Source-specific geochemical and health risk assessment of anthropogenically induced metals in a tropical urban waterway.

Thorough deliberation is necessary to safeguard the tropical urban streams near the shoreline from human interference, as it is becoming a notable environmental danger. Consequently, an in-depth study was carried out on a significant urban waterway located on the southern seashore of Bangladesh, which is positioned in the Bengal delta, renowned as the largest delta in the globe. The current investigation assesses the potential health hazards associated with trace metals (Hg, Cu, As, Pb, Ni, Zn, Cd, Cr, Fe, and Mn) and uses chemometric analysis to determine where they originate. Likewise geochemical methods are used to analyze the levels of trace metal enrichment and pollution in the sediments of the river. Almost all of the elements' mean concentrations were observed to be within the standard limits. The findings not only demonstrate the extent of trace metal contamination but also the health threats that it poses to the public (male, female, and children) by polluting the sediment. For all age groups of people, the hazard index was <1, suggesting there was no non-carcinogenic threat. Regardless of age and sex, exposure occurred in descending order: ingestion > dermal > inhalation. Total carcinogenic risk (TCR) values for males, females, and children were 1.45E-05, 1.56E-05, and 1.34E-04, respectively, recommending that children are at greater vulnerability than adults. The geochemical approach and chemometric analysis corroborate the human-induced impact of trace metal loading in the sediment of the waterway, which is predominantly caused by the oil industry, domestic garbage, and untreated waste discharge.

Assessment of essential and toxic elemental concentrations in tumor and non-tumor tissues with risk of colorectal carcinoma in Pakistan.

BACKGROUND: Colorectal tumor is a major cause of cancer morbidity and mortality both in USA and around the globe. Exposure to environmental toxicants such as toxic trace elements has been implicated in colorectal malignancy. However, data linking them to this cancer are generally lacking. METHODS: Accordingly, the current study was to investigate the distribution, correlation and chemometric evaluation of 20 elements (Ca, Na, Mg, K, Zn, Fe, Ag, Co, Pb, Sn, Ni, Cr, Sr, Mn, Li, Se, Cd, Cu, Hg and As) in the tumor tissues (n = 147) and adjacent non tumor tissues (n = 147) of same colorectal patients which were analyzed by flame atomic absorption spectrophometry employing nitric acid-perchloric acid based wet digestion method. RESULTS: On the average, Zn (p < 0.05), Ag (p < 0.001), Pb (p < 0.001), Ni (p < 0.01), Cr (p < 0.005) and Cd (p < 0.001) showed significantly higher levels in the tumor tissues compared with the non tumor tissues of patients, whereas mean levels of Ca (p < 0.01), Na (p < 0.05), Mg (p < 0.001), Fe (p < 0.001), Sn (p < 0.05) and Se (p < 0.01), were significantly elevated in the non tumor tissues than the tissues of tumor patients. Most of the elements revealed markedly disparities in their elemental levels based on food (vegetarian/nonvegetarian) habits and smoking (smoker/nonsmoker) habits of donor groups. The correlation study and multivariate statistical analyses demonstrated some significantly divergent associations and apportionment of the elements in the tumor tissues and non tumor tissues of donors. Noticeably, variations in the elemental levels were also noted for colorectal tumor types (lymphoma, carcinoids tumor and adenocarcinoma) and stages (I, II, III, & IV) in patients. CONCLUSION: Overall, the study revealed that disproportions in essential and toxic elemental concentrations in the tissues are involved in pathogenesis of the malignancy. These findings provide the data base that helps to oncologist for diagnosis and prognosis of colorectal malignant patients.

Metabolomic Profile of Volatile Organic Compounds from Leaves of Cashew Clones by HS-SPME/GC-MS for the Identification of Candidates for Anthracnose Resistance Markers.

Anthracnose caused by Colletotrichum gloeosporioides affects the leaves, inflorescences, nuts, and peduncles of cashew trees (Anacardium occidentale). The use of genetically improved plants and the insertion of dwarf cashew clones that are more resistant to phytopathogens are strategies to minimize the impact of anthracnose on cashew production. However, resistance mechanisms related to the biosynthesis of secondary metabolites remain unknown. Thus, this study promoted the investigation of the profile of volatile organic compounds of resistant cashew clone leaves ('CCP 76', 'BRS 226' and 'BRS 189') and susceptible ('BRS 265') to C. gloeosporioides, in the periods of non-infection and infection of the pathogen in the field (July-December 2019 - Brazil). Seventy-eight compounds were provisionally identified. Chemometric analyses, such as Principal Component Analysis (PCA), Discriminating Partial Least Squares Analysis (PLS-DA), Discriminating Analysis of Orthogonal Partial Least Squares (OPLS-DA), and Hierarchical Cluster Analysis (HCA), separated the samples into different groups, highlighting hexanal, (E)-hex-2-enal, (Z)-hex-2-en-1-ol, (E)-hex-3-en-1-ol, in addition to α-pinene, α-terpinene, γ-terpinene, ß-pinene, and δ-3-carene, in the samples of the resistant clones in comparison to the susceptible clone. According to the literature, these metabolites have antimicrobial activity and are therefore chemical marker candidates for resistance to C. gloeosporioides in cashew trees.

Optimization of experimental conditions by surface enhanced Raman Scattering (SERS) spectroscopy with gold nanoparticles suspensions.

Surface Enhanced Raman Scattering (SERS) spectroscopy is a rapid and innovative analysis technique involving metallic nanoparticles (NPs). The interaction between NPs and norepinephrine gives an exaltation of the Raman signal under certain experimental conditions. The control of the signal exaltation, crucial for sensitive analyses, remains one of the main limitations of this technique. The aim of this work is to optimize the exaltation conditions for an optimal SERS signal at two concentrations of norepinephrine (NOR) and spherical gold NPs in suspension. This first work will fix the optimal experimental conditions essential for the development of robust discriminant and quantitative analysis of catecholamine. Two complete 3-factors 3-levels experiment designs were performed at 20 µg.mL-1 and 100 µg.mL-1 norepinephrine concentrations, each experiment being repeated 3 times. The optimization factors were the process of synthesis (variation of the quantity of gold and citrate used for the three synthesis SA, SB and SC) and HCl (0.3 M, 0.5 M, 0.7 M) as well as the volume ratio of NPs and norepinephrine (0.5, 2, 3.5) for SERS acquisition. Spectral acquisitions were performed with a handheld Raman spectrometer with an excitation source at 785 nm. For each sample, 31 acquisitions were realized during 3 s every 8 s. The optimization parameter was the intensity of the characteristic band of norepinephrine at 1280 cm-1. A total of 5,042 spectra were acquired and the pre-treatment selected for all spectra was asymmetric least square combined to a smoothing of Savistsky Golay (ALS - SG). The optimal contact time between norepinephrine and NPs depends on the experimental conditions and was determined for each experiment according to the mean intensity between the three replicates. After interpretation of the experimental designs, the optimal conditions retained were the quantity of gold corresponding to SA and the HCl concentration 0.7 M for the two concentrations of norepinephrine. Indeed, the optimal volume ratio depend on the NOR concentration.

Volatile Oil Profile of Prickly Ash (Zanthoxylum) Pericarps from Different Locations in China.

Volatile oils of prickly ash (Zanthoxylum) pericarps have various potential biological functions with considerable relevance to food, pharmacological, and industrial applications. The volatile profile of oils extracted from prickly ash pericarps obtained from 72 plantations in China was determined by gas chromatography and mass spectrometry. Several chemometric analyses were used to better understand the volatile oil profile differences among different pericarps and to determine the key factors that affected geographical variations in the main volatile constituents of oils. A total of 47 constituents were detected with D-limonene, alfa-myrcene, and linalool as the most abundant. The volatile profile of pericarp oils was significantly affected by prickly ash species and some environmental factors, and the key factors that affected volatile profile variations for different prickly ash species were diverse. Chemometric analyses based on the volatile oil profile could properly distinguish Z. armatum pericarps from other pericarps. This study provides comprehensive information on the volatile oil profile of pericarps from different prickly ash species and different plantations, and it can be beneficial to a system for evaluating of pericarp quality. Moreover, this study speculates on the key environmental factors that cause volatile oil variations for each species, and can help to obtain better prickly ash pericarp volatile oils by improving the cultivated environments.

1H HR-MAS NMR and chemometric methods for discrimination and classification of Baccharis (Asteraceae): A proposal for quality control of Baccharis trimera.

Baccharis trimera is a species recognized by health agencies and recommended by the Brazilian Pharmacopoeia by having medicinal properties. In this work, HR-MAS NMR spectroscopy combined with chemometric tools, such as Principal Components Analysis (PCA), Partial Least Squares Discriminant Analysis (PLS-DA) and Soft Independent Modeling by Class Analogy (SIMCA), were used to evaluate the quality control and authenticity of commercial samples of Baccharis, as well as to discriminate B. trimera samples from other species of the Caulopterae section (B. articulata, B. trimera, B. junciformis, B. milleflora, and B. myriocephala). The high morphological similarity of these species makes it difficult for their identifications and discriminations, even by taxonomists. Different PCA pre-processing (autoscaling, Pareto scaling, and mean centering) allowed to discriminate B. trimera and B. myriocephala from the other species, mainly due to the presence of carquejyl acetate, indicated their chemical similarity. The 1H HR-MAS NMR spectral profile offers the possibility of tracking not only the chemical markers, such as the presence of carquejyl acetate, which can also be helpful in the B. trimera authentication/identification. The application of classification methods in standard samples revealed that PLS-DA models showed better performance on the calibration and validation sets than SIMCA model. However, PLS-DA and SIMCA applied to commercial samples showed that none of the commercial samples were classified as B. trimera, which suggested the lack of strict quality control regarding these products. The methodology developed in the present work might contribute to chemotaxonomy of the genus Baccharis.

Comparative quality of the forms of decoction pieces evaluated by multidimensional chemical analysis and chemometrics: Poria cocos, a pilot study.

Many Chinese medicinal materials (CMMs) are parts of plants or fungi that have been processed into different physical forms, termed decoction pieces, that are typically boiled in water for consumption. One CMM may have several decoction pieces forms, e.g., slices, small cubes (dice), or grains. The specifications that have different morphological parameters (shape, size and thickness) for these various decoction pieces have been developed over, in some cases, centuries of practice. Nevertheless, whether and how the form of decoction pieces affects the extraction (decoction) dynamics, and quality stability during storage has not been studied. Here, we investigated Poria cocos (PC) as a pilot study; we explore how the form of PC decoction pieces affects its chemistry using multidimensional chemical evaluation such as ultra-performance liquid chromatography-photodiode array-quadrupole time-of-flight mass spectrometry (UHPLC-PDA-QTOF-MS/MS), ultra-performance liquid chromatography-triple quadrupole mass spectrometry (UHPLC-QqQ-MS/MS) and high performance gel permeation chromatography coupled with charged aerosol detector (HPGPC-CAD), combined with analysis of variance (ANOVA), principal component analysis (PCA), factor analysis (FA) and hierarchical cluster analysis (HCA). The results indicated that different specifications had significant differences, and these specifications could be divided into four groups. The comprehensive results of the chemical analyses undertaken here indicate that the highest potentially available quality of PC decoction pieces was in the forms of curl, ultra-small grains and small grains, followed by thin slices. This information not only is conducive to promoting the standardization of the specification/form of PC decoction pieces and maximizing the benefits from its utilization, but also provide a promising strategy for assessing other CMM decoction pieces in different forms.

Raman spectroscopy for the differentiation of Arabic coffee genotypes.

The objective of this study was to evaluate the ability of Raman spectroscopy to identify the genotype of green coffee beans. Four genotypes of Arabic coffee: one Mundo Novo line (G1) and three Bourbon lines (G2, G3, and G4). The harvest was selected using a wet processing method. Raman spectra of the samples were obtained using a FT-Raman RFS/100 spectrometer in the spectral range of 3500-400 cm-1. The data were treated using chemometric unsupervised classification tools and supervised analysis. Using the unsupervised analysis (PCA), the apparent tendency of agglomeration between samples G1 and G3 was verified. These differences were present in the spectral bands that are characteristic of fatty acids and kahweol. Based on this information, a classification model to discriminate (PLS-DA) the Mundo Novo and Bourbon samples was utilized. Raman spectroscopy allowed the building of an adequate model to differentiate between coffee genotypes.

Advanced Analysis of Roots and Tubers by Hyperspectral Techniques.

Hyperspectral techniques in terms of spectroscopy and hyperspectral imaging have become reliable analytical tools to effectively describe quality attributes of roots and tubers (such as potato, sweet potato, cassava, yam, taro, and sugar beet). In addition to the ability for obtaining rapid information about food external or internal defects including sprout, bruise, and hollow heart, and identifying different grades of food quality, such techniques have also been implemented to determine physical properties (such as color, texture, and specific gravity) and chemical constituents (such as protein, vitamins, and carotenoids) in root and tuber products with avoidance of extensive sample preparation. Developments of related quality evaluation systems based on hyperspectral data that determine food quality parameters would bring about economic and technical values to the food industry. Consequently, a comprehensive review of hyperspectral literature is carried out in this chapter. The spectral data acquired, the multivariate statistical methods used, and the main breakthroughs of recent studies on quality determinations of root and tuber products are discussed and summarized. The conclusion elaborates the promise of how hyperspectral techniques can be applied for non-invasive and rapid evaluations of tuber quality properties.

A microclimate study on hypogea environments of ancient roman building.

Roman hypogea, vernacular settlements or crypts, are underground places characterised by specific and unique challenges (RH<90% and almost constant temperature throughout the whole year) related to their relative isolation from the outdoor environment. These sites often require adequate monitoring tools providing complete environmental information in order to carry out appropriate strategies for scheduling routine maintenance and designing suitable layouts for their preservation. In this work we present the results of a carefully planned thermo-hygrometric monitoring campaign conducted in a peculiar Roman building (130CE), the "Casa di Diana" Mithraeum, sited in Ostia Antica (archaeological site, Rome-Italy), with the aim of characterising the indoor environment as the structure suffers of several conservation problems (biocolonisation, efflorescences, evaporating and condensing cycle for wall-building materials). The campaign involving multipoint continuous measurement was carefully planned to better describe this micro-clime. In addition to underground environmental data available in literature, we have also performed, as a checkpoint control, a thermo-hygrometric monitoring campaign in the "Terme di Mitra" Hypogeum, a few meters from the "Casa di Diana". The recorded data was analysed by multivariate statistical and chemometric analyses. The results brought to light the presence of different microclimates (three areas) within a single Mithraeum: a room (pre-Mithraeum) and an area (Mithraeum: 2-4m) present a thermo-hygrometric environmental behaviour in accordance with a semi-confined environment, another area (Mithraeum: 1-2m) behaves accordingly with underground environments (although it cannot be described as such), and the last area (Mithraeum: 0-1m) where was recording RH values close to saturation (96-99%), associated with non-ventilated areas where the rising damp is "held" and not dispersed, describing an own micro-clime, comparable to a "small greenhouse". This study has allowed to identify some critical areas in view of planning future conservation solutions, without exporting the artefacts kept inside.

High-throughput characterization of sediment organic matter by pyrolysis-gas chromatography/mass spectrometry and multivariate curve resolution: A promising analytical tool in (paleo)limnology.

Molecular-level chemical information about organic matter (OM) in sediments helps to establish the sources of OM and the prevalent degradation/diagenetic processes, both essential for understanding the cycling of carbon (C) and of the elements associated with OM (toxic trace metals and nutrients) in lake ecosystems. Ideally, analytical methods for characterizing OM should allow high sample throughput, consume small amounts of sample and yield relevant chemical information, which are essential for multidisciplinary, high-temporal resolution and/or large spatial scale investigations. We have developed a high-throughput analytical method based on pyrolysis-gas chromatography/mass spectrometry and automated data processing to characterize sedimentary OM in sediments. Our method consumes 200 µg of freeze-dried and ground sediment sample. Pyrolysis was performed at 450°C, which was found to avoid degradation of specific biomarkers (e.g., lignin compounds, fresh carbohydrates/cellulose) compared to 650°C, which is in the range of temperatures commonly applied for environmental samples. The optimization was conducted using the top ten sediment samples of an annually resolved sediment record (containing 16-18% and 1.3-1.9% of total carbon and nitrogen, respectively). Several hundred pyrolytic compound peaks were detected of which over 200 were identified, which represent different classes of organic compounds (i.e., n-alkanes, n-alkenes, 2-ketones, carboxylic acids, carbohydrates, proteins, other N compounds, (methoxy)phenols, (poly)aromatics, chlorophyll and steroids/hopanoids). Technical reproducibility measured as relative standard deviation of the identified peaks in triplicate analyses was 5.5±4.3%, with 90% of the RSD values within 10% and 98% within 15%. Finally, a multivariate calibration model was calculated between the pyrolytic degradation compounds and the sediment depth (i.e., sediment age), which is a function of degradation processes and changes in OM source type. This allowed validation of the Py-GC/MS dataset against fundamental processes involved in OM cycling in aquatic ecosystems.