Neural network for evaluation of the impact of the UK COVID-19 national lockdown on atmospheric concentrations of PAHs and PBDEs.

The impact of measures to restrict population mobility during the COVID-19 pandemic on atmospheric concentrations of polycyclic aromatic hydrocarbons (PAH) and brominated flame retardants (BFRs) is poorly understood. This study analyses the effects of meteorological parameters and mobility restrictions during the COVID-19 pandemic on concentrations of PAH and BFRs at the University of Birmingham in the UK utilising a neural network (self-organising maps, SOM). Air sampling was performed using Polyurethane Foam (PUF) disk passive samplers between October 2019 and January 2021. Data on concentrations of PAH and BFRs were analysed using SOM and Spearman's rank correlation. Data on meteorological parameters (air temperature, wind, and relative humidity) and mobility restrictions during the pandemic were included in the analysis. Decabromodiphenyl ether (BDE-209) was the most abundant polybrominated diphenyl ether (PBDE) (23-91% Σ7PBDEs) but was detected at lower absolute concentrations (4.2-35.0 pg m-3) than in previous investigations in Birmingham. Air samples were clustered in five groups based on SOM analysis and the effects of meteorology and pandemic-related restrictions on population mobility could be visualised. Concentrations of most PAH decreased during the early stages of the pandemic when mobility was most restricted. SOM analysis also helped to identify the important influence of wind speed on contaminant concentrations, contributing to reduce the concentration of all analysed pollutants. In contrast, concentrations of most PBDEs remained similar or increased during the first COVID-19 lockdown which was attributed to their primarily indoor sources that were either unaffected or increased during lockdown.

Effect of the association of coagulation/flocculation, hydrodynamic cavitation, ozonation and activated carbon in landfill leachate treatment system.

Mature landfill wastewater is a complex effluent due to its low biodegradability and high organic matter content. Currently, mature leachate is treated on-site or transported to wastewater treatment plants (WWTPs). Many WWTPs do not have the capacity to receive mature leachate due to its high organic load leading to an increase in the cost of transportation to treatment plants more adapted to this type of wastewater and the possibility of environmental impacts. Many techniques are used in the treatment of mature leachates, such as coagulation/flocculation, biological reactors, membranes, and advanced oxidative processes. However, the isolated application of these techniques does not achieve efficiency to meet environmental standards. In this regard, this work developed a compact system that combines coagulation and flocculation (1st Stage), hydrodynamic cavitation and ozonation (2nd Stage), and activated carbon polishing (3rd Stage) for the treatment of mature landfill leachate. The synergetic combination of physicochemical and advanced oxidative processes showed a chemical oxygen demand (COD) removal efficiency of over 90% in less than three hours of treatment using the bioflocculant PGα21Ca. Also, the almost absolute removal of apparent color and turbidity was achieved. The remaining CODs of the treated mature leachate were lower when compared to typical domestic sewage of large capitals (COD ~ 600 mg L-1), which allows the interconnection of the sanitary landfill to the urban sewage collection network after treatment in this proposed system. The results obtained with the compact system can help in the design of landfill leachate treatment plants, as well as in the treatment of urban and industrial effluents which contains different compounds of emerging concern and persistence in the environment.

Impact of aquatic humic substances on speciation and toxicity of arsenic and cobalt to Ceriodaphnia dubia.

Humic substances (HS) interact with trace metals such as As and Co, affecting their mobility and availability in aquatic systems. However, their combined effects on toxicity to aquatic organisms are not totally understood. The objective of this study was to evaluate the toxicity of Co(II) and As(III) to the water flea Ceriodaphnia dubia in the presence of HS, considering element speciation. Toxicity assays were performed in the presence and absence of HS at two different concentrations of As(III) (10 and 20 µg/L) and Co(II) (50 and 100 µg/L). The free As(III) and Co(II) (< 1 kDa, fraction most potentially bioavailable) in the test solutions were determined via ultrafiltration. While free Co(II) decreased by approximately 80% in the presence of HS, free As(III) decreased just by 1%. Despite the higher percentage of As(III) potentially bioavailable, the presence of HS reduced significantly the toxicity of As at 20 µg/L (no toxicity was observed at 10 µg/L). This was attributed to direct effects of HS such as hormesis, hormone-like effects of HS and/or formation of protective coating. These effects also stimulated the reproduction, including in the assays in the absence of As and Co. HS reduced the toxicity of Co(II) at both test concentrations. The results of this investigation support that HS should be considered when safe limits for As and Co are defined.

Elevated concentrations of halogenated flame retardants in waste childcare articles from Ireland.

Concentrations of legacy and alternative halogenated flame retardants (HFRs) including chlorinated organophosphate esters (Cl-OPEs), were measured in waste childcare articles (n = 275 for Cl-OPEs, n = 187 for other HFRs) from the Republic of Ireland between 2019 and 2020. Articles studied comprised foams and fabrics from: child car seats, cot mattresses, changing mats, pushchairs, prams, and related items. Fifteen articles (7.7%) exceeded the European Union limit value of 1000 mg/kg for polybrominated diphenyl ethers (PBDEs) (all due to BDE-209), an additional 15 exceeded the limit for hexabromocyclododecane (HBCDD), with 7 articles exceeding the limit for both PBDEs and HBCDD. An even greater proportion of articles contained concentrations exceeding 1000 mg/kg for: tris(1-chloro-2-propyl) phosphate (TCIPP) (n = 73, 27%) and tris(1,3-dichloro-2-propyl) phosphate (TDCIPP) (n = 58, 21%), with concentrations greater than 1000 mg/kg also observed for: tris(2-chloroethyl) phosphate (TCEP) (n = 14, 5.1% articles), 2-ethylhexyl tetrabromobenzoate (EH-TBB) (n = 7, 3.7%), decabromodiphenyl ethane (DBDPE), and bis(2-ethylhexyl)tetrabromophthalate (BEH-TEBP) (both n = 5, 2.7%). Overall, 120 samples contained at least one HFR at a concentration exceeding 1000 mg/kg. In addition to the waste management implications of our findings, our data raise concerns about child exposure to HFRs during the use phase of these everyday items.

Chlorinated organophosphate esters in Irish waste foams and fabrics: Concentrations, preliminary assessment of temporal trends and evaluation of the impact of a concentration limit value.

Concentrations of the chlorinated organophosphate esters (Cl-OPEs): tris(2-chloroethyl) phosphate (TCEP), tris(1-chloro-2-propyl) phosphate (TCIPP), and tris(1,3-dichloro-2-propyl) phosphate (TDCIPP) were measured in 273 waste synthetic foam and fabric articles collected in Ireland between 2019 and 2020. Articles examined comprised: polystyrene building insulation foam, as well as foam fillings and fabric coverings from furniture, mattresses, end-of-life vehicles, curtains, and carpets. Cl-OPEs were also measured in 156 samples from the same categories (except for building insulation foam) collected in 2015-16. Concentrations of TCIPP and TDCIPP in most samples exceeded those of TCEP; with those of TCIPP and TDCIPP generally and for some waste categories significantly (p < 0.05) higher in samples collected in 2019-20. Given potential future restrictions on use of these Cl-OPEs, we identified articles containing concentrations that exceeded 1000 mg/kg, in line with a similar limit that at the time of sample collection existed for some brominated flame retardants within the European Union. In 2019-20, 82 articles contained at least one Cl-OPE above 1000 mg/kg, with at least one article exceeding this concentration in each waste category examined. By comparison, only 28 samples collected in 2015-16, contained at least one Cl-OPE >1000 mg/kg, and articles exceeding this concentration were restricted to furniture and mattress foam, along with foams and fabrics from end-of-life vehicles. In the event of the introduction of such a limit on Cl-OPE concentrations in waste, it will result in 7200 t/year of such waste (24 % of the total) being rendered unrecyclable, while removing 98 % of the estimated ∼147,000 kg/year of Cl-OPEs from the recycling stream.

Ecotoxicology and geostatistical techniques employed in subtropical reservoirs sediments after decades of copper sulfate application.

Spatial distribution linked to geostatistical techniques contributes to sum up information into an easier-to-comprehend knowledge. This study compares copper spatial distribution in surface sediments and subsequent categorization according to its toxicological potential in two reservoirs, Rio Grande (RG) and Itupararanga (ITU) (São Paulo-Brazil), where copper sulfate is applied and not applied, respectively. Sediments from 47 sites in RG and 52 sites in ITU were collected, and then, copper concentrations were interpolated using geostatistical techniques (kriging). The resulting sediment distributions were classified in categories based on sediment quality guides: threshold effect level and probable effect level; regional reference values (RRVs) and enrichment factor (EF). Copper presented a heterogenic distribution and higher concentrations in RG (2283.00 ± 1308.75 mg/kg) especially on the upstream downstream, associated with algicide application as well as the sediment grain size, contrary to ITU (21.81 ± 8.28 mg/kg) where a no-clear pattern of distribution was observed. Sediments in RG are predominantly categorized as "Very Bad", whereas sediments in ITU are mainly categorized as "Good", showing values higher than RRV. The classification is supported by the EF categorization, which in RG is primarily categorized as "Very High" contrasting to ITU classified as "Absent/Very Low". Copper total stock in superficial sediment estimated for RG is 4515.35 Ton of Cu and for ITU is 27.45 Ton of Cu.

POP-BFRs in consumer products: Evolution of the efficacy of XRF screening for legislative compliance over a 5-year interval and future trends.

In 2015-16, a study of approximately 500 waste plastic articles showed that portable X-ray fluorescence (XRF) was up to 95 % effective in screening for compliance with low persistent organic pollutant (POP) concentration limits (LPCLs) on brominated flame retardants (BFRs) in waste. The present study conducted in 2019-20 mirrors that conducted five years prior on a similar number and range of articles, testing the hypothesis that increased use of alternative BFRs as replacements for POP-BFRs will reduce the effectiveness of XRF as a tool for monitoring compliance with LPCLs. In comparing the results, the overall screening efficacy for LPCL compliance reduced from ~95 % to ~88 %, due in part to decreased prevalence of POP-BFRs and potentially increased presence of alternative flame retardants, particularly in goods with shorter lifecycles such as electronics. We additionally examined the impacts of a number of modifications to the XRF measurement protocol on its efficacy, including: using elemental Sb as a qualifier in detecting POP-BFRs in hard plastics; reduced XRF analysis time; and the elimination of background interference using a test stand. The rate at which hard plastics from electronic waste may be analysed by XRF can be substantially improved by reducing analysis time to 5 s, with minimal increase in false exceedances of the LPCL. Monitoring Sb does not appear an effective qualifier for the presence of POP-BFRs, as Sb seems to be used with a range of BFRs. Use of the test stand, while reducing interference, appeared to reduce accuracy when screening low density and thin samples. Despite a seeming increased use of alternative BFRs, screening of waste for compliance with LPCLs using rapid and low-cost screening methods such as portable XRF is still necessary as methods such as GC-MS cannot be scaled up to match the quantities of waste requiring screening.

Halogenated flame retardants in Irish waste polymers: Concentrations, legislative compliance, and preliminary assessment of temporal trends.

Halogenated flame retardants (HFRs) were measured in 470 waste plastic articles from Ireland between 2019 and 2020. We identified articles containing concentrations of polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCDD), and tetrabromobisphenol-A (TBBP-A) exceeding European Union limits. Enforcement of existing limits of 1000 mg/kg will render an estimated 3.1% (2800 t) of articles in the waste categories studied unrecyclable, increasing to: 4.0, 4.9, and 5.6% if limits were reduced to 500, 200, and 100 mg/kg respectively. Meanwhile, enforcing limits of 1,000, 500, 200, and 100 mg/kg will respectively remove 78, 82, 84, and 85% of PBDEs, HBCDD, and TBBP-A present in such waste. Other FRs targeted were detected infrequently and predominantly at very low concentrations. However, 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine (TTBP-TAZ) was detected in 3 display/IT product samples at 14,000 to 32,000 mg/kg, indicating elevated concentrations of FRs used as alternatives to PBDEs and HBCDD, will likely increase in future. Comparison with data for Ireland in 2015-16, revealed concentrations and exceedances of limits for PBDEs, HBCDD, and TBBP-A were similar or have declined. For end-of-life vehicle fabrics and foams, HBCDD and ΣPBDE concentrations declined significantly (p < 0.05) since 2015-16. Moreover, ΣPBDE concentrations in waste small domestic appliances are significantly lower in 2019-20, with a similarly significant decline for TBBP-A in waste IT and telecommunications articles. In contrast, HBCDD concentrations in waste extruded polystyrene increased significantly between 2015-16 and 2019-20. For other waste categories studied, no statistically significant temporal trends are evident (p > 0.05). Fewer samples exceeded PBDE and HBCDD limits in 2019-20 (7.8%) than 2015-16 (8.7%), while exceedances for TBBP-A fell from 2.4% in 2015-16 to 0.57% in 2019-20. While comparison between the 2015-16 and 2019-20 datasets provide a preliminary indication of changes, further monitoring is required if the impact of legislation designed to eliminate HFRs from the waste stream is to be fully evaluated.

Analyses of colloidal, truly dissolved, and DGT-labile metal species and phosphorus in mining area surrounded by tailing dams using self-organising maps.

The knowledge of size-distribution and lability of metals and nutrients in freshwater systems is important for estimation of the ecological effects of mining. However, it is still limited in several mining areas such as the Quadrilátero Ferrífero (Brazil) which was severely polluted by the collapse of the Fundão tailings dam in November 2015. In this study, results of an investigation from 2014 using a neural network named self-organising map (SO-Map) into the conditions of selected trace metals that are of particular importance to mining areas (Cr, Cu, Co, Mn, Ni, Pb, Zn) are presented. Additionally, P was considered by its high importance as a nutrient and sites later affected by the dam burst were also included by chance. Water samples were collected at six sites in dry and rainy seasons and filtered and ultrafiltered for determination of total dissolved (<0.45 µm) and truly dissolved (<1 kDa) fractions. Diffusive gradients in thin films (DGT) devices were deployed in situ for determination of the DGT-labile fraction. All data were analysed using SO-Map and Spearman's rank correlation. Phosphorus in the Carmo River occurred mainly in the truly dissolved and DGT-labile fractions. The higher amounts of this element in the river water (up to 263 µg L-1 of total P) might be related to untreated sewage discharge. Moreover, the concentrations of other trace metals (Mn, Cu, Co, Ni, Zn) were high, even under the "natural" conditions (before the dam failure) due to natural and anthropogenic factors such as local lithology and mining.

Human risk assessment of toxic elements (As, Cd, Hg, Pb) in marine fish from the Amazon.

The present study evaluated As, Hg, Pb and Cd burdens in both ecologically and commercially important 314 marine fishes belonging to 47 species sampled along the Amazon Coast. We specifically investigated variations in these four elements among different habitats and their relationships with trophic position and estimated potential human health risk by calculating the hazard quotient (HQ), hazard index (HI), and target cancer risk (TR). Our analyses revealed that Hg concentrations in reef-associated fish were over 2-fold those recorded in demersal fish (p < 0.001). A stable isotope analysis indicated that most of the fish species analyzed herein are secondary consumers (i.e., TP > 2.9) and their trophic positions exhibited a significant negative correlation to As, Pb and Cd. Positive significant relationships were noted between As-Cd, As-Pb, As-Hg, Hg-Cd and Cd-Pb, suggesting that these elements exhibit similar dispersion properties and bioaccumulation homology, probably arising from natural fluvial inputs from the Amazon basin system. Detected As concentrations were higher than established guidelines and legal limits in 63.8% of the examined species (n = 30), whereas Cd, Hg and Pb levels were generally very low. Estimated daily intake (EDI) of iAs, Hg and Pb were above reference dose (RfD) in more almost half of species analyzed and HQ values were each found to pose potential non-carcinogenic health risks if high amounts are consumed over time. HI indicates that the determined elements attained levels considered as potential human health hazards trough consumption of eight cartilaginous fish. The TR values of iAs and Pb were higher than the guideline value and given this, individuals who continuously consume cartilaginous fish contaminated with the toxic elements determined here will likely be under increased cancer risks in the long term.

Permanent occurrence of Raphidiopsis raciborskii and cyanotoxins in a subtropical reservoir polluted by domestic effluents (Itupararanga reservoir, São Paulo, Brazil).

Toxic cyanobacteria blooms are a frequent problem in subtropical reservoirs and freshwater systems. The purpose of this study was to investigate the occurrence of potentially toxic cyanobacteria and the environmental conditions associated with the presence of cyanotoxins in a Brazilian subtropical reservoir. Five collections were carried out at seven sampling locations in the reservoir, during the rainy and dry seasons, between the years 2016 and 2017. There was permanent occurrence of Raphidiopsis raciborskii (Woloszynska) Aguilera, Berrendero Gómez, Kastovsky, Echenique & Salerno (Phycologia 57(2):130-146, 2018), ranging between dominant and abundant, with an average biomass of 38.8 ± 29.9 mg L-1. Also abundant were Dolichospermum solitarium, D. planctonicum, Planktothrix isothrix, and Aphanizomenon gracile. Saxitoxin (STX) was detected in all the collected samples (0.11 ± 0.05 µg L-1). Microcystin (MC) was also detected, but at lower concentrations (0.01 ± 0.0 µg L-1). Low availability of NO3- and phosphorus limitation had significant effects on the R. raciborskii biomass and the levels of STX and MC. It was observed that R. raciborskii was sensitive to thermal stratification, at the same time that STX levels were higher. This suggested that STX was produced under conditions that restricted the growth of R. raciborskii. These are important findings, because they add information about the permanent occurrence of STX and R. raciborskii in an aquatic ecosystem limited by phosphorus, vulnerable to climatic variations, and polluted by domestic effluents.

Influence of terbium (III) ions on the photocatalytic activity of TiO2 and CeO2 for the degradation of methylene blue in industrial effluents.

This study reports the preparation of TiO2 and CeO2 doped with different quantities of terbium and discusses the influence of this dopant on the photocatalytic activity of the semiconductors, with respect to the degradation of methylene blue, under ultraviolet and solar radiations. The oxides obtained were characterized by X-ray diffraction, infrared vibrational spectroscopy, diffuse reflectance spectroscopy, scanning electron microscopy, and dispersive energy spectroscopy. The results indicate that the presence of the dopant in TiO2 favored the formation of the anatase crystalline phase to the detriment of rutile, increased the band gap energy, and decreased the size of the nanoparticles. Doping CeO2 with Tb resulted in a fluorite-type crystalline structure, reduced band gap, and smaller particle size. The photocatalytic activity decreases as the concentration of terbium increases regardless of the radiation source and nature of the oxide. Furthermore, a better performance was observed for all semiconductors excited by solar radiation in comparison to ultraviolet light. The samples of pure TiO2 and TiO2 doped with 0.5 and 1% terbium showed total removal of the dye after less than 120 min of reaction, while the samples of pure CeO2 and CeO2 doped with 0.5% terbium showed approximately 80% and 57% of dye removal after 120 min, suggesting that these materials can be promising for the treatment of industrial effluents.

Multianalytical characterization of biochar and hydrochar produced from waste biomasses for environmental and agricultural applications.

Biochar (BC) and hydrochar (HC) are solid by-products obtained from various types of biomasses through the processes of pyrolysis and hydrothermal carbonization, respectively. Both BC and HC represent a sustainable solution for carbon sequestration and can be used as soil amendments or sorbents for organic and inorganic pollutants. However, the properties of BC and HC largely depend on feedstock and production parameters, which significantly affect their proper use. A detailed characterization of these materials is therefore needed to assess their suitability for environmental and/or agricultural applications. In this work, two BC samples and two HC samples were characterized with a multianalytical approach, including total reflection X-ray fluorescence (TXRF) spectroscopy, scanning electron microscopy (SEM), Fourier-transform infrared (FT-IR) spectroscopy, thermogravimetric analyses (TG), and pyrolysis coupled to gas chromatography and mass spectrometry (Py-GC/MS). By comparing BC and HC data, HC showed a higher content of mineral elements, including important plant nutrients and potentially toxic elements. HC produced from solid urban wastes contained also some potentially toxic organic molecules, like chlorinated aromatic compounds. BC samples were characterized by a higher porosity and hydrophobicity than HC, thus being potentially more suitable for the sorption of organic pollutants. HC samples showed a higher content of cellulose and hemicellulose, resulting in a more hydrophilic but less thermally stable material than BC. In conclusion, both BC and HC have interesting properties for environmental and agricultural applications but careful selection of feedstock is needed, especially for HC production.

The Effects of Sediment Classification Pattern on a Water Column Organism, Ceriodaphnia dubia.

The sediment compartment stands out because it functions as both a temporary sink of pollutants and a potential source of these elements that may become available to the water column.This study aimed to correlate the concentrations of total metals in the crude sediment and in the interstitial water with the ecotoxicity in the water column using an a modified sediment ecotoxicity test with Ceriodaphnia dubia. The results indicate that the sediment may contribute to the toxicity in the water column and that such toxicity is possibly not related to the metals present. Based on the chemical analysis of the metals, the Canadian Sediment Quality Guidelines (SQGs) would frame the sediment as non-toxic to benthic organisms, but the SQGs have no reference standards for possible effects on nektonic organisms. Due to the complexity of this compartment, it is fundamental to evaluate the interactions of the different pollutants in the system and possible effects on the nektonic organisms.

Spatial distribution, bioavailability, and toxicity of metals in surface sediments of tropical reservoirs, Brazil.

Depending on the environmental conditions, surface sediments can retain all the contaminants present and provide a record of the anthropic activities affecting the aquatic environment. In order to analyze the impacts on reservoirs, surface sediments were collected in three characteristic regions (riverine, transitional, and limnetic zones) of seven reservoirs in São Paulo State, Brazil. Analyses were made of grain size, organic matter (OM), total phosphorus (TP), and total nitrogen (TN). Inductively coupled plasma-atomic emission spectroscopy (ICP-AES) was used to determine pseudo-total and bioavailable metals (Cu, Cd, Cr, Ni, Pb, Zn, Mn, Fe, and Al). A Horiba probe was used to measure dissolved oxygen (DO), pH, redox potential (ORP), and temperature (Temp) in the bottom water. The data were analyzed using multivariate statistics. Enrichment factors (EF), pollution load index values (PLI), and background values (BG) were also determined in order to evaluate the potential toxicity. Intra-reservoir and inter-reservoir spatial heterogeneity (p < 0.05) were observed using two-way analysis of similarities. Principal component analysis indicated greater influence of metals in the Barra Bonita, Salto Grande, and Rio Grande reservoirs, corroborating the PLI, EF, and BG data. Bioavailable Cu was found in the Rio Grande reservoir, possibly associated with copper sulfate used to control algal blooms, while bioavailable Ni in the Barra Bonita reservoir was attributed to the presence of industrial wastes and natural geology. The bottom water conditions indicated that the metals remained in insoluble forms.

Lethal and sublethal effects of metal-polluted sediments on Chironomus sancticaroli Strixino and Strixino, 1981.

The Cantareira Complex is one of the most important water supplies of the metropolitan region of São Paulo, Brazil. Previously, it was demonstrated that the sediments in this complex were polluted with metals and that Paiva Castro Reservoir-the last reservoir in the sequence, which receives water from the five previous reservoirs-was the reservoir with the greatest concentration of pollutants. Based on field data, it was noticed that copper concentrations in sediments were related to morphological alterations in chironomids. The present study provides novel monitoring methods and results for the complex by isolating the environmental and biological sources of variation. An adaptation of the in situ assay proposed by Soares et al. (Arch Environ Contam Toxicol 49:163-172, 2005), which uses a native tropical Chironomus species and low-cost materials, is also provided. The aim of this study was to isolate the effects of sediments from Paiva Castro on controlled populations of C. sancticaroli larvae using an in situ assay. A seven-day experiment was performed in triplicate. Third instar larvae were inoculated in chambers containing sediments from two distinct regions of Paiva Castro reservoir and a control site with sand. Five biological responses were considered: mouthpart alterations, larval length, width of cephalic capsule, mortality and total damage. The results suggest the effects of sediment toxicity on larvae include a reduction in length and a higher occurrence of total damage.

Análise de risco de contaminação de águas subterrâneas por resíduos de agrotóxicos no município de Campo Novo do Parecis (MT), Brasil / Risk analysis of groundwater contamination by pesticide residues in Campo Novo do Parecis (MT), Brazil

RESUMO Considerando a possibilidade de que os agrotóxicos utilizados nas principais culturas, como soja, algodão e milho, podem gerar resíduos que contaminam o meio ambiente, faz-se necessária uma análise preliminar sobre a possibilidade de contaminação das águas subterrâneas por resíduos de agrotóxicos utilizados nas principais regiões agrícolas do país. Uma dessas áreas agrícolas se localiza na cidade de Campo Novo do Parecis, Mato Grosso, região de estudo deste trabalho. Os principais agrotóxicos aplicados nas diferentes culturas da região foram avaliados quanto às suas propriedades físico-químicas, seus potenciais de contaminação de acordo com critérios da Agência de Proteção Ambiental dos Estados Unidos e pelo índice de vulnerabilidade de águas subterrâneas (GUS). As informações obtidas foram empregadas para avaliar o risco de contaminação das águas subterrâneas. De acordo com os resultados encontrados, a região apresenta risco real de contaminação ambiental por resíduos de agrotóxicos, uma vez que 45,6% dos agrotóxicos comumente empregados na agricultura local são classificados como extremamente tóxicos ou altamente tóxicos. Além disso, vários desses ingredientes aditivos, cerca de 22%, já foram detectados em diferentes compartimentos ambientais de outras regiões do estado de Mato Grosso.

ABSTRACT Considering the possibility that pesticides used in main crops, such as soybeans, cotton and corn, generate toxic residues that contaminate the environment, a preliminary analysis of the possibility of groundwater contamination is necessary in the main agricultural regions in Brazil. One of these agricultural areas is located in Campo Novo do Parecis, Mato Grosso, the study area of this work. The main pesticides used in different cultures of this region were evaluated considering their physicochemical properties, their contamination potentials according to criteria of the Environmental Protection Agency of the United States and the groundwater ubiquity score index (GUS). The information obtained was used to assess the risk of groundwater contamination. According to the results, the region presents a real risk of environmental contamination by pesticide residues, since 45.6% of the pesticides commonly used in local agriculture are classified as extremely toxic or highly toxic. In addition, several of these pesticides, about 22%, have been detected in different environmental compartments from other regions of the state of Mato Grosso, Brazil.

Toxicity assessment of arsenic and cobalt in the presence of aquatic humic substances of different molecular sizes.

The release of contaminants in aquatic ecosystems can be influenced by humic acids. In this study, toxicity tests using environmentally relevant concentrations of arsenic and cobalt were conducted both in the presence and absence of aquatic humic substances (AHS) and the fractions of different molecular sizes in the range of (<5, 5-10;10-30; 30-100 and >100kDa) using the microcrustacean Ceriodaphnia dubia. AHS together with arsenic reduced the toxicity, and the toxicity decreased in fractions of larger molecular size AHS. Despite the presence of cobalt, the reduction in toxicity was not observed and that depended on the molecular size of AHS. There was a trend of enhanced toxicity for Co in fractions of larger molecular sizes, opposed to that found for arsenic. Thus, the humic substances alter toxicity of trace elements, and this effect varies depending on the size of the humic substances.

Metals in sediments: bioavailability and toxicity in a tropical reservoir used for public water supply.

Sediments may be a repository of contaminants in freshwater ecosystems. One way to assess the quality of this compartment, in terms of potentially bioavailable metals, is by the analysis of acid-volatile sulfide (AVS) and simultaneously extracted metals (SEM). In order to investigate the bioavailability, toxicity, and compartmentalization of different metals (Cd, Cr, Cu, Ni, Pb, Zn), sampling of surface sediments was performed at nine stations along the Paiva Castro reservoir (São Paulo, Brazil). The metals were analyzed using atomic absorption spectroscopy. Sediment organic matter (OM), organic carbon (OC), and grain size were also measured. The parameters pH, EH, temperature, and dissolved oxygen were determined at the sediment-water interface. Chronic and acute toxicological tests were performed with sediments from the area where water was extracted for the public water supply. Low levels of OM, associated with loss of stratification in the water column, explained the relatively low AVS values. The molar ratio ∑[SEM]-[AVS]/fOC was less than 130 mmol/kg(-1) for all the sampling stations, indicating that the metals were not bioavailable. With the exception of Cd, metal levels were in accordance with background concentrations and the threshold effect level (TEL) established by the Canadian Council of Ministers of the Environment. The ecotoxicological tests confirmed the absence of toxic effects to biota. Application of principal component analysis indicated the presence of four compartments along the reservoir: (1) a riverine zone, potentially threatened by contamination with Cd; (2) an intermediate zone; (3) a limnic area; and (4) the area where water was taken for the public water supply.

Towards field trace metal speciation using electroanalytical techniques and tangential ultrafiltration.

In this work we propose a trace metal speciation methodology to determine the total, free and ultrafiltered (<1 KDa) metal fractions using electrochemical methods (SCP and AGNES) and tangential ultrafiltration (UF) experiments that can easily be carried out on-site. We tested our methodology spiking Cadmium ions into two natural waters samples from Itapanhau and Sorocabinha rivers in Sao Paulo State, Brazil. The limits of detection (LOD) was 1.6×10(-9) M for the total Cd(2+) determination performed by Stripping Chronopotentiometry (SCP) in the source and acidified ultrafiltered solution and 1.9×10(-9) M for the free Cd(2+) determination using Absence of gradients and Nernstian equilibrium stripping (AGNES), using a thin mercury film electrode. The total metal determination was performed by SCP in acidified samples and the results compared with graphite furnace atomic absorption spectroscopy (GF-AAS). The SCP results were adequate with a 96% of recovery from the known metal spike for the 12 samples tested. For the Itapanhau sample the free metal determined by AGNES and the ultrafiltered fraction are identical, while for the Sorocabinha the free metal in the source is significantly smaller than the ultrafiltered fraction, indicating that this sample must be rich in metal complexes with small inorganic ligands that are able to permeate the 1kDa membrane. The proposed metal speciation methodology validated in the laboratory combining UF and SCP/AGNES is able to be used in on-site experiments providing valid information regarding the total and free metal concentrations and additionally some insight on the role of small inorganic ligands to the metal complexation.