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.

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.

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.

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.

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.

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.

Occurrence and removal of estrogens in Brazilian wastewater treatment plants.

This paper evaluated the occurrence and removal efficiency of four estrogenic hormones in five biological wastewater treatment plants (WWTPs), located in the State of Ceará, Brazil. The five WWTPs comprised: two systems consisted of one facultative pond followed by two maturation ponds, one facultative pond, one activated sludge (AS) system followed by a chlorination step, and one upflow anaerobic sludge blanket (UASB) reactor followed by a chlorination step. Estrogen occurrence showed a wide variation among the analyzed influent and effluent samples. Estrone (E1) showed the highest occurrence in the influent (76%), whereas both 17ß-estradiol (E2) and 17α-ethynylestradiol (EE2) presented a 52% occurrence, and the compound 17ß-estradiol 17-acetate (E2-17A), a 32% one. The occurrence in the effluent samples was 48% for E1, 28% for E2, 12% for E2-17A, and 40% for EE2. The highest concentrations of E1 and EE2 hormones in the influent were 3050 and 3180 ng L(-1), respectively, whereas E2 and E2-17A had maximum concentrations of 776 and 2300 ng L(-1), respectively. The lowest efficiencies for the removal of estrogenic hormones were found in WWTP consisted of waste stabilization ponds, ranging from 54 to 79.9%. The high-rate systems (AS and UASB), which have chlorination as post-treatment, presented removal efficiencies of approximately 95%.

Adsorption of BTX (benzene, toluene, o-xylene, and p-xylene) from aqueous solutions by modified periodic mesoporous organosilica.

The capacity of a periodic mesoporous organosilica (PMO) to adsorb the aromatic compounds benzene, toluene, o-, and p-xylenes (BTX), which are usually present in produced waters, was investigated under both column and batch processes. The PMO was synthesized by condensation of 1,4 bis(triethoxisilyl)benzene (BTEB) under acidic conditions by using structure-directing agent (SDA) Pluronic P123 in the presence of KCl. Thermogravimetric analysis showed that the presence of the surfactant decreases the thermal stability of the PMO. The small-angle X-ray diffraction pattern, as well as the nitrogen adsorption/desorption isotherm measurements, revealed that the synthesized material has a crystalline structure, with hexagonally-ordered cylindrical mesopores. The adsorption kinetics study indicated an adsorption equilibrium time of 50 min and also showed that the data best fitted the pseudo-first order kinetic model. The intraparticle diffusion model was also tested and pointed to the occurrence of such process in all cases. Both Langmuir and Temkin models best represented the adsorption isotherms of toluene; Langmuir and Redlich-Peterson models best represented the data obtained for the other compounds. Adsorption capacity decreases in the order benzene>o-xylene>p-xylene>toluene. Satisfactory results were observed in the application of the synthesized PMO for the removal of BTX from aqueous solution.

Evaluation of polycyclic aromatic hydrocarbons in asphalt binder using matrix solid-phase dispersion and gas chromatography.

A method developed for the extraction and analysis of polycyclic aromatic hydrocarbons (PAHs) in the asphalt binder using a matrix solid-phase dispersion (MSPD) and gas chromatography is presented. The MSPD method was proposed as a rapid and easy approach to determining PAHs present in the maltenic phase of asphalt binder extracted through a mechanical shaking and sonication of the material. The recovery rates ranged from 62.77-89.92% (shaking) and from 56.54-93.6% (sonication) with relative standard deviations lower than 8.8%. The study shows that the recovery rates using shaking and sonication extractions are not significantly different at the p < 0.05 level. The limits of detection and quantification ranged from 0.7-1.8 mg/kg and 2.2-5.6 mg/kg, respectively. The proposed analytical method was applied to determine PAH levels in an asphalt binder from Brazil. The main PAHs found were BbF, BaP, Per, IncdP, DahA, and BghiP, with average concentrations of 10.2-20.7 mg/kg, but the PAHs Ace and Acy were not detected. However, Nap, Fl, Phen, Ant, Flr, Pyr, Chry, BaA, and BkF were present in average concentrations amounting to less than 10 mg/kg. The results showed that the MSPD method is potentially a valuable tool for the determination of PAHs in the asphalt binder.

Risk assessment of trihalomethanes from tap water in Fortaleza, Brazil.

The cancer risks (CR) by oral ingestion, dermal absorption, and inhalation exposure of trihalomethanes (THM) from tap water of ten districts in Fortaleza, Brazil were estimated. The mean levels of THM compounds were obtained in Fortaleza tap water as follow: 63.9 microg L(-1) for chloroform (CHCl(3)), 40.0 microg L(-1) for bromodichloromethane (CHBrCl(2)), and 15.6 microg L(-1) for dibromochloromethane (CHBr(2)Cl). Bromoform (CHBr(3)) was not detected. The mean CR for THMs in tap water is 3.96 x 10(-4). The results indicate that Fortaleza residents have a higher CR by inhalation than dermal absorption and oral ingestion. The CR for CHCl(3) contributes with 68% as compared with the total CR, followed by CHBrCl(2) (21%), and CHBr(2)Cl (11%). The hazard index (HI) is about ten times lower than unity, not indicating non-cancer effects.