Rice Bran and Its Potential To Complement the Nutritional Needs of Children and Elderly.

Rice bran is an agro-industrial by-product of low added value that can be used to complement human nutritional needs. In this work, the profile of minerals, fatty acids and amino acids in brown rice bran was determined, aiming to evaluate its potential to complement the nutritional needs of different age groups, according to recommendations of regulatory agencies. The brown rice bran was supplied by a rice processing industry located in the south of the state of Rio Grande do Sul. Minerals were quantified using an emission spectrometer; the fatty acid profile was determined by gas chromatography and the amino acids were quantified by high-performance liquid chromatography with fluorescence (HPLC-FL). The main minerals were phosphorus (P), magnesium (Mg), potassium (K) and calcium (Ca) (2,933, 1,029, 211 and 56 mg / 100 g of rice bran). Saturated, monounsaturated and polyunsaturated fatty acids in rice bran were 22.4, 36.2 and 34.5% of lipid content, respectively. The polar, neutral and charged amino acids represented 8.8, 9.3 and 12.8% of the protein content, respectively. The composition of this co-product of rice supply chain is a good alternative to the new demand on plant-based food supplying the recommended daily intake (RDI) of national and international food polices.

Vortex-assisted matrix solid-phase dispersion: An eco-friendly alternative for the determination of halogens in edible seaweed.

Edible seaweed has been widely consumed around the world through oriental cuisine and it is important to monitor the levels of some elements, especially halogens. This study proposes, for the first time, the development of an analytical method using the vortex-assisted matrix solid-phase dispersion (VA-MSPD) combined with alkaline extraction of halogens (F, Cl, Br, and I) in edible seaweed for further determination by ion chromatography. The proposed method was evaluated using edible seaweed of the Nori (Porphyra spp.) type and applied to samples of the Wakame (Undaria pinnatifida), Kombu (Laminaria ochroleuca), and Hijiki (Hizikia fusiformis) types. Important VA-MSPD parameters were investigated and using 0.1 g sample, 1 g sea sand as solid support, 50 mmol L-1 (NH4)2CO3 as extraction solution, and 5 min of maceration, higher extraction efficiencies were obtained. The method was linear within the evaluated range (R2 > 0.99) for all elements and no matrix effect was observed. The detection limits of the method were 27, 26, 19, and 28 µg g-1 for F, Cl, Br, and I, respectively. The accuracy was evaluated by a recovery test (ranging from 92 to 108%) and analysis of certified reference materials for apple leaves (NIST 1515) and peach leaves (NIST 1547), which had a good agreement (ranging from 97 to 101%) with the certified values. Comparing the results with those obtained by inductively coupled plasma-mass spectrometry after microwave-induced combustion, no significant difference was found between the results, and the relative standard deviations were lower than 12%. The proposed method proved to be efficient for the determination of halogens in different algae species, showing advantages such as simplicity and low cost, combined to the use of a material from renewable sources (sea sand) as a solid support, contributing to the principles of Green Analytical Chemistry.

Antifouling paint particles in soils: toxic impact that goes beyond the aquatic environment.

Antifouling paint particles (APPs) originate from vessel maintenance and cleaning activities and their potentially toxic components are found at high concentrations in nearby soils, yet no studies have investigated their toxicity to soil organisms. We investigated the effects of exposure to soils containing APPs on the mortality, biomass, and reproductive performance of the earthworm Eisenia andrei. Earthworms were exposed to contaminated soil from a boatyard and non-contaminated soils treated with different concentrations of APPs (0.01, 0.14 and 1.50%, w/w) for 56 days. An ecological risk assessment using a Hazard Quotient (HQ) was also carried out. Exposure to contaminated soils reduced worm survival, biomass, and reproductive performance and these effects were concentration-dependent. The HQ was high in soil samples with APPs in both acute and chronic tests, and copper contributed the most to the HQ. Copper, zinc, and lead had the highest concentrations and exceeded the Brazilian legal limits. A principal component analysis (PCA) was performed and showed that biomass and number of juveniles parameters was associated with the metals Cu, Sn and Zn, while the mortality parameter had no association with any analyzed metal. These findings highlighted that the synergistic effects of compounds present in the APPs, such as the booster biocides DCOIT, and metal mixtures should not be overlooked. We conclude that soils contaminated with APPs are toxic to earthworms. This reveals that the ecological impact of APPs goes beyond effects on aquatic environments, compromising key organisms of edaphic ecological processes.

Effects of substances released from a coal tar-based coating used to protect harbor structures on oysters.

Products coal tar-based are largely used as concrete structures as protective coatings but some questions about leaching and potential toxic effects remain unclear. A laboratory experiment exposing oysters to miniaturized concrete pillars painted with Lackpoxi N1761 over time was performed and trace elements and 17 PAH were monitored in seawater exposure media, and oyster tissues. The original paint composition was also analyzed, and high concentrations of trace elements and PAH were detected. Sharp increases in PAH concentrations were observed after 6-96 h in exposure media and oyster tissues, suggesting that these compounds were leached from the painted structures. In parallel, the integrity of the hemocytes lysosomal membranes of exposed organisms has been damaged. Based on the response of this biomarker, the use of Lackpoxi N1761 is potentially harmful to the environment and it is required that coal tar-based paints be evaluated according to the environmental risk assessment protocols.

Microwave-Induced Combustion in Disposable Vessels: A Novel Perspective for Sample Digestion.

A novel system for sample digestion was proposed based on microwave-induced combustion in disposable vessels (MIC-DV) for trace elements determination by inductively coupled plasma optical emission spectrometry (ICP-OES). As a proof of concept, botanical samples were digested by MIC-DV for further determination of Al, Cr, Cu, Fe, Mn, Sr, and Zn. The system consists of a quartz holder (a modified version of conventional MIC) placed inside disposable polypropylene (PP) vessels. The quartz holder was carefully designed to avoid excessive heating and damaging of the vessel walls. For the combustion, the PP vessels containing the quartz holder and sample were placed in a specially designed metallic rotor that prevents the heating of absorbing solution and allows the use of a domestic microwave oven for sample ignition. After combustion, the digestion vessel was shaken to ensure the analytes' absorption. The single-vessel principle was fulfilled, since no further dilution or liquid transfer was required and the same PP vessel used for digestion allowed solution storage until element determination. The influences of absorbing solution (diluted HNO3 and water) and sample mass (10 to 30 mg) were evaluated. By using the proposed MIC-DV system, low volumes of diluted absorbing solutions (5 mL of 1 mol L-1 HNO3) were possible, allowing the use of low reagent amounts and low energy consumption, since microwave irradiation is used only for sample ignition. The agreement with certified values ranged from 92 to 108% for all analytes, whereas the precision was below 15%. All of these advantages, combined with the use of low-cost disposable vessels and instrumentation, make MIC-DV suitable to be used for research and routine analysis.

Diphenyl diselenide dietary supplementation protects against fumonisin B1-induced oxidative stress in brains of the silver catfish Rhamdia quelen.

The trend toward using plant-based ingredients in aquafeeds has raised important concerns for aquaculture owing to the negative impacts of mycotoxins on fish health; with emphasis for contamination by fumonisin B1 (FB1). The brain is an important target of FB1; however, study of the pathways linked to brain damage is limited to an analysis of histopathological alterations. Reports have demonstrated the protective effects of dietary supplementation with diphenyl diselenide (Ph2Se2) in the brains of fish subjected to several environmental insults; nevertheless, its neuroprotective effects in fish fed with diets contaminated with FB1 remain unknown. Therefore, the aim of this study was to evaluate whether oxidative damage may be a pathway associated with FB1-induced neurotoxicity, as well as to evaluate whether dietary supplementation with Ph2Se2 prevents or reduces FB1-mediated brain oxidative damage in silver catfish. Brain reactive oxygen species (ROS), lipid peroxidation (LOOH) and protein carbonylation increased on day 30 post-feeding in animals that received FB1-contaminated diets compared to the control group, while brain antioxidant capacity against peroxyl radicals (ACAP) levels and catalase (CAT), glutathione peroxidase (GPx) and glutathione S-transferase (GST) activities were lower. Diphenyl diselenide dietary supplementation avoid increases in brain ROS levels, as well minimizing the augmentation of LOOH levels. Furthermore, Ph2Se2 prevented impairment of brain ACAP levels, as well as GPx and GST activities elicited by FB1-contaminated diets. These data suggest that dietary supplementation with 3 mg/kg Ph2Se2 prevented FB1-induced brain damage in silver catfish, and this protective effect occurred through avoided of excessive ROS production, as well as via prevention of brain lipid damage. Furthermore, Ph2Se2 exerted its neuroprotective effects via ameliorative effects on the enzymatic and non-enzymatic antioxidant defense systems, and may be an approach to prevent FB1-induced brain oxidative stress; however, is not an alternative to prevent the impairment on performance caused by FB1.

Infrared enthalpymetric methods: A new, fast and simple alternative for sodium determination in food sauces.

This work developed a new technique and an application of an existing approach to determine sodium in food sauces, involving enthalpimetric reactions in the infrared. Infrared Thermometric Titration (TT-IR) was utilized, with simple analyzers and low-cost measurement instruments for the acquisition of the surface temperature generated in the sodium precipitation reaction and development of software for the acquisition and processing of data using Raspberry Pi. The sodium was also quantified by Thermal Infrared Enthalpimetry (TIE), a recently developed technique. The rapid and simple quantification of sodium by the TT-IR and TIE showed the possibility of a selective reaction for sodium, using aluminum nitrate, potassium and ammonium fluoride in an acid medium, with reduction of the reagents and without the digestion step in the sample preparation. The results acquired through TT-IR and TIE corroborated the Flame Atomic Emission Spectrometry (FAES) with 96 to 103% and 95 to 102%, respectively.

Arsenic speciation analysis in rice milk using LC-ICP-MS.

The consumption of rice milk has increased, mainly by individuals intolerant to lactose or allergic to cow milk. However, rice milk contains As. In this sense, the concentration of As in rice milk should be controlled. In the present study it is proposed a methodology for determination of As(III), dimethylarsenic (DMA), monomethylarsenic (MMA) and As(V) species in rice milk using LC-ICP-MS. The main features of the methodology are fast analysis, easy and simple sample preparation, where the sample is 3-fold diluted in the mobile phase and then filtered. The four arsenic species investigated were detected in the analysed samples, being As(V) the main species. The limit of quantification of the method ranges from 0.25 to 0.43 µg L-1 As. The analyte recovery ranged from 81 to 116% for samples spiked to 1.00 µg L-1 or 5.00 µg L-1 As and the relative standard deviation was better than 5%.

Prepubertal exposure to low doses of sodium arsenite impairs spermatogenesis and epididymal histophysiology in rats.

For the first time, juvenile toxicity of inorganic arsenic (As) was investigated in male rats, focusing on reproductive effects. As is a metalloid naturally occurring in the environment, being the inorganic forms the most toxics. Contaminated drinking water and agricultural products are the main prospectors of intoxication for general population. In the present study, Wistar male rats (21 days old) were distributed into three groups (n = 10/group): control (received vehicle-filtered drinking water), As1 (received AsNaO2 at 0.01 mg L-1 ) and As2 (received AsNaO2 at 10 mg L-1 ). The animals were euthanized on PND 53. Testicular damages increased in As1 and As2 compared to control (ie, presence of vacuolization, acidophilic cells, and epithelium degeneration). Testicular interstitium of As1 and As2 presented fluid's increase and intense inflammatory infiltration. In the epididymis there was reduction of sperm amount in the lumen, besides epithelium areas presenting cribriform aspect in As1 and As2, exfoliation of cells in the light (in As1) and vacuoles (in As2). In epididymis interstitium, inflammatory infiltrates were observed in initial segment of As1 and As2. AsNaO2 changed immunolabeling pattern for androgen receptor in epididymis of As2, although serum testosterone levels was statistically comparable to control. Mass spectrometry revealed higher As concentrations in testis and epididymis of As2 compared to As1 and Control. These results indicate compromise of spermatogenesis and epididymal histophysiology in AsNaO2 -treated animals, possibly impairing sperm quality and fertility in long-term, even at low levels of exposure. Investigations about the reversibility of reproductive damages are necessary to better understand the mechanisms of As reproductive toxicity.

Brazil nut improves the oxidative metabolism of superoxide-hydrogen peroxide chemically-imbalanced human fibroblasts in a nutrigenomic manner.

There are some genes associated to the risk of chronic diseases that present potential nutrigenetic response, such as the human manganese-dependent superoxide dismutase gene (Val16Ala-SOD2, rs4880) for which homozygous genotypes (VV and AA) are associated with higher basal superoxide (S) and hydrogen peroxide (HP) levels, respectively. It is possible that the VV- and AA-imbalance could be attenuated by selenium(Se)-rich foods such as Brazil nut (BN). To test this hypothesis, we conducted an in vitro protocol triggering a chemical S-HP imbalance by exposure of dermal fibroblast cells (HFF-1) to paraquat, which generates high S levels (VV-like treatment) and porphyrin (MnTBAP), which generates high HP levels (AA-like treatment). Modulation of cell growth and pro-oxidative and antioxidant markers were evaluated. BN aqueous extract (BNAE) most effective concentration which increased cell growth and decreased oxidative metabolism indicators of imbalanced cells was 75 ng Se/mL. However, this effect was not directly affected by the S-HP imbalance: in AA-SOD2-like cells, thioredoxin reductase (TrxR-1) gene was upregulated and in VV-SOD2-like cells an upregulation of glutathione peroxidase (GPx-1) gene expression was observed, however, this regulation occured in a homeostatic manner. These results suggest that BNAE was able to minimize negative effects in both directions of the S-HP imbalance, by modulation of different oxidative-metabolic pathways.

Antifouling paint particles: Sources, occurrence, composition and dynamics.

Sources, occurrence, composition and dynamics of antifouling paint particles (APPs) were assessed in Patos Lagoon estuary (PLE), Southern Brazil. Ten areas including boatyards, a marina and artisanal fishing harbors were identified in the estuarine system as potential sources of APPs. The APPs generated in these areas were highly heterogeneous considering the size, shape and composition. Based on an estimate of antifouling paint usage and amount of boats in each studied area, artisanal fishing harbors could be the main source of particles to PLE. However, relatively high amounts of APPs, which ranged from 130 to 40,300 µg g-1, were detected in sediments collected in front of boatyards and a marina. The uneven distribution of APPs levels among the sediment samples were probably due to the presence of diffuse sources (fishing harbors) associated to "hotspots" (boatyards and marina) along the study area. Additionally, data of settling experiment indicate that size, shape and density of APPs, combined to local hydrodynamics, appears to contribute to the mobility of these residues within the estuary. In the main channel of PLE, smaller particles tend to be transported to adjacent coastal zone while particles tend to be deposited in the sediment surface of sheltered areas. Since different trace metals, and booster biocides were detected in APPs that were not correctly disposed, these particles can be considered as an important source of contamination to aquatic environments. The present data suggest that APPs represent an environmental problem for aquatic systems in Brazil, since the country lacks legislation in addition to inefficient control mechanisms. An improvement in boat maintenance processes are urgently needed to avoid this continuous release of APPs into the aquatic systems.

A feasible method for As speciation in several types of seafood by LC-ICP-MS/MS.

A method for arsenic speciation in shark, shrimp, squid, oyster and scallop using liquid chromatography coupled to inductively coupled plasma triple quadrupole mass spectrometry (LC-ICP-MS/MS) was proposed. Suitable sensitivity and selectivity by LC-ICP-MS/MS were obtained using 10 mmol L-1 (NH4)2HPO4 diluted in 1% methanol (pH 8.65) as mobile phase. Recoveries from 90 to 104% for arsenobetaine (AsB), arsenite [As(III)], dimethylarsinic acid (DMA), monomethylarsonic acid (MMA) and arsenate [As(V)] were obtained for all samples. A certificated reference material was also analyzed and the sum of As species was in agreement with the total As concentration. Limits of quantification (LOQ) for AsB, As(III), DMA, MMA, and As(V) were 6, 30, 6, 12 and 26 ng g-1, respectively. Higher concentration of AsB was found in all seafood, while As(III) and DMA were found only in oyster. Arsenate was found in squid and scallops, and MMA was below the LOQ in all samples.

Are antifouling paint particles a continuous source of toxic chemicals to the marine environment?

Antifouling paint particles (APPs) are generated during periodical maintenance of boat hulls. Chemical composition and toxicity (either chronic or acute) of APPs found in the sediment was evaluated using the epibenthic copepod Nitokra sp. The APPs analyzed showed the presence of high levels of metals such as Cu (234,247±268µgg-1), Zn (112,404±845µgg-1) and the booster biocide DCOIT (0.13µgg-1). Even at low concentrations (as from 5mgg-1 of APPs by mass of sediment) a significantly decrease in the fecundity was observed in laboratory tests. When the sediment was disturbed in elutriate test, a LC50 of 0.14% for APPs was found. This study was the first assessment of toxicity associated with the presence of APPs in sediment to benthic organisms, and it calls attention to the need of improving regulations in boatyards and marina areas.

Rapid microplate, green method for high-throughput evaluation of vinegar acidity using thermal infrared enthalpimetry.

Infrared thermal imaging was combined with disposable microplates to perform enthalpimetric analysis using an infrared camera to monitor temperature without contact. The proposed thermal infrared enthalpimetry (TIE) method was used to determine the total, fixed and volatile acidities of vinegars. Sample preparation and analysis were performed in the same vessel, avoiding excessive sample handling and reducing energy expenditure by more than ten times. The results agreed with those of the conventional method for different kinds of vinegars, with values of 1.7%, and 2.3% for repeatability and intermediate precision, respectively. A linear calibration curve was obtained from 0.040 to 1.30molL(-1). The proposed method provided rapid results (within 10s) for four samples simultaneously, a sample throughput of up to 480 samples per hour. In addition, the method complies with at least eight of twelve recommendations for green analytical chemistry, making TIE a promising tool for routine vinegar analysis.