A new approach for routine quantification of microplastics using Nile Red and automated software (MP-VAT).

Microplastics are widespread contaminants in the environment. However, most identification protocols rely on long and subjective visual counting, which could be improved using staining dyes. Thus, the objective of this work is to identify the best staining dye protocol and create an objective and quick automated counting software for microplastics. Tests were conducted to identify the most appropriate of eight staining dye solutions and of six wavelengths for virgin and weathered synthetic polymers, textile fibers, natural organic matter and filters. Nile Red produced the best results (without interfering in infrared spectra) rendering microplastics fluorescent at 254 nm, but with limited number of fluorescent polymers, and at 470 nm (with orange filter), with fluorescence of plastics as well as natural organic matter (requiring a digestion step). Next, a script was developed in ImageJ for the automatic quantification and characterization in shape (fiber, fragment, particle) and size of fluorescent microplastics, the Microplastics Visual Analysis Tool (MP-VAT). MP-VAT was evaluated, producing recovery rates in the range of 89.0-111.1% in spiked filters under 470 nm. Furthermore, this package is accompanied by a script that sets a scale from a known filter diameter, MP-SCALE, and a script that allows user threshold setting, MP-ACT.

Persistence of urban organic aerosols composition: Decoding their structural complexity and seasonal variability.

Organic Aerosols (OAs) are typically defined as highly complex matrices whose composition changes in time and space. Focusing on time vector, this work uses two-dimensional nuclear magnetic resonance (2D NMR) techniques to examine the structural features of water-soluble (WSOM) and alkaline-soluble organic matter (ASOM) sequentially extracted from fine atmospheric aerosols collected in an urban setting during cold and warm seasons. This study reveals molecular signatures not previously decoded in NMR-related studies of OAs as meaningful source markers. Although the ASOM is less hydrophilic and structurally diverse than its WSOM counterpart, both fractions feature a core with heteroatom-rich branched aliphatics from both primary (natural and anthropogenic) and secondary origin, aromatic secondary organics originated from anthropogenic aromatic precursors, as well as primary saccharides and amino sugar derivatives from biogenic emissions. These common structures represent those 2D NMR spectral signatures that are present in both seasons and can thus be seen as an "annual background" profile of the structural composition of OAs at the urban location. Lignin-derived structures, nitroaromatics, disaccharides, and anhydrosaccharides signatures were also identified in the WSOM samples only from periods identified as smoke impacted, which reflects the influence of biomass-burning sources. The NMR dataset on the H-C molecules backbone was also used to propose a semi-quantitative structural model of urban WSOM, which will aid efforts for more realistic studies relating the chemical properties of OAs with their atmospheric behavior.

Structural signatures of water-soluble organic aerosols in contrasting environments in South America and Western Europe.

This study describes and compares the key structural units present in water-soluble organic carbon (WSOC) fraction of atmospheric aerosols collected in different South American (Colombia - Medellín and Bogotá, Peru - Lima, Argentina - Buenos Aires, and Brazil - Rio de Janeiro, São Paulo, and Porto Velho, during moderate (MBB) and intense (IBB) biomass burning) and Western European (Portugal - Aveiro and Lisbon) locations. Proton nuclear magnetic resonance (1H NMR) spectroscopy was employed to assess the relative distribution of non-exchangeable proton functional groups in aerosol WSOC of diverse origin, for the first time to the authors' knowledge in South America. The relative contribution of the proton functional groups was in the order H-C > H-C-C= > H-C-O > Ar-H, except in Porto Velho during MBB, Medellín, Bogotá, and Buenos Aires, for which the relative contribution of H-C-O was higher than that of H-C-C=. The 1H NMR source attribution confirmed differences in aging processes or regional sources between the two geographic regions, allowing the differentiation between urban combustion-related aerosol and biological particles. The aerosol WSOC in Aveiro, Lisbon, and Rio de Janeiro during summer are more oxidized than those from the remaining locations, indicating the predominance of secondary organic aerosols. Fresh emissions, namely of smoke particles, becomes important during winter in Aveiro and São Paulo, and in Porto Velho during IBB. The biosphere is an important source altering the chemical composition of aerosol WSOC in South America locations. The source attribution in Medellín, Bogotá, Buenos Aires, and Lima confirmed the mixed contributions of biological material, secondary formation, as well as urban and biomass burning emissions. Overall, the information and knowledge acquired in this study provide important diagnostic tools for future studies aiming at understanding the water-soluble organic aerosol problem, their sources and impact at a wider geographic scale.

Tracing of aerosol sources in an urban environment using chemical, Sr isotope, and mineralogical characterization.

In the framework of two national research projects (ORGANOSOL and CN-linkAIR), fine particulate matter (PM2.5) was sampled for 17 months at an urban location in the Western European Coast. The PM2.5 samples were analyzed for organic carbon (OC), water-soluble organic carbon (WSOC), elemental carbon (EC), major water-soluble inorganic ions, mineralogical, and for the first time in this region, strontium isotope (87Sr/86Sr) composition. Organic matter dominates the identifiable urban PM2.5 mass, followed by secondary inorganic aerosols. The acquired data resulted also in a seasonal overview of the carbonaceous and inorganic aerosol composition, with an important contribution from primary biomass burning and secondary formation processes in colder and warmer periods, respectively. The fossil-related primary EC seems to be continually present throughout the sampling period. The 87Sr/86Sr ratios were measured on both the labile and residual PM2.5 fractions as well as on the bulk PM2.5 samples. Regardless of the air mass origin, the residual fractions are more radiogenic (representative of a natural crustal dust source) than the labile fractions, whose 87Sr/86Sr ratios are comparable to that of seawater. The 87Sr/86Sr ratios and the mineralogical composition data further suggest that sea salt and mineral dust are important primary natural sources of fine aerosols throughout the sampling period.

Two chemically distinct light-absorbing pools of urban organic aerosols: A comprehensive multidimensional analysis of trends.

The chemical and light-absorption dynamics of organic aerosols (OAs), a master variable in the atmosphere, have yet to be resolved. This study uses a comprehensive multidimensional analysis approach for exploiting simultaneously the compositional changes over a molecular size continuum and associated light-absorption (ultraviolet absorbance and fluorescence) properties of two chemically distinct pools of urban OAs chromophores. Up to 45% of aerosol organic carbon (OC) is soluble in water and consists of a complex mixture of fluorescent and UV-absorbing constituents, with diverse relative abundances, hydrophobic, and molecular weight (Mw) characteristics between warm and cold periods. In contrast, the refractory alkaline-soluble OC pool (up to 18%) is represented along a similar Mw and light-absorption continuum throughout the different seasons. Results suggest that these alkaline-soluble chromophores may actually originate from primary OAs sources in the urban site. This work shows that the comprehensive multidimensional analysis method is a powerful and complementary tool for the characterization of OAs fractions. The great diversity in the chemical composition and optical properties of OAs chromophores, including both water-soluble and alkaline-soluble OC, may be an important contribution to explain the contrasting photo-reactivity and atmospheric behavior of OAs.

A simple approach to reduce dimensionality from comprehensive two-dimensional liquid chromatography coupled with a multichannel detector.

Comprehensive two-dimensional liquid chromatographic (LC×LC) systems play an ever increasing role in separation and characterization of complex samples. When coupled with multichannel detectors, such as the diode array detector, these LC×LC systems become especially useful for non-target analysis and identification of patterns based on the information extracted from those complex samples. Nevertheless, due to the large amount of data generated by these systems, the extraction of useful information for the identification of patterns still is one of the major drawbacks for a wider application of this technique. As a preliminary step in data treatment, we have developed a simple and fast way to deal with this large amount of multi-dimensional data by identifying the three-dimensional (3D) regional maxima of each chromatographic peak generated in a LC×LC-DAD system: retention times at the peak maximum in the first- and second-dimensions and the wavelength of the maximum UV absorption. This dataset is then used to build a 3D fingerprinting of the given sample, which alongside the 3D fingerprinting of other samples, can be used to identify different patterns associated with the specific properties of every sample under study. The applicability of the developed methodology was further assessed by performing a non-target LC×LC-DAD analysis of four Portuguese red wine samples.

A generalization of a chromatographic response function for application in non-target one- and two-dimensional chromatography of complex samples.

New flexible chromatographic response functions for one-dimensional (DCRF(f)) and two-dimensional chromatography (DCRF(f,2D)) are put forward and tested for estimating the quality index of separation in non-targeted chromatographic analysis of complex samples. These functions, based on already tested functions, have three clear-cut criteria: number of chromatographic peaks, degree of chromatographic separation, and time spent in the analysis. However, unlike the existing functions, they allow an accurate weighing and adjustment of these criteria according to the needs of the analyst. Special attention was given to the time spent in the analysis by introducing a time-saving criterion, which allowed its application in time dependent chromatographic systems. The performance and flexibility of the strategies based on the developed response functions are tested in different chromatographic scenarios and for several application possibilities using simulated chromatograms.

Trends in data processing of comprehensive two-dimensional chromatography: state of the art.

The operation of advanced chromatographic systems, namely comprehensive two-dimensional (2D) chromatography coupled to multidimensional detectors, allows achieving a great deal of data that need special care to be processed in order to characterize and quantify as much as possible the analytes under study. The aim of this review is to identify the main trends, research needs and gaps on the techniques for data processing of multidimensional data sets obtained from comprehensive 2D chromatography. The following topics have been identified as the most promising for new developments in the near future: data acquisition and handling, peak detection and quantification, measurement of overlapping of 2D peaks, and data analysis software for 2D chromatography. The rational supporting most of the data processing techniques is based on the generalization of one-dimensional (1D) chromatography although algorithms, such as the inverted watershed algorithm, use the 2D chromatographic data as such. However, for processing more complex N-way data there is a need for using more sophisticated techniques. Apart from using other concepts from 1D chromatography, which have not been tested for 2D chromatography, there is still room for new improvements and developments in algorithms and software for dealing with 2D comprehensive chromatographic data.

A new chromatographic response function for assessing the separation quality in comprehensive two-dimensional liquid chromatography.

A new chromatographic response function (CRF(2D)) is proposed and tested for the estimation of the quality index of separation in comprehensive two-dimensional liquid chromatography (2D-LC) of complex organic mixtures. This objective function is based on the concept of peak purity for one-dimensional liquid chromatography, which has been redefined for 2D-LC. The new CRF(2D) also includes other separation quality criteria, namely the number of 2D peaks appearing in the chromatogram and the analysis time. To compute the peak purity for a given 2D peak, three important steps have been tackled in this study: (a) the development of an alternative algorithm for detecting 2D peaks automatically from real experimental 2D-LC data; (b) the application of a mathematical model to fit the obtained chromatographic data; and (c) the estimation of the volume of the overlapping region between two or more 2D peaks. The performance of the developed CRF(2D) was compared to that of an existing resolution measure, using simulated chromatograms. The capability of the new function to qualify the overall separation degree that it is attained under different chromatographic conditions was further assessed through a 2D-LC study of a mixture of four aromatic compounds.