Juliana Maria Oliveira Souza

Speciation of arsenic in rice and estimation of daily intake of different arsenic species by Brazilians through rice consumption

Rice is an important source of essential elements. However, rice may also contain toxic elements such as arsenic. Therefore, in the present study, the concentration of total arsenic and five main chemical species of arsenic (As(3+), As(5+), DMA, MMA and AsB) were evaluated in 44 different rice samples (white, parboiled white, brown, parboiled brown, parboiled organic and organic white) from different Brazilian regions using high-performance liquid chromatography hyphenated to inductively coupled plasma mass spectrometry (HPLC-ICP-MS). The mean level of total arsenic was 222.8 ng g(-1) and the daily intake of inorganic arsenic (the most toxic form) from rice consumption was estimated as 10% of the Provisional Tolerable Daily Intake (PTDI) with a daily ingestion of 88 g of rice. Inorganic arsenic (As(3+), As(5+)) and dimethylarsinic acid (DMA) are the predominant forms in all samples. The percentages of species were 38.7; 39.7; 3.7 and 17.8% for DMA, As(3+), MMA and As(5+), respectively. Moreover, rice samples harvested in the state of Rio Grande do Sul presented more fractions of inorganic arsenic than rice in Minas Gerais or Goiás, which could lead to different risks of arsenic exposure.

A fast method for bisphenol A and six analogues (S, F, Z, P, AF, AP) determination in urine samples based on dispersive liquid-liquid microextraction and liquid chromatography-tandem mass spectrometry.

In this study, a novel method combining dispersive liquid-liquid microextraction (DLLME) and fast liquid chromatography coupled to mass spectrometry (LC-MS/MS) was developed and validated for the extraction and determination of bisphenol A (BPA) and six bisphenol analogues, namely bisphenol S (BPS), bisphenol F (BPF), bisphenol P (BPP), bisphenol Z (BPZ), bisphenol AP (BPAP) and bisphenol AF (BPAF) in human urine samples. Type and volume of extraction and disperser solvents, pH sample, ionic strength, and agitation were evaluated. The matrix-matched calibration curves of all analytes were linear with correlation coefficients higher than 0.99 in the range level of 0.5-20.0ngmL(-1). The relative standard deviation (RSD), precision, at three concentrations (1.0, 8.0 and 15.0ngmL(-1)) was lower than 15% with accuracy ranging from 90 to 112%. The biomonitoring capability of the new method was confirmed with the analysis of 50 human urine samples randomly collected from Brazilians. BPA was detected in 92% of the analyzed samples at concentrations ranging

A systematic study of the disposition and metabolism of mercury species in mice after exposure to low levels of thimerosal (ethylmercury).

Thimerosal (TM) is an ethylmercury (etHg)-containing preservative used in some vaccines despite very limited knowledge on the kinetics and direct interaction/effects in mammals׳ tissues after exposure. Thus, this study aimed to evaluate the kinetics of Hg species in mice in a time course analysis after intramuscular injection of TM, by estimating Hg half-lives in blood and tissues. Mice were exposed to one single intramuscular dose of 20 µg of Hg as TM. Blood, brain, heart, kidney and liver were collected at 0.5 hour (h), 1 h, 8 h, 16 h, 144 h, 720 h and 1980 h after TM exposure (n=4). Hg species in animal tissues were identified and quantified by speciation analysis via liquid chromatography hyphenated with inductively coupled mass spectrometry (LC-ICP-MS). It was found that the transport of etHg from muscle to tissues and its conversion to inorganic Hg (inoHg) occur rapidly. Moreover, the conversion extent is modulated in part by the partitioning between EtHg in plasma and in whole blood, since etHg is rapidly converted in red cells but not in a plasma compartment. Furthermore, the dealkylation mechanism in red cells appears to be mediated by the Fenton reaction (hydroxyl radical formation). Interestingly, after 0.5 h of TM exposure, the highest levels of both etHg and inoHg were found in kidneys (accounting for more than 70% of the total Hg in the animal body), whereas the brain contributed least to the Hg body burden (accounts for <1.0% of total body Hg). Thirty days after TM exposure, most Hg had been excreted while the liver presented the majority of the remaining Hg. Estimated half-lives (in days) were 8.8 for blood, 10.7 for brain, 7.8 for heart, 7.7 for liver and 45.2 for kidney. Taken together, our findings demonstrated that TM (etHg) kinetics more closely approximates Hg(2+) than methylmercury (meHg) while the kidney must be considered a potential target for etHg toxicity.

Arsenic speciation in Brazilian rice grains organically and traditionally cultivated: Is there any difference in arsenic content?

Inorganic arsenic contamination in rice is a global public concern due to the risks associated. In spite of being an important issue, few studies concerning differences between inorganic arsenic in rice grains under organic and conventional methods of cultivation are available in Brazil, which is an important producer and consumer. In the present work, samples of polished and husked rice (organic and conventional) and gastronomic rice (Arborio, Carnaroli and red/black rice) were analyzed and the results compared to FAO/Codex maximum limits. The total determination and speciation analysis of arsenic were carried out by ICP-MS and HPLC-ICP-MS, respectively. The results showed no significant statistical differences in total As concentration in organic rice (157.7±56.1ngg-1) vs. conventional rice (137.4±46.6ngg-1) and also in organic husked rice (227.7±95.5ngg-1) vs. conventional husked (217.7±60.9ngg-1). However, inorganic As was 45% higher in organic polished rice than in conventional polished rice and 41% higher in organic husked rice than in conventional husked rice. Gastronomic rice presented total arsenic ranging from 65.4 to 348ngg-1 for black and Arborio rice, respectively. Regarding the maximum levels adopted by Codex for i-As (200ngg-1), no violation was found.

Formulation and evaluation of thermoresponsive polymeric blend as a vaginal controlled delivery system

AbstractThermoresponsive polymers have the ability to undergo rapid changes in response to subtle environmental conditions and make stimuli-responsive materials attractive. They are candidates for minimally invasive, targeted and personalized drug delivery applications. Curcumin (CUR) is a phytochemical compound characterized by its low intrinsic toxicity and a wide variety of therapeutic effects. The modulating of the viscoelastic properties and bioadhesive characteristics of the thermoresponsive hydrogel (poloxamer 407) was achieved using a ternary system formed with chitosan and hydroxypropylmethylcellulose K4M (M20). The curcumin in solid dispersion form (CUR-SD) was used in the hydrogel preparation. The physical–chemical, physiomechanical, oxidative stress properties and antioxidant activity were evaluated and compared. Curcumin in SD form is more soluble and stable than in the physical mixture (PM) or free form. The transition from liquid to gel (Tsol–gel) temperature of the M20-SD formulation occurred at 36 °C. The CUR delivery profiles followed the Hixson–Crowell’s model. The M20-SD formulation showed antioxidant activity and as a strong inhibitor of oxidative stress. Analysis of results suggests that CUR-SD thermoresponsive hydrogel can be used via to the vaginal route for the treatment of mucosal inflammation and infectious disease, including HPV. The elastomeric hydrogel is formed by covalently cross-linked long and flexible polymer chains aggregated with water. The analysis results showed that M20-SD could remain at the application site for a sufficient time to permit the controlled delivery and to improve the therapeutic activity of CUR. In this research, a thermosensitive system with proper physiomechanical properties and prepared with biocompatible materials was used to increase mucoadhesion, to control drug delivery and to decrease the local irritation. Thus, Tsol–gel temperatures approximately between 26–27 and 37–38 °C were found. The solid dispersion increases the solubility and stability of curcumin. This formulation was designed for treatment of vaginal mucositis, HPV, bacterial infection and other vaginal diseases.

Distribution of arsenic and oxidative stress in mice after rice ingestion

This study evaluated the effects of rice naturally contaminated with arsenic (As) and the same As-species added as solubilized-salt on the redox state and the As distribution in male mice. The total As amount in the Brazilian polished rice used in this study was 169.81±6.12ngg-1. Indeed, the concentrations of As species were 40.77ngg-1 (arsenite, As3+), 65.71ngg-1 (dimethylarsinic acid, DMA), 11.90ngg-1 (monomethylarsonic acid, MMA), and 25.96ngg-1 (arsenate, As5+). In this sense, animals were randomly divided into seven groups with six mice per group: I) control: habitual food; II) rice I: diet containing 10% of rice naturally containing As (4.08μg As3+/kg diet, 6.57μg DMA/kg diet, 1.19μg MMA/kg diet, and 2.60μg As5+/kg diet); III) rice II: diet containing 20% of rice naturally containing As (8.15μg As3+/kg diet, 13.14μg DMA/kg diet, 2.38μg MMA/kg diet, and 5.19μg As5+/kg diet); IV) rice III: diet containing 40% of rice naturally containing As (16.31μg As3+/kg diet, 26.28μg DMA/kg diet, 4.76μg MMA/kg diet, and 10.38μg As5+/kg diet); V) spiked feed I: diet containing As species as solubilized-salt (concentration equivalent to group II); VI) spiked feed II: diet containing As species as solubilized-salt (concentration equivalent to group III); VII) spiked feed III: diet containing As species as solubilized-salt (concentration equivalent to group IV). The time of treatment was 100days. After euthanasia, it was observed an increase in total As concentration in tissue samples of groups treated with diet containing rice naturally contaminated and diet containing As species. For instance, the highest As concentrations (higher than 330ngg-1) was observed in the bladder of animals belonging to Rice II and III and spiked feed III groups. Furthermore, it was verified the highest As concentrations in bladder > hair > lung > kidney > liver > blood. We also observed the presence of DMA and As5+ in liver and kidneys. Regarding oxidative stress biomarkers, we observed significant reduction of Glutathione (GSH) concentration in blood of animals belonging to groups IV, V, VI and VII. Besides, the antioxidant enzymes activities, Glutathione Peroxidase (GSH-Px), Catalase (CAT) and superoxide dismutase (SOD), increased significantly in blood of animals belonging to group VII. On the other hand, it was not observed differences in nitric oxide (NO) levels among all the groups used in this study and the control group. Thus, we conclude that some minor effects were found in mice exposed to the diet containing the highest amount of rice naturally contaminated with As species. These findings contribute to evaluate the safety of human dietary consumption.