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.

Preliminary assessment of toxicity of aerosol samples from central-west Brazil using Artemia spp. bioassays.

The present study reports the development of a bioassay using Artemia spp. to analyse the preliminary ecotoxicity of atmospheric aerosols (PM), which can affect the environment and human health. Herein, PM samples were collected in the city of Goiânia (Brazil) in 2016, extracted with ultrapure water and subsequently filtered through membranes with different pore sizes (100, 0.8, and 0.22 µm), and the extracts employed in the bioassays. The mortality rates (endpoint analysed) declined to membranes with smaller pore sizes (15 ± 4%, 47 ± 10% and 43 ± 9% for pore sizes of 100 µm, 0.8 µm and 0.22 µm, respectively). In general, the toxicity of the extract depended on its concentration, except for the sample with a higher negative particle surface charge, which presents a lower affinity for the negatively charged surfaces of cellular membranes. Moreover, although the PM concentration was higher for the sample collected during the dry season (September), the mortality rate was not significantly different to that determined for a sample with similar physical and chemical characteristics collected in the rainy season (December). This result demonstrates the importance of monitoring PM toxicities and their chemical and physical characteristics, in addition to their concentrations. Therefore, the new protocol to provide a preliminary analysis of the toxicity of the extracts of aerosol emerges as a useful, accessible, and fast tool for monitoring possible environmental hazards, and can simplify fieldwork.

Microbial diversity and metabolic inference of diclofenac removal in optimised batch heterotrophic-denitrifying conditions by means of factorial design.

Using the Response Surface Methodology (RSM) and Rotational Central Composite Design (RCCD), this study evaluated the removal of DCF under denitrifying conditions, with ethanol as cosubstrate, in batch reactors, being 1 L Erlenmeyer flasks (330 mL of reactional volume) containing Dofing medium and kept under agitation at 130 rpm and incubated at mesophilic temperature (30 °C). It considered the individual and multiple effects of the variables: nitrate (130 - 230 mg NO3- L-1), DCF (60-100 µg DCF L-1) and ethanol (130 - 230 mg EtOH L-1). The highest drug removal efficiency (17.5%) and total nitrate removal were obtained at 176.6 ± 4.3 mg NO3 -L-1, 76.8 ± 3.7 µg DCF L-1, and 180.0 ± 2.5 mg EtOH L-1. Under such conditions, the addition of ethanol and nitrate was significant for the additional removal of diclofenac (p > 0.05). The prevalence of Rhodanobacter, Haliangium and Terrimonas in the inoculum biomass (activated sludge systems) was identified through the 16S rRNA gene sequencing. The potential of these genera to remove nitrate and degrade diclofenac was inferred, and the main enzymes potentially involved in this process were α-methylacyl-CoA racemase, long-chain fatty acid-CoA ligase, catalases and pseudoperoxidases.

Influence of cosubstrate and hydraulic retention time on the removal of drugs and hygiene products in sanitary sewage in an anaerobic Expanded Granular Sludge Bed reactor.

Diclofenac (DCF), ibuprofen (IBU), propranolol (PRO), triclosan (TCS) and linear alkylbenzene sulfonate (LAS) can be recalcitrant in Wastewater Treatment Plants (WWTP). The removal of these compounds was investigated in scale-up (69 L) Expanded Granular Sludge Bed (EGSB) reactor, fed with sanitary sewage from the São Carlos-SP (Brazil) WWTP and 200 mg L-1 of ethanol. The EGSB was operated in three phases: (I) hydraulic retention time (HRT) of 36±4 h; (II) HRT of 20±2 h and (III) HRT of 20±2 h with ethanol. Phases I and II showed no significant difference in the removal of LAS (63 ± 11-65 ± 12 %), DCF (37 ± 18-35 ± 11 %), IBU (43 ± 18-44 ± 16 %) and PRO (46 ± 25-51 ± 23 %) for 13±2-15 ± 2 mg L-1, 106 ± 32-462 ± 294 µg L-1, 166 ± 55-462 ± 213 µg L-1 and 201 ± 113-250 ± 141 µg L-1 influent, respectively. Higher TCS removal was obtained in phase I (72 ± 17 % for 127 ± 120 µg L-1 influent) when compared to phase II (51 ± 13 % for 135 ± 119 µg L-1 influent). This was due to its greater adsorption (40 %) in the initial phase. Phase III had higher removal of DCF (42 ± 10 % for 107 ± 26 µg L-1 influent), IBU (50 ± 15 % for 164 ± 47 µg L-1 influent) and TCS (85 ± 15 % for 185 ± 148 µg L-1 influent) and lower removal of LAS (35 ± 14 % for 12 ± 3 mg L-1 influent) and PRO (-142 ± 177 % for 188 ± 88 µg L-1 influent). Bacteria similar to Syntrophobacter, Smithella, Macellibacteroides, Syntrophus, Blvii28_wastewater-sludge_group and Bacteroides were identified in phase I with relative abundance of 3.1 %-4.7 %. Syntrophobacter was more abundant (15.4 %) in phase II, while in phase III, it was Smithella (12.7 %) and Caldisericum (15.1 %). Regarding the Archaea Domain, Methanosaeta was more abundant in phases I (84 %) and II (67 %), while in phase III it was Methanobacterium (86 %).

Influence of metabolic cosubstrates on methanogenic potential and degradation of triclosan and propranolol in sanitary sewage.

Triclosan (TCS) and propranolol (PRO) are emerging micropollutants that are difficult to remove in wastewater treatment plants. In this study, methanogenic potential (P) of anaerobic sludge submitted to TCS (3.6 ± 0.1 to 15.5 ± 0.1 mg L-1) and PRO (6.1 ± 0.1 to 55.9 ± 1.2 mg L-1) in sanitary sewage, was investigated in batch reactors. The use of cosubstrates (200 mg L-1 of organic matter) ethanol, methanol:ethanol and fumarate was evaluated for micropollutant degradation. Without cosubstrates, P values for 5.0 ± 0.1 mgTCS L-1, 15.5 ± 0.1 mgTCS L-1 and 55.0 ± 1.3 mgPRO L-1 were 50.53%, 98.24% and 17.66% lower in relation to Control assay (855 ± 5 µmolCH4) with sanitary sewage, without micropollutants and cosubstrates, respectively. The use of fumarate, ethanol and methanol:ethanol favored greater methane production, with P values of 2144 ± 45 µmolCH4, 2960 ± 185 µmolCH4 and 2239 ± 171 µmolCH4 for 5.1 ± 0.1 mgTCS L-1, respectively; and of 10,827 ± 185 µmolCH4, 10,946 ± 108 µmolCH4 and 10,809 ± 210 µmolCH4 for 55.0 ± 1.3 mgPRO L-1, respectively. Greater degradation of TCS (77.1 ± 0.1% for 5.1 ± 0.1 mg L-1) and PRO (24.1 ± 0.1% for 55.9 ± 1.2 mg L-1) was obtained with ethanol. However, with 28.5 ± 0.5 mg PRO L-1, greater degradation (88.4 ± 0.9%) was obtained without cosubstrates. With TCS, via sequencing of rRNA 16S gene, for Bacteria Domain, greater abundance of phylum Chloroflexi and of the genera Longilinea, Arcobacter, Mesotoga and Sulfuricurvum were identified. With PRO, the genus VadinBC27 was the most abundant. Methanosaeta was dominant in TCS with ethanol, while in PRO without cosubstrates, Methanobacterium and Methanosaeta were the most abundant. The use of metabolic cosubstrates is a favorable strategy to obtain greater methanogenic potential and degradation of TCS and PRO.

Methanogenic potential of diclofenac and ibuprofen in sanitary sewage using metabolic cosubstrates.

Diclofenac (DCF) and ibuprofen (IBU) are widely used anti-inflammatory drugs and are frequently detected in wastewater from Wastewater Treatment Plants and in aquatic environments. In this study, the methanogenic potential (P) of anaerobic sludge subjected to DCF (7.11 ± 0.02 to 44.41 ± 0.05 mg L-1) and IBU (6.11 ± 0.01 to 42.61 ± 0.05 mg L-1), in sanitary sewage, was investigated in batch reactors. Cosubstrates (200 mg L-1 of organic matter) in the form of ethanol, methanol:ethanol and fumarate were tested separately for the removal of drugs. In the DCF assays, P was 6943 ± 121 µmolCH4, 9379 ± 259 µmolCH4, 9897 ± 212 µmolCH4 and 11,530 ± 368 µmolCH4 for control, fumarate, methanol:ethanol and ethanol conditions, respectively. In the IBU assays, under the same conditions, P was 6145 ± 101 µmolCH4, 6947 ± 66 µmolCH4, 8141 ± 191 µmolCH4and 10,583 ± 512 µmolCH4, respectively. Without cosubstrates, drug removal was below 18% for 43.10 ± 0.01 mgDCF L-1 and 43.12 ± 0.03 mgIBU L-1, respectively. Higher P and removal of DCF (28.24 ± 1.10%) and IBU (18.72 ± 1.60%) with ethanol was observed for 43.20 ± 0.01 mgDCF L-1 and 43.42 ± 0.03 mgIBU L-1, respectively. This aspect was better evidenced with DCF due to its molecular structure, a condition that resulted in a higher diversity of bacterial populations. Through the 16S rRNA sequencing, bacteria genera capable of performing aromatic ring cleavage, ß-oxidation and oxidation of ethanol and fatty acids were identified. Higher relative abundance (>0.6%) was observed for Smithella, Sulfuricurvum and Synthophus for the Bacteria Domain and Methanosaeta (>79%) for the Archaea Domain. The use of ethanol favored greater mineralization of organic matter and greater methane production, which can directly assist in the metabolic pathways of microorganisms.

Remediation of Eutrophic Aquatic Ecosystems: Evaluation of Phosphorus Adsorption by Sawdust.

A wide range of anthropogenic activities have caused various problems to the aquatic environment, leading to economic, social, and environmental losses. The use of materials for the recovery of water quality is very important due to the water scarcity scenario present in different parts of the world. The use of sawdust as an organic adsorbent for P removal in eutrophic environments attempts to address both water quality preservation and possible application of the organic adsorbent as fertilizer for agricultural practices. This use will result in important contributions to the water and food security. In this work, we performed laboratory experiments to study P adsorption and to evaluate possible adsorption of metals and emerging contaminants by sawdust. The experiments were carried out in 36 microcosms (glass jars), using 50% of the flasks as treatments (containing bags with sawdust) and the rest of the flasks as control (water and sediment without sawdust). For future application of sawdust as a fertilizer it is important to be aware of the presence of possible pathogenic microorganisms, thus the presence of helminth eggs was determined in the sawdust. The results showed the tendency of P adsorption by the biosorbent; maximum adsorption occurred at 214 d (41 µg P g-1 ), after the P desorption occurred. No helminth eggs or emerging contaminants and toxic metal were detected in the sawdust after its use as biosorbent, providing an important subsidy regarding the use of the biosorbent as soil fertilizer. Integr Environ Assess Manag 2019;00:1-12. © 2019 SETAC.

Biosorbent, a promising material for remediation of eutrophic environments: studies in microcosm.

Eutrophication is considered a global environmental problem that causes economic and biodiversity loss. Together with excess phosphorus in some aquatic environments, there is the depletion of phosphate rock deposits, which can directly affect fertilizer production and therefore global food security. Thus, the present work aimed to study a new remediation technique for eutrophic environments that enables the recovery of these environments through phosphorus adsorption in sawdust, creating the possibility to apply the phosphorus-enriched material as an agricultural fertilizer. The study was conducted in 36 microcosm flasks with water and sediment samples from a eutrophic reservoir in Ibirité/MG. The experiment was carried out using 18 control flasks and 18 others as treatment, consisting of water and eutrophic environment sediment and, additionally, two bags, containing 10 g of sawdust in each bag. The phosphorus adsorption on sawdust was more intense after 49 days of immersion in the microcosm, and reductions of 90% in the concentration of reactive soluble phosphorus were observed in the water column of the microcosm treatment at 159 days of the experiment. Based on the results, it can be concluded that, although the phosphorus concentration adsorbed on sawdust (16.2 µg g-1) is considered low, the use of the biosorbent is a particularly promising technique for remediation of eutrophic environments, as well as the possible reuse of the adsorbed phosphorus as a fertilizer in agriculture.

A critical comparison of different approaches to sediment-quality assessments in the Santos Estuarine System in Brazil.

This study focuses on the discussion of different lines of evidence (LoEs) applied to a sediment-quality assessment that considered the following: chemical concentrations of metals; polycyclic aromatic hydrocarbons (PAHs) in estuarine waters, sediments, and oysters (native and caged Crassostrea brasiliana); PAHs in semipermeable membrane devices (SPMDs); simultaneously extracted metals-acid volatile sulfides (SEM-AVS); benthic community assessment (the exploratory benthic index and the relative benthic index); chronic toxicity tests with the sea urchin Lytechinus variegatus; and bioaccumulation models. Significantly contaminated sediments from the Santos Estuarine System and the consequent toxicity of tested organisms were measured. Caged oysters presented bioaccumulation rates ≤2,500% of total PAH content and 200% of metal content when compared with control organisms from an uncontaminated area. SPMD results presented the same bioaccumulation pattern as caged oysters but at lower concentrations. Benthic communities presented some alterations, and there was a predominance of tolerant species in the inner part of the estuary. According to the SEM-AVS approach, metals should be assumed to be nonbioavailable, but experiments with transplanted C. brasiliana showed metal bioaccumulation, particularly in the cases of chromium, copper, mercury, and zinc. The weight-of-evidence approach was applied to compare and harmonize LoEs commonly used in sediment-quality assessments and to then classify estuary environments according to both their potential for having adverse effects on the biota and their possible ecological risks. All of the results of these approaches (except for SEM-AVS) were found to complement each other.

Non-targeted analyses of organic compounds in urban wastewater.

A large number of organic pollutants that cause damage to the ecosystem and threaten human health are transported to wastewater treatment plants (WWTPs). The problems regarding water pollution in Latin America have been well documented, and there is no evidence of substantive efforts to change the situation. In the present work, two methods to study wastewater samples are employed: non-targeted 1D ((13)C and (1)H) and 2D NMR spectroscopic analysis to characterize the largest possible number of compounds from urban wastewater and analysis by HPLC-(UV/MS)-SPE-ASS-NMR to detect non-specific recalcitrant organic compounds in treated wastewater without the use of common standards. The set of data is composed of several compounds with the concentration ranging considerably with treatment and seasonality. An anomalous discharge, the influence of stormwater on the wastewater composition and the presence of recalcitrant compounds (linear alkylbenzene sulfonate surfactant homologs) in the effluent were further identified. The seasonal variations and abnormality in the composition of organic compounds in sewage indicated that the procedure that was employed can be useful in the identification of the pollution source and to enhance the effectiveness of WWTPs in designing preventive action to protect the equipment and preserve the environment.

A 3-year study on occurrence of emerging contaminants in an urban stream of São Paulo State of Southeast Brazil.

This manuscript reports a 3-year study on occurrence of pharmaceuticals, hormones, and triclosan in surface waters of a central urban region of São Paulo State of Southeast Brazil (the Monjolinho River in São Carlos). Water samples collected once at every 2 months were pre-concentrated by solid-phase extraction (SPE) and analyzed by liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS). The most frequently detected compounds in higher concentrations were caffeine, paracetamol, and atenolol (maximum concentrations 129,585, 30,421, and 8199 ng L(-1), respectively), while hormones estrone and 17-ß-estradiol were the least detected, in levels up to 14.8 ng L(-1). There was an increasing trend in concentrations of most of the compounds along the river course, especially downstream of the river where there is discharge of both wastewater treatment plant effluent and raw sewage from a particular region of São Carlos city. Concentrations of contaminants were higher during dry periods as a result of decline in the water levels. Decrease in concentrations near the river mouth occurred to different extents for each compound. It was high for caffeine and atenolol, but was very low for carbamazepine and diclofenac. The present study reports the first data about the occurrence of some major emerging contaminants in the Monjolinho River. Besides its regional significance, this work may assist in composing a dataset for water contamination diagnosis focusing on emerging contaminants, both in the Brazilian as well as in the Global studies related to aquatic ecosystems. Such datasets can be helpful for making future public policies on water quality, since these compounds are not yet legally regulated.

Use of a La(III)-modified bentonite for effective phosphate removal from aqueous media.

A bentonite from the Northeast Brazilian region was modified with lanthanum (NT-25La) using an ion exchange process. Lanthanum incorporation in the natural clay, as well as the properties of the clay materials, were confirmed by X-ray diffraction, X-ray fluorescence, specific surface area and scanning electron microscopy (SEM/EDX). Phosphate adsorption equilibrium and kinetic tests were performed at different temperatures. The adsorption data have shown that NT-25La reaches equilibrium between modified clay and phosphate solution within 60 min of contact. The phosphate retention at room temperature reached 95%, when initial phosphate concentration in solution was 5 mg L(-1). A kinetic-order variable model provided satisfactory fitting of the kinetic data. Adsorption of phosphate was best described by a Langmuir isotherm, with maximum phosphate sorption capacity of 14.0 mg g(-1). Two distinct adsorption mechanisms were observed that may influence the adsorption processes. The investigation pointed out that the phosphate adsorption occurs via physisorption processes and that the use of NT-25La provides a maximum phosphate sorption capacity higher than many commercial adsorbents.

Assessment of organic and inorganic contaminants in sediments of an urban tropical eutrophic reservoir.

Although the Ibirité reservoir (an urban tropical eutrophic reservoir) has been the recipient of the discharge of a large volume of raw urban sewage, the key cause of ecosystem degradation has been historically solely attributed to the discharge of effluents from an oil refinery. This fact motivated an investigation to unravel the compositions of contaminants in the sediments to evaluate their distributions, possible sources, and potential impacts on sediment­water quality. The concentrations of polycyclic aromatic and aliphatic hydrocarbons and of metals and metalloids were, in general, significantly lower than some selected polluted sites used for comparison. Calculated distribution indexes showed that the hydrocarbon sources were petrogenic, pyrogenic, and biogenic. Only a few PAHs exceeded the threshold effects level (TEL) guideline. Industrial activities are the presumed sources of metals and metalloids except for copper, which is from copper sulfate used as algaecide in the reservoir. The bioavailable concentrations of some metal and metalloid exceeded the TEL­PEL guidelines. The acid volatile sulfide concentration was greater than that of the simultaneously extracted metals in the clayey­silty reservoir sediments, whereas the opposite result was observed for the sandy sediments of the tributaries. The sediment interstitial water toxic units were >1 for metals, thus indicating that metals are potentially toxic to the benthos. Considering the data set generated in this study, it can be concluded that the degradation of Ibirité reservoir and its tributaries cannot be solely attributed to the input of hydrocarbons, but predominantly to the discharge of raw urban sewage and effluents from other industrial sources.