Electrochemical Sensors Based on Transition Metal Materials for Phenolic Compound Detection.

Electrochemical sensors have been recognized as crucial tools for monitoring comprehensive chemical information, especially in the detection of a significant class of molecules known as phenolic compounds. These compounds can be present in water as hazardous analytes and trace contaminants, as well as in living organisms where they regulate their metabolism. The sensitive detection of phenolic compounds requires highly efficient and cost-effective electrocatalysts to enable the development of high-performance sensors. Therefore, this review focuses on the development of advanced materials with excellent catalytic activity as alternative electrocatalysts to conventional ones, with a specific emphasis on transition metal-based electrocatalysts for the detection of phenolic compounds. This research is particularly relevant in diverse sectors such as water quality, food safety, and healthcare.

Developing a Compost Quality Index (CQI) Based on the Electrochemical Quantification of Cd (HA) Reactivity.

The present work demonstrates the use of Cd2+ as a reactivity probe of the fulvic acids (FAs), humic acids (HAs) and dissolved organic matter (DOM) compost extracts. Significant differences were observed between the extracts, with the HA extract showing the highest reactivity. Comparing the different composts, the largest reactivity variation was again observed for HA then FA and finally DOM extracts. The Cd2+ binding extent was used to calculate the quality of composts and compared with a reference of uncomposted organic fertiliser (FLW), leading to the definition of an operational scale of compost quality. The parameter equivalent mass of fertiliser (mEF) was used for this scale sorted the seven composts from 0.353 to 1.09 kg FLW, for compost of sewage sludge (CSS) and vermicompost of domestic waste (CVDW), respectively. The significance of this parameter was verified through a correlation analysis between binding extent and the effect of compost application on lettuce crop growth in a field trial. The results demonstrate the potentiality of FA and HA extracts as markers of compost bioactivity and the use of Cd2+ as a reactivity probe.

Characterization of antimicrobial effect of organotin-based catalysts on diesel-biodiesel deteriogenic microorganisms.

Organotin compounds are applied in several industrial reactions and can present antifungal and antibacterial activities. Incorrect handling and storage practices of biodiesel and diesel-biodiesel blends can lead to microbial development, impacting its final quality. Concerning this problem, this work investigated the antimicrobial action of two organotin catalysts used in biodiesel production with four isolated microroorganisms (Bacillus pumilus, Pseudomonas aeruginosa, Pseudallescheria boydii, and Aureobasidium pullulans) and a pool of microorganisms (ASTM E1259 standard practice). Samples of soybean biodiesel with different concentrations of dibutyl tin dilaurate (catalyst 1) and di-n-butyl-oxo-stannane (catalyst 2) were prepared and added of mineral medium. The pool of microorganisms was inoculated and incubated at 30 °C and final biomass was weighted after 14 days. Thereafter, soybean biodiesel with catalyst 2 was used. Fungal biomass was weighted, and plate count was used to assess bacterial growth. Results show that catalysts 1 and 2 presented no inhibitory activity on the pool of microorganisms evaluated. A slight inhibitory activity was observed for B. pumilus and A. pullulans growth, but not for P. boydii, P. aeruginosa, or the pool of microorganisms. All experiment exhibited acidification higher than sterile control. Infrared analysis show less microbiological degradation products in the tin-protected fuel with ASTM inoculum. These results suggest that these tin-based catalysts show no toxic effect on native microbial population and a slight effect on some isolated microbial population in laboratory scale and for the first time shows that these organotin compounds can be employed safely as biodiesel catalyst. Graphical abstract.

Simulation of a surface spill of different diesel/biodiesel mixtures in an ultisol, using natural attenuation and bioaugmentation/biostimulation.

Accidents caused by leaks and/or spills on soils need to be addressed. Natural attenuation, biostimulation and bioaugmentation can be useful bioremediation strategies for decontamination processes in soils of diesel/biodiesel mixtures. The purpose of this study was to evaluate the degradation rate of the different fuels (B0, B20 and B100) in an ultisol under natural attenuation and biostimulation/bioaugmentation during 60 days of incubation in a controlled microcosm simulating a surface spill over soil. The degradation of different diesel/biodiesel mixtures was monitored for up to 60 days by dehydrogenase activity, respirometry by CO2 release, the most probable number of heterotrophic and degrading microorganism and gas chromatography. The bacterial inoculum employed for biostimulation/bioaugmentation strategy consisted of Bacillus megaterium, Bacillus pumilus, Pseudomonas aeruginosa, and Stenotrophomonas maltophilia. The two bioremediation strategies have showed great degradation rates. The natural attenuation was effective for B0 and B20 treatments. The addition of the bacterial consortium and macronutrients contributed to the increased degradation of pure biodiesel in relation to natural attenuation, with higher rates for CO2 release, enzymatic and degrading activity. It is suggested that the bacterial consortium has proven effective for presenting significant values for such parameters until the end of the 60-day incubation period.

Metal resistance mechanisms in Gram-negative bacteria and their potential to remove Hg in the presence of other metals.

Contamination of the environment by heavy metals has been increasing in recent years due to industrial activities. Thus research involving microorganisms capable of surviving in multi-contaminated environments is extremely important. The objectives of the present study were to evaluate the removal of mercury alone and in the presence of cadmium, nickel and lead by four mercury-resistant microorganisms; estimate the removal of Cd, Ni and Pb; understand the mechanisms involved (reduction, siderophores, biofilms, biosorption and bioaccumulation) in the metal resistance of the isolate Pseudomonas sp. B50D; and determine the capacity of Pseudomonas sp. B50D in removing Hg, Cd, Ni and Pb from an industrial effluent. It was shown that the four isolates evaluated were capable of removing from 62% to 95% of mercury from a culture medium with no addition of other metals. The isolate Pseudomonas sp. B50D showed the best performance in the removal of mercury when evaluated concomitantly with other metals. This isolate was capable of removing 75% of Hg in the presence of Cd and 91% in the presence of Ni and Pb. With respect to the other metals it removed 60%, 15% and 85% of Cd, Ni and Pb, respectively. In tests with effluent, the isolate Pseudomonas sp. B50D removed 85% of Hg but did not remove the other metals. This isolate presented reduction, biosorption, biofilm production and siderophore production as its metal resistance mechanisms. Pseudomonas sp. B50D was thus a candidate with potential for application in the bioremediation of effluents with complex metal contaminations.

Simplified 2,4-dinitrophenylhydrazine spectrophotometric assay for quantification of carbonyls in oxidized proteins.

This work proposes a modification of the 2,4-dinitrophenylhydrazine (DNPH) spectrophotometric assay commonly used to evaluate the concentration of carbonyl groups in oxidized proteins. In this approach NaOH is added to the protein solution after the addition of DNPH, shifting the maximum absorbance wavelength of the derivatized protein from 370 to 450nm. This reduces the interference of DNPH and allows the direct quantification in the sample solution without the need for the precipitation, washing, and resuspension steps that are carried out in the traditional DNPH method. The two methods were compared under various conditions and are statistically equivalent.

Cobalt-nickel phosphide supported on reduced graphene oxide for sensitive electrochemical detection of bisphenol A.

Bisphenol A (BPA) is a commonly utilized phenolic contaminant in several manufacturing processes, contributing to environmental pollution. Therefore, the detection of BPA holds significant importance for monitoring water quality. In this work, we report a robust electrochemical detection method for BPA utilizing cobalt-nickel bimetal phosphide nanoparticles (CoNiP) supported on reduced graphene oxide (rGO). The CoNiP@rGO-modified glassy carbon electrode exhibits remarkable electrochemical activity in BPA detection. The detection mechanism is controlled by adsorption-mediated electron transfer, showcasing a low limit of detection (LOD) at 0.38 nM and a high sensitivity of 96.4 A M-1 cm-2 within the linear range of 0.001-8 µM. Furthermore, our developed sensor demonstrates good reproducibility and successfully detected BPA in actual water samples. The electrochemical activity of CoNiP@rGO was also characterized for hydroquinone (HQ) detected through a diffusion-controlled mechanism, displaying an excellent sensitivity of 36.4 A M-1 cm-2 across a broad linear range. These findings underscore the promising potential of CoNiP@rGO as a candidate for electrochemical detection of phenolic contaminants, especially in the sensing of BPA in environmental water samples. This efficacy is attributed to the modulation of its electronic properties, combined with its large electroactive surface area and low electron-transfer resistance.

Direct electroanalytical method for alternative assessment of global antioxidant capacity using microchannel electrodes.

A new electroanalytical method for the characterization of global antioxidant capacity is proposed based on chronoamperometric responses monitored at microchannel band electrodes. This approach does not require any titrating species, biological elements, or precalibration curves. A thin-layer regime is established at the working electrode according to the geometry of the device and hydrodynamic flow rate. Under these conditions, the currents are directly proportional to the total concentration of antioxidants and do not depend on their respective diffusion coefficients. Measurements were performed with synthetic solutions and mixtures of four antioxidants used as sample tests: trolox, ascorbic acid, gallic acid, and caffeic acid. Operating potentials were selected at the formal potentials of some reactive oxygen species to simulate their oxidative attacks. The very good agreement obtained between simulations and experimental data validated this new electroanalytical procedure. These results pave the way for the concept of innovative sensor-type microfluidic devices for alternative determination of antioxidant capacity.

Isolation and characterization of bacteria from mercury contaminated sites in Rio Grande do Sul, Brazil, and assessment of methylmercury removal capability of a Pseudomonas putida V1 strain.

Methylmercury (MeHg) is one of the most dangerous heavy metal for living organisms that may be found in environment. Given the crescent industrialization of Brazil and considering that mercury is a residue of several industrial processes, there is an increasing need to encounter and develop remediation approaches of mercury contaminated sites. The aim of this study was to isolate and characterize methylmercury resistant bacteria from soils and sludge sewage from Rio Grande do Sul, Brazil. Sixteen bacteria were isolated from these contaminated sites and some isolates were highly resistant to methylmercury (>8.7 µM). All the isolates were identified by 16S rDNA. Pseudomonas putida V1 was able to volatilize approximately 90 % of methylmercury added to growth media and to resist to copper, lead, nickel, chromate, zinc, cobalt, manganese and barium. In the presence of high concentrations of methylmercury (12 µM), cell growth was limited, but P. putida V1 was still able to remove up to 29 % of this compound from culture medium. This bacterium removed an average of 77 % of methylmercury from culture medium with pH in the range 4.0-6.0. In addition, methylmercury was efficiently removed (>80 %) in temperature of 21-25 °C. Polymerase chain reactions indicated the presence of merA but not merB in P. putida V1. The growth and ability of P. putida V1 to remove methylmercury in a wide range of pH (4.0 and 8.0) and temperature (10-35 °C), its tolerance to other heavy metals and ability to grow in the presence of up to 11.5 µM of methylmercury, suggest this strain as a new potential resource for degrading methylmercury contaminated sites.

Facile preparation of a Pt-ERGO composite modified screen-printed electrode for the sensitive determination of phenolic compounds.

The mass production of screen-printed electrochemical devices with integrated electrodes has facilitated the widespread adoption of electroanalytical methods. The SPEs (screen-printed electrodes) overcome some obstacles associated with the use of conventional electrochemical cells, making them accessible to untrained operators. Despite their advantages, SPEs require activation/modification of the working electrode (WE) to enhance sensitivity. Nanomaterials, with metal nanoparticles (NPs) dispersed in polymers and/or carbon NPs has gaining popularity for this purpose. In this study, we describe a modification of carbon SPEs (SPCEs) using Pt NPs and reduced graphene oxide (ERGO). The Pt-ERGO@SPCE is prepared by galvanostatic reduction of drop-casted precursors directly onto the WE surface, eliminating complex synthetic steps and high temperatures. After optimizing Pt amount and reduction extent, the modified SPCEs were tested for detecting hydroquinone (HQ) and bisphenol A (BPA). DPV results show significantly increased sensitivity for the quantification of both compounds. The modified SPCEs demonstrates promising performance: precision (5 % HQ, 8 % BPA), detection limits (1.4 µM HQ, 4.6 µM BPA), sensitivity (1688 µA mM-1 HQ, 441 µA mM-1 BPA), and recoveries (98-113 % HQ, 98-104 % BPA). This simple electrode modification holds great potential, allowing the preparation of the sensor by personnel who may lack access to well-equipped laboratories, particularly in developing countries.

Behavior of deteriogenic fungi in aviation fuels (fossil and biofuel) during simulated storage.

Biofuels are expected to play a major role in reducing carbon emissions in the aviation sector globally. Farnesane ("2,6,10-trimethyldodecane") is a biofuel derived from the synthesized iso-paraffin route wich can be blended with jet fuel; however, the microbial behavior in farnesane/jet fuel blends remains unknown. The chemical and biological stability of blends should be investigated to ensure they meet the quality requirements for aviation fuels. This work aimed at evaluating the behavior of two fungi Hormoconis resinae (F089) and Exophiala phaeomuriformis (UFRGS Q4.2) in jet fuel, farnesane, and in 10% farnesane blend during simulated storage. Microcosms (150-mL flasks) were assembled with and without fungi containing Bushnell & Haas mineral medium for 28 days at a temperature of 20±2°C. The fungal growth (biomass), pH, surface tension, and changes in the fuel's hydrocarbon chains were evaluated. This study revealed thatthe treatment containing H. resinae showed a biomass of 19 mg, 12 mg, and 2 mg for jet fuel, blend, and farnesane respectively. The pH was reduced from 7.2 to 4.3 observed in jet fuel treatment The degradation results showed that compounds with carbon chains between C9 and C11, in jet fuel, and blend treatments were preferably degraded. The highest biomass (70.9 mg) produced by E. phaeomuriformis was in 10% farnesane blend, after 21 days. However, no significant decrease was observed on pH and surface tension measurements across the treatments as well as on the hydrocarbons when compared to the controls. This study revealed that farnesane neither inhibited nor promoted greater growth on both microorganisms.

Capability of a selected bacterial consortium for degrading diesel/biodiesel blends (B20): enzyme and biosurfactant production.

The search for alternative sources of energy, such as biodiesel, has been stimulated, since this biofuel is highly susceptible for biodegradation and has low toxicity, thus, reducing the impact in ecosystems. The objective of this study was to select a bacterial consortium with potential for degrading diesel/biodiesel blends (B20) obtained from areas contaminated with hydrocarbons/esters. In order to evaluate the biodegrability of the blend, six enzyme assays were conducted: alkane hydroxylase, Catechol 1,2-dioxygenase, Catechol 2,3-dioxygenase, Protocatechol 3,4-dioxygenase, ρ-NPA hydrolysis (esterase), and release of fatty acids through titration (lipase), with estimative of total protein and biosurfactant production (surface tension measurement and emulsifying index E(24)). The best results obtained allowed the selection of four bacteria isolates (Bacillus megaterium, Bacillus pumilus, Pseudomonas aeruginosa, and Stenotrophomonas maltophilia) for compiling a consortium, which will be used for bioaugmentation strategies in soils contaminated with these fuels. This consortium exhibited high potential for biodegradation of biodiesel, and might be an efficient alternative for cleaning up these contaminated environments.

Bioprospection and selection of bacteria isolated from environments contaminated with petrochemical residues for application in bioremediation.

The use of microorganisms with hydrocarbon degrading capability and biosurfactant producers have emerged as an alternative for sustainable treatment of environmental passives. In this study 45 bacteria were isolated from samples contaminated with petrochemical residues, from which 21 were obtained from Landfarming soil contaminated with oily sludge, 11 were obtained from petrochemical industry effluents and 13 were originated directly from oily sludge. The metabolization capability of different carbon sources, growth capacity and tolerance, biosurfactant production and enzymes detection were determined. A preliminary selection carried out through the analysis of capability for degrading hydrocarbons showed that 22% of the isolates were able to degrade all carbon sources employed. On the other hand, in 36% of the isolates, the degradation of the oily sludge started within 18-48 h. Those isolates were considered as the most efficient ones. Twenty isolates, identified based on partial sequencing of the 16S rRNA gene, were pre-selected. These isolates showed ability for growing in a medium containing 1% of oily sludge as the sole carbon source, tolerance in a medium containing up to 30% of oily sludge, ability for biosurfactant production, and expression of enzymes involved in degradation of aliphatic and aromatic compounds. Five bacteria, identified as Stenotrophomonas acidaminiphila BB5, Bacillus megaterium BB6, Bacillus cibi, Pseudomonas aeruginosa, and Bacillus cereus BS20 were shown to be promising for use as inoculum in bioremediation processes (bioaugmentation) of areas contaminated with petrochemical residues since they can use oily sludge as the sole carbon source and produce biosurfactants.

Biodegradation of commercial gasoline (24% ethanol added) in liquid medium by microorganisms isolated from a landfarming site.

Isolation of soil microorganisms from a landfarming site with a 19-year history of petrochemical residues disposal was carried out. After isolation, the bacteria behavior in mineral medium with 1% commercial gasoline (24% ethanol) was evaluated. Parameters employed for microorganism evaluation and selection of those with the greatest degradation potential were: microbial growth; biosurfactant generation and compound reduction in commercial gasoline. Starting from bacteria that presented the best degradation results, consortiums formed by 4 distinct microorganisms were formed. A microbial growth in the presence of commercial gasoline was observed and, for most of the bacteria, degradations of compounds such as benzene, toluene and xylenes (BTX) as well as biosurfactant production was observed. Ethanol was partially degraded by the bacterial isolates although the data does not allow affirming that it was degraded preferentially to the aromatic hydrocarbons investigated. The analyzed consortiums present an efficiency of 95% to 98% for most of the commercial gasoline compounds and a preferential attack to ethanol under the essay condition was not observed within 72 h.

Development of a Pencil Drawn Paper-based Analytical Device to Detect Lysergic Acid Diethylamide (LSD)*, †.

The need for agile and proper identification of drugs of abuse has encouraged the scientific community to improve and to develop new methodologies. The drug lysergic acid diethylamide (LSD) is still widely used due to its hallucinogenic effects. The use of voltammetric methods to analyze narcotics has increased in recent years, and the possibility of miniaturizing the electrochemical equipment allows these methods to be applied outside the laboratory; for example, in crime scenes. In addition to portability, the search for affordable and sustainable materials for use in electroanalytical research has grown in recent decades. In this context, employing paper substrate, graphite pencil, and silver paint to construct paper-based electrodes is a great alternative. Here, a paper-based device comprising three electrodes was drawn on 300 g/m2 watercolor paper with 8B pencils, and its efficiency was compared to the efficiency of a commercially available screen-printed carbon electrode. Square wave voltammetry was used for LSD analysis in aqueous medium containing 0.05 mol/L LiClO4 . The limits of detection and quantification were 0.38 and 1.27 µmol/L, respectively. Both electrodes exhibited a similar voltammetric response, which was also confirmed during analysis of a seized LSD sample, with recovery of less than 10%. The seized samples were previously analyzed by GCMS technique, employing the full scan spectra against the software spectral library. The electrode selectivity was also tested against 3,4-methylenedioxymethamphetamine (MDMA) and methamphetamine. It was possible to differentiate these compounds from LSD, indicating that the developed paper-based device has potential application in forensic chemistry analyses.

Use of digital images to count colonies of biodiesel deteriogenic microorganisms.

This work presents a novel, robust procedure for the semi-automated counting of colony-forming units of Bacillus pumilus (a bacterium) and Meyerozyma guilliermondii (a yeast) both isolated from diesel oil. The counting is performed from digital images of Petri dishes containing the samples by a developed Python code, and the images are acquired from a low-cost scanning apparatus. The counting algorithm is based on the similar morphological characteristics of the bacterium and the yeast colonies. It was compared with classical counting methodology, and the results showed calibration and validation curves with a coefficient of determination (R2) of 0.99 and 0.98, respectively. The developed methodology is a valuable alternative to estimate the microbial contamination of biofuels.

Presence of antibiotic resistance genes and its association with antibiotic occurrence in Dilúvio River in southern Brazil.

It is known that antibiotics are widely used in human and veterinary medicine. In some countries the use is controlled, however few restrictions to their use are enforced in many countries. Antibiotics and their metabolites can reach the water bodies through sewage systems, especially in those countries with partial or absent wastewater treatment systems. The overuse and misuse of antibiotics has been linked with the increase of antibiotic resistant bacteria. The relation between the occurrence of antibiotics and resistance genes in surface waters has been widely studied worldwide evincing the great importance of this subject. In this work, a methodology for quantification of 40 antibiotics of 5 different classes, in river water, by SPE-LC-MS/MS was validated. Samples were taken during a two-year period from Dilúvio River, a stream that crosses the city of Porto Alegre (RS - Brazil) and receives in nature domestic effluent. The methodology met the requirements of validation, with Limit of Quantification varying from 20 ng L-1 to 100 ng L-1. A total of 48 samples was analyzed for the presence of antibiotics for two years. From the 40 antibiotics analyzed, 8 of them (Azithromycin, Cephalexin, ciprofloxacin, clindamycin, norfloxacin, sulfadiazine, sulfamethoxazole and trimethoprim) were present in all sampling points in the range of

Improved enrichment and isolation of polycyclic aromatic hydrocarbons (PAH)-degrading microorganisms in soil using anthracene as a model PAH.

Lack of attention to soil and microbial characteristics that influence PAHs degradation has been a leading cause of failures in isolation of efficient PAH degraders and bioaugumentation processes with microbial consortia. This study compared the classic method of isolation of PAHs-degraders with a modified method employing a pre-enrichment respirometric analysis. The modified enrichment of PAH degrading microorganisms using in vitro microcosm resulted to reduced enrichment period and more efficient PAH-degrading microbial consortia. Results indicate that natural soils with strong heterotrophic microbial activity determined through pre-enrichment analysis, are better suited for the isolation of efficient PAH degrading microorganisms with significant reduction of the enrichment period.

Evaluation of total polyphenol content of wines by means of voltammetric techniques: Cyclic voltammetry vs differential pulse voltammetry.

Taking advantage of the low oxidation potential of polyphenolic compounds, voltammetric techniques, such as cyclic voltammetry (CV) and differential pulse voltammetry (DPV) are used rather indiscriminately. In this work, we report Total Polyphenols results (TPP) obtained by these two techniques from a set of nine samples of red and Tawny Port wine. The CV and DPV voltammograms display significant correlations with the physical-chemical parameters used to characterize red and Tawny Port wines, particularly with polyphenols. Although data obtained from CV and DPV for a single polyphenol are directly proportional, important deviations are found between voltammetric results from wines. Results from CV tend to be larger than those from DPV. This difference, that can reach 50% of the TPP value, was related to the presence of total sulphur dioxide. In view of the present study, the polyphenol quantification in wines should be performed by DPV to minimize the interference of SO2.

Microbial consortium bioaugmentation of a polycyclic aromatic hydrocarbons contaminated soil.

In this study we evaluated the capacity of a defined microbial consortium (five bacteria: Mycobacterium fortuitum, Bacillus cereus, Microbacterium sp., Gordonia polyisoprenivorans, Microbacteriaceae bacterium, Naphthalene-utilizing bacterium; and a fungus identified as Fusarium oxysporum) isolated from a PAHs contaminated landfarm site to degrade and mineralize different concentrations (0, 250, 500 and 1000 mg kg(-1)) of anthracene, phenanthrene and pyrene in soil. PAHs degradation and mineralization was evaluated by gas chromatography and respirometry, respectively. The microbial consortium degraded on average, 99%, 99% and 96% of the different concentrations of anthracene, phenanthrene and pyrene in the soil, in 70 days, respectively. This consortium mineralized 78%, on average, of the different concentrations of the 3 PAHs in soil after 70 days. Contrarily, the autochthonous soil microbial population showed no substantial mineralization of the PAHs. Bacterial and fungal isolates from the consortium, when inoculated separately to the soil, were less effective in anthracene mineralization compared to the consortium. This signifies synergistic promotion of PAHs mineralization by mixtures of the monoculture isolates (the microbial consortium).