The impact of chronic and acute problems on sea turtles: The consequences of the oil spill and ingestion of anthropogenic debris on the tropical semi-arid coast of Ceará, Brazil.

Sea turtle mortality is often related to materials that reach the coast from different anthropic activities worldwide. This study aimed to investigate whether sea turtle mortality was related to older marine problems, such as solid waste, or one of the largest oil spill accidents on the Brazilian coast, that occurred in 2019. We posed three questions: 1) Are there solid residues in the digestive tract samples, and which typology is the most abundant? 2) Can meso­ and macro-waste marine pollutants cause mortality? 3) Is the dark material found really oil? A total of 25 gastrointestinal content (GC) samples were obtained, of which 22 ingested waste of anthropogenic origin and 18 were necropsied. These 22 samples were obtained during or after the 2019 oil spill, of which 17 specimens were affected, making it possible to suggest oil ingestion with the cause of death in the animals that could be necropsied. Macroscopic data showed that the most abundant solid waste was plastic (76.05 %), followed by fabrics (12.18 %) and oil-like materials. However, chemical data confirmed only three specimens with oil levels ranging from remnants to high. It was possible to infer possible causes of death in 16 of the total 18 necropsied cases: Most deaths were due to respiratory arrest (62.5 %), followed by pulmonary edema (12.5 %), cachexia syndrome (12.5 %), circulatory shock (6.25 %), and head trauma (6.25 %), which may have been caused by contact with solid waste, oil, or both. The study showed that not all dark material found in the GCs of turtles killed in oiled areas is truly oil, and in this sense, a chemical analysis step to prove the evidence of oil must be added to international protocols.

Concentrations, sources and risks of polycyclic aromatic hydrocarbons in sediments from the Parnaiba Delta basin, Northeast Brazil.

The Parnaíba River is the main river in the Parnaíba Delta basin, the largest delta in the Americas. About 18 polycyclic aromatic hydrocarbons (PAHs) were identified and the environmental risk associated with the sediments was evaluated. The study found that PAHs levels ranged from 5.92 to 1521.17 ng g-1, which was classified as low to high pollution, and that there were multiple sources of pollution along the river, with pyrolytic sources predominating, mainly from urban activity such as trucking, although the influence of rural activity cannot be ruled out. PAHs correlated with black carbon and organic matter and showed high correlation with acenaphthylene, phenanthrene, pyrene, benzo(a)anthracene, chrysene, benzo(ghi)perylene, and ∑PAHs. The benzo(a)pyrene levels were classified as a risk to aquatic life because the threshold effect level and the probable effect level were exceeded. In addition, the sediments were classified as slightly contaminated with a benzo(a)pyrene toxicity equivalent value of 108.43 ng g-1. Thus, the priority level PAH exhibited carcinogenic and mutagenic activity that posed a potential risk to human health.

Degradation of xanthene-based dyes by photoactivated persulfate: experimental and computational studies.

Dyes are naked-eye detectable even at low concentration levels and can cause environmental damage when released into aquatic effluents; therefore, methods for removing the residual color from the aquatic media are always a current issue. In this paper, degradation of three xanthene dyes, Rhodamine B, Eosin Y, and Sodium Fluorescein, using photoactivated persulfate was evaluated at pH 3.0 and 11.0. The dyes' degradation followed a pseudo-first-order reaction. Although the solution is completely decolorized in 40 min at pH 3.0, achieving 75% mineralization requires a longer reaction time of 180 min. Furthermore, GC-MS analyses indicate that degradation products are mainly low-molecular weight acids, CO2 and H2O. Experiments carried out in dark and under UV irradiation showed substantial contribution of radical (SO4•- and HO•) and non-radical pathways to dye degradation in both pH. Additionally, to get more insights into the degradation pathways, HOMO-LUMO energy gaps of the dyes were calculated by DFT using MPW1PW91/MidiXo level of theory and, in general, the lower the bandgap, the faster the degradation. Fukui functions revealed that the preferential sites to radical attack were the xanthene or the benzoate portion depending on the pH, wherein attack to the xanthene ring provided better kinetic and mineralization results.

Is there a similarity between the 2019 and 2022 oil spills that occurred on the coast of Ceará (Northeast Brazil)? An analysis based on forensic environmental geochemistry.

The main objective of this study was to investigate the 2019 and 2022 oil spill events that occurred off the coast of the State of Ceará, Northeastern Brazil. To further assess these mysterious oil spills, we investigated whether the oils stranded on the beaches of Ceará in 2019 and 2022 had the same origin, whether their compositional differences were due to weathering processes, and whether the materials from both were natural or industrially processed. We collected oil samples in October 2019 and January 2022, soon after their appearance on the beaches. We applied a forensic environmental geochemistry approach using both one-dimensional and two-dimensional gas chromatography to assess chemical composition. The collected material had characteristics of crude oil and not refined oils. In addition, the 2022 oil samples collected over 130 km of the east coast of Ceará had a similar chemical profile and were thus considered to originate from the same source. However, these oils had distinct biomarker profiles compared to those of the 2019 oils, including resistant terpanes and triaromatic steranes, thus excluding the hypothesis that the oil that reached the coast of Ceará in January 2022 is related to the tragedy that occurred in 2019. From a geochemical perspective, the oil released in 2019 is more thermally mature than that released in 2022, with both having source rocks with distinct types of organic matter and depositional environments. As the coast of Ceará has vast ecological diversity and Marine Protected Areas, the possibility of occasional oil spills in the area causing severe environmental pollution should be investigated from multiple perspectives, including forensic environmental geochemistry.

Dealing with complex contamination scenarios: using a multi-geochemical approach to assess environmental quality and identify pollution sources in a semi-arid estuary from Brazil.

The Jundiaí-Potengi Estuary (EJP) is located on the semi-arid coast of northeastern Brazil and is influenced by multiple sources of contamination. The sediment quality of EJP was assessed by using a multi-geochemical approach during the dry and wet seasons. Sediments were analyzed for concentrations of nutrients, metals, polycyclic aromatic hydrocarbons (PAHs), pesticides, hormones (natural and synthetic), and sterols. The results were integrated by multivariate methods. The sediment was altered by the presence of contaminants from anthropogenic and natural sources. The middle and lower estuarine areas were considered more degraded in both seasons. In these regions, metals, hormones, sterols, and PAHs were found, indicating that these regions are severely affected by industrial, sanitary and aquaculture effluents, combustion of fossil fuels, and oil spills. The upstream region was contaminated by pesticides. The contamination pattern along the EJP shows the prevalence of local sources which continuously release the chemicals into the estuary. Worse conditions occurred during the rainy season, when the runoff from urban and rural areas is more intense and carries a greater load of contaminants to the EJP.

Tracking the historical urban and rural sources of fecal pollution in a South American tropical semi-arid region using sterols and endocrine-disrupting chemicals.

Sterols and endocrine-disrupting chemicals were analyzed in two dated sediment cores collected in the Jaguaribe river to determine the recent decades' influence of urbanization and agropastoral activities on the inputs of fecal pollution in a semi-arid region of Brazil. Stigmasterol and sitosterol were the most abundant of the 6 sterols examined in both cores, indicating an important contribution of organic matter from mangrove forests to the study region. Coprostanol presented a continuous increase in concentrations from the 1930s to the 2000s in one core, however, showing higher concentrations (>100 ng g-1) in the upper layers of both cores. The sterols diagnostic ratios indicated fecal pollution through both cores, especially from the 1940s to 1970s. The coprostanol levels followed the variations in population growth in the state of Ceará. Estriol and estrone were the most abundant estrogenic hormones found in both cores. These compounds are probably related to the intense livestock activities in the Ceará state, especially after the 1970s. The baseline levels of fecal sterols and estrogen hormones found in this study possibly represent a previous unimpacted scenario and may be used for future evaluations of fecal pollution from urbanization and livestock activities.

Selenium in Brazil nuts: An overview of agronomical aspects, recent trends in analytical chemistry, and health outcomes.

Se is an essential element in mammals. We review how its bioavailability in soil and the ability of plants to accumulate Se in foods depends on the soil Se profile (including levels and formats), besides to describe how the various selenoproteins have important biochemical functions in the body and directly impact human health. Owing to its favorable characteristics, the scientific community has investigated selenomethionine in most nut matrices. Among nuts, Brazil nuts have been highlighted as one of the richest sources of bioavailable Se. We summarize the most commonly used analytical methods for Se species and total Se determination in nuts. We also discuss the chemical forms of Se metabolized by mammals, human biochemistry and health outcomes from daily dietary intake of Se from Brazil nuts. These findings may facilitate the understanding of the importance of adequate dietary Se intake and enable researchers to define methods to determine Se species.

Chemometric tools applied to optimize a fast solid-phase microextraction method for analysis of polycyclic aromatic hydrocarbons in produced water.

Chemometric tools are powerful strategies to efficiently optimize many processes. These tools were employed to optimize a fast-solid phase microextraction procedure, which was used for the analysis of polycyclic aromatic hydrocarbons (PAHs) in oil-based produced water using a Headspace-Solid Phase Microextraction technique (HS-SPME/GC-MS). This optimization was achieved with a 24 factorial design approach, where the final conditions for this extraction procedure were 10 µg L-1, 1 h, 92 °C (at headspace), and 0.62 mol L-1 for PAHs concentration, fiber exposition to headspace, temperature, and NaCl concentration, respectively. The limit of detection (LOD) in this protocol ranged from 0.2 to 41.4 ng L-1, while recovery values from 67.65 to 113.10%. Besides that, relative standard deviation (RSD) were lower than 8.39% considering high molecular weight compounds. Moreover, the proposed methodology in this work does not require any previous treatment of the sample and allows to quantify a higher number of PAHs. Notably, naphthalene was the major PAHs compound quantified in all samples of the produced water at 99.99 µg L-1. Altogether, these results supported this methodology as a suitable analytical strategy for fast determination of PAHs in produced water from oil-based industry.

Statistical evaluation of analytical curves for quantification of pesticides in bananas.

The aim of this paper is to statistically validate the analytical curves of a chromatography method to identify and quantify azoxystrobin, difenoconazole and propiconazole residues in banana pulp, using QuEChERS and GC-SQ/MS. A matrix-matched calibration was used and analytical curves were estimated by weighted least squares regression (WLS), confirming heteroscedasticity for all compounds. Statistical tests were performed to confirm the quality adjustment of the proposed linear model. The correlation coefficient for azoxystrobin, difenoconazole and propiconazole were, respectively, 0.9985, 0.9966 and 0.9997 (concentration range: 0.05 and 2.0 mg kg-1). The limits of detection and quantification were, respectively, between 0.007 and 0.066 mg kg-1, and between 0.022 and 0.199 mg kg-1, below the maximum limits stipulated by Brazilian, American, and European legislation. Only difenoconazole had an insignificant matrix effect (6.8%). Thus, the weighted least squares method is shown to be a safe linear regression model, providing greater reliability of the results.

Evaluation of different strategies for determination of selenomethionine (SeMet) in selenized yeast by asymmetrical flow field flow fractionation coupled to inductively coupled plasma mass spectrometry (AF4-ICP-MS).

This manuscript exemplifies the prospective use of asymmetrical flow field flow fractionation (AF4) coupled to inductively coupled plasma mass spectrometry (ICP-MS) as a simple tool for chemical speciation of selenomethionine (SeMet) in selenized yeast. Several popular sample preparation methods were evaluated for their suitability to determine selenomethionine (SeMet) in selenized yeast by AF4-ICP-MS. These included water, methanesulfonic acid (MSA), formic acid (FA) and alkaline extractions. Alkaline extraction (using sodium dodecyl sulfate buffer) provided the best recovery/determination conditions for SeMet based on analysis of NRC certified reference material (CRM) SELM-1 since it minimized hydrolysis of the protein peptide bonds optimally required for the AF4 separation. The analytical performance of three different AF4 membranes (5, 10 and 500 kDa regenerated cellulose) was also evaluated. No significant difference in the recovery of SeMet was observed when using 5 and 10 kDa RC membranes, whereas the 500 kDa membrane resulted in a significant loss. The proposed method presents appropriate instrument and intra-assay precisions of 4.4-9.2% and 3.8% RSD, respectively, a detection limit of 0.49 µg L-1 SeMet as Se and good linearity with correlation coefficients (R) between 0.996 - 0.999. This is the first report of use of AF4-ICP-MS for species specific quantitation of SeMet in selenized yeast demonstrating its efficient use as an alternative method to other traditional chromatographic techniques.

A socio-environmental perspective on pesticide use and food production.

Pesticides are part of a large group of organic compounds with different physicochemical characteristics, designed to control and prevent pests in various crops and plantations, improving productivity. This works provides a perspective on pesticide use in current agriculture with the aim of identifying the influence of pesticides on food production and their impact on the environment. Therefore, it is necessary to highlight the importance of determining pesticide residues in food, aiming to ensure food safety, since these compounds can represent risks to human health and the environment. The effects of pesticides on humans range from headaches, nausea and skin and eye irritation to chronic problems such as cancer and neurological disorders, and extend to other non-target organisms such as birds, fish and bees, contaminating water, soil, and plants, as opposed to the benefits of increased production, consequently other measures for pesticide consumption need to be evaluate to ensure human health, food safety and environmental protection. It is important to note that chromatographic techniques and mass spectrometry assist in the determination of pesticide residues and evaluate the quality of the food that reaches the consumer, and together with the Maximum Residue Limits (MRLs), established by the legislation of each country, these instrumentation act to control the exposure of population to pesticides. Although the MRL is used as a parameter for food quality, the global differences in pesticide legislation do not guarantee the consumer safety. In this sense, a brief analysis of MRL inefficiency is also present in this paper.

Reactive Adsorption of Parabens on Synthesized Micro- and Mesoporous Silica from Coal Fly Ash: pH Effect on the Modification Process.

Parabens are widely used as preservatives in food, pharmaceutical, and cosmetic products. These compounds are known for their estrogen agonist activity. This research investigates the synthesis of micro- and mesoporous silica from coal fly ash at different pH values (13, 11, 9, and 7) as well as its use as an adsorbent for the removal of parabens. The materials were characterized, and X-ray fluorescence (XRF) analysis revealed that the fly ash acid treatment reduced the presence of aluminum, iron, and calcium oxides and also that silica synthesized at lower pH values (7 and 9) showed a higher SiO2 content. X-ray diffraction (XRD) and scanning electron microscopy (SEM) analyses revealed microporous silica formation for silica synthesized at pH 13 and mesoporous silica at pH 7, 9, and 11. Adsorption tests were performed with materials, and FA-AT7 showed a higher adsorption capacity. The effect of factors (A) adsorbent mass, (B) initial paraben concentration, and (C) agitation rate on the adsorption process was studied for the FA-AT7 adsorbent using a factorial experimental design. Standardized Pareto charts revealed a negative effect of factor A, positive effect of factor B, and negative interaction effects of factors A-B for all studied parabens. Isotherms and multicomponent kinetic studies were performed. A linear type-III isotherm was obtained, and adsorption equilibrium was reached at approximately 10 min.

Evaluating the presence of pesticides in bananas: An integrative review.

INTRODUCTION: Pesticides are organic compounds widely used in modern agriculture, being relevant for helping plantations and increasing food production. The banana, a fruit with oriental origin, stands out for being widely produced in tropical and subtropical regions which, like other matrices, is susceptible to pest action. This review aims to evaluate the presence of pesticides in bananas according to Brazilian, European and Codex legislation. METHODS: Four databases, ScienceDirect, SciELO, PubMed and Springer, were used to find relevant articles in the literature addressing methods for the determination of pesticide residues in bananas using the terms "banana", "chromatography", "pesticides" and "determination". The search stages included reading abstracts and titles, reading the full text, extracting data and analyzing data from eligible articles. The search was restricted to original research articles published in English from 2008 to 2018. RESULTS: 404 articles were found from the initial research, with only 15 studies being considered eligible for this review. Mass spectrometry is the most widely used detection technique. 5 articles were seen to use a multiresidue method to analyze only bananas (pulp), and from these, only 2 studies used methods to analyze the pulp and peel. The articles analyzed 172 samples, with 59.3% of these being conducted in Europe, 32.5% being conducted in Asia and only 8.1% in South America. A total of 79.1%, 32.4% and 42.6% of samples were unsatisfactory according to the Brazilian, European and Codex legislation, respectively, with these samples being contaminated with pesticide residues. CONCLUSION: This review presents the scarcity of articles aimed at identifying pesticide residues in bananas and the urgency of checking the quality of the fruit that reaches the population. The MRLs allowed by different legislations have clear divergences that do not ensure the lowest concentration values that guarantee consumer safety.

Influence of sediment parameters on the distribution and fate of PAHs in an estuarine tropical region located in the Brazilian semi-arid (Jaguaribe River, Ceará coast).

18 polycyclic aromatic hydrocarbons (PAHs) were evaluated in the Jaguaribe River to explore the influence of grain size, organic carbon, humic and fulvic acids and black carbon on their adsorption onto sediment. The ∑PAHs concentrations variated from 0.6 to 3752.0 ng g-1 with highest concentrations in the estuarine zone. The PAHs predominant source along the river was from mixed sources, mainly related to biomass combustion, small oil spills related to recreational nautical activities and runoff from cities. Organic and inorganic parameters presented influence on PAHs distribution along the river, with humic acid as a determinant factor. These research findings are of importance to an assessment of the fate and transport of PAHs in estuarine systems.

Diagnostic detection systems and QuEChERS methods for multiclass pesticide analyses in different types of fruits: An overview from the last decade.

This manuscript is a bibliographic review about analyses of different classes of pesticide in fruits using QuEChERS as sample preparation methodology. The aim is to clarify different trends and facilitate decision-making by the scientific community in order to carry out further studies in this field. It is well known that different countries have different pesticides regulations for maximum level of pesticide residue permitted. The comparative analysis amongst the main producer countries reveals that for some fruits they are not studied enough. Recent improvements to QuEChERS make it possible to minimize the pesticides instability due the matrix pH, and achieving cleaner extracts. Regarding the detection systems, the tandem MS are preferred once they have high sensitivity and selectivity, although traditional techniques (GC-ECD and HPLC-DAD) are still commonly used due to their accessibility and good sensitivity to some pesticides. Also, studies involving metabolites usually show that they are more toxic than their precursor compounds.

Efficiency of ESI and APCI ionization sources in LC-MS/MS systems for analysis of 22 pesticide residues in food matrix.

The intensive use of pesticides has led to the need to optimize analytical methodologies for the control of residues in food. The present study aims to compare the efficiency of different ion sources (Eletrospray Ionization-ESI and Atmospheric Pressure Chemical Ionization - APCI) in LC-MS/MS systems, when analysing 22 pesticides in a cabbage matrix. The method performance was evaluated during a validation study. Organophosphates, triazoles, pyrethroids and triazines compounds showed good linearity in the range 0.5-200 µg.Kg-1. Statistical tests were used to evaluate linearity. LOQm values varied from 0.50 to 1.0 µg.Kg-1 to the ESI source, and 1.0-2.0 µg.Kg-1 for the APCI source. Matrix effect was more intense when using the APCI source. Accuracy and precision were evaluated at three levels of concentration (2; 20 and 100 µg Kg-1). Most of the compounds presented recovery between 70 and 120%. ESI-LC-MS/MS system showed greater efficiency in multiresidue analysis in the cabbage matrix.

Influence of anthropogenic activities and risk assessment on protected mangrove forest using traditional and emerging molecular markers (Ceará coast, northeastern Brazil).

Anthropogenic molecular markers were used to assess chemicals inputs and ecological risks associated from multiple sources to sediments in one of the largest tropical mangrove forests of South America, with a particular focus on lesser studied compounds resulting from rural activities. Total concentrations ranged from 23.4 to 228.2 ng g-1 for polycyclic aromatic hydrocarbons (∑PAHs), 750.4 to 5912.5 ng g-1 for aliphatic hydrocarbons (∑AHs), 32.4 to 696.6 ng g-1 for pesticides (∑pesticides), 23.1 to 2109.7 ng g-1 for coprostanol and sterols (∑sterols), 139.3 to 580.2 ng g-1 for naturals hormones (∑natural hormones) and 334.1 to 823.4 ng g-1 for synthetics hormones (∑synthetic hormones). The PAHs and AHs used as traditional anthropogenic markers showed a mixture between natural and anthropogenic sources, related mainly to inputs from higher plants, phytoplankton and both, biomass and petroleum combustion. Rural activities linked to agricultural pest control are the predominant source of pesticides, although minor inputs from pesticides used in urban public health campaigns and household activities were also detected. Synthetic hormones levels are two to three orders of magnitude greater than natural hormones levels and no correlations were observed between the main sewage markers and synthetic hormone concentrations, rural activities such as animal husbandry, which use drugs in management, may be the predominant anthropogenic sources of these compounds in the region. Traditional markers failed to detect ecological risks in rural areas, where synthetic substances (e.g. pesticides and hormones) are widely used and introduced in the environment.

Emerging and traditional organic markers: Baseline study showing the influence of untraditional anthropogenic activities on coastal zones with multiple activities (Ceará coast, Northeast Brazil).

Molecular markers are useful tools to characterize natural and anthropogenic impacts on coastal zones. Distribution of n-alkanes showed that the Pacoti River was predominantly influenced by terrigenous input. Distribution of polycyclic aromatic hydrocarbon (PAH) indices showed a mix of natural sources, especially pyrogenic influences. Sterol and hormone levels showed sewage discharge. Integrated geographic assessment showed that pyrogenic process and sewage discharge are predominant along the river because of natural and different anthropogenic activities. The upstream region is influenced by rural activities such as livestock and discharge from the sewage treatment plant, whereas the estuarine region is influenced by urban and industrial activities, predominantly the discharge of treated or untreated sewage, vehicle traffic, and manufacture of red ceramics. On the other hand, on the river mouth, there is the predominance of aquaculture activities. Traditional anthropogenic markers are not sufficient for producing a comprehensive assessment of anthropogenic impacts in areas with multiple activities.

Emerging and Traditional Organic Markers in Areas with Multiple Anthropogenic Activities: Development of an Analytical Protocol and Its Application in Environmental Assessment Studies.

This work describes the development of an analytical protocol combining cleanup by liquid-solid extraction and GC-MS for the determination of emerging and traditional multi-molecular markers. The procedure was used for the environmental assessment of a coastal region with multiple human activities. Global recovery rates ranged from 45.49% to 119.4% for the 46 substances analyzed: pesticides (73.7%-97.7%), PAHs (52.5%-93.7%), sterols (66.7%-119.4%) and natural and synthetic hormones (45.5%-119.1%) and the rates were compared to those reported in studies on both individual classes and multi-classes of contaminants. The analytical protocol demonstrated satisfactory efficiency and could be used successfully in environmental assessments and source assignment studies. The environmental assessment study revealed that the Acaraú River in northeastern Brazil is influenced by the combination of urban and rural activities. The sources of PAHs are vehicular traffic and the burning of biomass; pesticides stem from pest control in agribusiness and public health campaigns; sterols and hormones stem from a combination of natural inputs, human sewage (treated and raw) and animal husbandry activities.

Effect of ozonization in degradation of trifluralin residues in aqueous and food matrices.

This study investigates the oxidation of trifluralin residues during ozonation in aqueous and food matrices (tomato). Domestic ozonation equipment with average production of 23.9 mg O3 L-1 h-1 was used in the tests. Modern chromatographic systems (SPME-GC-IT/MS/MS and QuEChERS-GC-IT/MS/MS) were applied for extraction and detection of trifluralin residue in fortified samples of ultrapure water, tap water, superficial water and tomato fruit. The samples were submitted to the ozonation process during 0, 5, 10 and 20 min. Treatment at 5 min was able to degrade 71.5% of herbicide trifluralin in surface water. The removal (%) in ultrapure water reached 83.4% after 20 min of ozonation. The degradation of trifluralin in fortified tomato samples (0.025-0.1 mg kg-1) were conducted with ozonation at 20 min, and it ranged from 84.4 to 92.7%. After treatment, levels of trifluralin in tomato remained within the established MRLs to EU, USEPA and ANVISA (Brazil). The data provided evidence that ozone is effective for removing trace trifluralin from water and foods.