Interpretation of Recent Unrest Events (Bradyseism) at Campi Flegrei, Napoli (Italy): Comparison of Models Based on Cyclical Hydrothermal Events versus Shallow Magmatic Intrusive Events

Several recent models that have been put forth to explain bradyseism at Campi Flegrei (CF), Italy, are discussed. Data obtained during long-term monitoring of the CF volcanic district has led to the development of a model based on lithological-structural and stratigraphic features that produce anisotropic and heterogeneous permeability features showing large variations both horizontally and vertically; these data are inconsistent with a model in which bradyseism is driven exclusively by shallow magmatic intrusions. CF bradyseism events are driven by cyclical magmatic-hydrothermal activity. Bradyseism events are characterized by cyclical, constant invariant signals repeating over time, such as area deformation along with a spatially well-defined seismogenic volume. These similarities have been defined as “bradyseism signatures” that allow us to relate the bradyseism with impending eruption precursors. Bradyseism is governed by an impermeable shallow layer (B-layer), which is the cap of an anticlinal geological structure culminating at Pozzuoli, where maximum uplift is recorded. This B-layer acts as a throttling valve between the upper aquifer and the deeper hydrothermal system that experiences short (1-102 yr) timescale fluctuations between lithostatic/hydrostatic pressure. The hydrothermal system also communicates episodically with a cooling and quasi-steady-state long timescale (103-104 yr) magmatic system enclosed by an impermeable carapace (A layer). Connectivity between hydrostatic and lithostatic reservoirs is episodically turned on and off causing alternatively subsidence (when the systems are connected) or uplift (when the systems are disconnected), depending on whether permeability by fractures is established or not. Earthquake swarms are the manifestation of hydrofracturing which allows fluid expansion; this same process promotes silica precipitation that seals cracks and serves to isolate the two reservoirs. Faults and fractures promote outgassing and reduce the vertical uplift rate depending on fluid pressure gradients and spatial and temporal variations in the permeability field. The miniuplift episodes also show “bradyseism signatures” and are well explained in the context of the short timescale process.

Structural evidence for extracellular silica formation by diatoms

The silica cell wall of diatoms, a widespread group of unicellular microalgae, is an exquisite example for the ability of organisms to finely sculpt minerals under strict biological control. The prevailing paradigm for diatom silicification is that this is invariably an intracellular process, occurring inside specialized silica deposition vesicles that are responsible for silica precipitation and morphogenesis. Here, we study the formation of long silicified extensions that characterize many diatom species. We use cryo-electron tomography to image silica formation in situ, in 3D, and at a nanometer-scale resolution. Remarkably, our data suggest that, contradictory to the ruling paradigm, these intricate structures form outside the cytoplasm. In addition, the formation of these silica extensions is halted at low silicon concentrations that still support the formation of other cell wall elements, further alluding to a different silicification mechanism. The identification of this unconventional strategy expands the suite of mechanisms that diatoms use for silicification.

Learning Principles in the Biochemistry of Plant Silica Precipitation

<p>Plants produce silica in large quantities, up to 2-10% per dry weight, depending on growth conditions and plant species. The roots absorb monosilicic acid from the soil, and it is transported with water and distributed in nearly all plant tissues. With evapotranspiration, the silicic acid solution is concentrated, and eventually silica forms at leaf epidermis. Nonetheless, the distribution of silica deposits is not uniform within plant tissues. This suggests that there are biological processes that control the deposition of the mineral. In a recent work, the protein Siliplant1 (Slp1) was discovered to precipitate silica in plants. Slp1 is expressed in sorghum leaf epidermal cells called silica cells. Biological molecules active in silica formation typically present positive charge moieties and form some 3D aggregation pattern that allows monosilicic acid to condense into bigger organized structures. Slp1 contains a 24 amino acid N-terminal signal peptide, followed by 124 amino acid linking sequence and a 7-repeat sequence. Slp1 without the signal peptide and a short, conserved peptide appearing five times in Slp1 precipitate silica <em>in vitro</em>. However, the activity of other parts of Slp1 in silica precipitation remains unknown. To analyze sequence motifs that precipitate silica, we synthesized segments of the repeating sequence in Slp1, and characterized the precipitation reactions by yield and spectroscopy. Thermal gravimetric and electron microscopy analyses are planned. Preliminary results show that the most conserved region in the repeating sequence precipitates silica at a concentration range of 1-1.5 mg/mL in a 100 mM silicic acid solution. Under buffered conditions, this peptide is positively charged, precipitating silica at pH between 6 and 7. In contrast, silica-gel formed at pH 8 or 5 after overnight incubation. In comparison, the full length Slp1 (missing the signal peptide) precipitates silica at an estimated concentration of 2.9 mg/mL and pH 6-8. Peptides flanking the conserved sequence did not precipitate silica. Precipitation reactions with combinations of peptides precipitated silica only when the conserved peptide was mixed with the peptide following it at a 1:1 ratio. This part of Slp1 presents –OH moieties that may interact with silica. The reaction produced silica gel as well as silica. When the conserved region was mixed with a preceding peptide, only silica-gel formed. This region presents acidic groups that may block the positive charge on the conserved region. We conclude that the conserved peptide is the only part of the Slp1 repeating region that actively precipitates silica. The peptides flanking the conserved region are not directly involved in silica precipitation.  However, they may allow silica precipitation at increased pH, as seen in the full length Slp1. Further investigation is planned to understand their roles in silica formation.</p>

Syngenetic rapid growth of ellipsoidal silica concretions with bitumen cores

Isolated silica concretions in calcareous sediments have unique shapes and distinct sharp boundaries and are considered to form by diagenesis of biogenic siliceous grains. However, the details and rates of syngenetic formation of these spherical concretions are still not fully clear. Here we present a model for concretion growth by diffusion, with chemical buffering involving decomposition of organic matter leading to a pH change in the pore-water and preservation of residual bitumen cores in the concretions. The model is compatible with some pervasive silica precipitation. Based on the observed elemental distributions, C, N, S, bulk carbon isotope and carbon preference index (CPI) measurements of the silica-enriched concretions, bitumen cores and surrounding calcareous rocks, the rate of diffusive concretion growth during early diagenesis is shown using a diffusion-growth diagram. This approach reveals that ellipsoidal SiO2 concretions with a diameter of a few cm formed rapidly and the precipitated silica preserved the bitumen cores. Our work provides a generalized chemical buffering model involving organic matter that can explain the rapid syngenetic growth of other types of silica accumulation in calcareous sediments.

Transition from unclassified Ktedonobacterales to Actinobacteria during amorphous silica precipitation in a quartzite cave environment

The orthoquartzite Imawarì Yeuta cave hosts exceptional silica speleothems and represents a unique model system to study the geomicrobiology associated to silica amorphization processes under aphotic and stable physical–chemical conditions. In this study, three consecutive evolution steps in the formation of a peculiar blackish coralloid silica speleothem were studied using a combination of morphological, mineralogical/elemental and microbiological analyses. Microbial communities were characterized using Illumina sequencing of 16S rRNA gene and clone library analysis of carbon monoxide dehydrogenase (coxL) and hydrogenase (hypD) genes involved in atmospheric trace gases utilization. The first stage of the silica amorphization process was dominated by members of a still undescribed microbial lineage belonging to the Ktedonobacterales order, probably involved in the pioneering colonization of quartzitic environments. Actinobacteria of the Pseudonocardiaceae and Acidothermaceae families dominated the intermediate amorphous silica speleothem and the final coralloid silica speleothem, respectively. The atmospheric trace gases oxidizers mostly corresponded to the main bacterial taxa present in each speleothem stage. These results provide novel understanding of the microbial community structure accompanying amorphization processes and of coxL and hypD gene expression possibly driving atmospheric trace gases metabolism in dark oligotrophic caves.

A Biomimetic Peptide has no Effect on the Isotopic Fractionation during in Vitro Silica Precipitation

The stable isotopic composition of diatom silica is used as a proxy for nutrient utilisation in natural waters. This approach provides essential insight into the current and historic links between biological production, carbon cycling and climate. However, estimates of isotopic fractionation during diatom silica production from both laboratory and field studies are variable, and the biochemical pathways responsible remain unknown. Here, we investigate silicon isotopic fractionation through a series of chemical precipitation experiments that are analogous to the first stages of intracellular silica formation within the diatom silicon deposition vesicle. The novelty of our experiment is the inclusion of the R5 peptide, which is closely related to a natural biomolecule known to play a role in diatom silicification. Our results suggest that the presence of R5 induces a systematic but non-significant difference in fractionation behaviour. It thus appears that silicon isotopic fractionation in vitro is largely driven by an early kinetic fractionation during rapid precipitation that correlates with the initial amount of dissolved silica in the system. Our findings raise the question of how environmental changes might impact silicon isotopic fractionation in diatoms, and whether frustule archives record information in addition to silica consumption in surface water.