100 years of high GEM concentration in the Central Italian Herbarium and Tropical Herbarium Studies Centre (Florence, Italy).

Up to 1980s, the most used preservative for herbaria specimens was HgCl2, sublimating at ambient air conditions; ionic Hg then reduces to Hg0 (gaseous elemental mercury, GEM) and diffuses throughout poor ventilated environments. High GEM levels may indeed persist for decades, representing a health hazard. In this study, we present new GEM data from the Central Italian Herbarium and Tropical Herbarium Studies Centre of the University of Florence (Italy). These herbaria host one of the largest collection of plants in the world. Here, HgCl2 was documented as plant preservative up to the 1920s. GEM surveys were conducted in July 2013 and July and December 2017, to account for temporal and seasonal variations. Herbaria show GEM concentrations well above those of external locations, with peak levels within specimen storage cabinets, exceeding 50,000 ng/m3. GEM concentrations up to ~7800 ng/m3 were observed where the most ancient collections are stored and no ventilation systems were active. On the contrary, lower GEM concentrations were observed at the first floor. Here, lower and more homogeneously distributed GEM concentrations were measured in 2017 than in 2013 since the air-conditioning system was updated in early 2017. GEM concentrations were similar to other herbaria worldwide and lower than Italian permissible exposure limit of 20,000 ng/m3 (8-hr working day). Our results indicate that after a century from the latest HgCl2 treatment GEM concentrations are still high, i.e., the treatment itself is almost irreversible. Air conditioning and renewing is probably the less expensive and more effective method for GEM lowering.

Exploration of geochemical data with compositional canonical biplots.

The study of the relationships between two compositions is of paramount importance in geochemical data analysis. This paper develops a compositional version of canonical correlation analysis, called CoDA-CCO, for this purpose. We consider two approaches, using the centred log-ratio transformation and the calculation of all possible pairwise log-ratios within sets. The relationships between both approaches are pointed out, and their merits are discussed. The related covariance matrices are structurally singular, and this is efficiently dealt with by using generalized inverses. We develop compositional canonical biplots and detail their properties. The canonical biplots are shown to be powerful tools for discovering the most salient relationships between two compositions. Some guidelines for compositional canonical biplot construction are discussed. A geochemical data set with X-ray fluorescence spectrometry measurements on major oxides and trace elements of European floodplains is used to illustrate the proposed method. The relationships between an analysis based on centred log-ratios and on isometric log-ratios are also shown.

Type of probability distribution reflects how close mixing dynamics in river chemistry are to thermodynamic equilibrium.

The distribution of geochemical species are typically either (log)normally distributed or follow power laws. Here we link these types of distributions to the dynamics of the system that generates these distributions, showing that power laws can emerge in dissipative systems far from equilibrium while (log)normal distributions are found for species for which the concentrations are close to equilibrium. We use observations of the chemical composition of river water from the sampling space in central Italy as well as discharge data to test this interpretation. We estimate the dissipation rate that results when groundwater drains into the river and the dissolved chemical species mix with the river water. We show that calcium (Ca2+) and bicarbonate (HCO3-) concentrations are close to saturation along most of the downstream length of the Arno river, with decreasing dissipation rates and a lognormal distribution, while sodium (Na+) and chloride (Cl-) concentrations increase substantially downstream, show increased dissipation rates, and are power-law distributed. This supports our hypothesis that power law distributions appear to be indicative of dissipative systems far from thermodynamic equilibrium, while (log)normal distributions indicate weakly dissipative systems close to equilibrium. What this implies is that probability distributions are likely to be indicative of the thermodynamics of the system and the magnitude of disequilibrium constrains the range over which power-law scaling may be observed. This should help us to better identify the generalities and mechanisms that result in these common types of distributions and to better classify variability in systems according to how dissipative these are.

Are geochemical regime shifts identifiable in river waters? Exploring the compositional dynamics of the Tiber River (Italy).

Rivers are dynamic and sensitive systems that change their chemical composition from source to mouth. This is due to the influence of a set of variables controlled by hydro-litho-eco-atmospheric processes and anthropic pressures which are, in turn, affected by catchment attributes. This work proposes a new way of thinking about river geochemistry focused on environmental interconnections rather than single chemical variables. Abrupt changes in the system state (composition) of a certain environmental media, driven by perturbations, may trigger Geochemical Regime Shifts (GRSs). This eventuality is explored in the Tiber River (central Italy) chemistry by Compositional Data Analysis, robust Principal Component Analysis and score-distance graphs. Data variability and the interlinks between response and forcing variables are investigated for different drained areas. A potential GRS is detected for major elements in the lower reaches resulting from a threshold-like state response caused by lithological forcing. On the contrary, trace elements respond gradually to environmental drivers, showing no abrupt changes. The findings outline mechanisms and factors influencing the river's self-restoring capability at a basin-wide scale, providing a better comprehension of the circumstances controlling the equilibrium dynamics of river water systems.

Unveiling the changes in urban atmospheric CO2 in the time of COVID-19 pandemic: A case study of Florence (Italy).

The outbreak of COVID-19 pandemic was accompanied by global mobility restrictions and slowdown in manufacturing activities. Accordingly, cities experienced a significant decrease of CO2 emissions. In this study, continuous measurements of CO2 fluxes, atmospheric CO2 concentrations and δ13C-CO2 values were performed in the historical center of Florence (Italy) before, during and after the almost two-month long national lockdown. The temporal trends of the analyzed parameters, combined with the variations in emitting source categories (from inventory data), evidenced a fast response of flux measurements to variations in the strength of the emitting sources. Similarly, the δ13C-CO2 values recorded the change in the prevailing sources contributing to urban atmospheric CO2, confirming the effectiveness of carbon isotopic data as geochemical tracers for identifying and quantifying the relative contributions of emitting sources. Although the direct impact of restriction measurements on CO2 concentrations was less clear due to seasonal trends and background fluctuations, an in-depth analysis of the daily local CO2 enhancement with respect to the background values revealed a progressive decrease throughout the lockdown phase at the end of the heating season (>10 ppm), followed by a net increase (ca. 5 ppm) with the resumption of traffic. Finally, the investigation of the shape of the frequency distribution of the analyzed variables revealed interesting aspects concerning the dynamics of the systems.

Grasping at straws: a re-evaluation of sweepstakes colonisation of islands by mammals.

Natural rafting is an easy, non-evidence-based solution often used to explain the presence of a variety of species on isolated islands. The question arises as to whether this solution is based on solid scientific grounds. It is a plausible colonisation route only if intricate networks of variables are considered and many different conditions satisfied. This review provides a descriptive account of some of the most critical issues underlying the theory of natural rafting that should be addressed by its supporters. These include: (i) biological variables; (ii) characteristics of the vessels; and (iii) physical variables. Natural rafting may explain the dispersal of poikilotherms with low metabolic rates and low resource requirements that could withstand trans-oceanic crossings, but explaining the transport of homeothermic terrestrial mammals to oceanic islands is more problematic. Drifting at sea exposes organisms to high concentrations of salt, high temperature and humidity excursions, starvation, and above all to dehydration. A sufficiently large group of healthy reproductive individuals of the two sexes should either be transported together, or be able to reassemble after separate crossings, to prevent inbreeding, genetic drift and ultimately extinction. Any vessels of flotsam occupied must minimally provide the animals they transport with sufficient provisions to survive the journey, offer minimum friction and drag through water, and be transported by appropriately directed, sustained, high-speed currents. Thus, a 'sweepstakes colonisation' event would be the result of a lucky combination of all, or at least the majority, of these factors. Some cases throw doubt on the use of a natural rafting model to explain known animal colonisations, with one of the most striking examples being Madagascar. This island is far from the nearest mainland coasts and the sea currents in the Mozambique Channel are directed towards Africa rather than Madagascar, yet, the island was colonised by terrestrial mammals (e.g. extinct hippopotamuses, lemurs, carnivores, rodents and tenrecs) unable to swim and to survive long journeys at sea. In order to assess the feasibility of the natural rafting model in a case such as Madagascar, tests were performed using three variables for which enough information could be obtained from the literature: length of survival without food, survival without water, and sea current speed. The distributions of these variables appear to be log-normal and multiplicative, or follow a power-law, rather than being Gaussian. The tests suggest that a distributional analysis is a more suitable approach than the use of geometric probability to calculate the probabilities associated with the examined data. Such non-linear and self-organising systems may reach a critical point governed by different competing factors. Mammals with high survival requirements, such as lemurs and hippopotamuses, thus may have a virtually zero probability of reaching distant islands by natural rafting. Our results raise doubts as to the validity of a natural rafting model, and we urge a rethinking of the modes in which numerous islands were colonised by land mammals and a careful revision of past geological and phylogeographic work.

Chemical variability of artificial stone powders in relation to their health effects.

The occurrence of highly severe silica-related diseases among the resin- and silica-based artificial stone workers was claimed, associated to an extremely short latency. High levels of exposure and intrinsic properties of AS are thought to modulate the development of silicosis and auto-immune diseases. This study compares parent materials and processed dusts, to shed light on changes of AS occurring in the manufacturing process, through an XRF, EPR and XAS investigation. We point out the extremely wide variability of the materials, the occurrence of chemical signatures impressed by the processing techniques, and the unprecedented generation of stable radicals associated to the lysis of the Si-O chemical bond inside the resin coated respirable crystalline silica. These results suggest that the AS processing in industrial stone workshops can create respirable dusts with peculiar physical and chemical properties, to be correlated to the observed clinical evidences.

Green and scalable synthesis of nanocrystalline kuramite.

The new generation of solar cells aims to overcome many of the issues created by silicon-based devices (e.g., decommissioning, flexibility and high-energy production costs). Due to the scarcity of the resources involved in the process and the need for the reduction of potential pollution, a greener approach to solar cell material production is required. Among others, the solvothermal approach for the synthesis of nanocrystalline Cu-Sn-S (CTS) materials fulfils all of these requirements. The material constraints must be considered, not only for the final product, but for the whole production process. Most works reporting the successful synthesis of CTS have employed surfactants, high pressure or noxious solvents. In this paper, we demonstrate the synthesis of nanocrystalline kuramite by means of a simpler, greener and scalable solvothermal synthesis. We exploited a multianalytical characterization approach (X-ray diffraction, extended X-ray absorption fine structure, field emission scanning electron microscopy, Raman spectroscopy and electronic microprobe analysis (EMPA)) to discriminate kuramite from other closely related polymorphs. Moreover, we confirmed the presence of structural defects due to a relevant antisite population.

Determination of organic acids in plants of Silene paradoxa L. by HPLC.

According to the general behavior that organic acids steadily bind metals, a specific and highly reproducible HPLC separation method with photodiode array detection has been improved for their determination and quantification in biological materials. The separation was carried out on an Alltima C-18 reverse phase column. The mobile phase was 125 mM KH2PO4, adjusted to pH 2.5 with concentrated H3PO4, and optimum separation efficiency was obtained by using a 2 mL min(-1) flow rate. Detection wavelength for quantitative measurement was 210 nm. The run time of each sample was 20 min, with a spectra collection frequency of 5 spectra s(-1). Organic acids were identified by comparing the retention times of the samples against retention times of the standards and confirmed with spectral (190-700 nm) signature. Because organic acids could steadily bind metals in plant tissues and due to the strong matrix effect observed, the addition method was applied for quantitative analysis and its performance evaluated.

Paradoxical effects of density on measurement of copper tolerance in Silene paradoxa L.

This work investigated if the assessment of tolerance to trace metals can depend on plant density in the experimental design. A non-metallicolous and a metallicolous populations of Silene paradoxa were hydroponically cultivated at increasing density and in both the absence (-Cu conditions) and excess of copper (+Cu conditions). In -Cu conditions, the metallicolous population showed a lower susceptibility to plant density in comparison to the non-metallicolous one, explained by a higher capacity of the metallicolous population to exploit resources. In +Cu conditions, an alleviating effect of increasing density was found in roots. Such effect was present to a greater extent in the non-metallicolous population, thus making the populations equally copper-tolerant at the highest density used. In shoots, an additive effect of increasing plant density to copper toxicity was reported. Its higher intensity in the metallicolous population reverted the copper tolerance relationship at the highest plant densities used. In both populations, a density-induced decrease in root copper accumulation was observed, thus concurring to the reported mitigation in +Cu conditions. Our work revealed the importance of density studies on the optimization of eco-toxicological bioassays and of metal tolerance assessment and it can be considered the first example of an alleviating effect of increasing plant number on copper stress in a metallophyte.

Tracing the 87Sr/86Sr from rocks and soils to vine and wine: An experimental study on geologic and pedologic characterisation of vineyards using radiogenic isotope of heavy elements.

In this paper we report an experimental study to assess the process of Sr-isotope uptake from the soil and its transfer to the grapevine and then to the wine made through micro-vinification. The experimental work has been carried out with a deep control of the boundary conditions (i.e., type of soil, geologic substratum, ground water supply, etc.) on 11 selected vine-plant sites over a period of four harvest years. Sr-isotopes have been determined on grape-bunches, grapevine sap, on the bioavailable fraction of the soil, on bulk soil, and on the rocks of the substratum. No significant Sr-isotope variability has been observed among micro-vinifications from different harvest years. A slight but significant Sr-isotope variability occurred among wines from rows embedded on different soil type. The Sr-isotope data on micro-vinifications well match those of grapevine sap and bioavailable fraction of soils, all of them falling well within the whole geological range of the bedrock, despite an evident decoupling between bioavailable fraction, whole soils and bedrocks does exist. This decoupling has been ascribed to differential geochemical behaviour of minerals in response to pedogenetic processes. The findings of our experiments indicate that the biological activity of the vine is not able to change the original 87Sr/86Sr composition up-taken from the bio-available fraction of the soil. Thus, the 87Sr/86Sr of the wine is an unadulterated feature of the terroir.

From vine to wine: Data on 87Sr/86Sr from rocks and soils as a geologic and pedologic characterisation of vineyards.

This data article describes the soils characterisation, bedrock geochemical composition and descriptive statistics of 87Sr/86Sr in wines, grape saps, labile fractions of soils (bio-available), whole soils, and bedrocks used to explore the Sr isotope conservation from rocks and soils to vine and wine. These data also describe the reproducibility of the isotopic composition of wine over four harvest years (2008-2011) on 11 selected experimental parcels (sampling point). The data reported in this paper are related to the research article (Braschi et al., 2018) [1].

Under fungal attack on a metalliferous soil: ROS or not ROS? Insights from Silene paradoxa L. growing under copper stress.

We investigated how the adaptation to metalliferous environments can influence the plant response to biotic stress. In a metallicolous and a non-metallicolous population of Silene paradoxa the induction of oxidative stress and the production of callose and volatiles were evaluated in the presence of copper and of the PAMP fungal protein cerato-platanin, separately and in combination. Our results showed incompatibility between the ordinary ROS-mediated response to fungal attack and the acquired mechanisms of preventing oxidative stress in the tolerant population. A similar situation was also demonstrated by the sensitive population growing in the presence of copper but, in this case, with a lack of certain responses, such as callose production. In addition, in terms of the joint behaviour of emitted volatiles, multivariate statistics showed that not only did the populations respond differently to the presence of copper or biotic stress, but also that the biotic and abiotic stresses interacted in different ways in the two populations. Our results demonstrated that the same incompatibility of hyperaccumulators in ROS-mediated biotic stress signals also seemed to be exhibited by the excluder metallophyte, but without the advantage of being able to rely on the elemental defence for plant protection from natural enemies.

Conservation of (87)Sr/(86)Sr isotopic ratios during the winemaking processes of 'Red' wines to validate their use as geographic tracer.

(87)Sr/(86)Sr has been determined in wines, musts grape juices, soils and rocks from six selected vineyards of 'Cesanese' wine area. Cesanese is a monocultivar wine from a small region characterised by different geologic substrata, a key locality to test the influence of both substratum and winemaking procedure on the (87)Sr/(86)Sr of wines. Experimental work has been performed on wines from different vintage years to check possible seasonal variations. The data reveal that (87)Sr/(86)Sr does not change through time, to validate the selection of wineries performed, and in addition no isotopic variations are observed during winemaking. Indeed, no significant isotopic variations have been observed in musts and wines. These findings reinforce the hypothesis that the isotopic signature of wines is strongly related to the bioavailable fraction of the soil rather than to its bulk. The data corroborate the possibility that Sr-isotopes of high-quality wines can be used as a reliable tool for fingerprinting wine geographic provenance.