Assessing the Character of the C6F5 Ligand from the Electrochemical and Photophysical Properties of [Ni(C6F5)2(N∧N)] Complexes.

Organonickel complexes containing α-diimine ligands [Ni(C6F5)2(N∧N)] (N∧N = 2,2'-bipyridine (bpy), 2,9-dimethyl-1,10-phenanthroline (dmphen), 3,4,7,8-tetramethyl-1,10-phenanthroline (tmphen), dipyrido[3,2-a:2',3'-c]phenazine (dppz), 1,4-bis(isopropyl)-1,4-diazabutadiene (iPr-DAB), and 1,4-bis(2,6-dimethylphenyl)-1,4-diazabutadiene (Xyl-DAB) were prepared and studied structurally, spectroscopically, and electrochemically. Their molecular structures from single-crystal X-ray diffraction show near-perfect square planar Ni(II) coordination except in the case of dmphen. Primary reversible electrochemical reductions in the range from -1 to -2 V vs ferrocene/ferrocenium couple lead to mainly diimine-localized radical anion complexes, while secondary reductions in the range from -2 to -2.5 V lead to dianion complexes, as shown through spectroelectrochemistry. Irreversible metal-centered oxidations at around 0.7 V result in rapid aryl-aryl reductive elimination and formation of decafluorobiphenyl. No photoluminescence was detected for the complexes containing chromophoric α-diimine ligands at room temperature. At 77 K in frozen glassy 2-Me-THF matrices, weak photoluminescence was detected for the dmphen and tmphen derivatives, with broad emission bands peaking around 570 nm. All results are rationalized with the support of (TD-)DFT calculations, highlighting the role of the C6F5 ligand in different systems.

Aliphatic and polycyclic aromatic hydrocarbons in surface sediments as a tool for the assessment of the contamination status of mangrove forests in Rio de Janeiro (Brazil).

The distribution of aliphatic and polycyclic aromatic hydrocarbons (PAHs) in surface sediments from mangrove forests of the Rio de Janeiro State was investigated. Ten sampling stations were selected in the mangroves of Sepetiba Bay and the Jacarepaguá Lagoon Complex (JLC), which are areas affected by multiple human activities. The total aliphatic hydrocarbons concentrations showed marked variation between samples (27-407 µg g-1), mostly related to the total organic carbon contents. The total PAHs concentration ranged between 38 and 792 ng g-1. Diagnostic indices and statistical analysis showed that the mangrove forests can be divided into three groups: the western portion of Sepetiba Bay with the lowest level of contamination; the inner portion of the bay with the most intense presence of local sources of contamination, especially of pyrolytic character; and the JLC with a greater accumulation of hydrocarbons, mainly derived from petroleum combustion, resultant from the intense urbanization.

Community-based assessment of marine resources contamination after a large-scale oil spill.

As of August 2019, several oil slicks reached the Brazilian coast, compromising local ecosystems and the economy of coastal communities. In this context, this study aimed to assess seafood quality at the Canavieiras Extractive Reserve (RESEX), located in the state of Bahia, Northeastern Brazil, by determining polycyclic aromatic hydrocarbons (PAHs) concentrations in local biota following the oil spill. It was designed and carried out in a participatory manner, involving RESEX fishers, shellfish and crab gatherers and managers, as well as university researchers. A total of 72 biota samples were analyzed, and the sum of the 16 priority USEPA PAHs ranged from less than the limit of detection to 30.81 ng g-1 (w.w.). When also considering alkylated compounds, concentrations ranged from 3.53 to 360.75 ng g-1 (w.w.). No sample contained PAHs concentrations suggestive of human consumption risks. No difference in PAHs concentrations between the six studied areas and regarding different biota feeding habits were observed. Higher PAHs concentrations were generally noted in molluscs, as these organisms do not have enzyme systems capable of metabolizing these compounds. This initiative demonstrated the feasibility of participatory construction resulting in a study concerning valued species to local communities, ensuring a contribution to local fishing and marketing activities.

Fecal sterols as sewage contamination indicators in Brazilian mangroves.

Recent sewage contamination in Brazilian mangrove forests was evaluated using fecal sterols as biomarkers and socioeconomic indicators. The sterols were quantified by gas chromatography/mass spectrometry (GC/MS). Total fecal sterol concentrations ranged between 2.50 2.50 and 39.03 µg g-1 and coprostanol, between 0.23 and 6.97 µg g-1. Mangroves located in less urbanized regions presented low coprostanol levels and low coprostanol/cholesterol and (5ß/5ß + 5α) stanol ratios in sediment, while urban mangrove forests presented moderate fecal contamination. In the latter, an intense contribution of untreated domestic effluents associated to metropolitan areas was noted, leading to a significant correlation between coprostanol concentrations and inadequate sanitation, reflecting environmental problems associated to disorderly urbanization processes coupled to the absence of an adequate urban infrastructure. However, even in metropolitan areas, fecal sterol levels did not reach those of highly contaminated regions, probably due to the intense and accelerated degradation process typical of tropical environments. However, this study highlights the importance of fecal contamination assessment in mangrove areas since the presence of untreated sewage in these ecosystems is an issue of public and environmental health.

Assessment of brazilian mangroves hydrocarbon contamination from a latitudinal perspective.

The present study investigated the contamination of Brazilian mangroves sediments by aliphatic hydrocarbons (AHs) and polycyclic aromatic hydrocarbons (PAHs). Samples were obtained from mangroves located along the brazilian coast, between the northern coast and the austral limit of the occurrence of this ecosystem. Total AH ranged from 1.9 to 311.3 µg g-1 and compound distribution pointed to biogenic sources, mainly from mangrove forests, and petrogenic sources, with a significant presence of an unresolved complex mixture in some areas. PAH values (34.4-977.3 ng g-1) indicated low to moderate contamination levels in mangrove sediments, reflecting the socioeconomic diversity observed along the Brazilian coast. The predominant PAH sources ranged from pyrolytic to petrogenic. According to sediment quality reference values, the evaluated sediments are not likely to cause biological effects, but deserve attention due to the current expansion scenario of oil prospecting activities off the Brazilian coast.

Offshore drilling effects in Brazilian SE marine sediments: a meta-analytical approach.

The exploration and production of oil and gas reserves often result to drill cutting accumulations on the seafloor adjacent to drill locations. In this study, the detection of drilling influence on marine sediments was performed by meta-analytical comparison between data from pre- and post-drilling surveys undertaken in offshore Campos Basin, southeast of Brazil. Besides this overall appraisal on the geochemical variables, a multivariate assessment, considering only the post-drilling data, was performed. Among the variables, fines content, carbonates, total organic carbon, barium, chromium, copper, iron, manganese, nickel, lead, vanadium, zinc, and total petroleum hydrocarbons, only barium, copper, and hydrocarbons were related to drilling impacts. In relation to the point of discharge, relative elevated levels in the post-drilling campaigns were observed preferentially up to 500 m in the northeast and southwest directions, associated to the Brazil Current-predominant direction. Other distributed concentrations in the surroundings seem to indicate the dilution and dispersion of drilling waste promoted by meteoceanographic factors.

Unsymmetrical N-Aryl-1-(pyridin-2-yl)methanimine Ligands in Organonickel(II) Complexes: More Than a Blend of 2,2'-Bipyridine and N,N-Diaryl-α-diimines?

The new organonickel complexes [(R-PyMA)Ni(Mes)X] [R-PyMA = N-aryl-1-(pyridin-2-yl)methanimine; aryl = phenyl, 2,6-Me2-, 3,5-Me2-, 2,4,6-Me3-, 2,6-iPr2-, 3,5-(OMe)2-, 2-NO2-4-Me-, 4-NO2-, 2-CF3-, and 2-CF3-6-F-phenyl; Mes = 2,4,6-trimethylphenyl; X = F, Cl, Br, or I] were obtained as approximate 1/1 cis and trans isomeric mixtures or pure cis isomers depending on the PyMA ligand and X. The [(R-PyMA)Ni(Mes)X] complexes with X = Br or Cl were directly synthesized from the precursors trans-[(PPh3)2Ni(Mes)X], while [(PyMA)Ni(Mes)X] derivatives with X = F or I were obtained from [(PyMA)Ni(Mes)Br] through X exchange reactions. Although density functional theory (DFT) calculations show a preference for the sterically favored cis isomers, both isomers could be observed in many cases; in three cases, even single crystals for X-ray diffraction could be obtained for the trans isomers. Possible intermediates for the isomerization were investigated by DFT calculations. All complexes were studied by multiple spectroscopic means, electrochemistry, and spectroelectrochemistry (for the reduction processes). The long-wavelength metal-to-ligand charge-transfer (MLCT) absorptions vary markedly with the R substituent of the ligand and the cathodic electrochemical potentials to a far smaller degree. Both are almost invariable upon variation of X. All of this is in line with Ni-based and π*-based lowest unoccupied molecular orbitals (LUMOs). In line with the unsymmetric character of the NPy^Nmethanimine ligand, electrochemistry and MLCT transitions seem to not correspond to the same type of π* LUMO, making these PyMA ligands more interesting than the symmetric heteroaromatic polypyridine ligands such as 2,2'-bipyridine (bpy; NPy^NPy) and N,N-diaryl-substituted aliphatic α-diimines (Nmethanimine^Nmethanimine) such as the diaza-1,3-butadienes (DAB). First attempts to use these complexes in Negishi-type cross-coupling reactions were successful.

Hydrocarbons in sediments of a chronically contaminated bay: the challenge of source assignment.

Aliphatic hydrocarbons and 39 PAH (parental and alkylated homologs) determined in ca. 100 sediment samples from the Guanabara Bay, Rio de Janeiro, were evaluated for source discrimination using new approaches. Concentrations of total PAH were in the range of 96-135,000 µg kg(-1) similar to other coastal urbanized embayment. Traditional diagnostic ratios were not as efficient PAH source indicators, e.g. biomass combustion was assigned as the major source of the pyrolytic PAH although the hydrographic basin is highly industrialized and urbanized. It is proved petrogenic imprint cannot be detected if only the 16 USEPA PAH are determined. The high production in the eutrophic system is not apparent in the aliphatic fraction dominated by land derived n-alkanes due to the effectiveness of microbial degradation. The present work demonstrates the complexity of hydrocarbon forensics when applied to chronically contaminated environments.

Hydrocarbon composition and distribution in a coastal region under influence of oil production in northeast Brazil.

Waters and sediments from the Potiguar Basin (NE Brazilian coast) were investigated for the presence and nature of polycyclic aromatic hydrocarbons (PAH) and aliphatic hydrocarbons. The region receives treated produced waters through a submarine outfall system serving the industrial district. The total dispersed/dissolved concentrations in the water column ranged from 10-50 ng L(-1) for ∑16PAH and 5-10 µg L(-1) for total aliphatic hydrocarbons. In the sediments, hydrocarbon concentrations were low (0.5-10 ng g(-1)for ∑16PAH and 0.01-5.0 µg g(-1) for total aliphatic hydrocarbons) and were consistent with the low organic carbon content of the local sandy sediments. These data indicate little and/or absence of anthropogenic influence on hydrocarbon distribution in water and sediment. Therefore, the measured values may be taken as background values for the region and can be used as future reference following new developments of the petroleum industry in the Potiguar Basin.

Electrochemistry and spectroscopy of organometallic terpyridine nickel complexes.

Organonickel complexes [(R'terpy)Ni(aryl)]X (R'terpy = derivatives of 2,2';6',2''-terpyridine; aryl = 2,6-dimethylphenyl = Xyl or 2,4,6-trimethylphenyl = Mes; X = Br or PF(6)) have been investigated by multiple electrochemical methods as well as combined electrochemical/spectroscopic techniques (spectroelectrochemistry). Reversible electrochemical reduction fills successively pi* orbitals in the terpy ligand. Some of the occurring species were characterized spectroscopically (EPR and UV/vis/NIR spectroelectrochemistry). The presumably nickel-centered oxidation occurs irreversibly.