Assessing the water quality in a World Heritage Site using biomarkers in top fish predators.

The use of biomarkers in fish for biomonitoring is a valuable approach to reveal effects of human impacts on biota health. Top predator fish are effective models for monitoring human activities' impacts on aquatic ecosystems. The Guaraguaçu River is the largest river-system on coastal region of South Brazil and a World Heritage site. The river receives contaminants from disorderly urban growth, including discharges of domestic sewage and small fishery boats, particularly during the tourist season. Our study aimed to assess impact of anthropogenic activities on water quality in the Guaraguaçu River by analyzing environmental contamination biomarkers in the top fish predator Hoplias malabaricus. Fish were collected using a fyke net trap across sectors representing a gradient of anthropic impact: sector 1 - pristine; sector 2 - impacted; and sector 3 - less impacted. Water samples were collected to analyze the presence of trace elements and pesticide. Biomarkers of the antioxidant system, histopathology, genotoxicity, neurotoxicity, and concentration of trace elements were analyzed in fish tissues. In water samples Al, Fe and Mn were detected, but no pesticides were found. In fish muscle, zinc and iron were detected. Brain acetylcholinesterase activity decreased in impacted sectors, indicating neurotoxic effects. The antioxidant system increased activity in gills and liver, and damage from lipoperoxidation was observed, particularly in sector 2 when compared to sector 1, suggesting oxidative stress. Histopathological biomarkers revealed lesions in the liver and gills of fish in impacted sectors. Micronuclei, a genotoxicity biomarker, were observed in organisms from all sectors. Our results demonstrate detrimental effects of poor water quality on biota health, even when contaminants are not detected in water.

Ripening stage impacts nutritional components, antiglycemic potential, digestibility and antioxidant properties of grumixama (Eugenia brasiliensis Lam.) fruit.

This study aimed to determine the nutritional components (macronutrients ans minerals) and α-amylase inhibition capacity of freeze-dried grumixama (Eugenia brasiliensis Lam) seeds (S) and pulp/peel (P) portions, at ripe and mid-ripe stages. In vitro digestion was also performed on S and P from grumixama to assess the bioaccessibility of total phenolic compound (TPC), flavonoids (TFC), and anthocyanins (TAC), as well as to examine their impact on antioxidant activity (DPPH, ABTS, FRAP). The ripening process impacts the bioactive compounds and individual phenolics of S and P portions. The ripe S was source of myricetin and exhibited higher antioxidant activity, while mid-ripe S was high in flavonoids and cinnamic acid with higher antiglycemic potential. Ripe P showed higher soluble fiber, carbohydrate, TAC, and caffeic acid content, whereas mid-ripe P had increased mineral content (calcium, potassium, manganese), catechin, and TPC. After in vitro digestion, the P portion showed a bioaccessibility of total phenolic content (TPC) and total flavonoid content (TFC) exceeding 40% at intestinal phase. In contrast, the S portions had better release of TPC and TFC and antioxidant activity at gastric phase. Considering the outstanding nutritional and biological properties of grumixama fruit, freeze-dried S and P portions from both ripening stages possess could be explored as valuable sources of nutrients and antioxidant compounds.

Lichens as bio-monitors of polycyclic aromatic hydrocarbons: Measuring the impact of features and traffic patterns.

The role of road characteristics, including gradient and speed control devices, in influencing emission dynamics remains to be fully elucidated. Most studies have focused on fuel consumption as an indirect indicator of sector emissions instead of directly quantifying specific pollutants, like polycyclic aromatic hydrocarbons (PAHs). This research approach is often due to the complexities involved in capturing these pollutants and their subsequent analysis. Bio-monitors, such as lichens, offer an economically viable method. Their wide distribution across various habitats enables the comparison of PAH levels in diverse environments. Against this background, The present work analyses the ability of tropical lichens to indicate the effect that traffic patterns and geometric design features of roads (traffic activity, road gradient, traffic control devices, and vehicular speed) have on the emission of PAH concentration. Results showed that PAHs in lichens strongly correlated with the road gradient (Spearman correlation, p<0.005 with R=0.98). Each 1% increase in road gradient implies a rise of 24 ngPAH/gLichen in National Road. Additionally, a trend coherent of PAH concentration with the vehicle speed profile was observed on Panamericana Road. Speed control devices were associated with higher concentrations of PAHs due to acceleration and braking actions that increment fuel consumption. Finally, the results evidenced that lichens helped determine the source of aromatics and their carcinogenic potential using the diagnostic ratio of PAHs and the carcinogenic equivalence sum, respectively.

Osmoregulatory responses in the neotropical fish species Astyanax lacustris, exposed to single and combined microplastics, polycyclic aromatic hydrocarbons, and their mixture.

Microplastic (MP) pollution poses a significant environmental threat. These MPs can adsorb toxic compounds such as polycyclic aromatic hydrocarbons (PAH), which are highly lipophilic and carcinogenic. To assess the potential effects of virgin MP, PAH, and MP+PAH in association with osmoregulation and energetic substrate, we conducted experiments with the tetra cardinal Astyanax lacustris. The environmentally relevant concentration of MP (10 mg L-1) and 20 % of the LC50-96 h of crude oil for A. lacustris (2.28 µg L-1) were used during the 96-h exposure. Fish were exposed to virgin MP, PAH, MPC (MP loaded with PAH), PAH+MP (PAH and MP in association), and the control without (CT) and with handling (CH). After 96 h, blood was collected for osmoregulatory parameters (plasma osmolality; Na+, K+, Cl-, Mg2+; glycose and lactate); gills for osmoregulatory enzyme activities (Na+, K+ ATPase, H+ ATPase, and carbonic anhydrase); and white muscle samples were used to determine glycogen as an energetic substrate. The low molecular weight PAH was not detected in PAH-loaded MP (MPC) and PAH in combination with MP (PAH+MP). The PAH concentration of the MPC and PAH+MP was similar and low compared to other works. Virgin MP, PAH, MPC, and PAH+MP were able to cause muscle glycogen depletion. The activity of v-type H+ ATPase and plasma Na+ concentrations were lower in PAH with MP (MPC). However, the hydromineral balance (K+, Mg2+, Cl-, and osmolality) was not affected by any treatment. In this sense, we can conclude that the MPC caused osmoregulatory disturbances not seen in the MP associated with PAH (MP+PAH). However, this seems unrelated to the PAH leaking from the MPC or the PAH absorption to the virgin MP once the PAH concentrations from the MPC and PAH+MP were similar.

Exploratory evaluation of iron and its speciation in surface waters of Admiralty Bay, King George Island, Antarctica.

The determination of dissolved iron concentrations and speciation was conducted for the first time in surface seawater coastline samples collected during the austral summer of 2020 in Admiralty Bay, King George Island, Antarctica. The technique of competitive ligand exchange/adsorptive cathodic stripping voltammetry with 2,3-dihydroxynaphthalene as the competing ligand was evaluated, showing a sensitivity between 14.25 and 21.05 nA nmol L-1 min-1, with an LOD of 14 pmol L-1 and a mean blank contribution of 0.248 nmol L-1. Physicochemical parameters such as pH (7.85 ± 0.2), salinity (32.7 ± 0.8) and dissolved oxygen (51.3 ± 26.6%) were compatible with those of the literature; however, the average temperature (4.2 ± 0.8 °C) was higher, possibly as a reflection of global warming. The dissolved iron mean value was 18.9 ± 6.1 nmol L-1, with a total ligand concentration of 23.6 ± 12.2 nmol L-1 and a conditional stability complex constant of 12.2 ± 0.2, indicating humic substances as possible ligands. On average, the calculated free iron concentrations were 0.7 ± 0.3 pmol L-1. Relatively high concentrations of iron indicate a possible local source of Fe, likely predominantly from upwelling sediments and secondarily from ice-melting waters, which does not limit the growth of the phytoplankton.

Aromatic hydrocarbons extracted by headspace and microextraction methods in water-soluble fractions from crude oil, fuels and lubricants.

Two extraction protocols were developed for the determination of mono- and poly-aromatic hydrocarbons in water-soluble fractions from gasoline, diesel, crude, mineral insulating, and lubricant oils. Development of the procedures was based on clean miniaturized strategies, such as headspace extraction and vortex-assisted dispersive liquid micro-extraction, together with quantification by gas chromatography-mass spectrometry. The mono-aromatic hydrocarbons were extracted using the headspace extraction method. The linear range obtained was 10-500 µg L-1, with r2 > 0.99. Based on the parameters of the analytical curves, detection and quantification limits of 2.56-3.20 and 7.76-9.71 µg L-1 were estimated. In addition, the method showed adequate recoveries of 69.4-83.5%, with a satisfactory precision of 4.7-17.1% (n = 5). Micro-extraction was applied for the poly-aromatics and the most favorable variables were sample volume (5.00 mL) in sodium chloride medium (1%, w/v), trichloromethane as extractor solvent (75 µL), acetone as disperser (925 µL) and vortexing for 1 min. Under these conditions, analytical curves of 0.15-4.00 µg L-1 were obtained and limits of determination and quantification were 0.03-0.15 and 0.09-0.46 µg L-1, respectively. Recovery values of 87.6-124.5% and a maximum relative standard deviation of 18.9% (n = 5) verify satisfactory accuracy and precision. This led to the achievement of enrichment factors for poly-aromatic hydrocarbons of 41-89 times. Finally, the methods were employed in samples of water-soluble fractions for the determination of analytes. The values followed the order: gasoline > diesel > crude > lubricant > mineral insulating oil. These results indicate an increase in lighter fractions, followed by poly-aromatics in more refined products.

Alternative Ecosorbent for the Determination of Trihalomethanes in Aqueous Samples in SPME Mode.

A new sorbent material based on modified clay with ionic liquid immobilized into an agarose film was developed as part of this study. It was applied to determine organochlorine pollutants, like disinfection byproducts, through headspace solid-phase microextraction-gas chromatography-electron capture detection (HS-SPME-GC-ECD). The disinfection byproducts determined in this study were used as model molecules because they were volatile compounds, with proven severe effects on human health. Their presence in aquatic environments is in trace concentrations (from pg L-1 to mg L-1). They are classified as emergent pollutants and their determination is a challenge for analytical chemists. The parameters which affected the extraction efficiency, i.e., number and distance between SPME discs, salt concentration, the temperature of extraction, extraction time, and desorption time, were optimized. A wide linear dynamic range of 10-1000 ng mL-1 and coefficients of determination better than 0.997 were achieved. The limits of detection and the limits of quantitation were found in the ranges of (1.7-3.7) ng mL-1 and (5.6-9.9) ng mL-1, respectively. The precision, expressed as relative standard deviation (RSD), was better than 8%. The developed sorbent exhibits good adsorption affinity. The applicability of the proposed methodology for the analysis of trihalomethanes in environmental and water samples showed recoveries in the range of 86-95%. Finally, the newly created method fully complied with the principles of green chemistry. Due to the fact that the sorbent holder was made of agarose, which is a wholly biodegradable material, sorbent clay is a widespread material in nature. Moreover, the reagents intercalated into the montmorillonite are new green solvents, and during the whole procedure, low amounts of organic solvents were used.

Determination of polycyclic aromatic hydrocarbons extracted from lichens by gas chromatography-mass spectrometry.

Lichens are well-known biomonitors for semi-volatile pollutants, due to their ability to absorb and retain different chemical compounds such as Polycyclic Aromatic Hydrocarbons (PAHs), directly linked to levels in the atmosphere. Based on that, this paper proposes an analytical method capable of quantifying 16 EPA-PAHs from lichens found in an intertropical zone, as a natural alternative to typical capture methods, with the aim of monitoring atmospheres polluted by toxic compounds. An analytical protocol, including sample pre-treatment, followed by ultrasound extraction, clean-up in a chromatographic column, concentration and quantification by Gas Chromatography-Mass Spectrometry (GC-MS) using Selective Ion Monitoring has been developed. Additionally, a set of guidelines on lichen collection and sample handling is given, in order to achieve representative samples.•Limits of quantification (LOQ) and detection (LOD) varied from 2.0 to 16 µg/L and 1.0 to 5.0 µg/L, respectively. Calibration curves had correlation coefficients higher than 0.99 in all cases.•Validation of the method for determining PAHs concentration associated to 30 lichen samples collected along two roads, with high and low traffic volumes was carried out.•The method showed good performance according to the sources of PAHs, traffic patterns and gradient in roads.

Accumulation of nylon microplastics and polybrominated diphenyl ethers and effects on gut microbial community of Chironomus sancticaroli.

Microplastics (MP) are emerging contaminants with the capacity to bind and transport hydrophobic organic compounds of environmental concern, such as polybrominated diphenyl ethers (PBDEs). The aim of this study was to investigate the ingestion of nylon (polyamide) MP alone and when associated with PBDEs and their effects on Chironomus sancticaroli larvae survival and microbiome structure. Survival, PBDE uptake and microbial community composition were measured in fourth instar larvae exposed for 96 h to BDEs- 47, 99, 100 and 153 in the presence and absence of 1% w/w MP in sediment. Microbiome community structures were determined through high throughput sequencing of 16S small subunit ribosomal RNA gene (16S rRNA). Initial experiments showed that larvae ingested MP faster at 0.5% w/w MP, while depuration was more efficient at 1% w/w MP, although retention of MP was seen even after 168 h depuration. No mortality was observed as a result of PBDEs and MP exposure. MP had a negative effect on PBDE concentration within larvae (η2 = 0.94) and a negative effect on sediment concentrations (η2 = 0.48). In all samples, microbial communities were dominated by Alphaproteobacteria, Betaproteobacteria, Actinobacteria and Gammaproteobacteria. Bacterial alpha diversity was not significantly affected by PBDEs or MP exposure. However, the abundance of discrete bacterial taxa was more sensitive to MP (X2 = 45.81, p = 0.02), and PBDE exposure. Our results highlight that C. sancticaroli showed no acute response to MPs and PBDEs, but that MPs influenced bacterial microbiome structure even after only short-term acute exposure.

Effects of cadmium on the female reproductive axis of a Neotropical fish.

Metals are one of the contaminants released from the increase of anthropic activities. They can be classified as endocrine disruptors once they can affect the reproductive parameters of different organisms. The aim of the study was to evaluate the potential effects of cadmium on regulatory reproduction axis (Hypothalamic-Pituitary-Gonadal-Liver, the HPGL axis) in females of Rhamdia quelen exposed to nominal concentrations of 0.1; 1; 10 and 100 µg.L-1 of cadmium. After 15 days, tissues were collected for hormonal quantification, brain aromatase (cyp19a1b), hepatic vitellogenin (vtg) gene expression, and biomarkers analysis. Cadmium was quantified in water, gonad and liver samples. The plasma levels of estradiol, testosterone and gonad and hepatosomatic indexes did not changed after Cd exposure. The cyp19a1b was not different among the groups. Cadmium was detected at higher concentrations in the liver compared to the gonads. No genotoxicity was observed, only erythrocytes nuclear alterations. Metallothionein was reduced at 10 µg.L-1 in the liver and 10 and 100 µg.L-1 in the gonad. Hepatic superoxide dismutase activity increased and this can lead to a hydrogen peroxide increase, one of reactive oxygen species. This increase without a compensation of other enzymes of the antioxidant system can lead to lipoperoxidation, as occurred at 100 µg.L-1. Hepatic vitellogenin gene expression increased as well as the injury index at 0,1 and 100 µg.L-1. The tested cadmium concentrations have been found in the freshwater ecosystems and can affect the female reproductive regulation axis HPGL of the Neotropical species R. quelen.

In vitro Bioaccessibility of Proteins, Phenolics, Flavonoids and Antioxidant Activity of Amaranthus viridis.

The aim of this study was to investigate the chemical composition, mineral content and report the effect of gastrointestinal digestion on the proteins, phenolics, flavonoids and antioxidant activity of morphological parts of Amaranthus viridis (AV). The macronutrients found in the greatest quantity were proteins (leave, inflorescence and seeds) and fiber (roots and stem). The main minerals were calcium, potassium, iron and zinc. All the plant parts showed total phenolic (TPC) and total flavonoid (TFC) compounds that were correlated with antioxidant capacity (DPPH, ABTS and FRAP); the leaves and inflorescence presented the greatest potential. The antioxidant compounds from the leaves, inflorescence and roots decreased after static in vitro digestion, while the TPC and TFC of the digested seeds increased by more than 55%. Approximately 90% of the protein content was bioaccessible. To the best of our knowledge, for the first time, the bioaccessibility of proteins, phenolics, flavonoids and antioxidant activity of the leave, inflorescence, seeds, roots and stem from AV were reported. Taking into consideration the excellent nutritional properties, the morphological parts of the plant can be potentially explored as a source of protein, fiber, minerals and antioxidant compounds.

Impact of polycyclic aromatic hydrocarbons in mangroves from the Colombian pacific coast: Evaluation in sediments and bivalves.

Bivalves and sediments were sampled from mangroves in the Pacific Coast of Colombia to evaluate the concentrations of the 16 polycyclic aromatic hydrocarbons (PAHs) prioritized by U.S.EPA. Mangroves are highly vulnerable to anthropogenic activities, such as oil spills, which affect sediments and the organisms that depend on that ecosystem. Twelve samples of mangrove and non-mangrove (sandy) sediments and 20 samples of Anadara tuberculosa from mangrove were collected in marine and estuarine areas. In sediments and A. tuberculosa, the highest concentration of Æ©16PAHs was found in estuarine mangroves close to the Rosario River mouth, ranging from 171.4 to 564.0 ng g-1 and 31.0 to 169.0 ng g-1, respectively. For the bivalve, the concentrations showed less variability than sediment, with 25% and 20% of bivalve samples exceeding the limits established by the European Regulatory Commission and Ministry of Health and Social Protection of Colombia, respectively, which can cause effects on people's health. The PAHs isomeric ratios determined in sediments indicated that these compounds were originated mainly from petrogenic sources. The PAHs profile reveals the dominance of 3 and 4 rings PAHs in sediments and dominance of 4 rings PAHs in bivalves.

Molecular and biochemical evaluation of effects of malathion, phenanthrene and cadmium on Chironomus sancticaroli (Diptera: Chironomidae) larvae.

In-vitro effects of sub-lethal concentrations of malathion, phenanthrene (Phe) and cadmium (Cd) were tested on Chironomus sancticaroli larvae in acute bioassays by measuring biochemical and molecular parameters. Malathion was evaluated at 0.001, 0.0564 and 0.1006 mg L-1; Phe at 0.0025, 1.25 and 2.44 mg L-1; and Cd at 0.001, 3.2 and 7.4 mg L-1. The recovery test carried out at the highest concentration of each compound showed that survival of larvae exposed to Phe ranged from 4% to 5%, while the effects of malathion and Cd were irreversible, not allowing the emergence of adults. Results showed that malathion and Cd inhibited AChE, EST-α and ES-ß activities at the two highest concentrations. Phe at 0.0025, 1.25 and 2.44 mg L-1; and Cd at 3.2 and 7.4 mg L-1 inhibited glutathione S-transferase activity. Oxidative stress was exclusively induced by the lowest concentration of malathion considering SOD activity once CAT was unaffected by the stressors. Lipid peroxidation was registered exclusively by malathion at the two highest concentrations, and total hemoglobin content was only reduced by Cd at the two highest concentrations. The relationship among biochemical results, examined using the PCA, evidenced that malathion and Cd concentrations were clustered into two groups, while Phe only formed one group. Four hemoglobin genes of C. sancticaroli were tested for the first time in this species, with Hemoglobin-C being upregulated by malathion. The toxicity ranking was malathion > Phe > Cd, while biochemical and molecular results showed the order malathion > Cd > Phe. Our results highlight the importance of combining different markers to understand the effects of the diverse compounds in aquatic organisms.

Multi-elemental analysis of particulate matter PM2.5 and PM10 by ICP OES.

The complexity of aerodynamic particulate matter's (PM) matrices poses a challenge for the extraction and quantification of metals, especially for analytes with low concentration. Aiming to solve this issue, a precise and accurate protocol with the ultrasound extraction combined with microwave radiation digestion (USMW), was applied to PM samples with excellent compensations in sample throughput, digestion efficiency, and energy consumption. After the digestion and extraction procedures, the inorganic analytes, including rare earth elements, were determined by ICP OES. Two types of particulate matter sampled from two stations, Gobernacion (GOB10 and GOB2.5) and Milan (MIL10), corresponding to PM2.5 and PM10, were digested with a combination between HF, HNO3, and H3BO3. The absolute limits of detection ranged from 0.42 pg m-³ for V, to 3459 pg m-³ for As. The accuracy of the experimental study was assessed using two certified reference materials (CRMs), Coal Fly Ash (NIST1633b) and Fly Ash (BCR176). The method presented good accuracy, with recoveries ranging from 90 to 115%, except for Al (120%) and Fe (123%). Considering the replicates for the determination of analyte elements, the repeatability was below 10% for the relative standard deviation (RSD). A cloud point extraction (CPE) procedure, with parameters optimized for the determination of Pd and Pt, was successfully applied in digested PM samples with detection limits of 1.43 and 2.05 pg m-³ for Pd and Pt in MIL10 sample, respectively, and 76.6 pg m-³ for Pd and 110 pg m-³ for Pt, in samples GOB10 and GOB2.5, respectively.

Beyond gold nanoparticles cytotoxicity: Potential to impair metastasis hallmarks.

Gold nanoparticle (AuNP)-based systems have been extensively investigated as diagnostic and therapeutic agents due to their tunable properties and easy surface functionalization. Upon cell uptake, AuNPs present an inherent cell impairment potential based on organelle and macromolecules damage, leading to cell death. Such cytotoxicity is concentration-dependent and completely undesirable, especially if unspecific. However, under non-cytotoxic concentrations, internalized AuNPs could potentially weaken cells and act as antitumor agents. Therefore, this study aimed to investigate the antitumor effect of ultrasmall AuNPs (~3 nm) stabilized by the anionic polysaccharide gum arabic (GA-AuNPs). Other than intrinsic cytotoxicity, the focus was downregulation of cancer hallmarks of aggressive tumors, using a highly metastatic model of melanoma. We first demonstrated that GA-AuNPs showed excellent stability under biological environment. Non-cytotoxic concentrations to seven different cell lines, including tumorigenic and non-tumorigenic cells, were determined by standard 2D in vitro assays. Gold concentrations ≤ 2.4 mg L-1 (16.5 nM AuNPs) were non-cytotoxic and therefore chosen for further analyses. Cells exposed to GA-AuNPs were uptaken by melanoma cells through endocytic processes. Next we described remarkable biological properties using non-cytotoxic concentrations of this nanomaterial. Invasion through an extracellular matrix barrier as well as 3D growth capacity (anchorage-independent colony formation and spheroids growth) were negatively affected by 2.4 mg L-1 GA-AuNPs. Additionally, exposed spheroids showed morphological changes, suggesting that GA-AuNPs could penetrate into the preformed tumor and affect its integrity. All together these results demonstrate that side effects, such as cytotoxicity, can be avoided by choosing the right concentration, nevertheless, preserving desirable effects such as modulation of key tumor cell malignancy features.

Genotoxic, metabolic, and biological responses of Chironomus sancticaroli Strixino & Strixino, 1981 (Diptera: Chironomidae) after exposure to BBP.

Benzyl butyl phthalate (BBP), which is widely used in industrial production, reaches the aquatic environment, mainly owing to improper disposal of plastic products. In the water, it remains adsorbed to sedimentary particles causing toxic effects in aquatic invertebrates such as Chironomidae, which are important in maintaining ecosystem dynamics and are an important link in the food chain. However, the effects of BBP on Chironomidae are still poorly known. Thus, the toxic effects of BBP on Chironomus sancticaroli at acute (48 h), subchronic (8 d), and chronic (25 d) exposures of concentrations between 0.1 and 2000 µg·L-1 were determined. Genotoxicity effects, changes in the oxidative stress pathway, and development and emergence of organisms were evaluated. Biochemical markers showed a reduction in cholinesterase (ChE) activity, indicating a neurotoxic effect on acute exposure (1-1000 µg·L-1). The antioxidant pathway, glutathione S-transferase (GST) activity showed reduction on acute (0.1; 1-2000 µg·L-1) and subchronic (1-2000 µg·L-1) exposures and reduction in superoxide dismutase (SOD) activity at all evaluated concentrations, suggesting oxidative stress. In contrast, lipid peroxidation was not observed. DNA damage occurred on acute (10 µg·L-1) and subchronic (10-2000 µg·L-1) exposures, indicating genotoxic effects. At concentrations above 10 µg·L-1, no emergence of adults occurred, while lower concentrations (0.1 and 1 µg·L-1) showed a reduction in the number of adults, mainly males. The observed effects indicate that BBP is genotoxic and causes biochemical alterations presenting high toxicity at the population level.

Potentiality of Epoxy-Montmorillonite Composite for Stir-Bar Sorptive Extraction for Determination of Atrazine

Abstract A new low-cost material is presented for the first time, aiming to study the sorption process for the stir-bar sorptive extraction (SBSE) technique. The bars were made using a composition of a commercial epoxy resin and montmorillonite, under different compositions and a final ratio of 70% (epoxy) and 30% (montmorillonite) was employed, providing the best mechanical and chemical resistance. A PTFE support was developed to hold the bars permitting the magnetic stirring, without turbulent behavior even under long times of stirring at 1000 rpm. The bars were employed to study the sorption of the herbicide atrazine (ATZ), and the best extraction conditions were: sample volume 20.0 mL, pH 6.0, extraction time of 15 min, room temperature, stirring speed of 100 rpm, and 10.0% (w v-1) NaCl. This preliminary evaluation suggests that the modified bars could be employed for ATZ sorption, affording close to 71% of ATZ removal, and presented robust characteristics to be used at least 80 times.

Morphologic, Structural, and Chemical Properties of Pulp Stones in Extracted Human Teeth.

INTRODUCTION: Pulp stones are mineral structures that develop in the pulp tissue triggered by several clinical conditions. The exact biochemical process behind the occurrence of pulp stones is uncertain. This study aimed to perform a structural and crystallographic characterization of pulp stones and dentin from extracted human teeth. METHODS: The sample consisted of 13 erupted and unerupted permanent human teeth diagnosed with pulp stones. The teeth were analyzed with scanning electron microscopy with secondary and backscattered electrons, energy-dispersive spectroscopy, micro-Raman spectroscopy, micro-X-ray diffraction, and inductively coupled plasma atomic emission spectroscopy. RESULTS: The pulp stones revealed a heterogeneous morphology and structure compared with each other. Compared with the adjacent dentin, the pulp stones had a similar structure. From a chemical point of view, oxygen, calcium, carbon, and phosphorus were the most prevalent chemical elements in the inner part of the stones, whereas on the surface carbon, nitrogen, sulfur, chlorine, aluminum, potassium, zinc, copper, and lead were the most prevalent. Copper, iron, and zinc were higher in the stones than the dentin (P < .05). Statistically significant differences between the chemical structure of stones from erupted and unerupted teeth were not detected (P > .05). CONCLUSIONS: Pulp stones have structural and chemical properties that are similar to dentin. Variations in morphology are common.

Acute exposure to the water-soluble fraction of gasoline (WSFG) affects oxygen consumption, nitrogenous-waste and Mg excretion, and activates anaerobic metabolism in the goldfish Carassius auratus.

Contamination of aquatic environments by petroleum and its products (e.g. gasoline) is a hazard for aquatic organisms as a result of the potential toxicity of monocyclic aromatic hydrocarbons (BTEX) and polycyclic aromatic hydrocarbons (PAH). Our goal was to evaluate the acute effects of the water-soluble fraction of gasoline (WSFG) on nitrogen excretion, osmoregulation, and metabolism of goldfish Carassius auratus. We first chemically characterized the WSFG and then tested its effects on these physiological aspects of C. auratus, in several different exposure scenarios (0, 0.25, 5, 10 and 25% of WSFG). The WSFG contained high concentrations BTEX (toluene 70% and benzene 17%) relative to PAH (<1%), and low levels of several metals (Al, Fe, Zn, Sr). Routine O2 uptake rate (MO2) of goldfish was inhibited by exposure to 5% WSFG, and during post-exposure recovery, MO2 increased in a dose-dependent fashion. Ammonia excretion was not affected by exposure to WSFG, but urea-N excretion increased progressively with the WSFG concentration. The same pattern of dose/response was observed for net Mg2+ loss rates and steadily increasing plasma lactate concentrations. Loss rates of Na+, Ca2+, K+ and Cl-, and plasma concentrations of Mg2+ and urea-N were not significantly altered. We propose that acute exposure to WSFG inhibits aerobic metabolism and activates anaerobic metabolism, breaking down ATP such that bound Mg2+ is liberated and the purine ring component is metabolized to urea-N, both of which are subsequently excreted.