Bees reflect better on their ecosystem health than their products.

Beehives constitute a source of environmental contaminants because forager bees explore their habitat and unintentionally accumulate them while foraging for food. Therefore, this review paper investigated different bee species and products from 55 countries to identify how they can help environmental biomonitoring by giving an overview of the past 11 years. Thereby is presented in this study the beehive's use as a bioindicator for metals, analytical techniques, data analysis, environmental compartments, common inorganic contaminants, reference thresholds for some metal concentrations in bees and honey, and other factors over more than 100 references. Most authors agree that the honey bee is a suitable bioindicator to assess toxic metal contamination, and among its products, propolis, pollen, and beeswax are more suited than honey. However, in some situations, when comparing bees with their products, bees are more efficient as potential environmental biomonitors. Some factors such as the colony location, floral sources, regional effects, and activities surrounding the apiary influence the bees, and the composition of their products is reflected by alterations in their chemical profile, making them suitable bioindicators.

Prepubertal to adulthood exposure to low doses of glyphosate-based herbicide increases the expression of the Havcr1 (Kim1) biomarker and causes mild kidney alterations.

Glyphosate is a nonselective and postemergent herbicide used to combat weeds in several crops, which raises concerns about risks to human health since residues are detected in urine, human milk, surface water and several types of food. Feces and urine are the major routes of elimination of glyphosate, making the kidney a sensitive target for the development of toxicity. In fact, farmers are at high risk of developing chronic kidney disease. In this sense, this study aims to investigate kidney function by measuring the serum levels of urea and creatinine, examining the histological morphology, and analyzing the mRNA expression of genes related to tubular transport of ions, urea and urates and the biomarker of kidney disease Kim1, and the levels of lead in the kidney in male Wistar rats orally exposed to low levels of glyphosate-based herbicide (GBH: 0, 0.5 or 5 mg/kg) from weaning to adult life by gavage. GBH0.5 showed reduced serum urea concentration, presence of tubulointerstitial swelling and mononuclear cell infiltration into the interstitium, increased gene expression of Kim1 and reduced gene expression of Slc14a1. GBH5 showed reduced serum urea and increased serum creatinine concentrations, tubulointerstitial swelling, interstitial fibrosis, and reduced expression of Trpm6 and Trpv5. Exposure to GBH did not affect the levels of Pb in the kidneys of animals. In conclusion, glyphosate at low doses may cause mild kidney damage. It is necessary to evaluate whether the long-term effects of this constant injury may contribute to the development of chronic kidney disease of uncertain etiology.

Determination of the Ca, Mn, Mg and Fe in honey from multiple species of stingless bee produced in Brazil.

Stingless Bees (SB) honey is a product used for different purposes, and it is worth highlighting the presence of metallic species, which can have a nutritional or toxic effect, depending on the metal present and/or the amount ingested. Therefore, the objective of this work was to quickly determine Fe, Mn, Mg and Ca in SB honey, using slurry sampling and FAAS of 88 honey samples from different regions of Brazil. The concentrations varied from < LOD to 364 µg g-1 (Ca). The order for average concentration in the samples was Ca > Mg > Mn > Fe. Through the principal component analysis, it was verified that the SB honey analyzed in the present study has higher contents of the evaluated metals than the honey of the species Apis mellifera and SB honey from other Brazilian states. Theoretical calculation demonstrated that there is a little contribution of SB honey to human diet in relation to the metals, being more significative for Mn.

Are there pharmaceutical compounds in sediments or in water? Determination of the distribution coefficient of benzodiazepine drugs in aquatic environment.

Alprazolam, clonazepam and diazepam are drugs belonging to the benzodiazepine class. These drugs might be important environmental contaminants in aquatic media. A total understanding of behavior and fate of drugs in aquatic environment is not available for these and other drugs. Thus, in this work, a complete optimization of sample treatment and extraction of analytes from sediments and water was described, as well a study of sediment/water distribution comparing it with sample characteristics. Ultrasound for 10 min and 3 steps using 3 mL of extraction solvent were chosen as the stirring form for extraction. A methanol/water (1:1) solution pH 12 was the best extraction solvent. Aiming to eliminate interferences, an addition of 10 µL of NaCl 3.06 mol L-1 was necessary after each step of extraction. Sediment and water samples were characterized, presenting different values on physical-chemical parameters. Six distinct sample sets of water and sediments were spiked with each benzodiazepine and analyzed. Kd values varied from 1.4 to 9.2 L kg-1 for clonazepam, 1.8-11.5 L kg-1 for alprazolam and 2.31-12  L kg-1 for diazepam. A principal component analysis showed high dependence on Kd with sample characteristics mainly related to sediments. In the systems, whose sediments presented high levels of clay, silt and organic matter, the drugs presented a great interaction with the solid part of the system, increasing the Kd value. Koc values varied from 149.25 to 634.13 L kg-1 for clonazepam, 186.57-852.48 L kg-1 for alprazolam, and 194.68-1189.81 L kg-1 for diazepam.

Effects of Silver Nanoparticle Exposure to the Testicular Antioxidant System during the Prepubertal Rat Stage.

Humans and environments are constantly exposed to a wide range of commercial products containing silver nanoparticles (AgNPs) in their composition. The hypothalamic-pituitary-testicular (HP-testicular) axis is sensitive to low doses of AgNPs with repercussions in sperm functionality. The oxidative stress may be related to the pathogenesis of sperm alterations because Ag+ ions are released from AgNPs in the corporal fluids. This study aimed to investigate the effects of AgNP exposure in the antioxidant defense system. For this, the transcript expression and the activity of catalase (CAT), superoxide dismutase (SOD), glutathione peroxidase (GPX), and glutathione reductase (GSR) enzymes were evaluated in the testis of rats exposed during the prepubertal period to increasing doses of AgNPs (1.875, 3.75, 7.5, or 15 µg of AgNPs/kg). The higher dose of AgNPs (15 µg/kg) investigated promoted increases in the activity of CAT, GPX, and GSR enzymes and in the expression of Gpx4 var1 transcript. The exposure to 7.5 µg/kg of AgNP increased the Gpx4 var1 mRNA expression. In the group that received 3.75 µg of AgNP/kg, the expression of Sod1, Gpx4 var2, and Gsr transcripts was decreased while the Gpx4 var1 mRNA expression was augmented. The lower dose of AgNPs tested (1.875 µg/kg) increased the expression of Cat and Gpx4 var1 transcripts. Thus, AgNP alters the expression and activity of the antioxidant enzymes in a nonmonotonic dose-response curve and directly or indirectly modulates the events related to spermatogenesis process.

Determination of Cu, Cd, Pb and Cr in yogurt by slurry sampling electrothermal atomic absorption spectrometry: A case study for Brazilian yogurt.

A slurry sampling electrothermal atomic absorption spectrometric method is proposed for the determination of trace elements such as Cu, Cr, Cd and Pb in yogurt. The main factors affecting the slurry preparation were optimized: nature and concentration of acid solution and sonication time. The analytical method was validated in-house by calibration, linearity, limits of detection and quantification, precision and accuracy test obtaining satisfactory results in all cases. The proposed method was applied for the determination of Cd, Cr, Cu and Pb in some Brazilian yogurt samples. For these samples, the concentrations ranged from 2.5±0.2 to 12.4±0.2ngg-1; 34±3 to 899±7ngg-1; <8.3 to 12±1ngg-1; and <35.4 to 210±16ngg-1 for Cd, Cu, Cr and Pb, respectively. The daily intake of Cd, Cu, Cr and Pb via consumption of these samples was estimated.

Rapid Screening Method for Detecting Ethinyl Estradiol in Natural Water Employing Voltammetry.

17α-Ethinyl estradiol (EE2), which is used worldwide in the treatment of some cancers and as a contraceptive, is often found in aquatic systems and is considered a pharmaceutically active compound (PhACs) in the environment. Current methods for the determination of this compound, such as chromatography, are expensive and lengthy and require large amounts of toxic organic solvents. In this work, a voltammetric procedure is developed and validated as a screening tool for detecting EE2 in water samples without prior extraction, clean-up, or derivatization steps. Application of the method we elaborate here to EE2 analysis is unprecedented. EE2 detection was carried out using differential pulse adsorptive cathodic stripping voltammetry (DP AdCSV) with a hanging mercury drop electrode (HMDE) in pH 7.0 Britton-Robinson buffer. The electrochemical process of EE2 reduction was investigated by cyclic voltammetry at different scan rates. Electroreduction of the hormone on a mercury electrode exhibited a peak at -1.16 ± 0.02 V versus Ag/AgCl. The experimental parameters were as follows: -0.7 V accumulation potential, 150 s accumulation time, and 60 mV s-1 scan rate. The limit of detection was 0.49 µg L-1 for a preconcentration time of 150 s. Relative standard deviations were less than 13%. The method was applied to the detection of EE2 in water samples with recoveries ranging from 93.7 to 102.5%.

New approach to the determination of contaminants of emerging concern in natural water: study of alprazolam employing adsorptive cathodic stripping voltammetry.

Contaminants of emerging concern (CECs) are chemicals, including pharmaceutical and personal care products, not commonly monitored in the aquatic environment. Pharmaceuticals are nowadays considered as an important environmental contaminant. Chromatography methods which require expensive equipment and complicated sample pretreatment are used for detection of CECs in natural water. Thus, in this study we proposed a simple, fast, and low-cost voltammetric method as a screening tool for the determination of CECs in natural water prior to chromatography. A case study was conducted with alprazolam (benzodiazepine). The method was optimized and validated in-house. The limit of quantification was 0.4 µg L(-1) for a 120 s preconcentration time. The recoveries ranged from 93 to 120 % for accuracy tests. A further proposal aim was to determine for the first time the occurrence of alprazolam in Brazilian river water and to evaluate its potential use as a marker of contamination by wastewater.

A comparison between characterization and biological properties of Brazilian fresh and aged propolis.

OBJECTIVE: As propolis is a highly valued bee product, we aimed to verify the quality of aged propolis, investigating their phenolic and flavonoid composition, levels of toxic metals, radical scavenging and antimicrobial activities. MATERIAL AND METHODS: Samples of fresh and aged propolis of six different beekeepers, from the same geographical location, were investigated in terms of their phenolic and flavonoid composition and levels of Pb, Cd, and Cr, as well as radical scavenging and antimicrobial activities. RESULTS: The two groups of propolis had similar qualitative composition by HPLC-PDA and ESI(-)-MS. Fresh propolis and aged propolis show no differences when average values of extraction yield, flavonoids, EC50, or MIC were compared and both types of propolis showed good antimicrobial activity at low concentrations. Only levels of phenolic compounds were higher in fresh propolis. CONCLUSION: The propolis samples considered in this study, aged or fresh, had similar qualitative composition, although they were collected in different periods. Samples only differed in their levels of total phenolic content. Moreover, aged propolis conserves significant radical scavenging and antimicrobial properties. We suggest that aged propolis should not be discarded but explored for alternative applications.

Relationship between geographical origin and contents of Pb, Cd, and Cr in honey samples from the state of Paraná (Brazil) with chemometric approach.

The aim of this study was to determine the trace elements, Pb, Cd, and Cr in honey samples from eight different regions from the state of Paraná (Brazil), using slurry sampling graphite furnace atomic absorption spectrometry. Chemometric analysis (principal component analysis (PCA)) was applied to classify honey samples according to their levels of the trace elements Pb, Cd, and Cr, which is also related to the geographical origin of honey samples. The mean concentration for the elements followed the order Pb > Cr > > Cd. The mean values were 200 ± 76, 88 ± 14, and 4.1 ± 4 ng g(-1) for Pb, Cr, and Cd, respectively. It could be verified that honey samples are geographically separated, especially with regard to Pb and Cd contents. Thus, honey can be considered a bioindicator of environmental contamination, suggesting possible contamination in soil, water, and air. This contamination can be related to natural or anthropogenic sources present in the study regions.

Propolis as an indicator of environmental contamination by metals.

Concentrations of eleven representative metals (Al, Ca, Cd, Cr, Cu, K, Mg, Mn, Na, Pb and Zn) in forty-two propolis samples were measured by electrothermal atomization and flame atomic absorption spectrometry after calcination in a muffle furnace. Samples were collected from different regions from Paraná State - Brazil where apiculture is an important economic activity. Results showed that the average content of Al, Ca, K, Mg, Mn, Na and Zn in propolis was 0.68, 1.66, 7.59, 1.27, 0.08, 0.58 and 0.02 mg g(-1), respectively. Levels of Al, Ca, and Mg were statistically different in some regions of Paraná and could be used to assign the geographical origin of the propolis. The average concentration of the Cd, Cr, and Pb in raw propolis was 0.13, 5.53 and 9.85 µg g(-1), respectively, and allowed for identification of specific areas with environmental contamination.

Direct determination of Cd, Pb and Cr in honey by slurry sampling electrothermal atomic absorption spectrometry.

Slurry sampling electrothermal atomic absorption spectrometry was used for direct determination of Cr, Pb and Cd in honey without sample pretreatment. The honey slurries were prepared in aqueous solution containing hydrogen peroxide and nitric acid. The slurries were directly introduced in the pyrolytic graphite tubes. Pd-Mg was used as a chemical modifier only for Cd determination. Analytical curves were performed with aqueous standards for Pb and Cr and with addition of fructose for Cd. The quantification limits for Cd, Pb and Cr were 2.0, 5.4 and 9.4ngg(-1), respectively. Acceptable precision of the methodology was obtained through repeatability and intermediate precision. In the accuracy study, recoveries were satisfactory (94-101%) for the three elements. The methodology was applied in honey from Paraná (Brazil). The concentrations of Pb, Cd and Cr ranged from 141 to 228ngg(-1), <2.0 to 8ngg(-1) and 83 to 94ngg(-1), respectively.

Fractionation and potential toxic risk of metals from superficial sediment in Itaipu Lake--boundary between Brazil and Paraguay.

The objective of this study was to evaluate fractions of metals (labile and pseudo-total) extracted from sediment samples collected in Itaipu Lake (boundary between Brazil and Paraguay) and to assess the dynamics and mobility of these fractions by identifying the same bioavailability and ecological risk to metals in the aquatic environment. The concentrations of metal ions were determined by flame atomic absorption spectrometry. There was a correlation between the metal ions, both in the labile and the pseudo-total, with regard to particle size. To assess metals concentrations in sediment, numerical sediment-quality guidelines were applied. The concentrations of aluminum, cadmium, iron, manganese, lead, and zinc in all sediment samples are lower than the proposed probable effects level (PEL), thus possibly indicating that there are no harmful effects from these metals. In contrast, concentrations of copper, chromium, and nickel exceeded the PEL in some samples, thus indicating that these stations are at potential risk. The level of contamination in sediments of Itaipu Lake for all metals was evaluated using contamination factor, degree of contamination, and sum-of-metals toxic unit.

Chromium fractionation and speciation in natural waters.

It is common for leather industries to dump chromium-contaminated effluent into rivers and other bodies of water. Thus, it is crucial to know the impacts caused by this practice to the environment. A study on chromium partitioning and speciation, with determination at trace levels, was carried out in a potentially contaminated creek. Chromium fractionation and speciation was performed using a flow-injection preconcentration system and detection by flame atomic absorption spectrometry. High levels of this element were found in the particulate material (449-9320 mg kg(-1)), which indicates its compatibility with this fraction. The concentration of Cr(iii) in the water samples collected ranged from 5.2-105.2 µg L(-1). Cr(vi) was always below of the DL (0.3 µg L(-1)). Chromium accumulation observed in the sediment (873-1691 mg kg(-1)) may confirm contamination due to the long term release of contaminated effluents in the creek.

Accumulation of chromium and lead in bryophytes and pteridophytes in a stream affected by tannery wastewater.

The concentrations of Cr and Pb were determined in bryophytes and pteridophytes sampled in a stream near a tannery in Guarapuava, southern Brazil. The concentrations of Cr and Pb were measured by cathodic and anodic voltammetry, respectively. These plants were used to evaluate the spatial distribution of elements in the examined stream, and contained elevated levels of Cr (0.71-24.07 µg/g) and Pb (4.33-24.20 µg/g). Chromium levels in plants near the tannery greatly exceeded background levels, indicating a severe to extreme degree of contamination with this metal. Lead levels were elevated to a lesser degree, indicating slight to moderate contamination for most plants collected near the tannery.