Analysis of the surface of different marbles by X-ray photoelectron spectroscopy (XPS) to evaluate decay by SO2 attack

Atmospheric pollution is one of the main agents of decay in monuments and other works of art located in industrialised urban centres. SO₂ is a permanent and abundant component of air pollution and, although it does not have an immediate visual effect, after continuous exposure, it can cause irreversible damage to building materials. Marble is one of the most commonly used ornamental stones in historical monuments and its mineralogical composition makes it very susceptible to damage caused by exposure to SO₂. To measure the chemical reactions caused on marble by the action of atmosphere rich in SO₂, selected calcitic and dolomitic samples were altered by weathering accelerated test. For this, seven marble types (four calcitic and three dolomitic) were exposed to high concentration of sulphur dioxide for 24 h in a climate chamber under controlled temperature and humidity conditions (20 °C and > 90 % HR). Changes on marble surfaces caused by reactions of SO₂ with calcite and dolomite were studied using two non-destructive techniques: chromatic change by means of colorimetry and chemical analysis using X-ray photoelectron spectroscopy (XPS). The development of new mineral phases was also observed by scanning electron microscopy. Colorimetric analysis revealed a decrease in lightness and chromatic parameters suggesting that these changes were due to the development of new mineral phases in all marbles. The XPS technique, which is generally used in the analysis of metals, is relatively new in the field of stone deterioration. It enabled us to recognise the development of sulphites and sulphates on marble surfaces with high precision, after just 24 h of exposure to high SO₂ concentrations and to distinguish different decay paths for calcitic and dolomitic marbles.     

Assessment of the physico-mechanical behaviour of gypsum-lime repair mortars as a function of curing time

Gypsum-based mortars were widely used during the Mudejar artistic period in Spain from the 12th to 16th century. During restoration works, compatibility between the new repair mortars and the original components is essential for an adequate intervention on the monument. The increasing interest of knowing the properties of the gypsum-lime-based mortars for restoration purposes justifies the research carried out. Different mortars compatible with traditional building materials were elaborated by varying the binder proportions, the type of aggregates, the binder/aggregate ratios and the curing time. The main goal of this paper is to characterize the mechanical behaviour and the pore structure of the mortars as a function of curing time. The influence between the different variables used to prepare the mortars and the development of the carbonation process over time is also considered. Mechanical strength and porosity measurements as well as X-ray diffraction and thermal analysis were performed after curing times of 1, 28 and 90 days. The results obtained confirmed a progressive increase in mechanical strength linked to the carbonation of the mortars prepared. Less lime binder and also aggregate contents showed the highest rise in strength over time, related to the highest initial porosity which favoured the carbon dioxide flow. The use of siliceous aggregates (GL-QS mortars) obtained the best results in the development of physico-mechanical properties over curing time. The knowledge obtained from the studied mortars provides practical information to establish a suitable mortar mixture for restoration works on historic buildings and modern architecture where gypsum-lime-based mortars are used.     

Closure of a seaway: stratigraphic record and facies (Guadix basin, Southern Spain)

During the late Tortonian (upper Miocene), the Guadix Basin in S Spain formed one of the Betic corridors that connected the Mediterranean Sea with the Atlantic Ocean. The closure of this connection occurred in a series of steps, documented by three sedimentary units. A lower unit, consisting of basinal marls, shallow-water calcarenites and sands records the formation of a wide seaway. During deposition of the following unit this narrowed to a strait no more than 2 km in wide, triggering an intensification of currents that caused migration of submarine dunes preserved as giant cross-beds in bioclastic sands and conglomerates. Current flowed from the Mediterranean to the Atlantic. The third unit constitutes the youngest marine episode of the filling of the Guadix Basin. At this stage, the connection between the Mediterranean Sea and the Atlantic Ocean was broken, and a system of coastal coral reefs was established in the northern part of the Basin.     

Impact of climate variability in the western Mediterranean during the last 20,000 years: oceanic and atmospheric responses

Eolian input fluctuations and paleoceanographic conditions in the western Mediterranean have been reconstructed by using a multi-proxy approach to infer climate variability for the last 20,000 yr. A sediment core from the East Alboran Sea basin provides high-resolution geochemical, mineralogical and grain size distribution records from the Last Glacial Maximum onward. The accurate chronology obtained, closely related with the North Greenland Ice core Project, has provided a detailed paleoclimate reconstruction at the centennial–millennial time scale. Mineral and chemical compositions as well as sediment grain size distribution have been used to establish both fluvial and eolian input variations, deep-water current intensity, and ventilation and productivity conditions at the time of deposition. During the cold period Greenland Stadial-2a, the analyzed proxies evidence significant climate oscillations. Redox proxies, showing marked Mn/Al and Fe/Al peaks, as well as granulometric parameters, support major changes in thermohaline circulation, with active circulation triggered by the Western Mediterranean Deep Water formation. Ba/Al ratios and the presence of authigenic barite point to high productivity during the Last Heinrich event. At this time, Zr/Al, Si/Al and Ti/Al ratios as well as quartz and palygorskite contents also corroborate dryer conditions in the Alboran borderlands, with a major reorganization of atmospheric circulation at the beginning of the deglaciation and during the Last Heinrich event. In contrast, a decreasing trend in the Zr/Al ratio and increasing Mg/Al, K/Al and illite + chlorite/kaolinite ratios would indicate enhanced river runoff and supporting lower eolian dust input and wetter periods during the Bölling–Alleröd. Short-term and abrupt climate oscillations such as the Intra-Alleröd Cold Period are likewise reflected by minor yet conspicuous changes in eolian proxies. During the Younger Dryas, we distinguish an initial cold and dry phase, with major westerlies intensity, thermohaline reactivation, and high productivity levels, and a second wetter phase characterized by sporadic rainfalls over poorly vegetated surrounding continental areas. Then, during the Holocene, alternating phases of major humidity and aridity were recorded by major fluctuations in detrital input. These are also correlated with recurrent forest cover declines reported from pollen records, with a noteworthy early decline in the African Humid Period. During the Holocene, an initial demise of the Last Organic-Rich Layer is also evidenced, tentatively associated with aspiration forces promoted by intense thermohaline circulation through the Gibraltar Strait.     

Paleontology,sedimentology and paleoenvironment of a new fossiliferous locality of the Jurassic Cañadón Asfalto Formation,Chubut Province,Argentina

A new Late Jurassic assemblage of “conchostracans”, ostracods, bivalves and caddisfly cases from the locality “Estancia La Sin Rumbo”, Chubut Province (Patagonia, Argentina) is recorded. The fossils occur in the upper part of an outcropping 45 m thick volcaniclastic lacustrine sequence of yellowish tuffs and tuffites of the Puesto Almada Member, which is the upper member of the Cañadón Asfalto Formation with U/Pb age of 161 ± 3 Ma. The sequence represents one sedimentary cycle composed of a (lower) hemicycle of expansion and a (higher) hemicycle of contraction of the water body. The invertebrates lived in small freshwater bodies during the periods of expansion of the lake. The occurrence of a great number of small spinicaudatans, associated with mud-cracks, is evidence of dry climatic conditions and suggests several local mortality events. The spinicaudatan record of the fushunograptid–orthestheriid (component of the Eosestheriopsis dianzhongensis fauna) and the presence of Congestheriella rauhuti Gallego and Shen, suggest a Late Jurassic (Oxfordian to Tithonian) age. Caddisfly cases are recorded for the first time in the Cañadón Asfalto Basin.     

Facies control of strata-bound ore deposits in carbonate rocks: The F-(Pb-Zn) deposits in the Alpine Triassic of the Alpujárrides,southern Spain

The strata-bound fluorite-(barite-)Pb-Zn ore deposits occurring within the more than 3,000 m thick Alpujárride Carbonate Formation of the Betic Cordillera, southern Spain, are linked to two defined stratigraphic positions (within the Anisian and at the Ladinian-Carnian transition) and to definite sedimentary contexts. These are highly restricted lagoons isolated from the open sea by calcarenitic barriers with noticeable development of algal mats in their inner margins. Preevaporitic deposition conditions are usually recognized. The ore-bearing horizons are located either at the transition from evaporitic to normal marine deposition (as in the case of the Anisian ore-bearing horizon) or at the transition from normal marine to evaporite deposition (as in the case of the uppermost Ladinian to lowermost Carnian ore-bearing horizon). These vertical facies changes correspond also to the transitions from predominantly terrigenous (continental and/or coastal) sedimentation to marine carbonate sedimentation (Anisian ore deposits) and vice versa (upper Ladinian-lower Carnian). It is proposed that the ore deposits in the Triassic Alpujárride Formation are controlled by certain facies associations in the lagoonal environment. The depositional environment determines the hydrologic regimes responsible for early diagenetic formation of fluorite and of the related ore minerals in a way similar to that of early-diagenetic dolomite. This hypothesis is consistent with field and petrographic observations and with available geochemical and itotopic data reported in other works. The present investigation intends to underline the role played by surface-linked ore formation processes, i.e., by ore-forming processes essentially linked to the environments in which sedimentation and early diagenesis takes place, in the genesis of numerous strata-bound Zn-Pb-(F-Ba) ore deposits in carbonate rocks.     

Arsenic and fluoride in a loess aquifer in the central area of Argentina

The objective of this study is to analyze the geochemical conditions associated with the presence of arsenic (As) and fluoride (F) in the phreatic aquifer of Coronel Moldes, in the central sector of the Argentine Chacopampean plain. The studied aquifer is composed of silty sand sediments of aeolian origin, typically loess-like sediments. The geochemical composition of water varies from sodium bicarbonate to sodium sulfate-chloride water. As contents range from low concentrations, below detection level, to 250 μg/l. High values of F (up to 12 mg/l) were recorded. A high As–F correlation was found (R ² = 0.84). The pH varied from 7.31 to 8.85 and the nitrates reached concentrations up to 200 mg/l, indicating an oxidant environment. The highest values of As and F agreed with sodium bicarbonate waters as well as with the highest values of pH recorded. There was a high correlation between As and F⁻ as well as between As and the Na/Ca ratio. The composition and texture of loess, low permeability and hydraulic gradients together with the geochemical features of sodium bicarbonate waters are proper conditions for the mobilization of As and F in groundwater in the central area of Argentina.     

Preservation of a heavily bored belemnite rostrum from the upper Maastrichtian of north-east Belgium

The robust calcite rostra (or guards) of belemnites were attractive substrates for some boring organisms in the Mesozoic. The rostra of belemnitellid coleoids are common at certain levels within the Gulpen and Maastricht formations of the extended type area of the Maastrichtian Stage (Upper Cretaceous) in the south-east Netherlands and north-east Belgium. A range of episkeletozoans have been reported from these substrates hitherto. A new specimen preserved as a natural mould in flint from the province of Liège, north-east Belgium, is distinctive, preserving a dense three-dimensional infestation of long, slender, unbranched and unsculptured borings of constant diameter, Trypanites? isp. These may be the spoor of polychaetes. Variations in diameter between borings suggests that the traces in this specimen may represent four separate infestations.