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Urban biocides used in facade paints and renders to prevent algae and fungal growth are released into the environment during rainfall, subsequently contaminating groundwater. However, quantitative data on the emission, transport and infiltration of urban biocides at the district scale are generally lacking. In this study, we quantified the fluxes of the urban biocide terbutryn and its major transformation product, terbutryn-sulfoxide, from building facades into stormwater, sediment, soil, and vegetation within a seven-year-old district employing sustainable stormwater management such as infiltration trenches and ponds. Combining four months of field observations with district scale modeling, we estimated initial concentrations of terbutryn in facade paint, quantified the emissions of terbutryn and terbutryn-sulfoxide from facades to soil, and evaluated terbutryn storage in soil under various painting scenarios. Terbutryn concentrations in sustainable stormwater management systems ranging from 2 to 67 ng L -1 , frequently exceeding predicted no-effect concentrations. The constant release of terbutryn and its transformation products in runoff highlighted the chronic exposure of non-target organisms to urban biocides. Terbutryn concentrations in topsoil and pond sediment indicated accumulation, while concentrations exceeding 1 μg g -1 in the vegetation suggested plant uptake. Model results revealed that a substantial portion (27 to 73 %) of biocides infiltrated near facades through permeable surfaces like gravel, while a smaller portion (7 to 39 %) reached the stormwater management systems. Additionally, significant biocide leaching in the topsoil (30 cm below the surface) underscored the potential for biocide contamination in groundwater. Overall, this district-scale study and modeling approach provide a comprehensive framework for evaluating scenarios and measures for sustainable stormwater management to mitigate the infiltration of urban biocides into groundwater., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

Environmental DNA (eDNA) analyses of species present in marine environments is the most effective biological diversity measurement tool currently available. eDNA sampling methods are an intrinsically important part of the eDNA biodiversity analysis process. Identification and development of eDNA sampling methods that are as rapid, affordable, versatile and practical as possible will improve rates of detection of marine species. Optimal outcomes of eDNA biodiversity surveys come from studies employing high levels of sampling replication, so any methods that make sampling faster and cheaper will improve scientific outcomes. eDNA sampling methods that can be applied more widely will also enable sampling from a greater range of marine surface micro-habitats, resulting in detection of a wider range of organisms. In this study, we compared diversity detection by several methods for sampling eDNA from submerged marine surfaces: polyurethane foam, nylon swabs, microfibre paint rollers, and sediment scoops. All of the methods produced a diverse range of species identifications, with >250 multicellular species represented by eDNA at the study site. We found that widely-available small paint rollers were an effective, readily available and affordable method for sampling eDNA from underwater marine surfaces. This approach enables the sampling of marine eDNA using extended poles, or potentially by remotely operated vehicles, where surface sampling by hand is impractical., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Michael Marnane reports a relationship with Chevron Energy Technology Co that includes: employment. Euan S Harvey reports a relationship with Chevron Energy Technology Co that includes: funding grants. Jason B Alexander reports financial support, article publishing charges, equipment, drugs, or supplies, and writing assistance were provided by Chevron Energy Technology Co. Travis Elsdon reports a relationship with Chevron Energy Technology Co that includes: employment. Sherralee S Lukehurst reports a relationship with BHP Group Ltd. that includes: funding grants. Simon Jarman reports a relationship with Chevron Energy Technology Co that includes: funding grants., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

Marinas are central hubs of global maritime leisure and transport, yet their operations can deteriorate the environmental quality of sediments. In response, this study investigated the metal contamination history associated with antifouling paint uses in a sediment core collected from Bracuhy marina (Southeast Brazil). Analysis target major and trace elements (Cu, Zn, Pb, Cd and Sn), rare earth elements (REEs), and Pb isotopes. The modification in Pb isotopic ratios and REEs pattern unequivocally revealed sediment provenance disruption following the marina construction. Metal distribution in the sediment core demonstrates that concentrations of Cu and Zn increased by up to 15 and 5 times, respectively, compared to the local background. This severe Cu and Zn contamination coincides with the onset of marina operations and can be attributed to the use of antifouling paints., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier Ltd.)

Paint used to coat surfaces in aquatic environments often contain biocides to prevent biofouling, and as these coatings degrade, antifouling paint particles (APPs) end up in aquatic, and especially marine, sediments. However, it is currently unclear what further influence APPs in the sediment have on biotic communities or processes. This study investigates how a variety of commercially-available APPs effect the marine microbial community by spiking different laboratory-manufactured APPs to sediment. Following exposure for 30 and 60 days, APPs caused a clear and consistent effect on the bacterial community composition as determined by 16S metabarcoding. This effect was strongest between 0 and 30 days, but continues to a lesser extent between 30 and 60 days. APPs appear to inhibit the highly diverse, but in general rarer, fraction of the community and/or select for specific community members to become more dominant. 71 antifouling-presence and 454 antifouling-absence indicator taxa were identified by indicator analysis. The difference in the level of classification in these two indicator groups was highly significant, with the antifouling-presence indicators having much higher percentage sequence identity to cultured taxa, while the antifouling-absence indicators appear to be made up of undescribed taxa, which may indicate that APPs act as a proxy for general anthropogenic influence or that APP contamination selects for taxa capable of being cultured. Given the clear and consistent effect APPs have on the surrounding sediment microbial community, further research into how APPs affect sediment functional processes and how such effects scale with concentration is recommended to better assess the wider consequences of these pollutants for marine biogeochemical cycles in the future. SYNOPSIS: Microplastic-paint particles are commonly found in marine sediment but little is known about how these, especially antifouling, paint particles affect sediment microbial communities. This study demonstrates that antifouling paint particles fundamentally alter sediment microbial communities., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

Housing-based lead paint dust is the most common source of lead exposure for US-born children. Although year of housing construction is a critical indicator of the lead hazard to US children, not all housing of the same age poses the same risk to children. Additional information about housing condition is required to differentiate the housing-based lead risk at the parcel level. This study aimed to identify and assess a method for gathering and using observations of exterior housing conditions to identify active housing-based lead hazards at the parcel level. We used a dataset of pediatric blood lead observations (sample years 2000-2013, ages 6-72 months, n = 6,589) to assess associations between observations of exterior housing conditions and housing-based lead risk. We used graphical and Lasso regression methods to estimate the likelihood of an elevated blood lead observation (≥3.5 μg/dL). Our methods estimate a monotonic increase in the likelihood of an elevated blood lead observation as housing conditions deteriorate with the largest changes associated with homes in the greatest disrepair. Additionally we estimate that age of home construction works in consort with housing conditions to amplify risks among those houses built before 1952. Our analysis indicates that a survey of external housing conditions can be used in combination with age of housing in the identification process, at the parcel level, of homes that pose a housing-based lead hazard to children., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022. Published by Elsevier Inc.)

Butanol is a common organic solvent used in latex paint, and one of its isomers, tert-butanol, is toxic and can cause potential harm to the human body. Therefore, it is of great significance to develop a qualitative and quantitative detection method for butanol isomers. In this study, we combined the advantages of rapid detection of proton transfer reaction mass spectrometry (PTR-MS) with the separation and qualitative capabilities of gas chromatography-mass spectrometry (GC-MS) to achieve the detection of isomers, building a fast gas chromatography proton transfer reaction mass spectrometry (FastGC-PTR-MS) equipment. Firstly, the developed technology was optimized using standard samples of several common volatile organic compounds. The retention times of acetonitrile, acetone, and alcohols were less than 50 s, and the retention times of the benzene series were less than 110 s, on the premise that these isomers could be basically separated (resolution R > 1.0). Compared with a commercial GC-MS equipment, the detection times were shortened by 5-6 times and 2-4 times, respectively. Then the FastGC-PTR-MS was applied to detect the isomers of butanol in latex paint. The results showed that the headspace of brand D latex paint mainly contained five substances: tert-butanol, n-butanol, acetaldehyde, methanol, and acetone. Tert-butanol and n-butanol could be completely separated (R > 1.5). The concentration of tert-butanol was 4.41 ppmv, far below the 100 ppmv maximum allowable workplace concentration. The developed FastGC-PTR-MS can be used for rapid qualitative and quantitative detection of butanol isomers in latex paint. The new equipment has the potential to play an important role in indoor environmental safety applications., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022. Published by Elsevier B.V.)

Proteomic approaches based on mass spectrometry have become increasingly popular for protein binder's identification in works of art. The identification of the binder employed may offer key information on paintings and other polychrome objects and contribute to assess their historical and technical context, also providing useful hints for a proper restoration and/or conservation treatment. Usually, the protocols employed to this purpose are invasive and at least micro sampling is required. Here, we present a simple transferable method for a quasi-non-invasive analysis of binders in artworks based on the use of a very small poly (2-hydroxyethyl methacrylate)/poly (vinylpyrrolidone) hydrogel (3 mm × 3 mm) previously loaded with trypsin for the in-situ digestion of proteins and applied onto the objects' surface. Upon extraction of digested peptides from the hydrogel, they were examined by MALDI-TOF-MS and/or LC-ESI-MS/MS. The method was validated on fresh and aged model pictorial layers; optical microscope images, and spectrophotocolorimetry confirmed that neither damage nor color alteration of the painting layer occurred, and no hydrogel residue was left. X-ray photoelectron spectroscopy carried out on paint models confirmed that the treatment with trypsin-loaded gels did not modify the pigment composition, even on aged samples. The protocol was successfully applied to a painting on wood mockup aged thirty years, a statue dated XV century exposed in San Lorenzo church (Bisceglie, Bari, Apulia), and a liturgical scroll Benedictio ignis et fontis (Benedizionale) of the Museo Diocesano of Bari dated eleventh century; in all these objects the proteinaceous binder was readily and successfully identified., Competing Interests: Declaration of competing interest The authors declare no conflict-of-interest., (Copyright © 2020 Elsevier B.V. All rights reserved.)

The painting "Donna Nuda" by Leonardo was acquired by Catherine II (the Great) from the R. Walpole collection, Houghton Hall, England, in 1779 for the Hermitage in St. Petersburg. By exploiting the EVA film technology (ethylene vinyl acetate polymer embedded with strong cation and anion exchangers and with C 8 and/or C 18 resins) we have explored the surface of the painting in order to ascertain the techniques used in its drawing. Five EVA films were affixed on the body and on the landscape for 60 min. Upon elution from the recovered films, the harvested material was analyzed by gas-chromatography/mass spectrometry as well as by liquid chromatography/mass spectrometry. "Tempera grassa" (consisting of linseed oil admixed with egg yolk) was used in the entire painting. The surface was then protected by a layer of conifer resin. It is hypothesized that access to the layer underneath the protective layer was obtained via micro-cracks on the conifer resin itself. Rosemary oil was used as diluent to slow down the drying process and so to perform the glazing technique, thus obtaining the "aerial perspective" in correspondence of the landscape. To our reckoning, this is the first time in which a Leonardo painting is analyzed in depth but also in which his artistic technique is deciphered via modern techniques for exploring Cultural Heritage. The EVA film technology might be used for ascertaining the authenticity of paintings and uncover frauds. SIGNIFICANCE STATEMENT: Leonardo da Vinci was the most famous Italian polymath of the Renaissance and one of the most important innovators of his time. He was the author of several important artworks such as "La Gioconda", but he also painted the "Donna Nuda" conserved at the Hermitage Museum. Although some attempts permitted the identification of part of the materials used by Leonardo, to date no analytical investigations were able to fully characterize and decipher the recipes. We explored the surface of the "Donna Nuda" painting through a non-invasive approach that uses a functionalized film to adsorb nano-scopic amounts of materials that were then analyzed by mass spectrometry. This method has the potential to revolutionize the approaches used to analyze cultural heritage., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Safer by design (SBD) modifications of nanomaterials (NMs) have been pursued, aiming to maintain functionality and yet reduce hazard and support sustainable nanotechnology. The present case study involves copper oxide nanomaterials (CuO NMs) used in paint that have been surface modified by a SBD approach to particles coated with citrate (CIT - ), ascorbate (ASC - ), polyethylenimine (PEI + ), and polyvinylpyrrolidone (PVP). We assessed the effect of the 4 different surface modified (CIT, ASC, PVP and PEI) NMs plus the pristine non-coated (PRI NM) and a Cu salt (CuCl 2 ), using the soil multispecies test system (samples at 28-56-84 days). Further, the species were tested individually, and Cu was measured in the test media (soil and soil solution) and organisms. There was a potential relationship with zeta potential, and toxicity of CuO NMs was as follows: -PEI (+28 mV) caused the least impact, -ASC and -CIT (-17 mV, -18 mV) the most, while PVP and PRI (-8 mV, -9 mV) caused an intermediate response. Differences were not explained by the contribution of soluble Cu. Coating interfered with the release of Cu 2+ and/or the activation of copper regulators and detoxification mechanisms in the organisms, i.e. time to reach some kind of stability in organisms' uptake was shorter for -ASC and longer for -PVP during prolonged time. Thus, one of the main findings is that NMs hazard assessment requires long term testing to understand predicted effects across materials. Further, the coverage using a multispecies approach offers increased relevance and a more ecosystem qualified response., (Copyright © 2019. Published by Elsevier B.V.)

Antifouling coatings are used to protect boat hulls from fouling organisms. The paints are designed to release biocides and by this prevent fouling organisms to attach. Until now the simultaneous release of the bulk plastic material has been over-looked. In this study the amount of antifouling paints on ships and leisure boats in Scandinavian countries and Germany has been compared and a calculation of the release of micro plastics has been performed. The result shows that use of a biocide-free hard coating will completely reduce outlet of biocides and the input of polymers will dramatically be reduced from at the most 5% in comparison to traditional paints where the release rate of plastics is estimated to be 70-85%. The advantage for the boat owners will be large since the hard maintenance work will be reduced, release of micro plastics will be low and thus lead to an improved environment., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Environmental concerns have been changing the way of looking for solutions to problems. The hydrosphere, together with its biosphere, has been feeling the impact of many pollutants, used for instance in the marine industry for economic reasons or lack of knowledge of their effects. In particular biocides, applied as coatings in paints, are released into the waters becoming toxic and persistent extending their action to an area far beyond the initial coated surface they should protect. In order to minimize these side effects, two biocides, Irgarol (I) and Econea (E), were covalently attached to polyurethane (PU) and foul-release silicone based (PDMS) marine paints through an isocyanate linker. Their antifouling bioactivity was better in PDMS coatings, both for single (Econea) and combined biocides (E/I ratio = 1.5) with contents lower than 0.6 wt%. The treated samples remained almost clean after more than one year immersion in the Portuguese shore of the Atlantic Ocean, and after about 24 weeks under the tropical conditions of Singapore (Fouling rate < 1%). Complementary biofilm adhesion susceptibility tests against Pseudoalteromonas tunicata D2 showed adhesion reduction higher than 90% for PU formulations containing single biocides and close to 100% for PDMS with combined biocides. The eco-toxicity assessment evidenced a low environmental impact, in accordance with the European standards. In addition, shipping field trial tests showed the best antifouling performance for the Econea-based PDMS formulations (E = 0.6 wt%), which remained clean for about nine months in open seawaters, proving the efficacy of this non-release strategy, when applied under dynamic conditions., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Organotin compounds (OTCs) are persistent pollutants and are considered as chemicals of environmental concern. They enter the marine environment from the antifouling paints containing organotin compounds on the hulls of ships and boats. We report the results of a study conducted in 2015 on the level of butyltins (TBT, DBT, and MBT) and phenyltins (TPhT, DPhT, and MPhT) in the sediments collected from three fishing harbors (Jubail, Khobar, and Qatif) and a reference site (Half Moon Bay). The concentrations of OTCs in the sediments vary widely among the different sampling locations. Overall, the phenyltins contribute more than the butyltins and the order of the abundance is: MPhT > DPhT > MBT > DBT > TPhT. In most stations, the concentrations of MBT are higher than DBT. The sediments from Khobar and Qatif are moderately polluted, whereas those from the Jubail are ranked as highly polluted. The concentrations of TBT at all study sites are less than the detection limit, and hence, the environmental and ecotoxicological risks are low., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Paints are often used on chopsticks, however, a paucity of studies has assessed metals in the paints and the associated health risk. In this study, total Pb, Cd, Cr, Co, and Ni concentrations in paints were assessed for 72 wood and 29 stainless steel chopsticks with different colors while metal solubilization from paints in simulated saliva, 0.07 M HCl, and 1% citric acid solutions was measured for 9 samples having total Pb > 90 mg kg -1 , representing exposure scenarios of mouthing, incidental paint ingestion, and metal migration in food. Results showed that Pb (0.12-500,000 mg kg -1 ), Cd (0.002-120,000 mg kg -1 ), Cr (2.2-8400 mg kg -1 ), Co (0.004-2600 mg kg -1 ), and Ni (0.10-150,000 mg kg -1 ) concentrations varied considerably among paint samples. Most samples showed low metal concentrations, however, high metal concentrations were observed in red and green paints on stainless steel chopsticks, while paints on wood chopsticks showed lower metal concentrations. Estimation of daily metal intakes incorporating metal solubilization data in saliva, 0.07 M HCl, and 1% citric acid solutions suggested that the health risk via saliva contact was negligible, while unacceptable health risk was observed for Pb and Cd via their solubilization in 0.07 M HCl and 1% citric acid solutions from paints with high Pb and Cd concentrations. To avoid Pb and Cd exposure, use of metal-based paints on chopsticks should be banned, particularly in countries where food is regularly consumed with chopsticks., (Copyright © 2018 Elsevier Inc. All rights reserved.)

Exposure to low levels of lead in children can cause cognitive deficits (reduced IQ) and behavioral changes such as reduced attention span and increased antisocial behavior. There are no mandatory limits on lead in paint in Israel, with the exception of paints used on toys and children's furniture. However, paints in playgrounds and public areas may be a source of exposure to lead in young children. In this study, we quantified lead concentrations in painted surfaces in public playgrounds and public areas, and in spray paints in Israel, using X-ray fluorescence (XRF). Lead was detected in 43/48 (90%) of surfaces; concentrations exceeded the US regulatory limit for lead in paint (90 ppm) in 4/5 (80%) of tested surfaces on wooden picnic tables and benches, and 22/25 (88%) of surfaces in playgrounds. In 15 surfaces, lead concentrations were 10-700 times higher than the US limit. Out of 11 spray paints sampled, three (27%) had concentrations above the US standard for residential paints. In order to prevent exposure of the general public to lead in playgrounds and public areas and in spray paints, we recommend an integrated approach, including regulatory restrictions (mandatory lead limit of 90 ppm in all paints except labeled industrial paints); awareness raising in the public and in national agencies and local authorities responsible for maintenance in playgrounds, schools and public areas; and encouragement of voluntary measures by industry to prevent sale of industrial paints for use in areas accessible to the public., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Epidemiologic studies regarding solvent-based paints (SBPs) containing VOCs have demonstrated a strong correlation between chronic and acute adverse health effects and the SBPs. Therefore, new environmentally friendly paints as substitutes containing less or none VOCs have been rapidly developed in research for future sustainable use. However, a few studies focusing on penetration and exposure condition of the substitute have been reported duo to the complexity and inaccessibility of painting industry. Surveys specifically looking at the present status of exposure condition were conducted to ascertain the popularization of water-based paints (WBPs) which concluded that markers of SBPs were detected in all 134 samples indicating bad industrial penetration. VOCs exposure concentrations of painters ranged from 3.8 to 18.2mg/m 3 for WBPs, 3.5×10 3 to 14.8×10 3 mg/m 3 for SBPs, respectively. The negative correlation between ambient concentration and breathing zone concentration suggested the former was incapable of representing the actual exposure concentration. The real-time concentration was proved to be closely associated with the activity patterns while the mean concentration level was found mostly dependent on the paint types. Authentic inhalation dose ranged from 7.68 to 15.84mg (WBPs) and 3.84 to 15.59g (SBPs), respectively, for occupational painters (work 8h per day) and the total inhalation dose was estimated through a new conception. The findings suggested that WBPs could significantly reduce VOCs emission and occupational exposure., (Copyright © 2017 Elsevier B.V. All rights reserved.)

The ultra-high performance supercritical fluid chromatography-mass spectrometry (UHPSFC/MS) procedure for analysis of native monosaccharides was developed. Chromatographic conditions were investigated to separate a mixture of four hexoses, three pentoses, two deoxyhexoses and two uronic acids. Increasing water content in methanol modifier to 5% and formic acid to 4% improved peak shapes of neutral monosaccharides and allowed complete elution of highly polar uronic acids in a single run. An Acquity HSS C18SB column outperformed other three tested stationary phases (BEH (silica), BEH 2-ethylpyridine, CSH Fluoro-Phenyl) in terms of separation of isomers and analysis time (4.5 min). Limits of detection were in the range 0.01-0.12 ng μL -1 . Owing to separation of anomers, identification of critical pairs (arabinose-xylose and glucose-galactose) was possible. Feasibility of the new method was demonstrated on plant-derived polysaccharide binders. Samples of watercolor paints, painted paper and three plant gums widely encountered in painting media (Arabic, cherry and tragacanth) were decomposed prior the analysis by microwave-assisted hydrolysis at 40 bar initial pressure using 2 mol L -1 trifluoroacetic acid. Among tested temperatures, 120 °C ensured appropriate hydrolysis efficiency for different types of gum and avoided excessive degradation of labile monosaccharides. Procedure recovery tested on gum Arabic was 101% with an RSD below 8%. Aqueous hydrolysates containing monosaccharides in different ratios specific to each type of plant gum were diluted or analyzed directly. Filtration of samples before hydrolysis reduced interferences from a paper support and identification of gum Arabic in watercolor-painted paper samples was demonstrated. Successful identification of pure gum Arabic was confirmed for sample quantities as little as 1 μg. Two classification approaches were compared and principal component analysis was superior to analysis based on peak area ratios of monosaccharides. The proposed procedure using UHPSFC/MS represents an interesting alternative which can compete with other chromatographic methods in the field of saccharide analysis in terms of speed, sensitivity and simplicity of workflow., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Lead, cadmium, nickel, manganese, cobalt and copper contents of some play dough, face and finger paint samples were determined by using a new solid phase extraction method which has been developed by using multi-walled carbon nanotube with patent blue (V) sodium salt to selectively separate and preconcentrate these metal ions. Flame atomic absorption spectrometry was used to determine the metal ions. Analytical parameters affecting the complex formation and solid phase extraction performance such as pH, the amount of ligand and volume of sample solution were investigated. The recoveries of the studied metal ions were not affected by the foreign ions. Analytes were recovered quantitatively at pH 5.5 and with a nitric acid of 2molL -1 as eluent. Analysis of a certified reference material was performed to validate the method before applying it to determine the metal ions in the real samples. Detection limits were found to be as Pb(II): 7.71μgL -1 , Cu(II): 1.43μgL -1 , Cd(III): 0.21μgL -1 , Mn(II): 0.47μgL -1 , Ni(II): 3.52μgL -1 and Co(II): 1.96μgL -1 ., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Tributyltin and triphenyltin have been extensively applied in anti-fouling paints since the 1960s. Hence, organotin compounds (OTCs), especially butyltins and phenyltins, in seafood has been of concern for decades. Even though the "International Convention on the Control of Harmful Anti-Fouling Systems on Ships, 2001" entered into force internationally in 2008 and prohibited the use of OTCs in anti-fouling paints used on ships, the analysis of OTCs in seafood was not commonly included in routine monitoring programmes. Besides, species of triphenyltin, including triphenyltin hydroxide and acetate, have been used as pesticides and may accumulate in food. Moreover, the European Food Safety Agency established a group tolerable daily intake for tributyltin, dibutyltin, triphenyltin and dioctyltin in 2004 as they exert their immunotoxic effects by similar mode of action and potency. Therefore, suitable methods are needed to analyze butyl-, phenyl- and octyl-tins simultaneously in food without affecting their moieties. This review aims to provide background information in this area., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Lipid binders have traditionally been determined in paintings by using gas chromatography/mass spectrometry (GC/MS) to identify the characteristic profiles and ratios of fatty acids . However, the presence of mixtures in contemporary and modern oil paints makes the GC/MS determination of fatty acids insufficient to fully characterize the lipid binding media. In this study we prove that triacylglycerol (TAG) profiling by high-performance liquid chromatography with high-resolution tandem mass spectrometry, using ESI in positive and negative ionization modes is highly effective. We exploited this analytical approach to study the curing and degradation processes undergone by six plant oils used in the formulation of media in modern paints, using both natural and artificial ageing experiments. We believe that is the first time that a negative ionization mode has been applied for this purpose and that a survey with HPLC-ESI-Q-ToF has been carried out to study the ageing kinetics of plant oils. TAG profiling enabled us to study the evolution over time of the constituents of modern oils, with respect to curing and ageing. The data analyzed in this study demonstrate that our approach is efficient to study the oxidation of TAGs during ageing. The data also improve current knowledge on the properties of vegetable oils, which could lead to the development of new paint materials and conservation treatments for modern and contemporary works of art., (Copyright © 2016 Elsevier B.V. All rights reserved.)

In the present study, antifouling paint booster biocides, Irgarol 1051 and diuron were measured in ports and marinas of Bushehr, Iran. Results showed that in seawater samples taken from ports and marinas, Irgarol was found at the range of less than LOD to 63.4ngL(-1) and diuron was found to be at the range of less than LOD to 29.1ngL(-1) (in Jalali marina). 3,4-dichloroaniline (3,4-DCA), as a degradation product of diuron, was also analyzed and its maximum concentration was 390ngL(-1). Results for analysis of Irgarol 1051 in sediments showed a maximum concentration of 35.4ngg(-1) dry weight in Bandargah marina. A comparison between the results of this study and those of other published works showed that Irgarol and diuron pollutions in ports and marinas of Bushehr located in the Persian Gulf were less than the average of reports from other parts of the world., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Dry weight concentrations of lead in paints on a variety of structures in the urban and suburban environs of a British city (Plymouth, south west England) were determined in situ and ex situ by field-portable X-ray fluorescence spectrometry. Lead was detected in 221 out of 272 analyses, with overall median and mean concentrations of 4180 μg g(-1) and 29,300 μg g(-1), respectively, and a maximum concentration of 390,000 μg g(-1). Highest concentrations were observed in extant paints on poorly maintained, metallic structures, including railings, gates, telephone kiosks and bridges, in various yellow road line paints, and in paints of varying condition on public playground facilities (ramps, climbing frames, monkey bars). Occupants of households in the vicinity of structures that are shedding leaded paint are at potential risk of exposure from paint particles being tracked in on shoes and clothing while children in contact with leaded paints in playgrounds and recreational areas are at potential risk from the direct ingestion of paint flakes. Since the issues highlighted in the present study are neither likely to be restricted to this city, nor to the UK, a greater, general awareness and understanding of the sources and routes of exposure of exterior leaded paint is called for., (Copyright © 2015 Elsevier B.V. All rights reserved.)

In this work we use a water-soluble cationic perylene derivative (compound 1) as the G-quadruplex (G4) structure fluorescence indicator to construct a fluorescent biosensor for simple, rapid and label-free detection of Pb(2+). In the absence of Pb(2+), strong electrostatic interactions between compound 1 and the G-rich DNA probe (PW17) induced the aggregation of compound 1 and resulted in the fluorescence quenching. In the presence of Pb(2+), the PW17 formed Pb(2+)-stabilized G4 structure, which reduced the aggregation of compound 1 and gave rise to high fluorescence. This allowed us to use convenient "mix-and-detect" protocol for quantitative analysis of Pb(2+). Since Pb(2+) can specially induce PW17 to form compact DNA fold, our proposed biosensor displayed high selectivity for Pb(2+). It also exhibited a high sensitivity to Pb(2+), with a limit of detection of 5.0nM observed. Furthermore, the biosensor was applied for the detection of Pb(2+) in urine and paint samples, and both showed satisfactory results., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Despite the ban of applying TBT coatings on leisure boats in the late 80s, recent studies show an ongoing spread of TBT from leisure boats, particularly during hull cleaning events. Therefore, countries in EU have adopted expensive measures to clean this wash water. A more cost-efficient measure is to focus directly on the source, i.e. identify leisure boats with high concentrations of TBT and prescribe boat owners to remove the paint. We have developed a new antifouling paint application for a handheld X-ray fluorescence (XRF) analyzer to be used for identifying boats with high area concentrations (µg/cm(2)) of Sn (indication that the hull contains TBT paint residues). Copper and zinc are also included in the application since these metals are used in the vast majority of today's paints. A blind test with up to four layers of TBT-, copper- and zinc-based paints showed good correlation between XRF-measured area concentrations and chemically analyzed concentrations. Future usage of the applications involves identification of boat hulls in particular with high Sn concentrations and also with high Cu and Zn concentrations. This method has the potential to become a useful tool in regulatory management of existence and use of toxic elements on boat hulls., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Between 1950 and 1980, lead and chromium along with other metals have been used in paint coatings to protect bridges from corrosion. In New York State with 4500 bridges in 11 Regions 2385 of the bridges have been rehabilitated and subsequently repainted after 1989 when commercial use of lead based paint was prohibited. The purpose of this research was to address the concentration and distribution of trace metals in the paint waste generated during bridge rehabilitation. Using hypothesis testing and stratified sampling theory, a representative sample size of 24 bridges from across the state was selected that resulted in 117 paint waste samples. Field portable X-ray fluorescence (FP-XRF) analysis revealed metal concentrations ranged from 5 to 168,090 mg kg(-1) for Pb, 49,367 to 799,210 mg kg(-1) for Fe, and 27 to 425,510 mg kg(-1) for Zn. Eighty percent of the samples exhibited lead concentrations greater than 5000 mg kg(-1). The elevated iron concentrations may be attributed to the application of steel grit as an abrasive blasting material routinely used by state Departments of Transportation in the paint removal process. Other metals including Ba and Cr were observed in the paint waste as well. As a result of the paint formulation, metals were found to be associated in the paint waste (Pb correlated with Cr (r=0.85)). The elevated metal concentrations observed raises concern over the potential impact of leaching from this waste stream., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Cuprous oxide is the most commonly used biocide in antifouling paints. However, copper has harmful effects not only on the fouling community but also on non-target species. In the current study, we investigated the use of thymol, eugenol and guaiacol in this role combined with small quantities of copper. Phenolic compounds were tested for anti-settlement activity against cyprid larvae of the barnacle Balanus amphitrite and for their toxicity to nauplius larvae. Thymol, eugenol and guaiacol were active for anti-settlement but guaiacol had the disadvantage of being toxic to nauplius larvae. However, all of them showed therapeutic ratio>1. Antifouling paints with thymol (low copper content/thymol, LCP/T), eugenol (low copper content/eugenol, LCP/E) and guaiacol (low copper content/guaiacol, LCP/G) combined with small copper content were formulated for field trials. After 12 months exposure in the sea, statistical analysis revealed that LCP/T and LCP/E paints were the most effective combinations and had similar performances to control paints with high copper content (traditional cuprous oxide based paints). In contrast, LCP/G paint was only partially effective in preventing and inhibiting biofouling and was colonized by some hard and soft foulers. However, this antifouling paint was effective against calcareous tubeworm Hydroides elegans. In the light of various potential applications, thymol, eugenol and guaiacol have thus to be considered in future antifouling formulations., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

This paper demonstrates that an educated methodology based on both non-invasive and micro invasive techniques in a two-step approach is a powerful tool to characterize the materials and stratigraphies of an Egyptian coffin, which was restored several times. This coffin, belonging to a certain Mesiset, is now located at the Museo Civico Archeologico of Bologna (inventory number MCABo EG 1963). Scholars attributed it to the late 22nd/early 25th dynasty by stylistic comparison. The first step of the diagnostic approach applied imaging techniques on the whole surface in order to select measurements spots and to unveil both original and restored areas. Images and close microscopic examination of the polychrome surface allowed selecting representative areas to be investigated in situ by portable spectroscopic techniques: X-ray Fluorescence (XRF), Fiber Optic Reflectance Spectroscopy (FORS) and Fourier Transform Infrared spectroscopy (FTIR). After the analysis of the results coming from the first step, very few selected samples were taken to clarify the stratigraphy of the polychrome layers. The first step, based on the combination of imaging and spectroscopic techniques in a totally non-invasive modality, is quite unique in the literature on Egyptian coffins and enabled us to reveal many differences in the ground layer's composition and to identify a remarkable number of pigments in the original and restored areas. This work offered also a chance to check the limitations of the non-invasive approach applied on a complex case, namely the right localization of different materials in the stratigraphy and the identification of binding media. Indeed, to dissolve any remaining doubts on superimposed layers belonging to different interventions, it was necessary to sample few micro-fragments in some selected areas and analyze them prepared as cross-sections. The original ground layer is made of calcite, while the restored areas show the presence of either a mixture of calcite and silicates or a gypsum ground, overlapped by lead white. The original pigments were identified as orpiment, cinnabar and red clay, Egyptian blue and green copper based pigments. Some other pigments, such as white lead, Naples yellow, cerulean blue and azurite were only found in the restored areas., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Nail polishes are cosmetic paints that may be susceptible of forensic analysis offering useful information to assist in a crime reconstruction. Although the nail polish appearance could allow a quick visual identification of the sample, this analysis is subjected to the perception and subjective interpretation of the forensic examiner. The chemical analysis of the nail polishes offers great deal of information not subjected to analyst interpretation. Confocal Raman spectroscopy is a well-suited technique for the analysis of paints due to its non-invasive and non-destructive nature and its ability to supply information about the organic and inorganic components of the sample. In this work, 77 regular and gel nail polishes were analyzed with confocal Raman spectroscopy using two laser wavelengths (532 and 780 nm). The sample behavior under the two laser wavelengths and the differences in the spectra taken at different points of the sample were studied for each nail polish. Additionally, the spectra obtained for all the nail polishes were visually compared. The results concluded that the longer laser wavelength prevents sample burning and fluorescence effects; the similarity among the spectra collected within the sample is not directly related with the presence of glitter particles; and 64% of the samples analyzed showed a characteristic spectrum. Additionally, the use of confocal Raman spectroscopy for the forensic analysis of nail polishes evidence in the form of flakes or smudges on different surfaces were studied. The results showed that both types of evidence can be analyzed by the technique. Also, two non-invasive sampling methods for the collection of the evidence from the nails of the suspect or the victim were proposed: (i) to use acetone-soaked cotton swabs to remove the nail varnishes and (ii) to scrape the nail polish from the nail with a blade. Both approaches, each exhibiting advantages and drawbacks in terms of transport and handling were appropriate for a further chemical analysis of the samples., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Folium and orchil are dyes of vegetal origin. Folium is obtained from Chrozophora tinctoria (L.) A. Juss., whereas orchil is obtained from Roccella and other genera of lichens. These dyes were used in the past to impart purple hue to paintings and textiles as substitutes for the more prised Tyrian purple dye, obtained from shellfish. Despite several citations in ancient technical treatises dating back at least to the Greek-Roman age, the identification of these dyes in artworks is rare. In the case of folium, an additional drawback is that its composition is presently unknown. In this work different non-invasive (FT-IR, FT-Raman, fibre optic reflectance spectrophotometry, spectrofluorimetry, X-ray fluorescence spectrometry) and micro-invasive (surface enhanced Raman spectroscopy, matrix assisted laser desorption ionisation-time of flight-mass spectrometry, inductively coupled plasma-mass spectrometry) techniques were used in order to increase the diagnostic information available on these dyes. Measurements were carried out on the dyes extracted from raw materials and on painted or dyed parchments. The possibility to distinguish between folium and orchil by chemical analysis is discussed., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Nowadays most low-field NMR sensors, such as the single-sided Profile NMR-MOUSE®, still suffer from poor sensitivity, either resulting from low magnetic field strengths and correspondingly low NMR frequencies, or lack of sensitivity. Generally, micro-coils can improve sensitivity, but due to their small size, and thus small inductance, they are mainly used for high-field NMR. Their main application field is parallel imaging, where those coils are typically assembled to receive-only coil-arrays and increase the field-of-view. Prominent signal combination techniques such as GRAPPA and SENSE are used to combine the spatially independent NMR signals to images in order to increase acquisition speed. A decisive disadvantage of today's single-sided NMR probes is the limited accessibility for NMR imaging. Although it is possible to use flat gradient coils on top of the NMR-MOUSE® to apply imaging techniques, such images can only be recorded with very long acquisition times, excluding the NMR-MOUSE® for lateral imaging of time-dependent processes. In this study sensitivity improved micro-structured RF coils, optimized for low frequencies, and correspondingly arrays of these coils, were employed to improve sensitivity and gave access to lateral spatial resolution within the sensitive plane at several observation points at the same time. Recently developed three- and four-coil arrays were combined with a Profile NMR-MOUSE® and characterized in terms of coil coupling, noise correlation and signal combination. The three-coil array was used for lateral imaging of moisture transport in travertine rock samples and to study the one-dimensional drying of paint., (Copyright © 2015 Elsevier Inc. All rights reserved.)

Temperature-related degradation of pure synthetic as well as partly oxidised natural vivianite has been studied by high-temperature X-ray diffraction (HT-XRD) covering the whole extent of the temperature-related stability of its structure. While temperatures around 70°C are already damaging to vivianite, exposition to 160°C results in complete amorphisation of both the vivianite and its oxidation products. As indicated by Mössbauer spectroscopy, temperature-induced oxidation of vivianite starts at 90°C. To study the occurring structural as well as accompanying colour changes in more detail, model vivianite paint layer samples with different historic binders were prepared and subjected to increased temperatures. Exposition to 80°C caused pronounced colour changes of all the samples: ground natural blue vivianite became grey--a colour change which has been described in actual works of art. Regarding the binders, the oil seemed to facilitate the transfer of heat to vivianite's grains. To simulate conditions of conservation treatment under which the painting is exposed to increased temperatures, oil-on-canvas mock-ups with vivianite were prepared and relined in a traditional way using iron. The treatment affected preferentially larger grains of vivianite; the micro-samples documented their change to grey, and their Raman spectra showed the change from vivianite to metavivianite., (Copyright © 2014 Elsevier B.V. All rights reserved.)

Lead concentrations in new enamel decorative paints were determined in three countries in different areas of the world where data were not previously available. The average total lead concentration of the enamel decorative paints purchased in Lebanon, Paraguay and Russia was 24,500ppm (ppm, dry weight), more than 270 times the current limit of 90ppm in Canada and in the United States. Sixty-three percent of these paints contained concentrations greater than 90ppm. Fifty-nine percent contained concentrations greater than 600ppm, the current limit in some countries. The maximum concentrations found were 236,000ppm in Lebanon, 169,000ppm in Paraguay and 52,900ppm in Russia. An average of 29% of the samples contained exceedingly high lead concentrations, >=10,000ppm. Five brands of paint were sampled in each of Lebanon and Paraguay and seven in Russia. Three colors from each brand were analyzed. For five of the six samples of the two brands in Lebanon with affiliations outside the country, the lead concentrations ranged from 1360ppm to 135,000ppm. In Lebanon the maximum concentration in the Egypt-affiliated brand (Sipes) was 135,000ppm and the maximum for the USA-affiliated brand (Dutch Boy) was 32,400ppm. Lead was not detected in any paints from the three of the four brands of paint purchased in Paraguay that had headquarters/affiliations in other countries (Brazil-Coralit), Germany (Suvinil) and USA (Novacor)). Two of the three paints from each of the other Paraguay brands contained high levels of lead with the maximum concentrations of 108,000 and 168,000ppm; one of these brands was manufactured under a license from ICI in the Netherlands. All of the paints purchased in Russia were from Russian brands and were manufactured in Russia. All three paints from one brand contained below detection levels of lead. The maximum levels of lead in the other six brands in Russia ranged from 3230 to 52,900ppm. The two brands with the highest lead concentration, TEKS and LAKRA, were produced by companies in the top three in market share.. Overall, lead concentrations were much higher in the colored paints such as red and yellow than in white paints. In each of the three countries a brand based in that country had a colored paint that either met a 90ppm limit or was close to meeting the limit-demonstrating that practical technology was available in each of these countries to produce low lead bright colored enamel decorative paints. Even though technology for producing paint without added lead existed in each of these countries, twenty-nine (29) percent of the paints analyzed contained exceedingly high concentrations (>=10,000ppm) of lead., (Copyright © 2015 Elsevier Inc. All rights reserved.)

Raman spectroscopic analysis of the pigments on an Italian painting described as a "Full Length Portrait of a Gentleman", known also as the "Malatesta", and attributed to the Renaissance period has established that these are consistent with the historical research provenance undertaken earlier. Evidence is found for the early 19th Century addition of chrome yellow to highlighted yellow ochre areas in comparison with a similar painting executed in 1801 by Sir Thomas Lawrence of John Kemble in the role of Hamlet, Prince of Denmark. The Raman data are novel in that no analytical studies have previously been made on this painting and reinforces the procedure whereby scientific analyses are accompanied by parallel historical research., (Copyright © 2014 Elsevier B.V. All rights reserved.)

In the present work, the use of portable instrumentation allowing in-situ reflection FTIR analyses is exploited to identify the coloring matters of northern-Italian illuminations dating to the XVI century. In order to build a database of spectra, reference paint samples were prepared spreading the pigments on parchment with two different binders, i.e. gum arabic and egg white, used in antiquity. Pigments for the database were chosen considering their use in the Middle Ages and in the Renaissance and their response in the mid- and near-IR region. The reflection FTIR spectra obtained resulted to be dominated by the specular reflection component, allowing the use of the Kramers-Kronig transform to convert them to the more conventional absorbance FTIR spectra. Several pigments could thus be identified in ancient illuminations, even if some green details showed a spectral pattern different with respect to the most common commercial green pigments of the database. Therefore, in addition, basic copper sulfates brochantite and posnjakite were synthesized and characterized. In three green details, posnjakite was identified, both as a pure compound and together with malachite., (Copyright © 2014 Elsevier B.V. All rights reserved.)

The Raman and complementary spectroscopic analyses were performed using the exceptional possibility of research on the XIX c. original paint materials of the artist palette of J. Matejko stored in the National Museum in Cracow. The yellow and ochre-based paints characteristic for Matejko's workshop and selected from the ensemble of 273 labelled tubes (brand of R. Ainé/Paris) supplied during the period of 1880-1893 were investigated. Highly specific Raman spectra were obtained for paints containing mixtures of the Zn- and Sn-modified Pb-Sb pigment, and also for the ochre-based ones. A clear pigment discrimination of the mixture of cadmium yellow (CdS), cinnabar (HgS) and lead white (2PbCO3⋅Pb(OH)2) was possible by means of Raman data collected under different excitations at 514 nm and 785 nm. It was shown that the Raman spectra complemented by the XRF, SEM-EDX and in some cases also by the LIPS and FTIR data ensure reliable pigment identification in multi-component paints containing secondary species and impurities. The reported spectral signatures will be used for non-destructive investigation of the collection of about 300 oil paintings of J. Matejko. In view of the comparative research on polish painting which point out that richness of modified Naples yellows clearly distinguish Matejko's artworks from other ones painted in the period of 1850-1883, the Raman data of these paints can provide support in the authentication studies., (Copyright © 2014 Elsevier B.V. All rights reserved.)

Samples were obtained from two world-famous 17th century panel paintings of the Gdańsk school of panting: 'Seven Acts of Charity' (1607, in St. Mary's Church in Gdańsk, Poland) by Anton Möller and 'Angelic Concert' (1611, in Diocesan Museum in Pelplin, Poland) by Hermann Han. Micro-Raman spectroscopy (MRS), optical microscopy (OM), and X-ray fluorescence (XRF) spectroscopy studies of the samples were performed to characterize the pigments present in the individual painting layers (a rich palette of white, black, blue, red, and yellow pigments) and the pictorial techniques used by the artists., (Copyright © 2014 Elsevier B.V. All rights reserved.)

The pigments used in the wall paintings of the Masjid-i Jāme of Abarqū, central Iran, as less-known pigments used in the history of Persian painting, were investigated with micro-Raman spectroscopy, micro X-ray fluorescence (micro-XRF), scanning electron microscopy (SEM), and polarised light microscopy (PLM). The results showed that the green, red, and blue pigments were atacamite, red lead, and smalt mixed with natural ultramarine blue respectively applied on a white substrate composed of white huntite. Moreover, the blue smalt was identified to be used on the white huntite and under the paint layer in order to delineate the design of the wall paintings and to act as a rough sketch for the subsequent use of the other pigments. Glushinskite, as a less-reported mineral in historical wall paintings, was identified by micro-Raman spectroscopy and hypothesised to be associated with the degradation of the white huntite binder. Furthermore, micro-Raman spectroscopy studies surprisingly revealed the mineral woodhouseite sparely mixed with the green pigment. This paper strongly suggests micro-Raman spectroscopy for identifying archaeological pigments and for diagnosing their deterioration products. Conducting scientific methods of analysis, the pigments identified in this study are reported for the first time to be used in Persian wall paintings., (Copyright © 2014 Elsevier B.V. All rights reserved.)

Lead is a hazardous compound that affects the central nervous system in people, particularly children, and may cause some reversible and irreversible diseases. Legal regulations try to prevent the exposure from products especially produced for children such as coating paints, jewelry, toys, bed linen, textile, etc. The aim of this study was to determine the lead levels of coating paints on children׳s outwear selling in district bazaar by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and to specify the percent of non-complying samples. Here we described the solid matrix calibration method and confirmed the results with the microwave-assisted acid digestion method. Both comparative methods were validated by analysis of the certified reference materials (NIST SRM-612 glass matrix, NIST SRM-2582 powdered paint and ERM-EC681k) and bias% for accuracy and RSD% for precision were calculated lower than 6.8% and 7.3%, respectively. The recovery ranges of laser ablation and microwave-assisted acid digestion method for Pb were found to be between 88.2-98.1% and 95.3-101.3%, respectively. The limits of detection values were determined as 0.162 mg kg(-1) for direct sampling in the ablation chamber and 0.002 ng mL(-1) for aqueous solutions. Correlation result of 16 samples (r=0.99) examined in both methods was satisfactory. In coating paint samples, 14.65% of 198 (n=29) did not comply with the 90 mg kg(-1) lead limit according to regulation. Validated quantitative laser ablation method may be preferred to quickly and reliably determine the Pb levels in other solid samples as well as coating paints., (Copyright © 2014 Elsevier B.V. All rights reserved.)

Paint flaking off abandoned vessels or generated during boat repair is hazardous to human health and wildlife. In this study, a means of screening paint fragments using a field portable-X-ray fluorescence (FP-XRF) spectrometer is described. The technique is capable of delivering rapid, surficial measurements of Ba, Cu, Pb and Zn down to concentrations less than 150 μg g(-1), and Sn and Cr to concentrations of a few hundred μg g(-1). Application of the technique to fragments collected from slipways, yards, hardstandings, abandoned boats and ships undergoing maintenance throughout the EU reveal highly variable concentrations of metals among samples from the same environment or from the same region of a given boat; in many cases, variability is also evident in different areas or on different surfaces of the same fragment. Of particular concern are elevated concentrations of substances that have been restricted or banned (e.g. Sn, an indicator of organotin, and up to concentrations of 40,000 μg g(-1), and Pb up to concentrations of 200,000 μg g(-1)). Although FP-XRF can rapidly screen samples whose composition and origin are unknown and can assist in instantaneous decision making, a full risk assessment will rely on additional analyses of the precise species (including organo-forms) of the metals present., (Copyright © 2014 Elsevier B.V. All rights reserved.)

Sherds representative of the three Portuguese faience production centers of the 17th century - Lisbon, Coimbra and Vila Nova were studied with the use of mostly non-invasive spectroscopies, namely: ground state diffuse reflectance absorption (GSDR), micro-Raman, Fourier-transform infrared (FT-IR) and proton induced X-ray (PIXE) or X-ray fluorescence emission (XRF). X-ray diffraction (XRD) experiments were also performed. The obtained results evidence a clear similarity in the pastes of the pottery produced Vila Nova and some of the ceramic pastes from Lisbon, in accordance with documental sources that described the use of Lisbon clays by Vila Nova potters, at least since mid 17th century. Quartz and Gehlenite are the main components of the Lisbon's pastes, but differences between the ceramic pastes were detected pointing out to the use of several clay sources. The spectroscopic trend exhibited Coimbra's pottery is remarkably different, Quartz and Diopside being the major components of these pastes, enabling one to well define a pattern for these ceramic bodies. The blue pigment from the Lisbon samples is a cobalt oxide that exists in the silicate glassy matrix, which enables the formation of detectable cobalt silicate microcrystals in most productions of the second half of the 17th century. No micro-Raman cobalt blue signature could be detected in the Vila Nova and Coimbra blue glazes. This is in accordance with the lower kiln temperatures in these two production centers and with Co(2+) ions dispersed in the silicate matrix. In all cases the white glaze is obtained with the use of tin oxide. Hausmannite was detected as the manganese oxide mineral used to produce the purple glaze (wine color "vinoso") in Lisbon., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Fragments of leaded paint sampled from abandoned boats have been ground as a composite and added in different quantities to aliquots of clean estuarine sediment in order to examine the mobility and bioaccessibility of Pb. Concentrations of Pb mobilised by sea water increased with increasing quantity of paint present, but the percentage of total Pb mobilised was greatest from paint-free sediment. Lead mobilisation was enhanced in the presence of the protein, bovine serum albumin, a surrogate for the digestive fluids of deposit-feeding invertebrates, but, likewise, the percentage of Pb mobilised was greatest from paint-free sediment. Lower percentage mobility and bioaccessibility in contaminated sediment than in paint-free sediment is attributed to the relatively low solubility and amenability of Pb compounds in the paint matrix. Despite the low mobility of Pb, however, sediment contaminated by as little as 0.2% paint is predicted to result in dissolved concentrations that exceed available water quality standards., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

The applicability of ATR-FTIR spectroscopy with partial least squares (PLS) data analysis was evaluated for quantifying the components of mixtures of paint binding media and pigments, and alkyd resins. PLS methods were created using a number of standard mixtures. Validation and measurement uncertainty estimation was carried out. Binary, ternary and quaternary mixtures of several common binding media and pigments were quantified, with standard measurement uncertainties in most cases below 3g/100g. Classes of components - aromatic anhydrides and alcohols - used in alkyd resin synthesis were also successfully quantified, with standard uncertainties in the range of 2-3g/100g. This is a more demanding application because in alkyd resins aromatic anhydrides and alcohols have reacted to form a polyester, and are not present in their original forms. Once a PLS method has been calibrated, analysis time and cost are significantly reduced from typical quantitative methods such as GC/MS. This is beneficial in the case of routine analysis where the components are known., (Copyright © 2014 Elsevier B.V. All rights reserved.)

N-alkyl-2-pyrrolidones are important organic solvents for varnishes in industry. This study investigates exposure to N-ethyl-2-pyrrolidone (NEP) in varnishing of hard plastic components in an automobile plant. Two specific biomarkers of exposure, 5-hydroxy-N-ethyl-2-pyrrolidone (5-HNEP) and 2-hydroxy-N-ethylsuccinimide (2-HESI), were analyzed in urine samples of 14 workers. For this purpose, pre-shift, post-shift and next day pre-shift urine samples were collected midweek. Twelve workers performed regular work tasks (loading, wiping and packing), whereas two workers performed special work tasks including cleaning the sprayer system with organic solvents containing N-alkyl-2-pyrrolidones. Spot urine samples of nine non-exposed persons of the same plant served as controls. Median post-shift urinary levels of workers with regular work tasks (5-HNEP: 0.15 mg/L; 2-HESI: 0.19 mg/L) were ∼5-fold higher compared to the controls (0.03 mg/L each). Continuously increasing metabolite levels, from pre-shift via post-shift to pre-shift samples of the following day, were observed in particular for the two workers with the special working tasks. Maximum levels were 31.01 mg/L (5-HNEP) and 8.45 mg/L (2-HESI). No clear trend was evident for workers with regular working tasks. In summary, we were able to show that workers can be exposed to NEP during varnishing tasks in the automobile industry., (Copyright © 2014 Elsevier Ireland Ltd. All rights reserved.)

An unambiguous identification of pigments in paint layers of works of art forms a substantial part of the description of a painting technique, which is essential for the evaluation of the work of art including determination of the period and/or region of its creation as well as its attribution to a workshop or an author. Copper pigments represent a significant group of materials used in historic paintings. Because of their substantial diversity and, on the other hand, similarity, their identification and differentiation is a challenging task. An analytical procedure for unambiguous determination of both mineral-type (azurite, malachite, posnjakite, atacamite, etc.) and verdigris-type (copper acetates) copper pigments in the paint layers is presented, including light microscopy under VIS and UV light, electron microscopy with elemental microanalysis, Fourier transformed infrared micro-spectroscopy (micro-FTIR), and X-ray powder micro-diffraction (micro-XRD). Micro-Raman measurements were largely hindered by fluorescence. The choice of the analytical methods meets the contemporary requirement of a detailed description of various components in heterogeneous and minute samples of paint layers without their destruction. It is beneficial to use the combination of phase sensitive methods such as micro-FTIR and micro-XRD, because it allows the identification of both mineral-type and verdigris-type copper pigments in one paint layer. In addition, preliminary results concerning the study of the loss of crystallinity of verdigris-type pigments in proteinaceous binding media and the effect of lead white and lead tin yellow as highly absorbing matrix on verdigris identification in paint layers are reported., (Copyright © 2014 Elsevier B.V. All rights reserved.)

Samples containing red pigment have been collected from two different archaeological sites dating to the Neolithic (Çatalhöyük in Turkey and Sheikh-e Abad in Iran) and have been analysed by a range of techniques. Sub-samples were examined by IR spectroscopy and X-ray diffraction, whilst thin sections were studied using optical polarising microscopy, synchrotron based IR microscopy and environmental scanning electron microscopy with energy dispersive X-ray analysis. Thin layers of red paint in a wall painting from Çatalhöyük were found to contain ochre (hematite and clay) as well as an unexpected component, grains of red and colourless obsidian, which have not been identified in any previous studies of the wall paintings at Çatalhöyük. These small grains of obsidian may have improved the reflective properties of the paint and made the artwork more vivid in the darkness of the buildings. Analysis of a roughly shaped ball of red sediment found on a possible working surface at Sheikh-e Abad revealed that the cause of the red colouring was the mineral hematite, which was probably from a source of terra rossa sediment in the local area. The results of this work suggest it is unlikely that this had been altered by the Neolithic people through mixing with other minerals., (Copyright © 2014 Elsevier B.V. All rights reserved.)

The description of emission processes of volatile and semi-volatile organic compounds (VOCs and SVOCs) from building products requires a detailed understanding of the material and the air flow conditions at the surface boundary. The mass flux between the surface of the material and air depends on the mass transfer coefficient (hm) through the boundary layer, the gas phase concentration of the target compound immediately adjacent to the material (y0), and the gas-phase concentration in bulk air (y(t)). In the present study emission experiments were performed in two chambers of quite different sizes (0.25 m(3) and 55 m(3)), and, in the larger chamber, at two different temperatures (23°C and 30°C). The emitting material was latex wall paint that had been doped with two plasticizers, diethylphthalate (DEP) and di-n-butylphthalate (DnBP). The phthalate content in the paint was varied in the small chamber experiment to evaluate the impact of the initial concentration in the bulk material (C0) on the emission rate. Boundary layer theory was applied to calculate hm for the specific phthalates from the Sherwood number (Sh) and the diffusion coefficient (Dair). Then y0 was determined based on the bulk gas-phase concentration at steady state (y¯). For both, DEP and DnBP, the y0 obtained was lower than the respective saturation vapor pressure (Ps). Furthermore, for both phthalates in latex paint, the material/air partition coefficient (C0/y0) was close in value to the octanol/air partition coefficient (KOA). This study provides a basis for designing phthalate emitting reference materials that mimic the emission behavior of common building materials., (Copyright © 2014 Elsevier B.V. All rights reserved.)

Fragments of flaking paint have been sampled from eighteen boats (including sailing barges, houseboats, a trawler and a ferry) abandoned on the intertidal mudflats of two estuaries in eastern England and analysed for Cu, Pb and Zn by X-ray fluorescence (XRF) spectrometry. Median concentrations of Pb on each boat ranged from about 350 to 35,000 μg g(-1), with individual concentrations exceeding 200,000 μg g(-1) in several cases. Median concentrations of Cu and Zn ranged from about 50 to 1900 μg g(-1) and 50 to 10,000 μg g(-1), respectively, with respective maxima of 172,000 μg g(-1) and 239,000 μg g(-1). Because of peeling paint, local sediment (analysed by ICP following acid digestion) was often measurably contaminated by the metals and, based on median, Al-normalised enrichment factors, in the order Pb>Zn>Cu. Due to its abundance and persistence in old paints, Pb is of greatest concern from both environmental and human health perspectives., (Copyright © 2014 Elsevier B.V. All rights reserved.)

The aim of the paper was to evaluate the influence of pigment concentration and its distribution in polymer binder on the possibility of colour identification and paint sample comparison. Two sets of paint samples: one containing red and another one green pigment were prepared. Each set consisted of 13 samples differing gradually in the concentration of pigment. To obtain the sets of various colour shades white paint was mixed with the appropriate pigment in the form of a concentrated suspension. After solvents evaporation the samples were examined using spectrometric methods. The resin and main filler were identified by IR method. Colour and white pigments were identified on the base of Raman spectra. Colour of samples were compared based on Vis spectrometry according to colour theory. It was found that samples are homogenous (parameter measuring colour similarity ΔE<3). The values of ΔE between the neighbouring samples in the set revealed decreasing linear function and between the first and following one--a logarithmic function., (Copyright © 2014 Elsevier B.V. All rights reserved.)

Paints with high lead concentrations (ppm) continue to be sold around the world in many developing countries and those with economies in transition representing a major preventable environmental health hazard that is being increased as the economies expand and paint consumption is increasing. Prior lead paint testing had been performed in Brazil and India and these countries were selected to examine the impact of a new regulatory limit in Brazil and the impact of efforts of non-governmental organizations and others to stop the use of lead compounds in manufacturing paints. Armenia and Kazakhstan, in Central Asia, were selected because no information on lead concentration in those regions was available, no regulatory activities were evident and non-governmental organizations in the IPEN network were available to participate. Another objective of this research was to evaluate the lead loading (µg/cm(2)) limit determined by X-Ray Fluorescence (XRF) for areas on toys that are too small to obtain a sample of sufficient size for laboratory analysis. The lead concentrations in more than three-fourths of the paints from Armenia and Kazakhstan exceeded 90 ppm, the limit in the United States, and 600 ppm, the limit in Brazil. The percentages were about one-half as high in Brazil and India. The average concentration in paints purchased in Armenia, 25,000 ppm, is among the highest that has been previously reported, that in Kazakhstan, 15,700 ppm, and India, 16,600, about median. The average concentration in Brazil, 5600 ppm, is among the lowest observed. Paints in Brazil that contained an average of 36,000 ppm before the regulatory limit became effective were below detection (< 9 ppm) in samples collected in the current study. The lack of any apparent public monitoring of paint lead content as part of regulatory enforcement makes it difficult to determine whether the regulation was a major factor contributing to the decline in lead use in these paints. Using data from the current study and those available from other studies 24 of 28 paints from major brands in India decreased from high concentrations to 90 ppm or lower. Since lead concentrations in golden yellow paints from these brands were found to decrease to ≤ 90 ppm, it is possible that all 28 of these paints now contain ≤ 90 ppm since yellow paints usually have the highest lead concentrations. Other brands in Brazil and India that have been analyzed only one time had lead concentrations up to 59,000 ppm and 134,000 ppm, respectively. Less than one-third of the paints had notations on their labels with information about lead content and these were sometimes inaccurate. The label from one brand indicating "no added lead" contained paint with 134,000 ppm lead, the highest found in this study. Three percent (3 of 98) of the paints with surface lead loading that did not exceed 2 µg/cm(2), the limit established by the Consumer Product Safety Improvement Act for small areas on toys, contained greater than 90 ppm lead and thus were false negatives. Of the new paint samples that contained ≤ 600 ppm, 88% contained ≤ 90 ppm. Of the samples that contained ≤ 90 ppm, 97% contained ≤ 45 ppm and 92% contained ≤ 15 ppm. Based on these data it appears to be technically feasible to manufacture paints containing ≤ 90 ppm and in many cases to produce paints that have lead concentrations that do not exceed 15 ppm., (Copyright © 2014 Elsevier Inc. All rights reserved.)

Samples from 75 paint products made by 21 domestic and foreign manufacturers were purchased from retail stores in five major cities in Nepal and tested for lead content. Information provided on product labels were noted. Samples were selected to be representative of the large number of brands and colors available in retail shops. Although a majority of the products purchased were manufactured in Nepal, paints from four additional countries were tested. Out of a total of 75 samples, 57 (76%) of the tested paints contained lead at concentrations greater than 90 ppm (ppm). Ninety-three percent of the paints that exceeded 90 ppm had levels in excess of 600 ppm. Lead concentrations in the tested paints ranged up to 200,000 ppm (20%) lead by weight and the median concentration was 5100 ppm. These results indicate that lead paint is commonly being sold for residential and other consumer applications in Nepal without any consumer warnings. Regulations are needed to specify the maximum concentration of lead allowed in paint products manufactured, imported, or distributed in the country to protect public health. Efforts must be made to get lead-containing paint products recalled from stores so that they are not used in homes, schools, and other child-occupied facilities., (Copyright © 2014 Elsevier Inc. All rights reserved.)

Painted metal knight shields of the Order of the Elephant produced during the last part of the 20th century are characterized by a striking variety in their conservation state. Three different coat systems were identified and investigated by Fourier transform infrared microscopy (μ-FTIR), micro-Raman spectroscopy (MRS), scanning electron microscopy-Energy dispersive X-ray spectroscopy (SEM-EDX) and Thermally assisted hydrolysis and methylation-gas chromatography-mass Spectrometry (THM-GC-MS). Chalking of the white paint layer on the first group of knight shields displayed in the window niches was found to be related to the use of titanium white of the anatase type. A pristine condition of the second group could be attributed to priming of the lead rich metal support with a zinc potassium chromate based primer and the use of mainly stable white pigments in the top coat. Severe delamination of the paint layer of the third group was caused by the formation of lead corrosion products between the paint layer and the metal support. The results are discussed in relation to the climatic conditions as well as the historical context of contemporary paint production and availability in Denmark., (Copyright © 2014 Elsevier B.V. All rights reserved.)