one prerequisite factor in glauconite genesis is the existence of a mineral or organic precursor, as microenvironment for the essential chemical exchanges (e.g., ODIN, 1988). The typi...
Data
The large discrepancy between field and laboratory measurements of mineral reaction rates is a long-standing problem in earth sciences, often attributed to factors extrinsic to the mineral itself. Nevertheless, differences in reaction rate are also observed within laboratory measurements, raising the possibility of intrinsic variations as well. Cri...
Article
Full-text available
We investigate the potential role of dolomite as a long-term buffer on Phanerozoic seawater composition. Using a comprehensive model of Phanerozoic geochemical cycling, we show how variations in the formation rate of sedimentary marine dolomite have buffered seawater saturation state. The total inventory of inorganic carbon reflects the sum of flux...
Article
Epochs of changing atmospheric CO2 and seawater CO2–carbonic acid system chemistry and acidification have occurred during the Phanerozoic at various time scales. On the longer geologic time scale, as sea level rose and fell and continental free board decreased and increased, respectively, the riverine fluxes of Ca, Mg, DIC, and total alkalinity to...
Article
The reactivity of crystal surfaces reflects the distribution and interaction of kinks, steps, and defect-related sites. During the dissolution of whole mineral grains, substantial changes are commonly observed along discontinuities such as grain edges, twin boundaries, and other complex macro-features [1]. We wish to understand the evolution of the...
Article
The micas are a unique class of minerals because of their layered structure. A frequent question arising in mica dissolution studies is whether this layered structure radically changes the dissolution mechanism. We address this question here, using data from VSI and AFM experiments involving muscovite to evaluate crystallographic controls on mica d...
Article
We present our recent results in the study of phyllosilicate dissolution kinetics. The major problem in this field is the influence of the layered structure on dissolution mechanism and the difference in reactivity between edge and basal faces. We use an integrated approach including experiments and modelling to understand real crystallographic con...
Article
In the 1950’s Burton, Cabrera and Frank developed BCF theory for crystal growth and some specific cases of crystal dissolution, e.g. the formation of etch pits along screw dislocations. Subsequently, we have struggled with attempts to develop a comprehensive theory and model that will describe and correctly predict how crystalline matter dissolves....
Article
Two disparate reaction mechanisms have been invoked to explain the reactivity of glass in contact with aqueous solution. One model is based on arguments from Transition State Theory (TST), which postulates that glass dissolution rates are surface reaction controlled. Alternatively, the second model argues that release of elements from glass to solu...
Article
Significant insight into reaction mechanism can be derived from the analysis of surface topography and kinetics of alteration of interfaces as a function of their environment. These data have largely been the purview of scanning and atomic force instruments, traditional optical microscopy, and electron beam technologies. We introduce here an integr...
Article
Dissolution of the fluorite (1 1 1) cleavage surface was investigated by means of in situ atomic force microscopy (AFM) and ex situ vertical scanning interferometry (VSI) experiments at pH range 1–3 in HCl solutions. Surface retreat was quantified at different pH values, yielding dissolution rates that were used to derive an empirical rate law for...
Article
Classical crystal models introduced by Kossel and Stranski [1,2] recognized the kink site in terms of its central role in crystal growth. The generation of these sites, and their concentration and distribution with respect to chemical equilibrium has been extensively developed in several key papers [3, 4, 5]; however, the sequence of events involve...
Article
It has been long recognized that crystal growth and dissolution processes are mainly governed by kink site reaction kinetics. Traditionally, it has been assumed that equilibrium is achieved if arrival and departure rates of lattice-building molecules are equal. New considerations, however, raise significant doubt that this simple model is correct....
Article
Bacterial adhesion, the formation of biofilms and the release of metabolic byproducts can all lead to the mobilization of elements that alter the chemistry of the surrounding fluid, and in turn impact mineral dissolution rates [1,2]. A great deal of attention has been given to understanding genesis and growth of biofilms on both organic and inorgan...
Article
Since the introduction of classical crystal models by Kossel and Stranski, the kink site has been recognized as having a central role in the kinetics of crystal growth and dissolution. The kink site is a unique surface site, defined by the property that the number of bonds that coordinate the surface atom, ion or molecule at that site is exactly ha...
Article
We revisit a fundamental question in mineral dissolution kinetics, namely: is the function of dissolution rate versus the distance from equilibrium continuous, or does the “switch” between two different reaction mechanisms cause a discontinuity, i.e., a kinetic bifurcation? Based on new insight from experimental results, including direct observatio...
Article
Inhibition processes such as formation of secondary minerals or microbial activity will modify mineral reaction rates in nature. Here we investigate occurrence, amount, and scale of surface reactivity anisotropy and consequences on mineral weathering kinetics. Calcite dissolution rates [1] show variations of about 3 orders of magnitudes on crystal...
Article
We present an experimental and theoretical study of sheet silicate dissolution kinetics. Sheet silicates have a layered structure that significantly affects the dissolution mechanism and rates. Dissolution of mineral powders [1,2] revealed a high variability in rates of 2 - 3 orders of magnitude, typically thought to reflect variation in basal to l...
Article
Dissolution of the fluorite (1 1 1) cleavage surface was investigated by means of in situ atomic force microscopy (AFM) and ex situ vertical scanning interferometry (VSI) experiments at pH range 1–3 in HCl solutions. Surface retreat was quantified at different pH values, yielding dissolution rates that were used to derive an empirical rate law for...
Article
To understand the development of biofilms on metal surfaces, analysis of initial bacterial attachment to surfaces is crucial. Here we present the results of a study, using Shewanella oneidensis MR-1 as a model organism, in which vertical scanning interferometry (VSI) was used to investigate the initial stages of cell attachment to glass, steel and...
Article
A quantitative understanding of corrosion reactions and their inhibition is critical in diverse problems involving the environmental impacts of waste disposal, catalysis, water treatment, and remediation of organic contaminants in groundwater. Conventionally, corrosion rate measurements have been accomplished by electrochemical techniques, e.g., do...
Article
Extensions of BCF theory indicate that if undersaturation does not exceed a critical value (i.e., ∆G ≥ ∆Gcrit), hollow cores of screw dislocations with large Burgers vectors will not open to form macroscopic etch pits [1]. This analysis has been expanded to a general framework of crystal dissolution that explains the oft-observed nonlinear decrease...
Article
Membrane Vesicles of Gram-negative Bacteria Recent research has shown that membrane vesicles (MVs) are a common particular feature of the matrix of gram-negative bacterial biofilms [1]. The ubiquitous distribution of MVs is evident from observations of biofilms from a variety of natural and artificial environments. Experiments with planktonic biofi...
Article
Tim Drever has moved our field forward with his strong focus on understanding the processes, inorganic and biological, that control the chemistry of surface water and groundwater. With his pioneering work he has often inspired our own research on crystal dissolution kinetics. It is thus an honor for us to participate in this session’s tribute to Ti...
Article
Full-text available
Production of acid mine drainage (AMD) is in large part due to pyrite oxidation. The tie-in between environmental remediation and pyrite oxidation requires understanding pyrite oxidation in aqueous systems. In this study, ex-situ measurements using vertical scanning interferometry (VSI) were utilized to investigate pyrite surface reactivity under A...
Article
Full-text available
The essential state of the Phanerozoic ocean-atmosphere system with respect to major lithophile and organic components can be bounded by sedimentary observational data and relatively few model assumptions. The model assumptions are in turn sufficient to constrain and compute the remaining fluxes that result in a comprehensive model describing atmos...
Chapter
The typical satellite view of Earth’s surface reveals ubiquitous contact between rocks and water (Fig. 3.1). Rocks are composed primarily of minerals, naturally crystallized materials having a periodic structure. The long-range structure of crystals, expressed internally as the periodic lattice, determines their fundamental physical and chemical pr...
Chapter
Full-text available
In this chapter, a new Earth system model termed MAGic (Mackenzie, Arvidson, Guidry interactive cycles) model is used to examine how the weathering fluxes of calcium (Ca), magnesium (Mg), carbon (C), sulfur (S), and phosphorus (P) have influenced biogeochemical cycles in the ocean over the past 500 million years. In addition, the fluxes of these fi...
Article
Laboratory investigations of calcium carbonate growth often employ stoichiometric solution compositions, with equivalent activities of calcium and carbonate species, or simply consider precipitation kinetics in the context of saturation state alone. However, nonstoichiometric solutions, with nonequivalent Ca2+ and CO32- activities, are the rule in...
Article
Biomineralization and crystal growth/dissolution studies typically express reaction kinetics as a function of the ion activity product (IAP) in saturation state expressions. However, there is increasing evidence that changes in the cation/anion solution ratio at constant IAP can influence mineral formation. This variation may thus be important in m...
Article
This study presents evidence of calcite (1 0 4) dissolution inhibition by dissolved manganese(II) through detailed observations of crystal surface morphology. Rates of dissolution have been quantified by direct measurement of surface-normal retreat and etch pit growth at far-from-equilibrium conditions using vertical scanning interferometry. The ap...
Article
In growth and dissolution of binary ionic crystals, a common assumption is that the cation plays a more fundamental kinetic role than the anion. This thinking derives from the recognition that a key step in ion transfer between solid and solution involves hydration (dissolution) or dehydration (crystallization). In the case of carbonate growth, the...
Article
Dissolution and corrosion of crystalline materials have been proven to be as complex as they are important. In recent years significant progress in our understanding of dissolution mechanisms and kinetics was based on experimental studies utilizing atomic force microscopy (AFM), interferometry (e.g., VSI and PSI) and other techniques. Building on t...
Article
The reactivity of a solid surface is strongly affected by the imposition of non-hydrostatic stress: the resulting strain rate is a driving force for mass transfer during pressure solution. Previous work [1,2] has shown that bacteria (e.g., Shewanella oneidensis MR-1) recognize and modify crystal surfaces through apparent recognition of surface ener...
Article
An overview is given of the thermodynamics and kinetics of CaCO3 formation and dissolution and how surface and nanoparticulate chemistry are important in understanding reactivity. Topics covered are major marine carbonate materials, carbonate mineral precipitation and dissolution kinetics relevant to seawater, oceanic sources of marine carbonates,...
Article
Single-walled carbon nanotubes have been functionalized and the specific surface areas of the functionalized nanotubes measured. Contrary to expectations, functionalization leads to a decrease in specific surface area compared to that of the unfunctionalized nanotubes. Treatment with a concentrated 1:1 nitric/sulfuric acid mixture followed by high-...
Article
Biomineralization and crystal growth studies typically normalize precipitation kinetics to the ion activity product (IAP), especially in the form of supersaturation expressions. However, changes in the cation/anion solution ratio at constant IAP may also be expected to influence mineral formation. Nonstoichiometric solutions, with nonequivalent Ca2...
Article
Free energy is regarded as a basic driving force in dissolution and growth kinetics, giving rise to reaction rate expressions in which Delta G_r occupies a central role, and where lattice ions are distinguished from other species that may enhance or suppress the overall rate. For example, in the case of calcite we question whether lattice ions Ca2+...
Article
Full-text available
A dynamical model (MAGic) is presented that describes the elemental cycling of sedimentary materials involving sodium, potassium, calcium, magnesium, chloride, carbon, oxygen, iron, sulfur and phosphorous through much of the Phanerozoic. The model incorporates the basic reactions controlling atmospheric carbon dioxide and oxygen concentrations, con...
Article
We present results from a long term geochemical cycling model, with a focus on the sensitivity of atmospheric carbon dioxide, oxygen, and the major element composition of seawater to seafloor spreading rates. This model incorporates rock weathering, basalt–seawater exchange reactions, and the formation and destruction of chemical sediments and orga...
Article
We present evidence of inhibition of calcite dissolution by dissolved magnesium through direct observations of the (104) surface using atomic force microscopy (AFM) and vertical scanning interferometry (VSI). Far from equilibrium, the pattern of magnesium inhibition is dependent on solution composition and specific to surface step geometry. In CO2-...