Polycyclic aromatic hydrocarbons in seawater after the mysterious oil spill of 2019 on the Pernambuco coast, northeast Brazil.

In 2019, one of Brazil's most significant environmental disasters occurred, involving an oil spill that directly affected Pernambuco state. Contamination along the coast was evaluated by the quantification of polycyclic aromatic hydrocarbons (PAHs) in fifty seawater samples collected in the summer and winter of 2021. Analysis using fluorescence spectroscopy revealed that for all the samples, levels of dissolved/dispersed petroleum hydrocarbons (DDPHs) were higher than the regional baseline for tropical western shores of the Atlantic Ocean. GC-MS analyses quantified 17 PAHs in the samples, with highest total PAHs concentrations of 234 ng L-1 in summer and 33.3 ng L-1 in winter, which were consistent with the highest risks observed in ecotoxicity assays. The use of diagnostic ratios showed that the coast was impacted by a mixture of PAHs from petrogenic and pyrolytic sources. The results indicated the need for continuous monitoring of the regions affected by the 2019 spill.

Impact on cholinesterase-inhibition and in silico investigations of sesquiterpenoids from Amazonian Siparuna guianensis Aubl.

The plant popularly known as "negramina" (Siparuna guianensis Aubl.), member of the family Siparunaceae produces an essential oil that presents several biological activities reported in literature. Here, the essential oil was obtained by hydrodistillation from fresh leaves collected in the state of Roraima, far north of the Amazon. Chemical composition of the essential oil was characterized by gas chromatography coupled to mass spectrometry (GC-MS) and flame ionization detector (GC-FID). The sesquiterpenoid shyobunone and its derivatives were identified as major compounds in the oil (>40%). The effect of S. guianensis essential oil on the acetylcholinesterase (AChE) activity from Crassostrea rhizophorae, Litopenaeus vannamei and Electrophorus electricus was tested by spectrophotometric assays. The essential oil has been identified as an AChE inhibitor. The mechanism of inhibition was investigated as well as spectrofluorimetric interactions between the essential oil and the enzyme. 1H NMR titration and molecular docking were also investigated. The spectrophotometric results revealed that shyobunone and its derivatives strongly interact with AChE with a kind of non-competitive inhibition. Interaction studies support the results of enzyme inhibition. Molecular coupling predicted that iso-shyobunone is the strongest ligand, corroborated by fluorescence suppression and 1H NMR titration results. In conclusion, Siparuna guianensis essential oil can be a new source of shyobunone and derivatives capable to reversibly inhibit AChE showing potential neuroprotective properties to be applied in the treatment of Alzheimer's disease.

Distribution and origin of sedimentary organic matter in an eutrophic estuary: Pina Sound - NE Brazil.

Eutrophic estuaries receive organic matter (OM) inputs from multiple sources. This study evaluated the distribution and origin of sedimentary OM in an eutrophic estuary (Pina Sound, NE Brazil). Thirteen samples were collected in the sublittoral in addition to major local sources. Biochemical (chlorophyll - Chl), elemental [(C/N)a and C/S ratios] and isotopic (δ 15N and δ 13C) analyses were carried out for characterizing OM and redox conditions. The SIAR mixing model was used to quantify contribution from main sources. At Pina Sound, distribution of OM is associated with mud, reflecting the hydrodynamics control on deposition of suspended particles. Microphytobenthic production is limited ([Chl a] < 1000 µg/g organic carbon) in the sublittoral where the Chl degradation products prevail (mean [Pheopigments] = 2643 ± 958 µg/g organic carbon). Anoxic conditions (C/S ratio ≈ 2) are typically observed in sediments of deeper portions of Pina Sound. Such sediments receive high organic loads and are subject to poor water renewal. According to SIAR mixing model, sedimentary OM of Pina Sound is composed of, on average: 50% phytoplankton, 24% sewage and 26% C3 plants. This reflects fertilization of Pina Sound with high loads of untreated sewage. Pina Sound has a great potential to retain sewage-derived OM.

Effects of pyriproxyfen on zebrafish brain mitochondria and acetylcholinesterase.

Pyriproxyfen is an insecticide used worldwide that acts as a biomimetic of juvenile hormone. This study investigated metabolic and synaptic impairments triggered by pyriproxyfen using zebrafish acetylcholinesterase (zbAChE) and mitochondria as markers. A brain zbAChE assay was performed in vitro and in vivo covering a range of pyriproxyfen concentrations (0.001-10 µmol/L) to assess inhibition kinetics. Docking simulations were performed to characterize inhibitory interactions. Zebrafish male adults were acutely exposed to 0.001, 0.01 and 0.1 µg/mL pyriproxyfen for 16 h. Mitochondrial respiration of brain tissues was assessed. ROS generation was estimated using H2DCF-DA and MitoSOX. Calcium transport was monitored by Calcium Green™ 5 N. NO synthesis activity was estimated using DAF-FM-DA. Brain acetylcholinesterase showed an in vivo IC20 of 0.30 µmol/L pyriproxyfen, and an IC50 of 92.5 µmol/L. The inhibitory effect on zbAChE activity was competitive-like. Respiratory control of Complex I/II decreased significantly after insecticide exposure. The MitoSOX test showed that O2- generation had a pyriproxyfen dose-dependent effect. Brain tissue lost 50% of Ca2+ uptake capacity at 0.1 µg/mL pyriproxyfen. Ca2+ release showed a clear mitochondrial impairment at lower pyriproxyfen exposures. Thus, Ca2+ transport imbalance caused by pyriproxyfen may be a novel deleterious mechanism of action. Overall, the results showed that pyriproxyfen can compromise multiple and interconnected pathways: (1) zbAChE impairment and (2) the functioning of the electron transport chain, ROS generation and calcium homeostasis in zebrafish brain mitochondria. Considering the many similarities between zebrafish and human, more caution is needed when pyriproxyfen is used in both urban and agricultural pest control.

Polychlorinated biphenyls and chlorinated pesticides in king mackerel caught off the coast of Pernambuco, northeastern Brazil: Occurrence, contaminant profile, biological parameters and human intake.

Persistent organic pollutants such as PCBs and DDTs are ubiquitous worldwide. Their lipophilic nature facilitates accumulation in fish tissues. This study investigated 182 PCB congeners and 14 organochlorine pesticides (DDTs, HCHs, chlordanes, heptachlor and mirex) in muscle and liver of king mackerel (Scomberomorus cavalla) caught off the northeastern coast of Brazil. Concentration of PCBs, DDTs and chlordanes in muscle averaged 31.5, 4.70 and 0.15ngg(-1) dry weight (dw), respectively. Mean levels of the same contaminants in liver were 145, 18.7 and 1.11ngg(-1) dw, respectively. HCHs, heptachlor and mirex were not detected in the samples. The metabolite p,p'-DDE dominated the composition of DDTs in both muscle and liver. However, a clear shift was observed in the proportions of p,p'-DDT and p,p'-DDD when comparing both tissues, suggesting metabolism in the liver. The PCBs profile revealed a depletion in mono- through tetra-CBs and an enrichment in penta- through deca-CBs. Biological parameters such as sex, maturity stage, age, body weight and total length did not influence contaminant levels in tissues. Dietary risk assessment indicated that S. cavalla from the northeastern coast of Brazil does not pose a health risk for humans.

Accumulation of semivolatile organic compounds in Antarctic vegetation: a case study of polybrominated diphenyl ethers.

Antarctic plant communities are dominated by lichens and mosses which accumulate semivolatile organic compounds (SOCs) such as polybrominated diphenyl ethers (PBDEs) directly from the atmosphere. Differences in the levels of PBDEs observed in lichens and mosses collected at King George Island in the austral summers 2004-05 and 2005-06 are probably explained by environmental and/or plant parameters. Contamination of lichens showed a positive correlation with local precipitation, suggesting that wet deposition processes are a major mechanism controlling the uptake of most PBDE congeners. These findings are in agreement with physical-chemical data supporting that tetra- through hepta-BDEs in the Antarctic atmosphere are basically bound to aerosols. Conversely, accumulation of PBDEs in mosses appears to be controlled by other environmental factors and/or plant-specific characteristics. Model simulations demonstrated that an ocean-atmosphere coupling may have played a role in the long-range transport of less volatile SOCs such as PBDEs to Antarctica. According to simulations, the atmosphere is the most important transport medium for PBDEs while the surface ocean serves as a temporary storage compartment, boosting the deposition/volatilization "hopping" effect similarly to vegetation on continents.