A time-course investigation of the human urinary excretion of the hydrogen sulfide biomarker trimethylsulfonium.

Hydrogen sulfide is a toxic gas but also recognized as an endogenously produced metabolite in humans playing key roles. We previously identified trimethylsulfonium, which can be a methylation product of hydrogen sulfide but the stability in the production of trimethylsulfonium has not been investigated. In the present work, the intra- and inter-individual variability in the excretion of trimethylsulfonium over 2 months in a group of healthy volunteers was investigated. Urinary levels of trimethylsulfonium (mean: 56 nM, 95% CI: 48-68 nM) were > 100-fold lower than the conventional hydrogen sulfide biomarker thiosulfate (13 µM, 12-15 µM) and the precursor for endogenous hydrogen sulfide production cystine (47 µM, 44-50 µM). There was no correlation between urinary trimethylsulfonium and thiosulfate. Higher intra-individual variability in the excretion of trimethylsulfonium (generally 2-8 fold) than that for cystine (generally 2-3 fold) was found. Trimethylsulfonium displayed significant inter-individual variability with two concentration clusters at 117 nM (97-141) and 27 nM (22-34). In conclusion, the observed inter- and intra-individual variability must be considered when using urinary trimethylsulfonium as a biomarker.

Comparative metagenomics at Solfatara and Pisciarelli hydrothermal systems in Italy reveal that ecological differences across substrates are not ubiquitous.

Introduction: Continental hydrothermal systems (CHSs) are geochemically complex, and they support microbial communities that vary across substrates. However, our understanding of these variations across the complete range of substrates in CHS is limited because many previous studies have focused predominantly on aqueous settings. Methods: Here we used metagenomes in the context of their environmental geochemistry to investigate the ecology of different substrates (i.e., water, mud and fumarolic deposits) from Solfatara and Pisciarelli. Results and Discussion: Results indicate that both locations are lithologically similar with distinct fluid geochemistry. In particular, all substrates from Solfatara have similar chemistry whereas Pisciarelli substrates have varying chemistry; with water and mud from bubbling pools exhibiting high SO4 2- and NH4 + concentrations. Species alpha diversity was found to be different between locations but not across substrates, and pH was shown to be the most important driver of both diversity and microbial community composition. Based on cluster analysis, microbial community structure differed significantly between Pisciarelli substrates but not between Solfatara substrates. Pisciarelli mud pools, were dominated by (hyper)thermophilic archaea, and on average, bacteria dominated Pisciarelli fumarolic deposits and all investigated Solfatara environments. Carbon fixation and sulfur oxidation were the most important metabolic pathways fueled by volcanic outgassing at both locations. Together, results demonstrate that ecological differences across substrates are not a widespread phenomenon but specific to the system. Therefore, this study demonstrates the importance of analyzing different substrates of a CHS to understand the full range of microbial ecology to avoid biased ecological assessments.

Trace determination of the hydrogen sulfide biomarker thiosulfate in human urine by HPLC coupled with element selective ICPMS/MS detection.

Hydrogen sulfide is a toxic gas but also established as a naturally occurring gaseous signaling molecule in humans, playing key physiological roles with particular involvement in lung disease including COVID-19. Thiosulfate is the conventional biomarker of hydrogen sulfide and is excreted in human urine at low micromolar levels. Thiosulfate is amenable to detection by the element-selective inductively coupled plasma tandem mass spectrometry (ICPMS/MS), but sulfur speciation in human samples at trace levels is challenging due to the high complexity of human sulfur metabolome and the utility of this detector under such settings has not been demonstrated. We report a method for thiosulfate determination in human urine at trace physiological levels by HPLC-ICPMS/MS. The method involved one-step derivatization to improve chromatographic behavior followed by direct injection. The instrumental limit of detection was 1.4 µg S L-1 (0.02 µM or 0.1 pmol). In a group of samples from volunteers (n = 24), measured thiosulfate concentrations in the diluted urine matrix were down to 8.0 µg S L-1 with a signal-to-noise ratio >10. The method was validated for recovery (80-110%), repeatability (RSD% <5%), and linearity (r2 = 0.9999, at a tested working concentration range of 0.01-1.0 mg S L-1), and the accuracy was assessed by comparing with HPLC-ESIMS/MS which showed agreement within ±20%. This work demonstrates the applicability of HPLC-ICPMS/MS for sulfur speciation at trace levels in a matrix with complex sulfur metabolome as human urine and provides a sensitive method for the determination of the hydrogen sulfide biomarker.

Arsenic contamination at the Bagnoli Bay seabed (South Italy) via particle tracking numerical modeling: Pollution patterns from stationary climatic forcings.

Almost 140 years of industrial exploitation have severely degraded the environment of Bagnoli Coroglio (BC), the westernmost neighborhood of the city of Naples (Italy). In this peculiar area, however, geogenic processes overlap with the impact of human activities, making it difficult to distinguish between anthropogenic and geogenic pollution sources. This is particularly true for Arsenic, the concentration of which in the marine sediments largely exceeds the tolerable level for human health and the background value for local pyroclastics. After several studies have used traditional tools based on multivariate statistics, this article attempts at tackling the problem via numerical modeling, which provides a deeper insight into the physics that governs the pollution process. Therefore, we use a particle tracking model to assess whether arsenic levels in the seabed can be affected by the influx of thermal water from an artificial channel outfalling at the westernmost part of the coast The climatic forcings that drive the marine circulation are simplified to basic "scenarios", in which wind and waves are stationary in strength and direction. Since the simulation time is much less than the contamination timescale, the comparison between numerical results and measurements is essentially qualitative and concerns the shape of contamination contours. It was found the primary forcing that enables seabed pollution is the tidal circulation, which, moreover, acts continuously in time. Quantitative arguments based on regression analysis suggest the discharge of thermal water explains almost a quarter of the observed pollution, which is consistent with previous research based on multivariate statistics.

The first application of compositional data analysis (CoDA) in a multivariate perspective for detection of pollution source in sea sediments: The Pozzuoli Bay (Italy) case study.

In the last decades, investigating geochemistry of sea sediments has been challenging in the eastern sector of Pozzuoli Bay, source of the metal(loid)s has been a matter of debate and the proposed origin of potentially toxic elements (PTEs) has been occasionally inconsistent. In this study, compositional data analysis (CoDA) was used because the results are independent of the measurement unit, the selected subgroup of elements and the order of chemicals in the dataset. The robust variant of principal component analysis (PCA) indicated that Hg, Cd, Cu, Pb and Zn were positively correlated with mud and organic matter in the sediments deposited in front of the former industrial site. Concentrations of these metals decrease along the cores and in the distal zone. Nevertheless, Al, As, V, Fe, Cr, Ni and sand form an association along the coast which strengthens with increasing distance from fumaroles in the proximal zone. It suggests that arsenic was mainly originated from the pyroclastic deposits of Campi Flegrei and some of the seepages with hydrothermal component, supported by low contribution of the variables in robust PCA of the sediments from distal zone. Therefore, this pioneering article suggests CoDA as a powerful tool for answering the long-lasting questions over sediment geochemistry in polluted areas.

A numerical study of arsenic contamination at the Bagnoli bay seabed by a semi-anthropogenic source. Analysis of current regime.

Bagnoli Coroglio is an urban district of the City of Naples (South Italy), which fronts the Tyrrhenian Sea for nearly 3 km. It is part of the Campi Flegrei caldera, one of the most explosive volcanic areas in Europe. The need for redeveloping the site after the intense industrial activities of the twentieth century has prompted a remarkable research effort to investigate the pollution's degree, nature, and extent at both the land and seafloor. This article focuses on releasing thermal waters from a natural channel as a source of arsenic contamination in the Bagnoli marine sediments; the thermal waters originate from the nearby Agnano hot-springs and have been conveying artificially to the track since the mid-XIX century. As a first part of the outcomes, the work describes the flow regime that characterizes the marine area. The analysis has been conducted via numerical simulations carried out with the software package Delft3D, developed by Deltares, which employs dynamically interfacing modules to account for wave propagation, generation of currents, and presence of coastal structures. Climatic inputs to the software (waves, winds, and tide) have specifically been gathered and analyzed within this research. The numerical study has permitted to furnish, for the first time, a clear and systematic view of the hydrodynamic forcings that characterize the area under investigation. In particular, a leading role in the transport of pollutants could be played by rip current systems, whose characteristics vary with climate intensity (waves and wind) and coastal structures characteristics. Due to its inherently dynamic nature, the proposed approach seems especially desirable in situations where different contamination sources are compared. As such, it could be successfully applied to other sites also.

The Evolution of Covid-19 in Italy after the Spring of 2020: An Unpredicted Summer Respite Followed by a Second Wave.

The coronavirus (COVID-19) pandemic was particularly invasive in Italy during the period between March and late April 2020, then decreased in both the number of infections and in the seriousness of the illness throughout the summer of 2020. In this work, we measure the severity of the disease by the ratio of Intensive Care Units (ICU) spaces occupied by COVID-19 patients and the number of Active Cases (AC) each month from April to October 2020. We also use the ratio of the number of Deaths (D) to the number of Active Cases. What clearly emerges, from rigorous statistical analysis, is a progressive decrease in both ratios until August, indicating progressive mitigation of the disease. This is particularly evident when comparing March-April with July-August; during the summer period the two ratios became roughly 18 times lower. We test such sharp decreases against possible bias in counting active cases and we confirm their statistical significance. We then interpret such evidence in terms of the well-known seasonality of the human immune system and the virus-inactivating effect of stronger UV rays in the summer. Both ratios, however, increased again in October, as ICU/AC began to increase in September 2020. These ratios and the exponential growth of infections in October indicate that the virus-if not contained by strict measures-will lead to unsustainable challenges for the Italian health system in the winter of 2020-2021.

The COVID-19 Infection in Italy: A Statistical Study of an Abnormally Severe Disease.

We statistically investigate the Coronavirus Disease 19 (COVID-19) pandemic, which became particularly invasive in Italy in March 2020. We show that the high apparent lethality or case fatality ratio (CFR) observed in Italy, as compared with other countries, is likely biased by a strong underestimation of the number of infection cases. To give a more realistic estimate of the lethality of COVID-19, we use the actual (March 2020) estimates of the infection fatality ratio (IFR) of the pandemic based on the minimum observed CFR and analyze data obtained from the Diamond Princess cruise ship, a good representation of a "laboratory" case-study from an isolated system in which all the people have been tested. From such analyses, we derive more realistic estimates of the real extent of the infection as well as more accurate indicators of how fast the infection propagates. We then isolate the dominant factors causing the abnormal severity of the disease in Italy. Finally, we use the death count-the only data estimated to be reliable enough-to predict the total number of people infected and the interval of time when the infection in Italy could end.

Long-Term Monitoring with Fiber Optics Distributed Temperature Sensing at Campi Flegrei: The Campi Flegrei Deep Drilling Project.

Monitoring volcanic phenomena is a key question, for both volcanological research and for civil protection purposes. This is particularly true in densely populated volcanic areas, like the Campi Flegrei caldera, which includes part of the large city of Naples (Italy). Borehole monitoring of volcanoes is the most promising way to improve classical methods of surface monitoring, although not commonly applied yet. Fiber optics technology is the most practical and suitable way to operate in such high temperature and aggressive environmental conditions. In this paper, we describe a fiber optics Distributed Temperature Sensing (DTS) sensor, which has been designed to continuously measure temperature all along a 500 m. deep well drilled in the west side of Naples (Bagnoli area), lying in the Campi Flegrei volcanic area. It has then been installed as part of the international 'Campi Flegrei Deep Drilling Project', and is continuously operating, giving insight on the time variation of temperature along the whole borehole depth. Such continuous monitoring of temperature can in turn indicate volcanic processes linked to magma dynamics and/or to changes in the hydrothermal system. The developed monitoring system, working at bottom temperatures higher than 100 °C, demonstrates the feasibility and effectiveness of using DTS for borehole volcanic monitoring.

Modelling of hydrogen sulfide dispersion from the geothermal power plants of Tuscany (Italy).

We applied the Eulerian code DISGAS (DISpersion of GAS) to investigate the dispersion of the hydrogen sulfide (H2S) from 32 geothermal power plants (out of 35 active) belonging to the geothermal districts of Larderello, Travale-Radicondoli and Monte Amiata, in Tuscany (Italy). An updated geographic database, for use in a GIS environment, was realized in order to process input data required by the code and to handle the outputs. The results suggest that H2S plumes emitted from geothermal power plants are mainly concentrated around the stacks of emission (H2S concentration up to 1100µg/m3) and rapidly dilute along the dominant local wind direction. Although estimated values of air H2S concentrations are orders of magnitude higher than in unpolluted areas, they do not indicate an immediate health risk for nearby communities, under the more frequent local atmospheric conditions. Starting from the estimated values, validated by measurements in the field, we make some considerations about the environmental impact of the H2S emission in all the geothermal areas of the Tuscany region.

Continuous in situ measurements of volcanic gases with a diode-laser-based spectrometer: CO2 and H2O concentration and soil degassing at Vulcano (Aeolian islands: Italy).

We report on a continuous-measurement campaign carried out in Vulcano (Aeolian islands, Sicily), devoted to the simultaneous monitoring of CO2 and H2O concentrations. The measurements were performed with an absorption spectrometer based on a semiconductor laser source emitting around a 2-microm wavelength. The emitted radiation was selectively absorbed by two molecular ro-vibrational transitions specific of the investigated species. Data for CO2 and H2O concentrations, and CO2 soil diffusive flux using an accumulation chamber configuration, were collected at several interesting sampling points on the island (Porto Levante beach- PLB, Fossa Grande Crater - FOG- and Valley of Palizzi, PAL). CO2/H2O values, measured on the ground, are very similar (around 0.019 (+/- 0.006)) and comparable to the previous discrete detected values of 0.213 (Fumarole F5-La Fossa crater rim) and 0.012 (Fumarole VFS - Baia Levante beach) obtaid during the 1977-1993 heating phase of the crater fumaroles. In this work much more homogeneous values are found in different points of the three sites investigated. The field work, although carried out in a limited time window (25th-28th August 2004), pointed out the new apparatus is suitable for continuous gas monitoring of the two species and their ratios, which are important geochemical indicators of volcanic activity, for which other reliable continuous monitoring systems are not yet available.