Arsenic contamination in drinking water and foods is a prevalent concern across the world. Routine testing of inorganic arsenic ensures food safety but requires a cost effective, rapid high throughput, and simple detection method. The objective of this work is to develop a green method using X-Ray fluorescence spectroscopy (XRF) to analyze inorganic arsenic (iAs) in food and their interaction with emerging food contaminants: microplastics and titanium dioxide nanoparticles. XRF measures the secondary X-ray that is characteristic of each element emitted by the sample. In a prior study, we developed an approach that combines the Gutzeit method and elemental analysis using XRF for arsenic detection in food. This approach is based on a commercial mercury bromide strip to capture arsine gas. Concerning the high toxicity of mercury bromide, we explored the feasibility of using a greener chemical, silver nitrate, to replace mercury bromide. This would benefit the safety of the operating personnel and reduce chemical hazard impact on the environment. In addition, organic acids and zinc nanoparticles were explored for iAs detection. Optimization of various reagents was done to maximize the efficacy of iAs capture and detection. The result demonstrated the greener method has a lower quantification (3.40 µg/L) compared to the original method based on mercury bromide (16.2 µg/L) due to less elemental interferences in the XRF spectrum. The standard curves of water and apple juice were compared, no significant difference was found, suggesting matrix interference is minimal. The spiked apple juice with 0 to 133 µg/L iAs had a good recovery ranging from 85-99% with an average relative standard deviation below 20%, indicating decent reproducibility. Other than iAs detection, we also explored the XRF to study the iAs and their interaction between microplastics and titanium dioxide nanoparticles, which are considered emerging contaminants of public concerns that may serve as vectors for pollutants and potentially enhances toxicity effects. We developed a screening method to quantify the adsorption under different conditions. The result showed iAs adsorption is highly dependent of particle size and surface morphology. In conclusion, this study demonstrates the feasibility and great potential of XRF quantification of inorganic arsenic in food matrices in a cost-effective and reliable manner and the capability of rapidly quantifying the interaction with emerging contaminants such as microplastics and titanium dioxide nanoparticles.

Concentrations of inorganic arsenic (iAs) metabolites in urine present intra- and interindividual variations, which are determined not only by the magnitude of exposure to iAs, but also by differences in genetic, environmental and dietary factors.

Arsenic (As) is a toxic semi-metallic element found in groundwater, soils, and plants. Natural and anthropogenic sources contribute to the distribution of arsenic in the environment. Arsenic’s toxic and mobile behavior is associated with its speciation ability. There are two types of arsenic available to the environment, inorganic and organic arsenic. Of the two, inorganic arsenic is more toxic to humans and more mobile in the environment. Two inorganic compounds responsible for arsenic contamination are trivalent arsenite, As (III), and pentavalent arsenate, As (V). Trivalent arsenate is considered to be more soluble, toxic, and mobile than pentavalent arsenate. Arsenic’s absorptive properties in plant cells and ability to attach to minerals causing secondary contamination are due to environmental factors such as pH, redox potential, and solubility. The current maximum contaminant level for arsenic in water is 10 µg/L (or ppb). Research on arsenic involving high concentrations already present in groundwater (>300ppb) are compared either with crops irrigated with such water or a human indicator (such as; hair, nails, blood, or urine) in order to determine exposure limits. In this current research, relationships between the area in the studies and the contaminated media (water, soil, vegetation) were tested to determine if arsenic in water was correlated with arsenic concentrations present in soil and vegetation. Commercially obtained ITS Quick Rapid Arsenic Test Kits were used to measure arsenic concentrations for the media tested. A method for analysis of arsenic in vegetation was developed, with an estimated 80% recovery. The pH and conductivity were also taken for water and soil samples as a means of correlative comparison. The development of faster and portable methods for arsenic concentration may provide means for predicting the relationship between all contaminated media. The purpose of the study was to determine the correlation between arsenic water concentration and pH for water, soil, or vegetation and whether it plays an overall role in the amount of arsenic present. As a result, water and soil pH played a significant role in the presence of arsenic in the water and vegetation, respectively. A moderate negative correlation between arsenic in water and water pH was discovered to have a Spearman’s rho value of -0.708 with a p ≤ 0.05. In addition, a significant negative correlation between soil pH and arsenic in vegetation was also discovered to have a Spearman’s rho of -0.628 at a p ≤ 0.05. Even though, pH was significantly correlated with arsenic concentrations in different media, there is evidence that pH plays a role also in the amount of arsenic available in the soil and vegetation. Further studies are recommended.

Drinking groundwater is the primary way humans accumulate arsenic. Chronic exposure to inorganic arsenic (iAs) (over decades) has been shown to be associated with multiple health effects at low levels (5-10 ppb) including: cancer, elevated blood pressure and cardiovascular disease, skin lesions, renal failure, and peripheral neuropathy. Using hypertension (or high blood pressure) as a surrogate marker for cardiovascular disease, we examined the effect of iAs alone and in a mixture with other metals using a cross-sectional study of adults in United States (National Health and Examination Survey, NHANES, 2005-2010) adjusting for covariates: urinary creatinine level (mg/dL), poverty index ratio (PIR, measure of socioeconomic status, 1 to 5), age, smoking (yes/no), alcohol usage, gender, non-Hispanic Black, and overweight (BMI>=25). A logistic regression model suggests that a one-unit increase in log of inorganic arsenic increases the odds of hypertension by a factor of 1.093 (95% Confidence Interval=0.935, 1.277) adjusted for these covariates , which indicates that there was not significant evidence to claim that inorganic arsenic is a risk factor for hypertension. Biomonitoring data provides evidence that humans are not only exposed to inorganic arsenic but also to mixtures of chemicals including inorganic arsenic, total mercury, cadmium, and lead. We tested for a mixture effect of these four environmental chemicals using weighted quantile sum (WQS) regression, which takes into account the correlation among the chemicals and with the outcome. For one-unit increase in the weighted sum, the adjusted odds of developing hypertension increases by a factor of 1.027 (95% CI=0.882,1.196), which is also not significant after taking into account the same covariates. The insignificant finding may be due to the low inorganic arsenic concentration (8-620 μg /L) in US drinking water, compared to those in countries like Bangladesh where the concentrations are much higher. Literature provides conflicting evidence of the association of inorganic arsenic and hypertension in low/moderate regions; future studies, especially a large cohort study, are needed to confirm if inorganic arsenic alone or with other metals is associated with hypertension in the United States.

Eukaryotic organisms contain their entire genome in the nucleus of their cells. In order to fit within the nucleus, genomic DNA wraps into nucleosomes, the basic, repeating unit of chromatin. Nucleosomes wrap around each other to form higher order chromatin structures. Here we study many factors that affect, or are effected by, chromatin structure including: (1) how low-dose inorganic arsenic (iAs) changes chromatin structures and their relation to global transcription and splicing patterns, and (2) how chromatin architectural proteins (CAPs) bind to and change nucleosome dynamics and DNA target site accessibility. Despite iAs’s non-mutagenic nature, chronic exposure to low doses of iAs is associated with a higher risk of skin, lung, and bladder cancers. We sought to identify the genome-wide changes to chromatin structure and splicing profiles behind the cell’s adaptive response to iAs and its removal. Furthermore, we extended our investigation into cells that had the iAs insult removed. Our results show that the iAs-induced epithelial to mesenchymal transition and changes to the transcriptome are coupled with changes to the higher order chromatin structure and CAP binding patterns. We hypothesize that CAPs, which bind the entry/exit and linker DNA of nucleosomes, regulate DNA target site accessibility by altering of the rate of spontaneous dissociation of DNA from nucleosome. Therefore, we investigated the effects of the repressive CAP histone H1, the activating CAP high mobility group D1 (HMGD1), and the neural CAP methyl CpG binding protein 2 (MeCP2) on the dynamics of short chromatin arrays and mononucleosomes and their effect on nucleosomal DNA accessibility. Using biochemical and biophysical analyses we show that all CAP-chromatin structures tested were susceptible to chromatin remodeling by ISWI and created more stable higher order structures than if CAPs were absent. Additionally, histone H1 and MeCP2 hinder model transcription factor Gal4 from binding its cognate DNA site within nucleosomal DNA. Overall, we show that chromatin structure is dynamic and changes in response to environmental signals and that CAPs change nucleosome dynamics that help to regulate chromatin structures and impact transcriptional profiles.

Os cações são importantes recursos pesqueiros que podem apresentar concentrações de mercúrio (Hg) e arsênio (As) muitas vezes acima do limite de tolerância, o que os tornam impróprios como alimento. No meio aquático estes contaminantes são convertidos em espécies orgânicas, em especial metilmercúrio (MeHg) e arsenobetaína (AB), respectivamente. O MeHg é neurotóxico, sendo o sistema nervoso em desenvolvimento o mais susceptível. A AB é pouco tóxica, no entanto, o As inorgânico está envolvido em processos de estresse oxidativo, mutagênese e principalmente carcinogênese. Neste trabalho, foi avaliada a eficiência da cisteína na remoção de Hg, a ocorência de As total e inorgânico, e a redução de sua concentração com o emprego de borohidreto de sódio e de preparos para o consumo. A redução máxima de Hg, de 59,4%, com cisteína a 0,5% em pH 5,0, não foi reproduzida quando pretendida a reutilização da solução do aminoácido, importante do ponto de vista prático. O cação-azul continha elevados níveis de As total, 1,98 a 22,56 µg/g (base úmida), que foram removidos com borohidreto de sódio em 99%, demonstrando a alta potencialidade do método usado. O As inorgânico, presente na quantidade média de 0,0086 µg/g (base úmida), foi reduzido em 27,7%. O preparo para o consumo, por cozimento em água, do cação-azul em cubos (1-2 cm3), resultou em maior remoção de As total, de 65,9 a 71,2%; no cação grelhado a redução foi de 55,4 a 60,2%. As amostras, grelhadas ou cozidas, adicionadas de sal e limão enriquecido com ácido ascórbico, e as grelhadas contendo sal e sal com limão, apresentaram redução na concentração de As inorgânico de 30,1 a 42,8%. / The shark are important fishery resources that may have concentrations of mercury (Hg) and arsenic (As) often above the limit of tolerance, which makes them unsuitable as food. In the aquatic environment these contaminants are converted to organic species, particularly methylmercury (MeHg) and arsenobetaína (AB), respectively. The MeHg is neurotoxic, and the developing nervous system more susceptible. AB is slightly toxic, however, the inorganic As is involved in processes of oxidative stress, mutagenesis and carcinogenesis mainly. In this study, we evaluated the efficiency of cysteine to remove mercury, the occurrence of the total and inorganic As, and the reduction of their concentration with the use of sodium borohydride and preparations for consumption. The maximum reduction of Hg, 59.4%, with 0.5% cysteine at pH 5.0, was not reproduced when you want to reuse the solution of the amino acid, important practical point of view. The blue-shark contained high levels of the total As, 1.98 to 22.56 µg/g (wet weight), which were removed with sodium borohydride in 99%, demonstrating the high potential of the method used. The inorganic As, present in the average amount of 0.0086 µg/g (wet weight) was reduced in 27.7%. Preparation for consumption by baking in water, the blue-shark into cubes (1-2 cm3) resulted in greater removal of the total As, 65.9 to 71.2%; in the grilled shark the reduction was 55,4 to 60.2%. The samples, grilled or baked, added salt and lemon enriched with ascorbic acid, and the grilled containing salt and salt with lemon, presented reduction in the concentrations of inorganic As from 30.1 to 42.8%.

Os cações são importantes recursos pesqueiros que podem apresentar concentrações de mercúrio (Hg) e arsênio (As) muitas vezes acima do limite de tolerância, o que os tornam impróprios como alimento. No meio aquático estes contaminantes são convertidos em espécies orgânicas, em especial metilmercúrio (MeHg) e arsenobetaína (AB), respectivamente. O MeHg é neurotóxico, sendo o sistema nervoso em desenvolvimento o mais susceptível. A AB é pouco tóxica, no entanto, o As inorgânico está envolvido em processos de estresse oxidativo, mutagênese e principalmente carcinogênese. Neste trabalho, foi avaliada a eficiência da cisteína na remoção de Hg, a ocorência de As total e inorgânico, e a redução de sua concentração com o emprego de borohidreto de sódio e de preparos para o consumo. A redução máxima de Hg, de 59,4%, com cisteína a 0,5% em pH 5,0, não foi reproduzida quando pretendida a reutilização da solução do aminoácido, importante do ponto de vista prático. O cação-azul continha elevados níveis de As total, 1,98 a 22,56 µg/g (base úmida), que foram removidos com borohidreto de sódio em 99%, demonstrando a alta potencialidade do método usado. O As inorgânico, presente na quantidade média de 0,0086 µg/g (base úmida), foi reduzido em 27,7%. O preparo para o consumo, por cozimento em água, do cação-azul em cubos (1-2 cm3), resultou em maior remoção de As total, de 65,9 a 71,2%; no cação grelhado a redução foi de 55,4 a 60,2%. As amostras, grelhadas ou cozidas, adicionadas de sal e limão enriquecido com ácido ascórbico, e as grelhadas contendo sal e sal com limão, apresentaram redução na concentração de As inorgânico de 30,1 a 42,8%. / The shark are important fishery resources that may have concentrations of mercury (Hg) and arsenic (As) often above the limit of tolerance, which makes them unsuitable as food. In the aquatic environment these contaminants are converted to organic species, particularly methylmercury (MeHg) and arsenobetaína (AB), respectively. The MeHg is neurotoxic, and the developing nervous system more susceptible. AB is slightly toxic, however, the inorganic As is involved in processes of oxidative stress, mutagenesis and carcinogenesis mainly. In this study, we evaluated the efficiency of cysteine to remove mercury, the occurrence of the total and inorganic As, and the reduction of their concentration with the use of sodium borohydride and preparations for consumption. The maximum reduction of Hg, 59.4%, with 0.5% cysteine at pH 5.0, was not reproduced when you want to reuse the solution of the amino acid, important practical point of view. The blue-shark contained high levels of the total As, 1.98 to 22.56 µg/g (wet weight), which were removed with sodium borohydride in 99%, demonstrating the high potential of the method used. The inorganic As, present in the average amount of 0.0086 µg/g (wet weight) was reduced in 27.7%. Preparation for consumption by baking in water, the blue-shark into cubes (1-2 cm3) resulted in greater removal of the total As, 65.9 to 71.2%; in the grilled shark the reduction was 55,4 to 60.2%. The samples, grilled or baked, added salt and lemon enriched with ascorbic acid, and the grilled containing salt and salt with lemon, presented reduction in the concentrations of inorganic As from 30.1 to 42.8%.