Historical Silk: A Novel Method to Evaluate Degumming with Non-Invasive Infrared Spectroscopy and Spectral Deconvolution.

To correctly manage a collection of historical silks, it is important to detect if the yarn has been originally subjected to degumming. This process is generally applied to eliminate sericin; the obtained fiber is named soft silk, in contrast with hard silk which is unprocessed. The distinction between hard and soft silk gives both historical information and useful indications for informed conservation. With this aim, 32 samples of silk textiles from traditional Japanese samurai armors (15th-20th century) were characterized in a non-invasive way. ATR-FTIR spectroscopy has been previously used to detect hard silk, but data interpretation is challenging. To overcome this difficulty, an innovative analytical protocol based on external reflection FTIR (ER-FTIR) spectroscopy was employed, coupled with spectral deconvolution and multivariate data analysis. The ER-FTIR technique is rapid, portable, and widely employed in the cultural heritage field, but rarely applied to the study of textiles. The ER-FTIR band assignment for silk was discussed for the first time. Then, the evaluation of the OH stretching signals allowed for a reliable distinction between hard and soft silk. Such an innovative point of view, which exploits a "weakness" of FTIR spectroscopy-the strong absorption from water molecules-to indirectly obtain the results, can have industrial applications too.

Trajectories of Seroprevalence and Neutralizing Activity of Antibodies against SARS-CoV-2 in Southern Switzerland between July 2020 and July 2021: An Ongoing, Prospective Population-Based Cohort Study.

OBJECTIVES: The COVID-19 pandemic continues, and evidence on infection- and vaccine-induced immunity is key. We assessed COVID-19 immunity and the neutralizing antibody response to virus variants across age groups in the Swiss population. STUDY DESIGN: We conducted a cohort study in representative community-dwelling residents aged five years or older in southern Switzerland (total population 353,343), and we collected blood samples in July 2020 (in adults only, N = 646), November-December 2020 (N = 1457), and June-July 2021 (N = 885). METHODS: We used a previously validated Luminex assay to measure antibodies targeting the spike (S) and the nucleocapsid (N) proteins of the virus and a high-throughput cell-free neutralization assay optimized for multiple spike protein variants. We calculated seroprevalence with a Bayesian logistic regression model accounting for the population's sociodemographic structure and the test performance, and we compared the neutralizing activity between vaccinated and convalescent participants across virus variants. RESULTS: The overall seroprevalence was 7.8% (95% CI: 5.4-10.4) by July 2020 and 20.2% (16.4-24.4) by December 2020. By July 2021, the overall seroprevalence increased substantially to 72.5% (69.1-76.4), with the highest estimates of 95.6% (92.8-97.8) among older adults, who developed up to 10.3 more antibodies via vaccination than after infection compared to 3.7 times more in adults. The neutralizing activity was significantly higher for vaccine-induced than infection-induced antibodies for all virus variants (all p values < 0.037). CONCLUSIONS: Vaccination chiefly contributed to the reduction in immunonaive individuals, particularly those in older age groups. Our findings on the greater neutralizing activity of vaccine-induced antibodies than infection-induced antibodies are greatly informative for future vaccination campaigns.

On the Determination of Cr(VI) in Cr(III)-Rich Particulates: From the Failure of Official Methods to the Development of an Alternative Protocol.

The goals of this work are the evaluation of the performances of official methods in the challenging determination of Cr(VI) in Cr(III)-rich particulate matter, and the development of a novel and robust analytical protocol for this issue. A liquid chromatography inductively coupled plasma mass spectrometry apparatus (LC-ICP-MS), together with an isotope-enriched spike addition technique, was used to allow the study of Cr(III)/Cr(VI) interconversions during the extraction step. An original separation strategy based on Cr(OH)3 head-column stacking was developed to tolerate high concentrations of Cr(III) (up to 10 mg/kg, with a Cr(VI) limit of detection of 0.51 µg/kg) without the need of any sample pretreatment. After observing, the official extraction protocols always yield false positive values in the challenging situation of particulate matter of leather industries (where huge amounts of Cr(III) are present), a new extraction strategy was developed. The novel procedure involves a 48-h extraction at room temperature using a pH-8 phosphate buffer, which demonstrated that no Cr(III)/Cr(VI) interconversions occur during this phase. To get rid of any possible interference caused by co-extracted substances, the measurement of the redox potential, together with the addition of a Fe(II)/Fe(III) redox buffer was performed to fix chromium speciation during the overall analytical protocol.

Biodeterioration of carbographic ribbon: Isolation, identification of causal agents and forensic implications.

This study is part of a comprehensive investigation that was performed in regard to a case of alterations on a carbographic ribbon used in a typewriter that was found and seized by inner security operations of the Arma dei Carabinieri, Italy. Thirty-six coded scripts possessing potentially and criminally liable content were present on the tape; however, only the 6th and 7th scripts exhibited alterations of an uncertain nature. The study included sampling that was performed under sterile conditions of a large surface area of carbographic ribbons. A protocol based on physico-chemical, microbiological, and biomolecular tools was established. Preliminary results revealed the presence of fungal contamination that was primarily located on the inner surface of the 6th and 7th scripts on the black carbographic ribbon. One fungal strain was isolated and identified by universal ITS-PCR primer and rDNA sequencing as Alternaria infectoria strain NIS4. Fungal growth was monitored for 3 weeks in the laboratory under different environmental conditions (temperature, open-closed system, and substrate). The A. infectoria NIS4 strain exhibited the best growth at 28°C under a closed system with RH near saturation. We also noted that the fungal growth was abundant at 15°C. Moreover, this fungus (a potential human pathogen) possessed the ability to colonize the surface of the new carbographic ribbon even when using mineral medium; however, this only occurred in a closed system environment and not in open systems due to rapid desiccation. Under our experimental conditions, the A. infectoria NIS4 strain could degrade gelatin as an organic matter present in trace amounts that are often used as a binder in a carbographic ribbon emulsions. The results revealed that the isolated microorganism was the major biological candidate capable of altering the investigated carbographic ribbon; however, these alterations could only occur under favourable environmental conditions. AIMS: Identify the cause of microbial alterations on a carbographic ribbon in a typewriter used in a hypogean Italian criminal house named "covo." METHODS AND RESULTS: The isolation and identification of biodeteriogens (Alternaria infectoria NIS4) were performed using both culture-dependent and-independent methods, including ITS regions-primed PCR and rDNA techniques. Environmental scanning electron microscopy (ESEM) and optical observations were also performed. Growth tests and biodeterioration simulation tests on carbographic ribbons at the lab scale were performed under different environmental conditions. The A. infectoria NIS4 strain exhibited biodeterioration activity on carbographic ribbons under environmental conditions that were extremely favourable for growth. A high ability to colonize carbographic ribbon surfaces with fast and abundant growth at both 15°C and 28°C under lab-scale conditions at RH near saturation was observed. CONCLUSIONS: In this forensic case study, the ability of the isolated micromycetes A. infectoria NIS4 strain to colonize and induce alterations and degradation in a carbographic ribbon stored under indoor environmental conditions was examined. When favourable conditions change over time, the risk of microbial colonization and the damage produced by the fungal biodeterioration processes on the synthetic material objects has been confirmed. SIGNIFICANCE AND IMPACT OF STUDY: The current study contributes to the knowledge of biodeterioration processes in carbographic ribbon and the responsible agents, and our study provides an example of how environmental microbiology can also aid in forensic studies.

Understanding the Microstructure of Mortars for Cultural Heritage Using X-ray CT and MIP.

In this study, the microstructure of mock-up mortar specimens for a historic environment, composed of different mixtures, was studied using mercury intrusion porosity (MIP) and microcomputed tomography (µCT), highlighting the advantages and drawbacks of both techniques. Porosity, sphericity, and pores size distribution were studied, evaluating changes according to mortar composition (aerial and hydraulic binders, quartz sand, and crushed limestone aggregate). The µCT results were rendered using 3D visualization software, which provides complementary information for the interpretation of the data obtained using 3D data-analysis software. Moreover, µCT contributes to the interpretation of MIP results of mortars. On the other hand, MIP showed significant ink-bottle effects in lime and cement mortars samples that should be taken into account when interpreting the results. Moreover, the MIP results highlighted how gypsum mortar samples display a porosity distribution that is best studied using this technique. This multi-analytical approach provides important insights into the interpretation of the porosimetric data obtained. This is crucial in the characterization of mortars and provides key information for the study of building materials and cultural heritage conservation.

Optimization of Copper Stain Removal from Marble through the Formation of Cu(II) Complexes in Agar Gels.

Copper complexes with different ligands (ethylenediaminetetraacetic acid, EDTA, ammonium citrate tribasic, TAC, and alanine, ALA) were studied in aqueous solutions and hydrogels with the aim of setting the optimal conditions for copper stain removal from marble by agar gels, with damage minimization. The stoichiometry and stability of copper complexes were monitored by ultraviolet-visible (UV-Vis) spectroscopy and the symmetry of Cu(II) centers in the different gel formulations was studied by electron paramagnetic resonance (EPR) spectroscopy. Cleaning effectiveness in optimized conditions was verified on marble laboratory specimens through color variations and by determining copper on gels by inductively coupled plasma-mass spectrometry (ICP-MS). Two copper complexes with TAC were identified, one having the known stoichiometry 1:1, and the other 1:2, Cu(TAC)2, never observed before. The stability of all the complexes at different pH was observed to increase with pH. At pH 10.0, the gel's effectiveness in removing copper salts from marble was the highest in the presence of ALA, followed by EDTA, TAC, and pure agar gel. Limited damage to the marble surface was observed when gels with added EDTA and TAC were employed, whereas agar gel with ALA was determined to be the most efficient and safe cleaning material.

Dry biocleaning of artwork: an innovative methodology for Cultural Heritage recovery?

An innovative methodology is proposed, based on applied biotechnology to the recovery of altered stonework: the "dry biocleaning", which envisages the use of dehydrated microbial cells without the use of free water or gel-based matrices. This methodology can be particularly useful for the recovery of highly-ornamented stoneworks, which cannot be treated using the conventional cleaning techniques. The experimental plan included initial laboratory tests on Carrara marble samples, inoculated with dehydrated Saccharomyces cerevisiae yeast cells, followed by on-site tests performed on "Quattro Fontane" (The Four Fountains), a travertine monumental complex in Rome (Italy), on altered highly ornamented areas of about 1,000 cm2. The mechanism is based on the spontaneous re-hydration process due to the environmental humidity and on the metabolic fermentative activity of the yeast cells. Evaluation by physical-chemical analyses, after 18 hours of the biocleaning, confirmed a better removal of salts and pollutants, compared to both nebulization treatment and control tests (without cells). The new proposed on-site dry biocleaning technique, adopting viable yeast cells, represents a promising method that can be further investigated and optimized for recovering specific altered Cultural Heritage stoneworks.

Application of Different Fourier Transform Infrared (FT-IR) Methods in the Characterization of Lime-Based Mortars with Oxblood.

Organic compounds have frequently been added into lime mortars for property modifications, in order to satisfy various functional needs in building techniques. This study applies Fourier transform infrared (FT-IR) spectroscopy in transmission, reflection, and attenuated total reflection (ATR) modes to characterize lime-based mortar specimens containing oxblood, which has been used as additive as a common practice of long history in many parts of the world. The specimens were prepared basing upon a 19th-century Italian historic recipe, with the intention to have a better understanding on the possible characteristics of such mortars. Thermal analysis, color measurement, and static contact angle test were also used. After curing, the specimens show a distinctive dark-red color on the top surface, which is different from the bulk. Color measurements on the surface suggest that this color was formed at an early stage and was able to maintain stable for a relatively long period of time. Both transmission and reflection FT-IR confirm the preferential accumulation of proteins on the top surface, which should have induced their water repellency according to the static contact angle test. In addition, specimens show weaker calcite bands in FT-IR transmission, reflection, as well as ATR spectra; the pattern of ATR spectra after the thermal analysis to 500 °C suggests the formation of amorphous calcium carbonate, which is related to the presence of oxblood.

Non-invasive techniques for revealing the palette of the Romantic painter Francesco Hayez.

This paper describes the first systematic analysis of the palette of Francesco Hayez, one of the most outstanding artists of European Romanticism, whose painting technique has never been extensively investigated despite the plethora of artistic studies. He lived in a particular moment in the history of painting, as in the first half of the 19th century many synthetic pigments were available, also in tin tubes, but traditional materials were still used. Sixteen paintings on canvas and on panels, created between 1823 and 1868, were analyzed in situ through non-invasive techniques (infrared reflectography and infrared reflection spectroscopy). Imaging investigation provided clues on painting technique, revealing some cases of pentimenti and underdrawings. A preliminary survey was carried out on a hundred pure pigments used up to the 19th century and on new synthetic colours, in order to attain reference spectra for the interpretation of painting spectra. The portable infrared instrument provided insight into Hayez's painting materials, identifying barite, ivory black, lead-tin yellow, Naples yellow, ochres, Prussian blue, and white lead. The pigments were often blended, to obtain a unique fabric appearance or to attain cold shades. The results pointed to a siccative oil as a binder, mixed with white lead so that it could act as a catalyzer in polymerization reactions, and in some cases with a proteinaceous binder and resins. The preparation was made with gypsum and white lead mixed with a siccative oil. The results showed that the artist used a typical traditional palette, throughout his career, in order to lead to brilliant colours and with long-term stability. Anyway, the possible presence of cobalt blue in a few paintings suggests that Hayez had probably started testing the new colours, since the second decade of 19th century.

Monuments as sampling surfaces of recent traffic pollution.

BACKGROUND, AIM AND SCOPE: A new approach towards monuments, considering them as a passive sampler of pollution, is presented. Cultural Heritage objects suffer daily the damages of environmental pollution, especially in those areas interested by heavy traffic. Since monuments undergo only periodic conservation or maintenance works, surfaces are able to accumulate atmospheric deposit and to record changes in its composition. An optimised analytical protocol was developed in order to quantify platinum and rhodium at trace level on surfaces. The two elements have become tracers of automobile emissions in recent years, since the introduction of catalytic converters, and could have catalytic effects on the decay reactions of natural and artificial stone materials. As a first case study, the cement mortar surfaces of a twentieth century monument, the Camerlata Fountain, in Como (Italy) were investigated. MATERIALS AND METHODS: The surfaces of the monument were scraped in areas both exposed to atmosphere and sheltered by the architectural elements of the building. The powders were dissolved by microwave-assisted mineralisation with a solution of HCl and HNO(3). The solution was filtered, irradiated and analysed by adsorptive cathodic stripping voltammetry. The powders were also analysed by infrared spectroscopy and X-ray diffraction in order to determine the chemical and mineralogical composition. RESULTS AND DISCUSSION: An analysis protocol was set up considering the matrix effect and the expected low concentrations of the two metals. The results enlightened variable concentration values and distribution areas of platinum (0.013-45 µg/kg) and rhodium (0.55-274.4 µg/kg), suggesting the ability of artificial stone surfaces to accumulate the two elements. The sample chemical and mineralogical composition was consistent with a typical cement plaster interested by decay phenomena. CONCLUSIONS: This work investigated the relation between Cultural Heritage and pollution by another point of view. The analytical protocol presented in this paper was effective in determining platinum and rhodium in traces on the investigated stone surfaces with negligible matrix effects. RECOMMENDATION AND PERSPECTIVES: The presence of platinum and rhodium on monument surfaces should be of significant interest when planning Cultural Heritage conservation. A better knowledge of the role of the two metals in decay phenomena could impact in a positive way artwork conservation.