Jose Antonio Carrero

Diagnosing the traffic impact on roadside soils through a multianalytical data analysis of the concentration profiles of traffic-related elements

The road traffic has become one of the most serious environmental problems in many cities and the main source of pollution of urban soils. To diagnose properly the magnitude of such impacts on roadside soils, eight urban and metropolitan soils were selected as a function of traffic density, distance to the road and years of operation, for which the concentration of 60 elements (major, minor and trace elements) were measured by semi-quantitative ICP-MS after acid digestion, as a first step in assessing the traffic impact. With this information, a comprehensive study was carried out focusing on the quantitative analysis of the concentration of 46 elements from the 8 sampling areas, analyzing the vertical and horizontal distributions of the metals in the roadside soils. The chemometric analysis showed that only the traffic-related elements accumulate in topsoil and present a high decreasing profile with depth and the distance to the road; however, this clear behavior takes places only in old roads that have undergone the traffic impact for a long time, but not in new roads or roads with low traffic density. Finally, the geoaccumulation indexes are suggested to be used instead of the local guidelines to assess the pollution state of the roadside soils, especially for the emerging trace elements like Antimony.

The cauliflower-like black crusts on sandstones: A natural passive sampler to evaluate the surrounding environmental pollution

Black crust in buildings can be formed as a result of different kind of chemical and physical reactions between the stone surface and environmental factors (e.g. acid aerosols emitted to the atmosphere, airborne particulate matter, etc.). Moreover, biological colonizations can also be present on them. This kind of pathology is widely present in limestones, but fewer are the case study dealing with the characterization of black crusts on sandstones. In this work we present an innovative methodology based on the use of cauliflower-like black crusts formed on sandstone material as natural passive sampler to evaluate the environmental pollution related with the emission of natural (crustal particles and marine aerosol particles) and metallic elements in the airborne particulate matter from the surrounding atmosphere. To illustrate its usefulness, different cauliflower-like black crusts growing in areas protected from the rain growing in an historical construction, La Galea Fortress, made up of sandstone and placed in the Abra Bay (Getxo, Basque Country, Spain) were characterized. This area suffers the anthropogenic emissions coming from the surrounding industry, traffic, sea port, and the natural ones coming from the surrounding marine atmosphere. The applied analytical methodology began with a previous elemental in situ screening in order to evaluate and compare the presence of the metals trapped in black crusts from different orientations using a hand-held energy dispersive X-Ray Fluorescence spectrometer. After this preliminary study, samples of black crusts were taken in order to characterize them in the laboratory using molecular techniques (Raman spectroscopy and XRD) and elemental techniques (ICP-MS, SEM-EDS and micro energy dispersive X-Ray Fluorescence). With the last two elemental techniques, imaging analyses were performed at different lateral resolutions in order to observe the distribution of the metals and other kind of particles trapped in the black crust samples. Additionally, a biological colonization found beneath the black crusts was also characterized using Phase Contrast microscopy.

The influence of rainwater composition on the conservation state of cementitious building materials

Rainwater is one of the main pollution tracers around the world. There are many reasons that can explain the presence of high concentrations of certain hazardous elements (HEs) in the rainwater (traffic, marine port activities, industry, etc.). In this work, rainwater samples were collected at six different locations in the Metropolitan Bilbao (Basque Country, north of Spain) during November 2014. HE concentrations were determined by means of inductively coupled plasma mass spectrometry (ICP-MS) and anions by ion chromatography. The pH and redox potential values on these samples were also assessed. According to the obtained results, different trends along the estuary of Bilbao have been observed. To corroborate some hypothesis, thermodynamic simulations and correlation analyses were also carried out using quantitative data. These trends are closely related to the surrounding pollution and marine influence. Finally, in order to ascertain the influence of the Metropolitan Bilbao rainwater on buildings materials, a recent construction was characterized. Using techniques such as Scanning Electron Microscopy coupled with Energy Dispersive X-Ray Spectroscopy (SEM–EDS) and Raman Spectroscopy, different types of sulfates and nitrates were observed.

Diffuse reflectance FTIR database for the interpretation of the spectra obtained with a handheld device on built heritage materials

FTIR handheld devices, working in the diffuse reflectance mode (DRIFT), are promising analytical instruments to perform in situ analyses on cultural heritage materials. However, in the analyses performed in situ with such DRIFT handheld devices, distortions in the DRIFT spectra can be observed in the measurements due to the presence of specular reflection, showing inverted bands in those IR bands with the highest absorption index. These distortions present in the spectra obtained with handheld devices make their resolution very difficult unless the working mode of the devices is well known and a suitable DRIFT database is available. With the aim of getting the most suitable tools to perform analyses in the field, this work has been developed considering two important aspects. In the first one, the differences between the spectra obtained in transmittance, attenuated total reflectance and diffuse reflectance modes of some compounds (nitrates, sulphates and carbonates) that could show the inverted bands when measured with a FTIR handheld device have been studied. In the second one, a preliminary database of several compounds that can be found as original (bulk) compounds or as efflorescence in affected built heritage materials, obtained in the laboratory in diffuse reflectance mode, is presented. Finally, the usefulness of the presented database has been tested using the spectra obtained in situ in the Fishermens association building (San Sebastian, Basque Country, north of Spain) on areas presenting several decaying processes.

Multispectroscopic and Isotopic Ratio Analysis To Characterize the Inorganic Binder Used on Pompeian Pink and Purple Lake Pigments

Because of the fact that pigments are not ubiquitous in the archeological record, the application of noninvasive analytical methods is a necessity. In this work, pink and purple lake pigments recovered from the excavations of the ancient city of Pompeii (Campania, Italy) and preserved in their original bowls at the Naples National Archaeological Museum (Italy) were analyzed to characterize the composition of their inorganic binders (mordants). In situ preliminary analyses using a hand-held energy dispersive X-ray fluorescence spectrometer (HH-ED-XRF) allowed us to determine the use of an aluminosilicate enriched in Cu and Pb. Scanning electron microscopy coupled to energy dispersive X-ray spectrometry (SEM-EDS) and benchtop ED-XRF analyses confirmed these results, while inductively coupled plasma mass spectrometry (ICPMS) allowed one to determine the concentration of major, minor, and trace elements. The use of other techniques such as X-ray diffraction (XRD), and micro-Raman and infrared spectroscopies allowed one to characterize the pigments at the molecular level. The high concentration of Cu detected in the pigments (1228-12937 μg g(-1)) could be related to the addition of Cu salts to obtain the desired final hue. The concentrations of Pb (987-2083 μg g(-1)) was also remarkable. Lead isotopic ratio analysis ((206)Pb/(207)Pb) suggested a possible origin related to the leaching of the ancient lead pipes from Pompeii and the subsequent transfer to the buried pigments or to the inorganic binder. Molecular analysis also showed that the binder is composed of an allophane-like clay. Moreover, it was possible to determine that to obtain the final purple hue of a specific pigment, Pompeian blue pigment was also mixed into the dyed clay.

The usefulness of a sediment bioassay with the gastropod Nassarius reticulatus in tributyltin monitoring programs

Despite the use of tributyltin (TBT) had been banned worldwide in 2008 there is still evidence of its deleterious presence in environment. We evaluate the usefulness of a 28days sediment bioassay with Nassarius reticulatus females to monitor TBT pollution, using imposex as endpoint. In addition, butyltins were determined in sediments and tissues, and, whenever posible, imposex was assessed in native N. reticulatus at the same sites where sediments were sampled. In the bioassay, a significant increase in imposex parameters was obtained with three sediments (Vi2, Vi3, and Vi4). No correlation was found between this and TBT concentrations in sediment although good correlations were obtained for TBT in tissues, putting in evidence TBT bioavailability in sediment. A significant decrease in imposex from 2008 to 2013 in native snails was only observed at sites that did not cause any effect in the bioassay. In contrast, imposex levels in 2013 were kept as high as 2008 in one of the sites where a significant imposex increase in the bioassay was observed. The bioassay proves thus to be a practical and ecological relevant tool, as: (i) it can be conducted in sites with no native populations of snails, (ii) it provides early identification of polluted sites, anticipating future imposex levels or early identification of recovering, and (iii) it yields information on the bioavailable fraction of the TBT in the sediment. Therefore, this tool can be of extreme usefulness under the scope of recent European legislative frameworks.

Accumulation and Translocation of Essential and Nonessential Elements by Tomato Plants (Solanum lycopersicum) Cultivated in Open-Air Plots under Organic or Conventional Farming Techniques.

A 5-month experiment was performed to study the accumulation of several inorganic elements in tomato plants cultivated using organic or synthetic fertilizer. Plants were harvested in triplicate at six sampling dates during their life cycle. Statistical and chemometric analysis of data indicated the sequestration of toxic elements and of Na, Zn, Fe, and Co in roots, while the rest of the elements, including Cd, were mainly translocated to aboveground organs. A general decreasing trend in element concentrations with time was observed for most of them. A negative correlation between some element concentrations and ripening stage of fruits was identified. Conventionally grown plants seemed to accumulate more Cd and Tl in their tissues, while organic ones were richer in some nutrients. However, there was no clear effect of the fertilizer used (organic vs synthetic) on the elemental composition of fruits.

Micro-Raman spectroscopic identification of natural mineral phases and their weathering products inside an abandoned zinc/lead mine

Mining activities provide a good source of minerals of different nature. On the one hand, the primary minerals for whose formation a geological time-scale is required. On the other hand, secondary minerals, formed from removed products after the earlier weathering and alteration states. These are characteristic of the local geology and the environment context that commonly appears due to the low chemical stability of their original primary minerals. This work shows how quickly the reactions promoting secondary minerals may have taken place, due to the fact that these were found in newly formed solid materials called efflorescences. To achieve this purpose, the sampling is crucial. It was carried out in such a way that tried to guarantee that the samples collected consisted in the very top soil matter (first 2 cm depth). Thus, unlike the deeper soil, the material analysed may have been newly formed due to the interactions that they had with the place weathering agents (i.e. air oxygen, humidity, and microbial activities). Raman spectroscopy has emerged as a good and fast non-destructive technique that provides molecular information of the local mineralogy without the need of any pre-treatment of the samples. At the same time, the work looked for information on the variety of non-stable lead and-or zinc containing minerals due to the possible health and environmental risks they convey. Among the different minerals identified, 16 were of primary nature while 23 may be classified as secondary minerals, probably formed in the last decades as the result of the extractive activities.

Diagnosing the Impact of Traffic on Roadside Soils Through Chemometric Analysis on the Concentrations of More Than 60 Metals Measured by ICP/MS

This study aims to establish the impact of traffic pollution at two parallel roads in the province of Biscay (North of Spain). Soil samples digestions were carried out following the EPA 3051A method and the extracts were analyzed by ICP/MS. A rapid screening method for the determination of more than 60 metals is proposed. The subsequent chemometric treatment of the obtained data shows the presence of more than ten traffic related metals: Cd, Cr, Cu, Hf, Mo, Nb, Ni, Pb, Sb, Sn, Sr, Zn and Zr. Different soil types (in the old road and in the highway) can be distinguished by means of its rare earth and alkaline metal concentration. Very high concentrations of Zn were found in soil under the guard rail.

Are children playgrounds safe play areas? Inorganic analysis and lead isotope ratios for contamination assessment in recreational (Brazilian) parks

In city playgrounds, there is a potential risk of harming children’s health by contamination coming from anthropogenic activities. With the aim to determinate the sources and the risk of hazardous elements, soil samples were collected in 19 selected playgrounds of different urban and rural areas from the Rio Grande do Sul state (Brazil). The concentration of 23 metals and metalloids and lead isotopic ratios were determined by ICP-MS. The methodology proposed here, firstly, classified the parks according to the average metal content by means of the NWACs (Normalized-and-Weighted Average Concentrations) and assess the contamination risk determining the Contamination Factors (CFs). Finally, statistical tools (correlation analysis and principal component analysis) were used to identify the most important contamination sources. The statistical tools used, together with lead isotopic composition analysis of the samples, revealed that coal combustion is the main source of contamination in the area. Vegetation was identified as a barrier for the contamination coming from the city. Nonetheless, some of the soils present a possible toxicological risk for humans. In fact, Cr, Sb, and Pb concentrations were higher than the Residential Intervention Values (VIRs) defined by the Environmental Protection Agency of the State of São Paulo, also in Brazil.