Non-target analysis of Danish wastewater treatment plant effluent: Statistical analysis of chemical fingerprinting as a step toward a future monitoring tool.

In an attempt to discover and characterize the plethora of xenobiotic substances, this study investigates chemical compounds released into the environment with wastewater effluents. A novel non-targeted screening methodology based on ultra-high resolution Orbitrap mass spectrometry and nanoflow ultra-high performance liquid chromatography together with a newly optimized data-processing pipeline were applied to effluent samples from two state-of-the-art and one small wastewater treatment facility. In total, 785 molecular structures were obtained, of which 38 were identified as single compounds, while 480 structures were identified at a putative level. Most of these substances were therapeutics and drugs, present as parent compounds and metabolites. Using R packages Phyloseq and MetacodeR, originally developed for bioinformatics, significant differences in xenobiotic presence in the wastewater effluents between the three sites were demonstrated.

Insights into the early-life chemical exposome of Nigerian infants and potential correlations with the developing gut microbiome.

Early-life exposure to natural and synthetic chemicals can impact acute and chronic health conditions. Here, a suspect screening workflow anchored on high-resolution mass spectrometry was applied to elucidate xenobiotics in breast milk and matching stool samples collected from Nigerian mother-infant pairs (n = 11) at three time points. Potential correlations between xenobiotic exposure and the developing gut microbiome, as determined by 16S rRNA gene amplicon sequencing, were subsequently explored. Overall, 12,192 and 16,461 features were acquired in the breast milk and stool samples, respectively. Following quality control and suspect screening, 562 and 864 features remained, respectively, with 149 of these features present in both matrices. Taking advantage of 242 authentic reference standards measured for confirmatory purposes of food bio-actives and toxicants, 34 features in breast milk and 68 features in stool were identified and semi-quantified. Moreover, 51 and 78 features were annotated with spectral library matching, as well as 416 and 652 by in silico fragmentation tools in breast milk and stool, respectively. The analytical workflow proved its versatility to simultaneously determine a diverse panel of chemical classes including mycotoxins, endocrine-disrupting chemicals (EDCs), antibiotics, plasticizers, perfluorinated alkylated substances (PFAS), and pesticides, although it was originally optimized for polyphenols. Spearman rank correlation of the identified features revealed significant correlations between chemicals of the same classification such as polyphenols. One-way ANOVA and differential abundance analysis of the data obtained from stool samples revealed that molecules of plant-based origin elevated as complementary foods were introduced to the infants' diets. Annotated compounds in the stool, such as tricetin, positively correlated with the genus Blautia. Moreover, vulgaxanthin negatively correlated with Escherichia-Shigella. Despite the limited sample size, this exploratory study provides high-quality exposure data of matched biospecimens obtained from mother-infant pairs in sub-Saharan Africa and shows potential correlations between the chemical exposome and the gut microbiome.

Detection and Imaging of Exposure-Related Metabolites and Xenobiotics in Hard Tissues by Laser Sampling and Mass Spectrometry.

The utility of two novel laser-based methods, laser ablation electrospray ionization (LAESI) and laser desorption ionization (LDI) from silicon nanopost array (NAPA), is explored via local analysis and mass spectrometry imaging (MSI) of hard tissues (tooth and hair) for the detection and mapping of organic components. Complex mass spectra are recorded in local analysis mode from tooth dentin and scalp hair samples. Nicotine and its metabolites (cotinine, hydroxycotinine, norcotinine, and nicotine) are detected by LAESI-MS in the teeth of rats exposed to tobacco smoke. The intensities of the detected metabolite peaks are proportional to the degree of exposure. Incorporating ion mobility separation in the LAESI-MS analysis of scalp hair enables the detection of cotinine in smoker hair along with other common molecular species, including endogenous steroid hormones and some lipids. Single hair strands are imaged by MALDI-MSI and NAPA-LDI-MSI to explore longitudinal variations in the level of small molecules. Comparing spectra integrated from NAPA-LDI-MSI and MALDI-MSI images reveals that the two techniques provide complementary information. There were 105 and 82 sample-related peaks for MALDI and NAPA, respectively, with an overlap of only 16 peaks, indicating a high degree of complementarity. Enhanced molecular coverage and spatial resolution offered by LAESI-MS and NAPA-LDI-MSI can reveal the distributions of known and potential biomarkers in hard tissues, facilitating exposome research.

Ecotoxicidad de nanopartículas metálicas y superparamagnéticas de óxido de hierro en dos especies / Ecotoxicity of metalic and superparamagnetics iron oxide nanoparticles in two species

Introducción: la nanotecnología y el empleo de materiales a nano escala son un área relativamente nueva de la ciencia y la tecnología con un gran crecimiento en el mercado global. Muchos de los productos no cuentan con estudios que garanticen su uso seguro, tanto para el hombre como para los ecosistemas. Los estudios ecotoxicológicos permiten evaluar los efectos de un determinado xenobiótico sobre especies representativas de los diferentes compartimentos ambientales. Objetivo: evaluar los efectos tóxicos de nanopartículas de Ag, Au, Ag/Ag y superparamagnéticas de óxido de hierro, en dos especies bioindicadoras de los ecosistemas terrestre y acuático. Métodos: como parte de los estudios de seguridad se realizaron ensayos de toxicidad aguda por contacto en lombriz de tierra de la especie Eisenia andrei, con una duración de 96 horas y estudios en anfibios de la especie Osteopillus septentrionales en diferentes etapas del desarrollo (embrionario y larval). Se evaluó la ocurrencia de mortalidad y de efectos tóxicos, en el caso del ensayo en lombriz de tierra; se determinó además la viabilidad celular. Resultados: los efectos tóxicos más significativos en el caso de la lombriz de tierra fueron, la ocurrencia de alteraciones fisiológicas y conductuales al ser expuesta a NPs de Ag de 3 nm y superparamagnéticas de óxido de hierro, estas últimas provocaron citotoxicidad a la concentración 1,38 mg/mL. En el caso de los anfibios se evidenció toxicidad en NPs de Ag 3 nm y superparamagnéticas de óxido de hierro. Conclusiones: todas las nanopartículas mostraron efectos tóxicos en las especies bioindicadoras evaluadas(AU)

Introduction: Nanotechnology and the use of nanoscale materials are a relatively new area of science and technology with big growth in the global market. Many of these products don't have studies that guarantee their safe use, both for man and for ecosystems. Ecotoxicological studies allow the evaluation of the effects of a particular xenobiotic on representative species of the different environmental compartments. Objective: To evaluate the toxic effects of nanoparticles of Ag, Au, Ag / Ag and super paramagnetic iron oxide in two bioindicators of terrestrial and aquatic ecosystems. Methods: Acute contact toxicity tests were carried out on ground worm of the Eisenia andrei species, with a duration of 96 hours and studies on amphibians of the species Osteopillus septentrionales at different stages of development (embryonic and larval). The occurrence of mortality and toxic effects was evaluated in the case of earthworm test; cell viability was also determined. Results: The most significant toxic effects in the case of earthworms were the occurrence of physiological and behavioral alterations when exposed to 3 nm Ag of superparamagnetic iron oxide nanoparticles, where the latter caused cytotoxicity at concentration of 1.38 mg / mL. In the case of amphibians, toxicity was evidenced in Ag 3 nm nanoparticles and superparamagnetic iron oxide. Conclusions: All nanoparticles showed toxic effects in the evaluated bioindicator species(AU)

Mycoremediation of Congo red dye by filamentous fungi

Azo, anthroquinone and triphenylmethane dyes are the major classes of synthetic colourants, which are difficult to degrade and have received considerable attention. Congo red, a diazo dye, is considered as a xenobiotic compound, and is recalcitrant to biodegradative processes. Nevertheless, during the last few years it has been demonstrated that several fungi, under certain environmental conditions, are able to transfer azo dyes to non toxic products using laccases. The aim of this work was to study the factors influencing mycoremediation of Congo red. Several basidiomycetes and deuteromycetes species were tested for the decolourisation of Congo red (0.05 g/l) in a semi synthetic broth at static and shaking conditions. Poor decolourisation was observed when the dye acted as the sole source of nitrogen, whereas semi synthetic broth supplemented with fertilizer resulted in better decolourisation. Decolourisation of Congo red was checked in the presence of salts of heavy metals such as mercuric chloride, lead acetate and zinc sulphate. Decolourisation parameters such as temperature, pH, and rpm were optimized and the decolourisation obtained at optimized conditions varied between 29.25- 97.28 percent at static condition and 82.1- 100 percent at shaking condition. Sodium dodecyl sulphate polyacrylamide gel electrophoretic analysis revealed bands with molecular weights ranging between 66.5 to 71 kDa, a characteristic of the fungal laccases. High efficiency decolourisation of Congo red makes these fungal forms a promising choice in biological treatment of waste water containing Congo red.

Conceitos e derivação de valores de referência para biomonitorização humana de contaminantes ambientais / Concepts and determination of reference values for human biomonitoring of environmental contaminants

Human biomonitoring (HBM) of environmental contaminants plays an important role in estimating exposure and evaluating risk, and thus it has been increasingly applied in the environmental field. The results of HBM must be compared with reference values (RV). The term "reference values" has always been related to the interpretation of clinical laboratory tests. For physicians, RV indicate "normal values" or "limits of normal"; in turn, toxicologists prefer the terms "background values" or "baseline values" to refer to the presence of contaminants in biological fluids. This discrepancy leads to the discussion concerning which should be the population selected to determine RV. Whereas clinical chemistry employs an altered health state as the main exclusion criterion to select a reference population (that is, a "healthy" population would be selected), in environmental toxicology the exclusion criterion is the abnormal exposure to xenobiotics. Therefore, the choice of population to determine RV is based on the very purpose of the RV to be determined. The present paper discusses the concepts and methodology used to determine RV for biomarkers of chemical environmental contaminants.

Xenobiotics enhance laccase activity in alkali-tolerant gama-proteobacterium JB / Xenobióticos aumentam a atividade de lacase em gama-Proteobacterium JB alcali-tolerante

Various genotoxic textile dyes, xenobiotics, substrates (10 µM) and agrochemicals (100 µg/ml) were tested for enhancement of alkalophilic laccase activity inã-proteobacterium JB. Neutral Red, Indigo Carmine, Naphthol Base Bordears and Sulphast Ruby dyes increased the activity by 3.7, 2.7, 2.6 and 2.3 fold respectively. Xenobiotics/substrates like p-toluidine, 8-hydroxyquinoline and anthracine increased it by 3.4, 2.8 and 2.3 fold respectively. Atrazine and trycyclozole pesticides enhanced the activityby 1.95 and 1.5 fold respectively.

Vários corantes têxteis genotóxicos, xenobióticos, substratos (10 mM) e agroquímicos (100 mM/mL) foram testados quanto ao aumento da atividade de lacase em ã-Proteobacterium JB. Os corantes Neutral Red, Indigo Carmine, Naphtol Base Bordears e Sulphast Ruby aumentaram a atividade em 3,7, 2,7, 2,6 e 2,3 vezes, respectivamente. Xenobióticos/substratos como p-toluidina, 8-hidroxiquinolina e antracina aumentaram a atividade em 3,4, 2,8 e 2,3 vezes, respectivamente. Atrazina e pesticidas triciclozol aumentaram a atividade em 1,95 e 1,5 vezes, respectivamente.

Validacao de metodos cromatograficos em analises toxicologicas / Validation of chromatographic methods in toxicological analyses

A identificacao e quantificacao de xenobioticos em amostras biologicas pressupoe a utilizacao de metodologia cuja validacao tenha sido devidamente estabelecida. Agencias internacionais, tais como, Environmental Protection Agency, Food and Drug Administration, American Industry Hygiene Association, etc., responsaveis por programas de seguranca da qualidade em analises toxicologicas exigem relatos dos processos de validacao. A maxima "faca o que esta escrito e escreva o que e feito" mostra a enfase dada a tal documentacao. A validacao de um metodo analitico inclui todos os procedimentos realizados para garantir a qualidade dos dados produzidos. Independentemente do processo analitico a ser utilizado, preconiza-se um protocolo composto, basicamente, de tres estagios. O primeiro relaciona-se a procedimentos de afericao de instrumentos e calibracao de equipamentos visando assegurar a confiabilidade das medidas. O segundo diz respeito ao estudo da estabilidade do xenobiotico na matriz, considerando as condicoes de armazenamento e ciclos de congelamento e descongelamento, recuperacao, precisao, exatidao, limites de deteccao e quantificacao, especificidade e intervalo dinamico. O terceiro estagio baseia-se nos procedimentos adotados pelo laboratorio para garantir que o procedimento, como um todo, esta sob controle. Neste trabalho descrevem-se principios praticos e recomendacoes gerais no sentido de indicar diretrizes para o estabelecimento de protocolos que atestem a validade do resultado analitico