Evidence of plastics contamination and sewage-derived residues in a Brazilian Hope Spot for conservation of marine biodiversity - Cagarras Islands and surrounding waters.

Cagarras Islands Archipelago, a no-take MPA in Southeast Brazil, was designated as Natural Monument (MONA Cagarras) and, more recently, recognized as Hope Spot for biodiversity conservation. This study aimed to assess plastic contamination by analyzing marine litter and microplastics in MONA Cagarras and surrounding waters. Marine litter (34.12 kg) was caught by artisanal fishermen in MONA Cagarras proximities, and plastics represented ∼79 %. Personal hygiene items and strains of hair were found, suggesting sewage-derived contamination from Ipanema SSO. Microplastics were detected in MONA Cagarras surface waters. Fragments and black particle were the most frequently found microplastic shape and color, respectively. µ-FTIR analysis identified, in descending order of occurrence, polystyrene-PS, polyethylene-PE, polyvinyl chloride-PVC, polypropylene-P, and polyamide-PA. Our integrated results of macro and microplastic contamination highlight an issue of effective conservation and health of marine biodiversity in MONA Cagarras and surrounding waters and a concern for better management of Brazilian MPAs.

How to Measure Polymer Degradation? An Analysis of Authors' Choices When Calculating the Carbonyl Index.

The carbonyl index aims to measure the degradation level and is used in plastic degradation research as a proxy for the general degradation level of collected plastic pieces. According to the choices for carbonyl index calculation, comparison using this index is prevented and must be unveiled by the authors, which does not always happen. In order to study the proper usage of the carbonyl index, regarding the choice of the reference band and the usage of the band intensity or the absorption area, we systematically reviewed the methodologies used for polypropylene as a case study. Based on 95 studies gathered from 2000 to 2024, two main methods were used to determine the carbonyl index: the ratio between the carbonyl band area and the reference band area (33.68%) and the ratio between the highest intensity of the carbonyl band and the reference band (66.31%). The reference band of choice and the type of calculation method produce different carbonyl index values for the same spectra and mean different information, preventing comparison among works with different calculations.

Effect of the age of garments used under real-life conditions on microfibre release from polyester and cotton clothing.

The release of microfibres from fabrics during laundering represents an important source of plastic and natural microfibres to aquatic environments. Garment age - how long the garment has been used - could be a key factor influencing the rate of release, yet most studies of microfibre shedding have only assessed newly manufactured products. To this end, we quantified microfibre release during laundering in domestic washing machines from polyester (PES) and cotton garments (n = 38) used in real-life conditions for periods between 1 and 31 years with different use intensities. In addition, to better understand the factors involved in microfibre releases, fibre composition (different PES percentages) and type of garments (T-shirts, polo shirts, uniforms, sports shirts, and sweatshirts) were examined. All garments released microfibres during washing, while the older garments presented higher releases for clothing with a PES/cotton blend. In general, older garments (15-31 years) released nearly twice as many fibres when washed than newer garments (1-10 years). The mass of microfibres released was consistently greater in garments with a higher proportion of cotton than PES (up to 1.774 mg g-1 in 2% PES and 0.366 mg g-1 in 100% PES fabrics), suggesting that cotton might be released more readily such that the relative proportion of PES in the garments could increase over time. Additionally, SEM images showed fibre damage, with fibres from the older garments exhibiting more peeling and splitting. While it is important to note that the overall environmental footprint is undoubtedly reduced by keeping garments in use for longer periods of time, older garments were shown to release more microfibres.

Revealing microplastic dynamics: the impact of precipitation and depth in urban river ecosystems.

Research on microplastics in Latin America is limited compared to a global perspective. Brazil plays a significant role in this context, as it possesses 12% of the world's freshwater reserves, constituting 53% of South America's water resources. There has been growing concern regarding the plastic pollution of the country's freshwater systems in recent years. Therefore, this study investigated the impact of plastic pollution on the Guaíba River, a significant watercourse in the southern region of Brazil that is subjected to high anthropogenic pressure. Additionally, we examined correlations between the presence of microplastics and key factors influencing their distribution in the river. Thus, freshwater was collected in seven sampling campaigns from 2019 to 2020, totaling 66 samples. The microplastics were quantified and characterized according to their color, shape, and polymeric composition. The concentration of microplastics varied between 2.9 and 53.8 items m-3, and the distribution and transport were positively influenced by the population density, precipitations, and depth of each sampling point. White-transparent color category (51%) and fragment shape (89%) were predominant among the found particles. Polyethylene (PE) and polypropylene (PP) represented 37% and 57% of the analyzed particles. The non-metric multidimensional scaling (nMDS) analysis indicated that similar contamination sources, such as domestic sewage, could influence three out of ten sampled points. Several microplastics presented the formation of cracks, with sizes smaller than 10 µm on their surface, which might indicate an erosion process, resulting in the formation of nanoplastics. The color fading observed in microplastics suggests that the particles were subjected to environmental stressors, leading to the leaching or degradation of the dye on the plastic. The results confirmed the ubiquity of microplastics in Guaíba River, highlighting the importance of improving the regulations on plastic waste disposal in the country to prevent the contamination of freshwater bodies.

How natural and anthropogenic factors should drive microplastic behavior and fate: The scenario of Brazilian urban freshwater.

Brazil maintains its position at the top of the global ranking of plastic producers, yet recycling efforts have been incipient. Recent data reveals an annual production of approximately 14 million tons of plastic waste, not accounting for the surge in the usage of plastic masks and related materials due to the COVID-19 pandemic. However, what remains largely unreported is that over half of post-consumer plastic packaging in Brazil is managed without any monitoring, and it remains unclear how this will contribute to the occurrence of plastic waste and microplastics in Brazilian freshwaters. This scenario requires the consideration of several other crucial factors. Studies have been carried out mainly in marine and estuarine waters, while data on freshwaters are lacking. Brazil has continental dimensions and the highest water availability on the planet, yet the demand for water is greatest in regions with medium to low supply. Many densely populated Brazilian urban areas face chronic flood problems, possess inadequate levels of wastewater treatment, and display inadequate solid waste management practices. Consequently, urban freshwater with tropical characteristics in Brazil presents an intriguing scenario and is complementary to the most commonly studied marine environments. In this study, we explore the nuances of pollution in Brazilian urban freshwater and discuss how various parameters, such as organic matter, suspended solids, temperature, and pH, among others, influence the behavior of microplastics and their interactions with organic and inorganic contaminants. Furthermore, we address how microplastic conditions, such as biofouling, the type of plastic, or degradation level, may impact their behavior. By analyzing how these conditions change, we propose priority themes for investigating the occurrence of microplastics in Brazilian urban freshwater systems under different degrees of human impact. Ultimately, this study aims to establish a network dedicated to standardized monitoring of microplastic pollution in Brazilian urban freshwaters.

First evidence of microplastic contamination in the freshwater of Lake Guaíba, Porto Alegre, Brazil.

The ubiquitous presence of microplastics in the aquatic environment has raised concern about their potential impacts on and risks to the biota. While the presence of microplastics in a marine environment has been well studied, the impact of microplastic contamination in freshwater bodies is understudied. In the present study, baseline data about contamination with microplastics in Lake Guaíba in southern Brazil are presented. The abundance, distribution, and composition of microplastics in the surface of this freshwater body were investigated, and these parameters were correlated with population density, land occupation, wind, and geohydrologic processes. The samples were collected with a manta net (60 µm mesh size). Microplastics were found in all the samples, with an average of 11.9 ± 0.6 to 61.2 ± 6.1 items m-3, which indicates the widespread contamination of the lake with plastic particles. The most frequent microplastic morphology was the fragment type in the size range of 100 to 250 µm, and the predominant colours were white/transparent and red. Measurement uncertainty of the visual microplastic counts showed that black colour microplastics is more susceptible to be mistaken, which might lead to an underestimation and/or overestimation of the total number of microplastics. Polypropylene and polyethylene together comprised most of the polymer types (98%). Micro-Fourier transform infrared (micro-FTIR) spectroscopy analyses showed that 58% of the analysed polymers were highly oxidised, indicating long residence of this particles in the water. In addition, our data show that the distribution of microplastics is strongly influenced by the geohydrological characteristics of the lake. Therefore, this research may provide information for further investigations of microplastic distribution in Lake Guaíba and can serve as a base to improve the regulations regarding waste management to effectively reduce microplastic pollution in freshwater systems. Additionally, the measurement uncertainty showed that black microplastics are more susceptible to variations in their measurements.

Photodegradation of Emerging Contaminant 2-(tiocyanomethylthio) Benzothiazole (TCMTB) in Aqueous Solution: Kinetics and Transformation Products.

Direct photolysis of the emerging contaminant 2-(thiocyanomethylthio) benzothiazole (TMCTB) was performed in aqueous solution at different concentrations with high-pressure mercury lamp (5.0, 8.0, 13.0, 16.0, 20.0, 23.0, 27.0, 35.0, 40.0, 45.0, and 50.0 mg L- 1) and with natural sunlight radiation (6.0, 30.0, and 60.0 mg L- 1). TCMTB underwent rapid degradation by direct photolysis with a high-pressure mercury lamp in aqueous solutions, with 99% removal after 30 min at all concentrations studied. For sunlight photolysis, TCMTB degradation was observed with 96%, 81%, and 64% removal for initial concentrations of 6.0, 30.0, and 60.0 mg L- 1, respectively, after 7 h of exposure to sunlight. The degradation of TCMTB in lab-scale wastewater had kinetic constant and t1/2 in the same order when compared to the photodegradation of TCMTB in aqueous solutions. In addition, the results showed that photolysis with a high-pressure mercury lamp and sunlight were governed by the same kinetic order, however the kinetic parameters showed that degradation with sunlight was 40 times slower than photolysis with the mercury lamp. Twelve transformation products (TP) were identified, and eight of the TP have not been described in the literature. Furthermore, prediction of toxicity with ECOSAR software was carried out for fish, daphnids, and green algae species. It showed that photolytic treatment is efficient for reducing the toxicity of the compound, since the degradation formed compounds with lower toxicity than the primary compound. In conclusion, this study suggests that photolysis is an efficient way to remove the studied contaminant, and it highlights the potential of this technique for the degradation of emerging contaminants in industrial wastewater treatment plants.

A preliminary nationwide survey of the presence of emerging contaminants in drinking and source waters in Brazil.

This is the first nationwide survey of emerging contaminants in Brazilian waters. One hundred drinking water samples were investigated in 22 Brazilian state capitals. In addition, seven source water samples from two of the most populous regions of the country were evaluated. Samples were collected from June to September of 2011 and again during the same period in 2012. The study covered emerging contaminants of different classes, including hormones, plasticizers, herbicides, triclosan and caffeine. The analytical method for the determination of the compounds was based on solid-phase extraction followed by analysis via liquid chromatography electrospray triple-quadrupole mass spectrometry (LC-MS/MS). Caffeine, triclosan, atrazine, phenolphthalein and bisphenol A were found in at least one of the samples collected in the two sampling campaigns. Caffeine and atrazine were the most frequently detected substances in both drinking and source water. Caffeine concentrations in drinking water ranged from 1.8ngL-1 to values above 2.0µgL-1 while source-water concentrations varied from 40ngL-1 to about 19µgL-1. For atrazine, concentrations were found in the range from 2.0 to 6.0ngL-1 in drinking water and at concentrations of up to 15ngL-1 in source water. The widespread presence of caffeine in samples of treated water is an indication of the presence of domestic sewage in the source water, considering that caffeine is a compound of anthropogenic origin.

Development of a new adsorbent from agro-industrial waste and its potential use in endocrine disruptor compound removal.

A new activated carbon (AC) material was prepared by pyrolysis of a mixture of coffee grounds, eucalyptus sawdust, calcium hydroxide and soybean oil at 800°C. This material was used as adsorbent for the removal of the endocrine disruptor compounds 17ß-estradiol (E2) and 17α-ethinylestradiol (EE2) from aqueous solutions. The carbon material was characterized by scanning electron microscopy (SEM), infrared spectroscopy (FTIR), N2 adsorption/desorption curves and point of zero charge (pHPZC). Variables including the initial pH of the adsorbate solutions, adsorbent masses and contact time were optimized. The optimum range of initial pH for removal of endocrine disruptor compounds (EDC) was 2.0-11.0. The kinetics of adsorption were investigated using general order, pseudo first-order and pseudo-second order kinetic models. The Sips isotherm model gave the best fits of the equilibrium data (298K). The maximum amounts of E2 and EE2 removed at 298K were 7.584 (E2) and 7.883mgg(-1) (EE2) using the AC as adsorbent. The carbon adsorbent was employed in SPE (solid phase extraction) of E2 and EE2 from aqueous solutions.

Influence of amide linkages on acidity determinations of humic substances Testing with model-mixtures.

A set of experiments, using model compounds, was carried out in order to evaluate the influence of amide linkages on acidity measurements of humic substances (HS). Three benzene-carboxylic acids (2,4-dihydroxybenzoic acid; 3,5-dihydroxybenzoic acid, and phthalic acid) and two peptides (dl-alanyl-dl-alanine, and glycil-l-leucine) were employed to simulate the major acidic functional groups present in humic material. The acidity of the samples was measured, using the Schnitzer and Gupta methods, for each compound separately, as well as for selected mixtures with different compound combinations. General results showed that, in the absence of peptides, phenolic groups with high pK(a) values are not detected in the barium hydroxide reaction and the data so obtained do not represent the real concentrations of the acidic groups. For the mixtures containing peptides, the presence of amide linkages distorts the results relative to the total acidity (TA) mainly because under the extreme conditions of the reaction with Ba(OH)(2) hydrolysis of the peptide occurs, consuming extra hydroxyl groups and increasing artificially the phenolic content. Such a condition is minimized by the reduction of the reaction time.