Distribution of metals in different environmental compartments and oxidative stress biomarkers in Bryconops caudomaculatus (Osteichthyes: Characiformes) from a bauxite mining area in the Eastern Amazon.

The Eastern Amazon is rich in bauxite ore. The extraction and processing of bauxite lead to the mobilization of Aluminum (Al) and other metals in environmental. We evaluated the metals (Al, Mn, Ba, and Cr) concentration in tissue, water, and sediment associated with antioxidant and oxidative damage responses in Bryconops caudomaculatus. The samplings were done in two hydrological periods (post-rain and post-dry periods) and at three points, located at two rivers: one in the surroundings of the mining area (P1) and other inside the mining area, upstream (P2), and downstream (P3). Defense antioxidant system biomarkers analyzed were total antioxidant capacity (ACAP) and glutathione-S-transferase (GST) activity. As an oxidative damage biomarker, the lipoperoxidation (LPO) was evaluated. Metals concentrations in the water and sediment were higher in the post-rain period compared to post-dry period. The water samples were acidic, with dissolved Al concentrations above the values established by local legislation at all points. In the gills, the metals accumulation was higher in fish from in the surrounding and upstream sites, and in the liver, was higher in fish from downstream site. Fish from the surrounding had increased antioxidant defenses, with higher ACAP in all tissues and higher GST in the gills. Consequently, they had lower levels of LPO. Fish from the mining area had decreased antioxidant defenses, with lower ACAP in all tissues and lower GST in the gills. Consequently, they had higher levels of LPO, indicating oxidative stress. The fish muscle was not responsive to GST and LPO at all sites. We conclude that the oxidative stress observed in the gills and liver of B. caudomaculatus from the area modified by the mining activity reflected the local anthropogenic impact status.

A new approach to ion exchange chromatography with conductivity detection for adulterants investigation in dietary supplements.

The extent of adulteration of dietary supplements has significantly increased in recent years. This situation worries health authorities and requires auxiliary analytical tools for the investigation of illegal substances purposely added. Ion exchange chromatography with conductivity detection is a consolidated analytical technique for the determination of inorganic compounds in various matrices. This technique has been applied to the pharmaceutical characterization of mainly impurities and degradation products. This work presents a new approach to ion exchange chromatography as a screening method to investigate the presence of amfepramone, femproporex, sibutramine, bisacodyl and amiloride in dietary supplements advertised for weight loss. The method was optimized and validated using a Metrosep C4 100/4.0 cation exchange column. The mobile phase consisted of 1.8 mm HNO3 containing 2% acetonitrile (v/v), with a flow rate of 0.9 ml min-1 , and nonsuppressed conductivity detection was applied. The limits of detection and quantification varied from 1.01 to 3.62 mg L-1 and from 1.48 to 8.72 mg L-1 , respectively. The proposed method was successful applied to 78 solid dietary supplement samples, in two of which adulterations were found. Moreover, ion exchange chromatography with conductivity detection could be easily used for quality control without prior complex sample pre-treatment.

Persea americana Mill. crude extract exhibits antinociceptive effect on UVB radiation-induced skin injury in mice.

Persea americana, popularly known as avocado, has been empirically used as analgesic and anti-inflammatory including in the skin disorder treatment. Species of the genus Persea also show a photoprotective effect against UVB radiation. We investigated the antinociceptive and anti-inflammatory effects from a topical formulation containing the P. americana leaf extract in a UVB irradiation-induced burn model in mice and performed a gel-formulation stability study. The antinociceptive and anti-inflammatory effect was evaluated through mechanical allodynia, paw oedema, and inflammatory cell infiltration. Phenolic compounds were quantified by UHPLC-MS/MS. The gel-formulation stability study was performed analyzing organoleptic characteristics, pH, and viscosity. P. americana (3%) gel was able to prevent the UVB irradiation-induced mechanical allodynia on the 2nd and 3rd day after irradiation with maximum inhibition of 60 ± 12% at 2nd day. Such effect may be attributed, at least in part, due the presence of (+)-catechin (302.2 ± 4.9 µg/g) followed by chlorogenic acid (130 ± 5.1 µg/g) and rutin (102.4 ± 0.9 µg/g) found in the extract. The gel was not able to prevent the inflammatory parameters such as edema and leukocyte infiltration induced by UVB irradiation. No changes important were detected in the stability study, mainly in low temperature. Our results suggest that P. americana gel-formulation, which presented stability, ensuring its quality and the therapeutic effect, could be an interesting strategy for the treatment of the pain associated with sunburn; this effect could be attributed to its biological constituents, especially catechin, chlorogenic acid, and rutin.

A rapid method for identification and quantification of prostaglandins in cerebral tissues by UHPLC-ESI-MS/MS for the lipidomic in vivo studies.

An analytical method utilizing liquid chromatography coupled to mass spectrometry with electrospray ionization has been developed for the identification of prostaglandins (PGs) in cerebral tissues. The five compounds identified (thromboxane B2, prostaglandin E2, prostaglandin D2, 6-keto-prostaglandin F1 alpha and prostaglandin F2 alpha) are cellular mediators of inflammation and are involved in a variety of physiological and pathological processes by acting on membrane receptors on the surfaces of target cells. The parameters of the electrospray ionization interface were optimized to obtain the highest possible sensitivity for all compounds studied. The limits of detection ranged from 0.25 to 1.09 µg L-1, and the limits of quantification ranged from 0.83 to 3.64 µg L-1. The method was validated and applied to samples of brain tissue from five mice. The sample concentrations of the four prostaglandins quantified ranged from 375 ȵg L-1for prostaglandin E2 to 6602 µg L-1 for prostaglandin D2. An advantage of this work that should be emphasized is the fast response of the method, which allows to obtaining the lipid profile after a 3 min chromatographic run.

Arctium minus crude extract presents antinociceptive effect in a mice acute gout attack model.

Gout is a disorder that triggers a severe inflammatory reaction which generates episodes of intense pain and discomfort to the patient. Arctium minus (Hill) Bernh. (Asteraceae) is known as "burdock" and displays anti-inflammatory, antinociceptive, against rheumatic pain and radical-scavenging activities. Species of the genus Arctium have been used in assistant therapy of gout and other inflammatory processes. We investigated the antinociceptive and anti-edematogenic effects of the crude extract of A. minus seeds in an acute gout attack model induced by intra-articular injection of monosodium urate (MSU) crystals in adult male Swiss mice (25-30 g). The crude extract of A. minus (100 mg/kg, p.o.) reduced the mechanical allodynia induced by the injection of MSU (1.25 mg/site, i.a.) from 4 until 8 h after its administration. A. minus seeds crude extract prevented mechanical allodynia at doses of 30 and 100 mg/kg, but not 10 mg/kg. Allopurinol (10 µg/mL) and A. minus crude extract (10-300 µg/mL) inhibited the xanthine oxidase activity in vitro. The A. minus seeds crude extract did not cause adverse effects since did not change the toxicological parameters evaluated. A. minus crude extract can be used as an assistant therapy of gout pain, supporting its traditional use, without causing adverse effects.

Toxicological Effects Induced by Silver Nanoparticles in Zebra Fish (Danio Rerio) and in the Bacteria Communities Living at Their Surface.

The antimicrobial activity of silver nanoparticles (AgNP) makes them useful in a wide range of products although their environmental impact is still uncertain. The main goal of this study was to evaluate short-term effects induced by AgNP on gills oxidative status and bacterial communities living at the skin mucus of zebrafish. Both the number of bacteria colony forming units and bacteria growth obtained from skin mucus were lower in all concentrations tested (25, 50 and 100 µg nAg/L). Besides, AgNP exposure caused a significant decrease in bacteria growth in zebrafish exposed to 100 µg nAg/L. AgNP accumulated in zebrafish gills at both highest concentrations tested, but this accumulation did not appear to result in oxidative stress. Overall the results indicated toxicological effects of AgNP on bacteria communities living at the zebrafish mucus surface. Although silver accumulation was verified in gills, no evidence of toxicity in terms of oxidative stress was found.

Interference of Parenteral Nutrition Components in Silicon-Mediated Protection Against Aluminum Bioaccumulation.

Aluminum and silicon are contaminants found in formulations used to prepare parenteral nutrition. Both elements are leached from glass containers, mainly during the heating cycle for sterilization. Insoluble and biologically inactive species of hydroxyaluminosilicates have been shown to form in solutions containing Al and Si. Therefore, this interaction may play an important role in protecting the body against Al toxicity. In this study, the bioavailability of Al in the presence of Si, calcium gluconate (Gluc.), and potassium phosphate (Phosf.) was investigated in rats. The rats were divided into 10 groups of 5 animals each: control, Al, Si, Al + Si, Gluc, Gluc + Al, Gluc + Al + Si, Phosf, Phosf + Al, and Phosf + Al + Si. The doses, consisting of 0.5 mg/kg/day Al and 2 mg/kg/day Si in the presence or absence of Gluc. or Phosf., were intraperitoneally administered for 3 months. Tissues were analyzed for Al and Si content. Al accumulated in the liver, kidneys, and bones, and the simultaneous administration of Si decreased Al accumulation in these tissues. The presence of Si reduced the amount of Al present by 72% in the liver, by 45% in the kidneys, and by 16% in bone. This effect was lees pronounced in the presence of parenteral nutrition compounds though. Si tissue accumulation was also observed, mainly when administered together with phosphate. These results suggest that Si may act as a protector against Al toxicity, by either reducing Al absorption or increasing its excretion, probably through hydroxyaluminosilicates formation. The presence of calcium gluconate and potassium phosphate decreases or inhibits this effect.

Silver nano/microparticle toxicity in the shrimp Litopenaeus vannamei (Boone, 1931).

The effects of silver nano/microparticles (AgP) on juvenile Litopenaeus vannamei shrimp were evaluated through several responses, aiming to use it as a prophylactic and therapeutic method. Shrimps (3.19 ± 0.13 g) were exposed to clear water for 3 h with increasing concentrations of nanosilver (0; 25; 100; and 400 µg/l). After 3 h of exposure, they were transferred to water without nanosilver for 30 days (recovery). The weight gain and weekly growth were not affected by AgNP. Total antioxidant capacity (ACAP) increased in the hepatopancreas (exposure period) and gills (recovery) in shrimp exposed to AgNP. In muscle, ACAP was induced in shrimp exposed to 100 µg/l AgNP (exposure). In the gills, there was an increase in TBARS in shrimp exposed to 100 µg/l AgNP (recovery). In the concentration of protein-associated sulfhydryl groups (P-SH), a decrease was observed in the hepatopancreas (recovery) in the 100 µg/l AgNP treatment. In chromaticity parameters, an increase in reddish tones was observed in shrimp exposed to 100 µg/l AgNP (recovery). An increase in granular hemocytes was verified in shrimp exposed to 25 and 400 µg/l AgNP during exposure. Tissues analyzed histologically showed normal patterns without apoptosis or necrosis processes, and after 30 d of recovery, only in one muscle sample of shrimp exposed to µg/l of AgNP was silver detected. It is concluded that a prophylactic action of short duration (3 h) mostly did not affected the welfare of shrimp L. vannamei and can be considered its use as a therapeutic strategy.

Evaluation of cardiotoxicity in Amazonian fish Bryconops caudomaculatus by acute exposure to aluminium in an acidic environment.

Aluminium (Al) is soluble in acidic waters and may become toxic to organisms. In this study, the acute effects of two Al concentrations were evaluated in the Amazonian fish Bryconops caudomaculatus. Antioxidant responses and lipid damage were assessed in gills, liver and muscle, along with the electrocardiography (ECG) and characterization of cardiac complex and wave intervals. Fish were essayed as follows: two control groups at neutral and acidic pH and two exposure groups at acidic pH (0.3 mg/L and 3.0 mg/L Al). Water samples were collected at 0h, 24h and 48h, for chloride (Cl-), fluoride (F-) and sulphate (SO42-) ion analyses, while total Al was quantified in muscle. Concentrations of Cl- and SO42- were constant over time whereas F- was not detected. Total Al concentrations in water and muscle were concentration-dependent. Antioxidant responses, total antioxidant capacity against peroxyl radicals (ACAP) and glutathione S-transferase were not triggered in fish tissues exposed to 0.3 mg/L Al; however, fish exposed to 3.0 mg/L Al presented increased and reduced ACAP in gills and liver, respectively. No changes in lipoperoxidation levels occurred among groups. Fish exposed to 0.3 mg/L Al showed prolonged intervals in ECG as a reflection of low heart rate (HR), with sinus bradycardia. Moreover, there was a marked prolongation of the PQ interval (time between the atrial activity and the start of ventricular activity), indicating interference on the cardiac cell automaticity. Fish exposed to the highest concentration of Al showed reduced wave intervals as a consequence of increased HR, with sinus arrhythmia, while ECG tracings did not present P waves (atrial contraction), indicating an atrioventricular blockade. In conclusion, 48h exposure sufficed to cause cardiotoxicity in B. caudomaculatus at either Al concentration. However, as oxidative stress was not observed, such cardiac alterations seem to be reversible under the experimental conditions established herein.

Extraction/Leaching of Metal-Containing Additives from Polyvinyl Chloride, Ethyl Vinyl Acetate, and Polypropylene Bags and Infusion Sets into Infusion Solutions.

Flexible medical devices are primarily made of plasticized polyvinyl chloride (PVC). In recent times, to avoid undesired migration of the PVC plasticizers, ethyl vinyl acetate (EVA) and polypropylene (PP) has replaced PVC. Nevertheless, other additives are necessary to generate useful polymeric materials. Metallic species present in such additives can also leach out into the infusion solutions. The migration of barium (Ba), cadmium (Cd), lead (Pb), tin (Sn), and zinc (Zn) from devices made from PVC, EVA, and PP was evaluated. Bags and infusion sets were decomposed and their metallic contents analyzed. Glucose, NaCl, and Tween 80 were assessed as extraction media. These solutions were stored in PVC, EVA, and PP bags, heat-sterilized, and stored for 8 months at room temperature. Aliquots were taken before and after sterilization and then once per month to determine the contents of the metals. Commercial glucose and NaCl infusions were analyzed by taking aliquots of the solutions from the bags and from the administration set after their administration to patients. The three polymers contained the five metals. Ba was found in the highest concentration in all samples, with a mean of 8.0 mg/kg in PVC, 4.2 mg/kg in EVA, and 4.7 mg/kg in PP samples. Despite this, the only element that migrated into the glucose, NaCl, and Tween 80 solutions was Zn. The same result was found for the commercial glucose and NaCl infusions. Moreover, the Zn concentration in the administration sets was on average 52% higher than that found in the bags.LAY ABSTRACT: Flexible medical devices for infusions and artificial nutrition are made of plastics, such as polyvinyl chloride (PVC), ethyl vinyl acetate (EVA), and polypropylene (PP). These polymers contain additives necessary to generate useful materials. Metallic species present in these additives can leach out into the infusion solutions and come into contact with patients. To assess the risk of patient exposure to these metals, we evaluated the migration behavior of barium (Ba), cadmium (Cd), lead (Pb), tin (Sn), and zinc (Zn) from devices made from PVC, EVA, and PP. Bags and infusion sets were analyzed. Glucose, NaCl, and Tween 80 were investigated as extraction media. The three polymers contained the five metals. Ba was found in the highest concentration in all samples. Despite this, the only element that migrated into the glucose, NaCl, and Tween 80 solutions was Zn.

An Ultra-High Performance Liquid Chromatography-Electrospray Tandem Mass Spectrometric Method for Screening and Simultaneous Determination of Anorexic, Anxiolytic, Antidepressant, Diuretic, Laxative and Stimulant Drugs in Dietary Supplements Marketed for Weight Loss.

The consumption of dietary supplements is increasing every year all over the world and has been accompanied by an increased frequency of adulteration of these products with synthetic pharmaceuticals. Analytical methods that allow testing for the presence of synthetic drugs in dietary supplements are needed to detect such fraudulent practices. To investigate the adulteration of dietary supplements marketed for weight loss using different commercial appeals, we developed an analytical method using ultra-high-performance liquid chromatography-electrospray tandem mass spectrometry (UHPLC-ESI-MS/MS) for simultaneous determination of 32 drugs, including anorexics, anxiolytics, antidepressants, diuretics, laxatives and stimulants. Separation was accomplished in 19 minutes using a Zorbax SB-C18 column and a gradient elution program with 0.05% formic acid in water/acetonitrile as a mobile phase. Limits of quantification ranged from 0.14 to 3.92 µg L-1, and accuracy ranged from 80.00 to 119.48%. A simple extraction procedure was used in the pretreatment step by dissolving the samples in 100% methanol followed by a 1000 to 10,000-fold dilution in the mobile phase and filtration through a Teflon membrane (0.2 µm). The method was applied to the screening and quantification of the drugs in 108 formulations marketed as food supplements for slimming, weight loss, thermogenics, and supplements for meal replacement. Caffeine and p-synephrine were found as stimulants in 80 samples, listed or not on the label.

Nasturtium officinale R. Br. effectively reduces the skin inflammation induced by croton oil via glucocorticoid receptor-dependent and NF-κB pathways without causing toxicological effects in mice.

ETHNOPHARMACOLOGICAL RELEVANCE: Inflammatory skin diseases treatments currently used cause adverse effects. Nasturtium officinale (watercress) is used popularly as an anti-inflammatory. However, until now, no study proved its effectiveness as a topical treatment to inflammatory skin diseases. The topical anti-inflammatory activity of N. officinale crude extract leaves (NoE) on an irritant contact dermatitis (ICD) model croton oil-induced in mice was investigated. MATERIALS AND METHODS: ICD models were induced by a single (1 mg/ear; acute) or repeated (0.4 mg/ear; chronic; 9 days total) croton oil application. NoE and dexamethasone solutions' (diluted in acetone; 20 µL/ear) or NoE gel, dexamethasone gel and base gel (15 mg/ear) were topically applied immediately after croton oil application. The NoE topical anti-inflammatory effect was evaluated for inflammatory parameters (ear edema, inflammatory cells infiltration, and inflammatory cytokines levels). NoE topical anti-inflammatory mechanism (NF-κB pathway and effect glucocorticoid-like) were assessed by western blot and ear edema analyses, respectively. UHPLC-MS/MS chromatography, gels accelerated stability and preliminary study of adverse effects was also performed. RESULTS: UHPLC-MS/MS of the NoE revealed the presence of coumaric acid, rutin, and ferulic acid. NoE gels stability study showed no relevant changes at low temperature. NoE, dexamethasone, NoE gel and dexamethasone gel inhibited the ear edema croton oil-induced by 82 ±â€¯6% (1 mg/ear), 99 ±â€¯1% (0.1 mg/ear), 81 ±â€¯8% (3%) and 70 ±â€¯6% (0.5%) for the acute model, and 49 ±â€¯7% (1 mg/ear), 80 ±â€¯4% (0.1 mg/ear), 41 ±â€¯8% (3%) and 46 ±â€¯14% (0.5%) for the chronic model, respectively. The same treatments also reduced the inflammatory cells infiltration by 62 ±â€¯3% (1 mg/ear), 97 ±â€¯2% (0.1 mg/ear), 60 ±â€¯3% (3%) and 66 ±â€¯6% (0.5%) for the acute model, respectively, and 25 ±â€¯8% (1 mg/ear) to NoE and 83 ±â€¯13% to dexamethasone to the chronic model. NoE and NoE gel reduced the pro-inflammatory cytokines levels (acute ICD model) by 62 ±â€¯5% and 71 ±â€¯3% (MIP-2) and 32 ±â€¯3% and 44 ±â€¯4% (IL-1ß), while dexamethasone solution's and gel reduced by 79 ±â€¯7% and 44 ±â€¯4% to MIP-2 and 98 ±â€¯2% and 83 ±â€¯9% to IL-1ß, respectively. NoE' and dexamethasone' solutions inhibited the reduction of IkB-α protein expression induced by croton oil by 100% and 80 ±â€¯14%, respectively. Besides, the mifepristone (glucocorticoid receptor antagonist) pre-treatment prevented the topical anti-edematogenic effect of NoE' and dexamethasone' solutions by 61 ±â€¯5% to NoE and 78 ±â€¯16% to dexamethasone. The repeated topical application of NoE did not cause adverse effects. CONCLUSION: Our results suggest the N. officinale use in the cutaneous inflammatory process treatment and demonstrate the NoE potential to develop a promising topical anti-inflammatory agent to treat inflammatory disorders.

Mansoa alliacea extract presents antinociceptive effect in a chronic inflammatory pain model in mice through opioid mechanisms.

In some chronic disorders, as in arthritis, the inflammatory pain persists beyond the inflammation control becoming pathological. Its treatment shows limited efficacy and adverse effects which compromises patients' quality of life. Mansoa alliacea, known as 'cipo alho', is popularly used as analgesic and others species of this genus show anti-inflammatory actions. We investigated the anti-inflammatory and antinociceptive potential of M. alliacea extract in an inflammatory pain model which presents inflammatory characteristics similar to those caused by arthritis, through of the intraplantar injection of complete Freund's adjuvant (CFA) in mice. The extract chromatographic analysis revealed the presence of ρ-coumaric, ferulic and chlorogenic acids, luteolin, and apigenin. The treatment with M. alliacea prevented and reversed the CFA-induced mechanical allodynia with maximum inhibition (Imax) of 100% and 90 ±â€¯10%, respectively. The co-administration of M. alliacea extract plus morphine enhanced the anti-allodynic effect with Imax of 100%. The M. alliacea extract also reverted the CFA-induced thermal hyperalgesia with Imax of 3.6 times greater compared to the vehicle and reduced the thermal threshold under physiological conditions. However, M. alliacea extract did not reduce the CFA-induced edema and myeloperoxidase activity. Additionally, non-selective and δ-selective opioid receptor antagonists, but not κ-opioid, prevented extract anti-allodynic effect with Imax of 98 ±â€¯2% and 93 ±â€¯2%, respectively. Moreover, M. alliacea extract did not induce adverse effects commonly caused by opioids and other analgesic drugs, at least in the tested pharmacological doses after the acute treatment. M. alliacea extract presents antinociceptive activity in an inflammatory pain model, which presents inflammatory characteristics similar to those arthritis-induced, without causing adverse effects in tested pharmacological doses. These effects seem to be mediated mainly via δ-opioid receptors.

Simultaneous determination of iron and nickel as contaminants in multimineral and multivitamin supplements by solid sampling HR-CS GF AAS.

A methodology to assay simultaneously iron and nickel present as contaminants in multimineral and multivitamin supplements was investigated. High-resolution continuum source graphite furnace atomic absorption spectrometry and direct solid sample analysis were used. Measurements were done with the secondary lines of Fe (352.604 nm) and Ni (352.454 nm) to avoid spectral interferences. The best temperatures for pyrolysis and atomization for Fe and Ni were 1000 and 2700 °C, respectively. Chemical modifiers were not necessary and no matrix effects were observed. Aqueous standard solutions were used for calibration. The limit of detection was 0.517 µg g-1 for Fe and 0.011 µg g-1 for Ni. The precision ranged from 4.3% to 17% and 4.4-20% for Fe and Ni, respectively. The method accuracy was confirmed by comparing statistically the results obtained by solid sampling with those of sample acid digestion. The proposed methodology was successfully applied to determine both metals in different multimineral and multivitamin supplements.

Tissue digestion for aluminum determination in experimental animal studies.

Four different procedures for the determination of aluminum in tissues by atomic absorption spectrometry (AAS) were investigated. They consisted of conventional acid digestion carried out before and after sample drying, associated or not with fat extraction. Drying was carried out in a conventional oven at 65 degrees C for 24 h. For fat extraction, different solvents and solvent mixtures were investigated considering both extraction yield and sample adequacy for further AAS measurement. Acid digestion was carried out with pure HNO3 or with its mixture with HClO4. After digestion, aluminum was measured by graphite furnace atomic absorption spectrometry. Tissues were collected from Al-exposed and nonexposed mice. The results indicated that drying the sample prior to digestion is advantageous as the amount of acid necessary can be significantly reduced. This procedure does not contribute to increase the aluminum level in the samples providing that careful measures to avoid contamination are taken, as the same procedures carried out without taking any precautions to avoid contamination produced imprecise results. Finally, aluminum was not found in the fatty fraction of any sample, even in exposed mice, demonstrating that aluminum does not accumulate in this part of the tissues.

Metal and metalloid distribution in different environmental compartments of the middle Xingu River in the Amazon, Brazil.

Concentrations of As, Cd, Cu, Cr, Pb, Hg, and Ni were analyzed during rainy and dry seasons in water, sediment, soil, and two fish species. The analysis took place at four points in the Xingu River, one point in the Fresco River, and two mining pits in the southeastern area of the Eastern Amazon, Brazil. In the water, the total concentration of As (>0.14µg/L) was higher than the local reference values at all sampling points and in both seasons. Ordination analysis (PCA) highlighted As and Cu elements in the water. PERMANOVA showed that the metals behaved differently in the water throughout the monitored season and between sampling points. The sites with mining activity were the regions that were the most contaminated by metals. Samples of sediment (Ni>18mg/kg and Cr>37.30mg/kg) and soil (Pb>72mg/kg, Cr>75mg/kg and Ni>30mg/Kg) showed concentrations above the recommended by local legislation. Metal values in the muscle of both fish species were relatively low at all sampling points and in both monitored seasons. Concentrations in water, sediment, and soil showed that some points of the Xingu River, Fresco River and mining pits are contaminated by trace elements, mainly As, Hg, Cr, Pb, and Ni. This was the first study about trace elements in the Middle Xingu River, which leads us to conclude that rainfall and cassiterite mining activities strongly influence the mobilization of metals, especially in abiotic compartments. However, the fish analyzed did not exhibit relevant levels of contamination. This indicates low risk for human consumption. Additionally, results highlight the need to establish local criteria to define contamination limits for different metals while taking into account local geochemistry particularities and biome diversity.

Determination of Antimony in Pharmaceutical Formulations and Beverages Using High-Resolution Continuum-Source Graphite Furnace Atomic Absorption Spectrometry.

A sensitive and accurate method, employing high-resolution continuum source atomic absorption spectrometry, for the determination of antimony (Sb) was developed. Conditions such as pyrolysis and atomization temperatures, the use of chemical modifiers, and sample pretreatment were optimized for the determination of Sb in pharmaceutical preparations and beverages stored in polyethylene terephthalate (PET) containers. In addition to container analysis, the influence of time of contact, temperature, and content composition on the migration of Sb was investigated. Twenty-six samples were periodically analyzed until finalize 1 year bottling. Eight mineral water samples were analyzed after storage at temperatures from 40 to 80°C for 48 h. Five different-colored PET samples were stored at 80°C for 20 days and periodically analyzed. Bottles, containing from 46.4 mg/kg Sb (amber PET) to 91.6 mg/kg Sb (colorless PET), leached Sb depending on the content ingredients, time of contact, and temperature. Although drinking water itself did not promote Sb migration at room temperature, juices and medicines did. After 1 year of storage, the Sb level in the samples ranged from 5 to 50 µg/L. The rate of leaching depended on the temperature, which was slow below 60°C, but rapidly increased at 60-80°C. The higher the Sb content in the bottle, the higher the amount of migration. Because Sb is a possible carcinogen to humans, containers for pharmaceutical use should be better controlled, and factors that increase Sb leaching in products that are widely consumed should be avoided.

Arsenic release from glass containers by action of intravenous nutrition formulation constituents.

Pharmacopoeias prescribe tests to determine the levels of arsenic in raw materials and glass containers. In this study, glass ampoules for injectables containing individually the main components of intravenous nutrition formulations were submitted to the hydrolytic resistance test by heating at 121 degrees C for 30 min. As(V) and As(III) levels in these solutions after heating were determined by hydride generation atomic absorption spectrometry. The arsenic content of substances used in these formulations was previously determined, as well as the arsenic content of the glass containers. The results showed that raw substances as well as glass containers contain arsenic. Moreover, arsenic is released during the heating (hydrolytic resistance test). However, the amount released and the arsenic species present in solution depend on the solution composition. While As(V) was the predominant specie in glass, solutions containing reducing substances such as glucose and vitamins had As(III) in higher concentration. Therefore, arsenic is released from glass containers during the heating for sterilization, and reacts with formulation constituents depending on their reducing properties.

A liquid chromatography-atmospheric pressure photoionization tandem mass spectrometric (LC-APPI-MS/MS) method for the determination of triterpenoids in medicinal plant extracts.

An analytical method using liquid chromatography-atmospheric pressure photoionization tandem mass spectrometry with toluene as a dopant was developed for the determination of triterpenes in medicinal plant extracts. The 12 compounds determined have been shown to exhibit biological activity, such as gastroprotective, hepatoprotective, anti-inflammatory, antiviral and anti-tumor effects. The parameters of the atmospheric pressure photoionization interface were optimized to obtain the highest possible sensitivity for all of the compounds. The limits of detection and quantification ranged from 0.4 to 157.9 µg l-1 and 1.3 to 526.4 µg l-1 , respectively. The method was validated and applied to extracts of five medicinal plants species (Mansoa alliacea (Lam.) A.H.Gentry, Bauhinia variegata var variegata, Bauhinia variegata var alboflava, Cecropia obtuse Trécul and Cecropia palmate Willd) from the Amazonian region. The concentrations of the six triterpenes quantified in the samples ranged from 0.424 mg kg-1 for ursolic acid to 371.96 mg kg-1 for ß-amyrin, which were quantified by using the standard addition method (n = 3). Copyright © 2016 John Wiley & Sons, Ltd.

Simultaneous determination of cobalt and nickel in vitamin B12 samples using high-resolution continuum source atomic absorption spectrometry.

Nickel and cobalt were simultaneously assayed in vitamin B12 formulations by using atomic spectrometry. The proposed method is based on a compromise between the proximity of specific Ni and Co spectral lines and the relative abundances of the analytes in the samples. The analytes were found in concentrations ranging from 9.48 to 26.20µg L(-1) (Ni) and from 156.90 to 279.25mg L(-1) (Co) in the commercial samples of vitamin B12. The limits of detection and quantification were 1.21 and 3.64mg L(-1) for Co and 0.39 and 1.19µg L(-1) for Ni. Sample cleanup was not necessary for the determinations, and the interferences were discussed.