Long-term effect of municipal solid waste compost on the recovery of a potentially toxic element (PTE)-contaminated soil: PTE mobility, distribution and bioaccessibility.

Compost from municipal solid waste (MSWC) can represent a resource for the environmental management of soils contaminated with potentially toxic elements (PTEs), since it can reduce their mobility and improve soil fertility. However, the long-term impact of compost on soil recovery has been poorly investigated. To this end, the influence of a MSWC added at different rates (i.e. 1.5, 3.0 and 4.5% w/w) to a multi-PTE-contaminated (e.g. Sb 412 mg kg-1, Pb 2664 mg kg-1 and Zn 7510 mg kg-1) sub-acidic soil (pH 6.4) was evaluated after 6 years since its addition. The MSWC significantly enhanced soil fertility parameters (i.e. total organic carbon, Olsen P and total N) and reduced the PTE labile fractions. The distribution maps of PTEs detected through µXRF analysis revealed the presence of Zn and Pb carbonates in the amended soils, or the formation of complexes between these PTEs and the functional groups of MSWC. A higher oral, inhalation and dermal bioaccessibility of each PTE was detected in the soil fine-grained fractions (< 2 and 2-10 µm) than in coarse particles (10-20 and 20-50 µm). The MSWC amendment generally did not modify the PTE bioaccessibility, while the relative bioaccessibility of cationic PTEs was greater than that of anionic ones (e.g. Cd > Zn > Pb > Sb > As). Pb and Sb showed the highest hazard quotients (e.g. 2.2 and 10 for Sb and Pb, respectively, in children). Overall, the results indicated that the MSWC used can be an effective option for the recovery of PTE-contaminated soils, even in the long term.

Combining micro- and portable-XRF as a tool for fast identification of virus infections in plants: The case study of ASa-Virus in Fraxinus ornus L.

Plant viruses can affect micro- and macro-nutrients homeostasis in woody plants, with fluctuation in the concentration of some elements at the leaf level due to the pathogen activity and/or the plant physiological response to the infection.Leaves of Fraxinus ornus L. (flowering ash) were sampled for three consecutive years in the city of Hamburg (Germany), from both trees showing the typical symptoms of the ash shoestring associated virus infection (ASaV+) and healthy trees (ASaV-). Such leaves were analyzed by µ-XRF, using both laboratory and synchrotron X-ray sources, and large differences between symptomatic and not symptomatic leaves were observed: ASaV+ samples showed uneven element distribution and regions of the lamina with severe depletions of P, S, and Ca. Differently, K appeared more concentrated. Thus, 139 leaflets sampled from various healthy and infected ash trees over the three-year period were analyzed for K and Ca concentration with a portable XRF instrument. We found that the K:Ca concentration ratio was always significantly higher in ASaV+ samples, and this trend was verified for all the samplings over the tree years. We conclude that the K:Ca ratio parameter has potential in the frame of trendsetting diagnostics and could be used, together with visual symptoms, for a rapid, non-destructive, on-site and cheap indirect ASaV detection.

TXRF spectral information enhanced by multivariate analysis: A new strategy for food fingerprint.

The increased costumers' request of safe and high-quality food products makes food traceability a priority for frauds identification and quality certification. Elemental profiling is one of the strategies used for food traceability, and TXRF spectroscopy is widely used in food analysis even if its potentialities have not been fully investigated. In this work, a new method for food traceability using directly TXRF spectra coupled with multivariate analyses, was tested. Twenty-four different beans' genotypes (Phaseolus vulgaris L.) grown onto two different sites have been studied. After the development of the method for beans' analysis, TXRF spectra were collected and processed with PCA combined with SNV and GLSW filter obtaining a perfect clustering of the seeds according to their geographical origin. Finally, using PLS-DA, beans were correctly classified demonstrating that TXRF spectra can be successfully used as fingerprint for food/seed traceability and that elemental quantification procedure is not necessary to this aim.

Fire-induced effects on the bioavailability of potentially toxic elements in a polluted agricultural soil: implications for Cr uptake by durum wheat plants.

Fire events can modify the distribution and speciation of potentially toxic elements (PTEs) in soil, especially if they are associated to organic matter (OM). In fact, OM can undergo substantial structural modifications at high temperatures, up to the complete mineralization. The present study aims to investigate the changes of PTEs' bioavailability to durum wheat (Triticum durum Desf.) plants after simulating fire events (up to 300 °C and 500 °C) in an agricultural soil polluted by Cr, Zn, Cu, and Pb. The PTEs' uptake and allocation in plant tissues were assessed using the RHIZOtest system. After the fire simulations, no evident risk of accumulation and translocation in plants was observed for Zn, Pb, and Cu. Conversely, a high accumulation in roots and a significant translocation to shoots were observed for Cr, which reached concentrations of 829 mg kg-1 in roots and 52 mg kg-1 in shoots at 500 °C. Additional experimental evidence suggested that Cr was taken up by plants grown on heated soils as Cr(VI). Once acquired by roots, only a small part of Cr (up to 6%) was translocated to shoots where it was likely present as mobile forms, as evidenced by micro X-ray fluorescence (µ-XRF) analyses. Overall, the results obtained provide evidence that the high temperatures occurring during fire events can increase the mobility and bioavailability of certain PTEs transforming apparently safe environments into potentially dangerous sources of pollution. These processes can ultimately affect the human health through the food chain transfer of PTEs or their migration into surface water and groundwater.

Evidence of hexavalent chromium formation and changes of Cr speciation after laboratory-simulated fires of composted tannery sludges long-term amended agricultural soils.

Controlled or accidental fires can impact agricultural soils amended with composted organic materials since high temperatures cause fast organic matter (OM) mineralization and soil properties modifications. During these events, potentially toxic elements (PTEs) associated with OM can be released and change their distribution and speciation thus becoming a threat to the environment and to crops. In this study, we investigated the changes of distribution and speciation of chromium in soils long-term amended with compost obtained from tannery sludges, after simulating fires of different intensity (300, 400 and 500 °C) likely to occur on agricultural soils. A combination of conventional soil chemical analyses and bulk and (sub)micro X-ray analyses allowed the observation of the formation of hexavalent chromium and changes of chromium speciation. Specifically, a strong decrease of Cr-OM associations was found with increasing temperature in favour of Cr-iron (hydr)oxides interactions and CaCrO4 formation. These data provide first evidence that fires can transform OM-stabilized Cr into more mobile, available and toxic Cr-forms potentially accessible for plant uptake, thus posing a risk for the food chain and the environment.

Overcome the limits of multi-contaminated industrial soils bioremediation: Insights from a multi-disciplinary study.

Phytoremediation can be a promising and sustainable strategy to recovery Potentially Toxic Elements (PTEs) contaminated soils. However, at the field level, this tool can be limited by many issues. Herein, we combined native plant species with different cover type (mono and poly culture) in an in-field mesocosm experiment for the remediation of multi-contaminated soils from Bagnoli brownfield site (Southern Italy). We preliminary gain insights about the physical, chemical and biological features of the soils and subsequently induced a potential variation in the soil microbiome. We found that polyculture better respond both in terms of pollutant phytostabilization efficiency and from a stress tolerance perspective. Among plant species, Festuca achieved the best performance due to the overexpression of metal transporters able in both PTEs influx and sequestration from the cytoplasm. We achieved a site-specific bio-factory, which represents a strategy for the sustainable and relatively fast recovery of large contaminated areas.

Fire effects on the distribution and bioavailability of potentially toxic elements (PTEs) in agricultural soils.

In the last years, uncontrolled fires are frequently occurring in forest and agricultural areas as an indirect effect of the rising aridity and global warming or caused by intentional illegal burnings. In addition, controlled burning is still largely used by farmers as an agricultural practice in many parts of the world. During fire events, soil can reach very high temperatures at the soil surface, causing dramatic changes of soil properties and elements biogeochemistry. Among soil elements, also potentially toxic elements (PTEs) can be affected by fires, becoming more or less mobile and bioavailable, depending on fire severity and soil characteristics. Such transformations could be particularly relevant in agricultural soils used for crop productions since fire events could modify PTEs speciation and uptake by plants and associated (micro)organisms thus endangering the whole food-chain. In this review, after describing the effects of fire on soil minerals and organic matter, the impact of fires on PTEs distribution and speciation in soils is presented, as well as their influence on soil microorganisms and plants uptake. The most common experimental methods used to simulate fires at the laboratory and field scale are briefly illustrated, and finally the impact that traditional and innovative agricultural practices can have on PTEs availability in burned agricultural soils is discussed in a future research perspective.

Antinutritional factors, mineral composition and functional properties of dry fractionated flours as influenced by the type of pulse.

Coarse (CF) and Fine (FF) fractions were obtained by dry fractionation (air classification) of raw micronized flour (RM) of kabuli chickpea, green pea, yellow and red lentil. Pea showed the highest phytate content in RM and CF. Stachyose was the main oligosaccharide in lentils, exceeding 50 mg g-1, whereas raffinose (39.9 mg g-1) was abundant in chickpea. Antinutritional factors were significantly enriched in FF, whereas decreased in CF. Total-reflection X-ray fluorescence identified potassium as the main macronutrient in pulses. Ca was highly variable, ranging from 0.92 to 0.28 g kg-1 in pea and yellow lentil, respectively. A significant shift of minerals was observed in FF, but despite the highest phytate content, phytate:Zn ratio of lentils was lower than RM, indicating that Zn was enriched more than phytates. Yellow lentil and pea FF showed a protein content higher than 55 g 100g-1. Dry fractionation significantly affected the physicochemical properties, indicating different potential use of fractions.

Plasmopara viticola infection affects mineral elements allocation and distribution in Vitis vinifera leaves.

Plasmopara viticola is one of the most important pathogens infecting Vitis vinifera plants. The interactions among P. viticola and both susceptible and resistant grapevine plants have been extensively characterised, at transcriptomic, proteomic and metabolomic levels. However, the involvement of plants ionome in the response against the pathogen has been completely neglected so far. Therefore, this study was aimed at investigating the possible role of leaf ionomic modulation during compatible and incompatible interactions between P. viticola and grapevine plants. In susceptible cultivars, a dramatic redistribution of mineral elements has been observed, thus uncovering a possible role for mineral nutrients in the response against pathogens. On the contrary, the resistant cultivars did not present substantial rearrangement of mineral elements at leaf level, except for manganese (Mn) and iron (Fe). This might demonstrate that, resistant cultivars, albeit expressing the resistance gene, still exploit a pathogen response mechanism based on the local increase in the concentration of microelements, which are involved in the synthesis of secondary metabolites and reactive oxygen species. Moreover, these data also highlight the link between the mineral nutrition and plants' response to pathogens, further stressing that appropriate fertilization strategies can be fundamental for the expression of response mechanisms against pathogens.

Fruit Development in Ficus carica L.: Morphological and Genetic Approaches to Fig Buds for an Evolution From Monoecy Toward Dioecy.

The mechanism behind the bud evolution towards breba or main crop in Ficus carica L. is uncertain. Anatomical and genetic studies may put a light on the possible similarities/differences between the two types of fruits. For this reason, we collected complimentary data from anatomical, X-ray imaging, and genetic techniques. The RNA seq together with structural genome annotation allowed the prediction of 34,629 known genes and 938 novel protein-coding genes. Transcriptome analysis of genes during bud differentiation revealed differentially expressed genes in two fig varieties (Dottato and Petrelli) and in breba and main crop. We chose Dottato and Petrelli because the first variety does not require pollination to set main crop and the latter does; moreover, Petrelli yields many brebas whereas Dottato few. Of the 1,615 and 1,904 loci expressed in Dottato and Petrelli, specifically in breba or main crop, respectively, only 256 genes appeared to be transcripts in both varieties. The buds of the two fig varieties were observed under optical microscope and using 3D X-ray tomography, highlighting differences mainly related to the stage of development. The X-ray images of buds showed a great structural similarity between breba and main crop during the initial stages of development. Analysis at the microscope indicated that inflorescence differentiation of breba was split in two seasons whereas that of main crop started at the end of winter of season 2 and was completed within 2 to 3 months. The higher expression of floral homeotic protein AGAMOUS in breba with respect to main crop, since this protein is required for normal development of stamens and carpels in the flower, may indicate an original role of these fruits for staminate flowers production for pollination of the main crop, as profichi in the caprifig. Several genes related to auxin (auxin efflux carrier, auxin response factor, auxin binding protein, auxin responsive protein) and to GA synthesis (GA20ox) were highly expressed in brebas with respect to main crop for the development of this parthenocarpic fruit.

Combined micro X-ray fluorescence and micro computed tomography for the study of extraterrestrial volcanic rocks. The case of North West Africa (NWA) 8657: A shergottite martian meteorite.

The combined potentiality of benchtop micro X-ray fluorescence spectroscopy (µ-XRF) and micro computed tomography (µ-CT) has been applied to describe microstructures, type and distribution of mineralogical phases as well as geological constraints on the history of the North West Africa (NWA) 8657 shergottite Martian meteorite. The 3D rendering of the sample was used to compute its vesiculation, infer the presence of cracks and reveal different shapes in its crystal habits including subhedral pyroxene phases and rounded sulphide and/or sulphates minerals. Phase discrimination was achieved by comparing chemical information about element distribution with mineral classes segmented as a function of their relative density. In particular, the relationships between the plagioclase/maskelynite phase and other minerals such as Ca-phosphates, the chemical zoning of Ca-pyroxenes and maskelynite and the presence of S-bearing phases in the form of K-sulphates and Fe-sulphides were revealed, which allowed reconstructing satisfactorily meteorite history. The successful performance of the combined approach used in this work shows promising for further application to other types of meteorites.

Assessing chromium pollution and natural stabilization processes in agricultural soils by bulk and micro X-ray analyses.

A combined approach based on multiple X-ray analytical techniques and conventional methods was adopted to investigate the distribution and speciation of Cr in a polluted agricultural soil, from the bulk-scale down to the (sub)micro-level. Soil samples were collected from two different points, together with a control sample taken from a nearby unpolluted site. The bulk characterization revealed that the polluted soils contained much higher concentrations of organic matter (OM) and potentially toxic elements (PTE) than the control. Chromium was the most abundant PTE (up to 5160 g kg-1), and was present only as Cr(III), as its oxidation to Cr(VI) was hindered by the high OM content. According to sequential extractions, Cr was mainly associated to the soil oxidisable fraction (74%) and to the residual fraction (25%). The amount of Cr potentially bioavailable for plant uptake (DTPA-extractable) was negligible. Characterization of soil thin sections by micro X-ray fluorescence (µXRF) and field emission scanning electron microscopy coupled with microanalysis (FEGSEM-EDX) showed that Cr was mainly distributed in aggregates ranging from tens micrometres to few millimetres in size. These aggregates were coated with an aluminosilicate layer and contained, in the inner part, Cr, Ca, Zn, P, S and Fe. Hyperspectral elaboration of µXRF data revealed that polluted soils were characterised by an exogenous organic-rich fraction containing Cr (not present in the control), and an endogenous aluminosilicate fraction (present also in the control), coating the Cr-containing aggregates. Analyses by high-resolution micro X-ray computed tomography (µCT) revealed a different morphology of the soil aggregates in polluted soils compared with the control. The finding of microscopic leather residues, combined with the results of bulk- and micro-characterizations, suggested that Cr pollution was likely ascribable to soil amendment with tannery waste-derived matrices. However, over the years, a natural process of Cr stabilization occurred in the soil thus reducing the environmental risks.

Macro-classification of meteorites by portable energy dispersive X-ray fluorescence spectroscopy (pED-XRF), principal component analysis (PCA) and machine learning algorithms.

The research on meteorites from hot and cold deserts is gaining advantages from the recent improvements of portable technologies such as X-ray fluorescence spectroscopy (XRF). The main advantages of portable instruments include the fast recognition of meteorites through their classification in macro-groups and discrimination from materials such as industrial slags, desert varnish covered rocks and iron oxides, named "meteor-wrongs". In this study, 18 meteorite samples of different nature and origin were discriminated and preliminarily classified into characteristic macro-groups: iron meteorites, stony meteorites and meteor-wrongs, combining a portable energy dispersive XRF instrument (pED-XRF), principal component analysis (PCA) and some machine learning algorithms applied to the XRF spectra. The results showed that 100% accuracy in sample classification was obtained by applying the cubic support vector machine (CSVM), fine kernel nearest neighbor (FKNN), subspace discriminant-ensemble classifiers (SD-EC) and subspace discriminant KNN-EC (SKNN-EC) algorithms on standardized spectra.

The fertilising potential of manure-based biogas fermentation residues: pelleted vs. liquid digestate.

Spreading of manure on agricultural soils is a main source of ammonia emissions and/or nitrate leaching. It has been addressed by the European Union with the Directives 2001/81/EC and 91/676/EEC to protect the environment and the human health. The disposal of manure has therefore become an economic and environmental challenge for farmers. Thus, the conversion of manure via anaerobic digestion in a biogas plant could be a sustainable solution, having the byproducts (solid and liquid digestates) the potential to be used as fertilizers for crops. This work aimed at characterizing and assessing the effect of digestates obtained from a local biogas plant (Biogas Wipptal, Gmbh), either in the form of liquid fraction or as a solid pellet on: (i) the fertility of the soils during an incubation experiment; (ii) the plant growth and nutritional status of different species (maize and cucumber). Moreover, an extensive characterization of the pellet was performed via X-ray microanalytical techniques. The data obtained showed that both digestates exhibit a fertilizing potential for crops, depending on the plant species and the fertilizer dose: the liquid fraction increases the shoot fresh weight at low dose in cucumber, conversely, the solid pellet increases the shoot fresh weight at high dose in maize. The liquid digestate may have the advantage to release nutrients (i.e. nitrogen) more rapidly to plants, but its storage represents the main constraint (i.e. ammonia volatilization). Indeed, pelleting the digestates could improve the storability of the fertilizer besides enhancing plant nutrient availability (i.e. phosphate and potassium), plant biomass and soil biochemical quality (i.e. microbial biomass and activity). The physical structure and chemical composition of pellet digestates allow nutrients to be easily mobilized over time, representing a possible source of mineral nutrients also in long-term applications.

Occurrence and distribution of high arsenic in sediments and groundwater of the Claromecó fluvial basin, southern Pampean plain (Argentina).

Occurrences of high arsenic (As) in sediments and groundwaters were investigated in the Claromecó fluvial basin, southern Pampean plain, Argentina. This investigation includes sedimentology, mineralogy, and hydrogeochemistry of the Neogene and Quaternary aquifers to determine possible sources and transport mechanisms for As in the Claromecó basin. Characterization of the sediments revealed homogeneous mineralogy in both Neogene highlands and Quaternary floodplains with abundant plagioclase, volcanic glass shards (VGS), K-feldspar, quartz, clay minerals and minor concentrations of clinopyroxenes, orthopyroxenes, hornblende, epidote, Fe-(oxy)hydroxides and fluorapatite. The sedimentary As concentrations ranged between 2.8 and 31 mg kg-1 in both aquifers. The average total dissolved As (dissolved AsT) concentrations was 47.2 ±â€¯30.8 µg L-1 (15.3-110 µg L-1) in groundwater in Neogene aquifer (GW1), while it was 97.1 ±â€¯30.6 µg L-1 (45-144 µg L-1) in Quaternary floodplain aquifer (GW2), with all samples exceeding WHO's guideline for dissolved AsT in safe drinking water of 10 µg L-1. Some GW1 (33%) and all GW2 samples contained high levels of fluoride (F-) ranging from 0.6 to 2.6 mg L-1 (1.37 ±â€¯0.59 mg L-1) in GW1 and 2 to 5 mg L-1 (3.2 ±â€¯0.9 mg L-1) in GW2 which also exceeded WHO's guideline for F- in safe drinking water of 1.5 mg L-1. Elevated concentrations of Na+, Cl- and SO42- in the Quaternary flood plain groundwater (GW2) could indicated some degree of sea water mixing as well as some contribution from inland processes (e.g. high evapotranspiration rates, long residence time and soil-water interactions). Dissolution of As bearing VGS or Fe-(oxy)hydroxides, alkaline desorption or competitive desorption with HCO3- from Fe-(oxy)hydroxides appear to be dominating processes of As mobilization, while desorption from fluorapatite elevate dissolved F- levels. This study provides valuable insights on As mobilization processes in Neogene and near coast Quaternary floodplain aquifer.

Correlations between As in Earthworms' Coelomic Fluid and As Bioavailability in Highly Polluted Soils as Revealed by Combined Laboratory X-ray Techniques.

Combined X-ray-based spectroscopy techniques were applied to investigate arsenic (As) bioaccumulation in earthworms (Eisenia andrei) exposed to six field-collected polluted soils (58-13 330 mg As kg-1). After 14 days of exposure to the arsenious soils, the As distribution in earthworms was examined by micro-X-ray fluorescence spectroscopy (µXRF), after epoxy resin embedding and preparing thin sections. Similar to µXRF data, XRF-computed tomography (XRF-CT) confirmed As accumulation in the coelom of intact earthworms. Therefore, total-reflection XRF was used to determine total As within both the whole earthworm's body (AsE) and coelomic fluid extracts (AsF). Bioaccumulation data (AsE and AsF) were thereafter evaluated in relation to total As concentration in soils (AsT) and to As mobile fraction in soils. A significant linear correlation (R2 = 0.97) was found between AsE and AsF, indicating that the As sequestrated into the coelomic fluid may reflect the total body concentration. Therefore, we may conclude that the As concentration in the coelomic fluid can be used as an index of As availability. This paper demonstrates that by combining different laboratory X-ray analytical techniques, compartmentalization and bioavailability of potentially toxic elements can be visualized and quantified within indicator-living organisms, thus contributing to an improved risk assessment for contaminated soils.

Characterization of As-polluted soils by laboratory X-ray-based techniques coupled with sequential extractions and electron microscopy: the case of Crocette gold mine in the Monte Rosa mining district (Italy).

Arsenic concentration and distribution were studied by combining laboratory X-ray-based techniques (wavelength dispersive X-ray fluorescence (WDXRF), micro X-ray fluorescence (µXRF), and X-ray powder diffraction (XRPD)), field emission scanning electron microscopy equipped with microanalysis (FE-SEM-EDX), and sequential extraction procedure (SEP) coupled to total reflection X-ray fluorescence (TXRF) analysis. This approach was applied to three contaminated soils and one mine tailing collected near the gold extraction plant at the Crocette gold mine (Macugnaga, VB) in the Monte Rosa mining district (Piedmont, Italy). Arsenic (As) concentration, measured with WDXRF, ranged from 145 to 40,200 mg/kg. XRPD analysis evidenced the presence of jarosite and the absence of any As-bearing mineral, suggesting a high weathering grade and strong oxidative conditions. However, small domains of Fe arsenate were identified by combining µXRF with FE-SEM-EDX. SEP results revealed that As was mainly associated to amorphous Fe oxides/hydroxides or hydroxysulfates (50-80%) and the combination of XRPD and FE-SEM-EDX suggested that this phase could be attributed to schwertmannite. On the basis of the reported results, As is scarcely mobile, even if a consistent As fraction (1-3 g As/kg of soil) is still potentially mobilizable. In general, the proposed combination of laboratory X-ray techniques could be successfully employed to unravel environmental issues related to metal(loid) pollution in soil and sediments.

Alkaline hydrothermal stabilization of Cr(VI) in soil using glass and aluminum from recycled municipal solid wastes.

Hexavalent chromium was stabilized in soil by using a mixture of glass and aluminum recovered from municipal solid wastes under alkaline hydrothermal conditions. Cr(VI) concentration was reduced by 94-98% already after 7days of treatment. After the same period, more than 90% of total Cr was stabilized in highly recalcitrant and scarcely mobile chemical forms, with 50% in the residual fraction (when the samples were treated at 1/10w/w mixture/soil ratio). Longer treatments increased Cr stabilization. X-ray microanalyses revealed that Cr was stabilized in geopolymeric structures within large aluminosilicate mineral aggregates (containing both amorphous and crystalline phases). 3D microstructural analyses showed a limited compaction of the soil with still a 20% internal porosity in the neoformed aggregates. Increased pH and salinity after the treatment can be restored by simple soil amendments and washing.

Application of micro X-ray fluorescence and micro computed tomography to the study of laser cleaning efficiency on limestone monuments covered by black crusts.

Laser cleaning is widely used to remove black crusts from weathered limestone monuments. The cleaning efficiency is commonly tested using conventional analytical techniques, which do not allow to analyze the same sample before and after the treatment. In this paper, micro computed tomography (µ-CT) and micro X-ray fluorescence spectroscopy (µ-XRF) techniques were used for the first time to evaluate the laser cleaning efficiency on two different encrusted quoins collected from a limestone monument. Analyses were carried out non-destructively on the same portion of the two lithotypes before and after the treatment. µ-XRF confirmed the presence of gypsum in the black crust, and showed a marked decrease of S and other typical elements after laser cleaning of both samples. µ-CT clearly showed the different structure of limestone before and after cleaning and the crust portion removed by the laser. The combination of the two techniques allowed to assess that, even if the two samples had a similar chemical composition, their response to laser cleaning was different on dependence of their different fabric/structure. In fact, in one sample calcium sulphate was still partially retained also after the black crust removal, whereas in the other sample the sulphate layer was almost completely ablated due to its more compact structure. In both cases, laser cleaning operation was shown not to cause any structural modification or mechanical damage of the original stone material. In conclusion, the use of these novel techniques appears very promising for studying the effects of laser ablation on rock samples in order to set the best working conditions for their cleaning.