Geochemical carbon dioxide removal potential of Spain.

Many countries have made pledges to reduce CO2 emissions over the upcoming decades to meet the Paris Agreement targets of limiting warming to no >1.5 °C, aiming for net zero by mid-century. To achieve national reduction targets, there is a further need for CO2 removal (CDR) approaches on a scale of millions of tonnes, necessitating a better understanding of feasible methods. One approach that is gaining attention is geochemical CDR, encompassing (1) in-situ injection of CO2-rich gases into Ca and Mg-rich rocks for geological storage by mineral carbonation, (2) ex-situ ocean alkalinity enhancement, enhanced weathering and mineral carbonation of alkaline-rich materials, and (3) electrochemical separation processes. In this context, Spain may host a notionally high geochemical CDR capacity thanks to its varied geological setting, including extensive mafic-ultramafic and carbonate rocks. However, pilot schemes and large-scale strategies for CDR implementation are presently absent in-country, partly due to gaps in current knowledge and lack of attention paid by regulatory bodies. Here, we identify possible materials, localities and avenues for future geochemical CDR research and implementation strategies within Spain. This study highlights the kilotonne to million tonne scale CDR options for Spain over the rest of the century, with attention paid to chemically and mineralogically appropriate materials, suitable implementation sites and potential strategies that could be followed. Mafic, ultramafic and carbonate rocks, mine tailings, fly ashes, slag by-products, desalination brines and ceramic wastes hosted and produced in Spain are of key interest, with industrial, agricultural and coastal areas providing opportunities to launch pilot schemes. Though there are obstacles to reaching the maximum CDR potential, this study helps to identify focused targets that will facilitate overcoming such barriers. The CDR potential of Spain warrants dedicated investigations to achieve the highest possible CDR to make valuable contributions to national reduction targets.

A Long Journey of CICA-17 Quinoa Variety to Salinity Conditions in Egypt: Mineral Concentration in the Seeds.

Quinoa may be a promising alternative solution for arid regions, and it is necessary to test yield and mineral accumulation in grains under different soil types. Field experiments with Chenopodium quinoa (cv. CICA-17) were performed in Egypt in non-saline (electrical conductivity, 1.9 dS m-1) and saline (20 dS m-1) soils. Thirty-four chemical elements were studied in these crops. Results show different yields and mineral accumulations in the grains. Potassium (K), P, Mg, Ca, Na, Mn, and Fe are the main elements occurring in the quinoa grains, but their concentrations change between both soil types. Besides, soil salinity induced changes in the mineral pattern distribution among the different grain organs. Sodium was detected in the pericarp but not in other tissues. Pericarp structure may be a shield to prevent sodium entry to the underlying tissues but not for chloride, increasing its content in saline conditions. Under saline conditions, yield decreased to near 47%, and grain sizes greater than 1.68 mm were unfavored. Quinoa may serve as a complementary crop in the marginal lands of Egypt. It has an excellent nutrition perspective due to its mineral content and has a high potential to adapt to semi-arid and arid environments.

Microscopic, chemical, and molecular-biological investigation of the decayed medieval stained window glasses of two Catalonian churches.

We investigated the decayed historical church window glasses of two Catalonian churches, both under Mediterranean climate. Glass surfaces were studied by scanning electron microscopy (SEM), energy dispersive spectrometry (EDS), and X-ray diffraction (XRD). Their chemical composition was determined by wavelength-dispersive spectrometry (WDS) microprobe analysis. The biodiversity was investigated by molecular methods: DNA extraction from glass, amplification by PCR targeting the16S rRNA and ITS regions, and fingerprint analyses by denaturing gradient gel electrophoresis (DGGE). Clone libraries containing either PCR fragments of the bacterial 16S rDNA or the fungal ITS regions were screened by DGGE. Clone inserts were sequenced and compared with the EMBL database. Similarity values ranged from 89 to 100% to known bacteria and fungi. Biological activity in both sites was evidenced in the form of orange patinas, bio-pitting, and mineral precipitation. Analyses revealed complex bacterial communities consisting of members of the phyla Proteobacteria, Bacteroidetes, Firmicutes, and Actinobacteria. Fungi showed less diversity than bacteria, and species of the genera Cladosporium and Phoma were dominant. The detected Actinobacteria and fungi may be responsible for the observed bio-pitting phenomenon. Moreover, some of the detected bacteria are known for their mineral precipitation capabilities. Sequence results also showed similarities with bacteria commonly found on deteriorated stone monuments, supporting the idea that medieval stained glass biodeterioration in the Mediterranean area shows a pattern comparable to that on stone.

Multivariate factorial analysis to design a robust batch leaching test to assess the volcanic ash geochemical hazard.

A method to obtain robust information on short term leaching behaviour of volcanic ashes has been developed independently on the sample age. A mixed factorial design (MFD) was employed as a multivariate strategy for the evaluation of the effects of selected control factors and their interactions (amount of sample (A), contact time (B), and liquid to solid ratio or L/S (C)) on the leaching process of selected metals (Na, K, Mg, Ca, Si, Al, V, Mn, Fe, and Co) and anions (Cl(-) and SO(4)(2-)). Box plots of the data acquired were used to evaluate the reproducibility achieved at different experimental conditions. Both the amount of sample (A) and leaching time (B) had a significant effect on the element stripping whereas the L/S ratio influenced only few elements. The lowest dispersion values have been observed when 1.0 g was leached with an L/S ratio equal to 10, shaking during 4 h. The entire method is completed within few hours, and it is simple, feasible and reliable in laboratory conditions.

Weathering patinas on the medieval (S. XIV) stained glass windows of the Pedralbes Monastery (Barcelona, Spain).

BACKGROUND, AIM, AND SCOPE: The first step in the restoration of a medieval stained glass window is the evaluation of its degree of degradation. This implies the study of the chemical composition of the stained glass as well as the new mineral phases developed on its surface (patinas). Patinas are clearly related to glass composition, time, environmental conditions, microenvironments developed in local zones, bioactivity, physical and chemical factors, etc. This study was carried out on patinas developed in selected Na-rich stained glass of the Santa Maria de Pedralbes Monastery (Barcelona, Spain). The location of this monument in the city (about 5 km from the shoreline and close to the Collserola hill flank) helped to determine the environmental conditions in which patinas developed. The aim of our study was to characterize the patinas formed on the surface of the selected glass of this monastery in order to understand the role of the chemical composition of the original glass (Na-rich) as well as the environmental conditions in which they developed. MATERIALS AND METHODS: Powdered samples of two different color-type patinas (ochre-orange and brownish) were collected in the external and internal parts of the stained glass windows of the Prebystery and Chapter House of the Pedralbes Monastery by using a precision (odontological) drill. These patinas were subsequently analyzed by X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR). RESULTS: XRD analyses evidenced the presence of sulfates (gypsum and thenardite), calcite, Ca-oxalates (whewellite and weddellite), and quartz forming part of the patinas. Although these mineral phases can be found in both color-type patinas, whewellite and thenardite are more common in the ochre-orange patinas. The results obtained were validated by the FTIR measurements. It has been observed, when thenardite is present, that gypsum occurs as traces. Thenardite is in most of the cases associated with whewellite and mainly occurs in the internal parts of the glass. In contrast, weddellite is limited to the absence of thenardite and whewellite and to the external parts of the stained glass. Quartz is present in all the patinas independent of their location and color. Calcite also occurs in many samples. It appears in both color-type patinas and, in some cases, is associated to the presence of weddellite but not to whewellite and/or thenardite. DISCUSSION: Glass composition together with environmental conditions and location of the patinas (internal or external parts of the stained glass window), as well as the provenance of the glass within the monastery, are the main factors that define the development of the new mineral phases. Moreover, the action of microorganisms, when present, can also strongly influence the development of some mineral phases. For example, the formation of calcite in the external parts of the stained glass (associated with the presence of oxalates) is related to the action of microorganisms. When calcite is formed in the internal parts of the glass and it is not associated with the presence of Ca-oxalates, an inorganic origin can be invoked. The presence of weddellite requires a very humid microenvironment with very little exposure to sunlight. In fact, this mineral phase has only been observed in the external parts of some glass located in the humid and shady side of the monastery. Whewellite (which only appears in the internal parts) needs a low degree of relative humidity. It has been observed that sulfur precipitating in basically one mineral phase (thenardite or gypsum) depends on the microenvironmental conditions of the moment and the glass composition. When thenardite occurs, it can be maintained that the original glass is of Na composition. The occurrence of quartz in all samples is interpreted as being due to the deposition of atmospheric particulate matter. The color of the patinas can be originated by different processes (presence of carotenes, organic pigmentation, atmospheric contamination, etc.). CONCLUSIONS: In the case of moderately weathered stained glass windows, the combination of XRD and FTIR techniques is very useful to obtain a fast preliminary evaluation of the degree of weathering of a stained glass window. The presence of specific mineral phases in the patina (e.g., thenardite) confirms the Na composition of the original stained glass. This is important since Na-rich glass underwent a lesser degree of weathering than K- or K-Ca-rich glass. However, their absence cannot preclude other possibilities. It has been extensively evidenced through time that environmental conditions play an important role on the formation of the different mineral phases which form part of the patinas. RECOMMENDATIONS AND PERSPECTIVES: The first step in the restoration of a stained glass window is the evaluation of the degree of deterioration of the glass. This evaluation includes a chemical analysis of the glass as well as a characterization of the patinas developed on their surfaces. The obtained results will be essential in order to define the best restoration practices to be followed.