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.

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.

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.

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.

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.

Adsorption/desorption of arsenic by tropical peat: influence of organic matter, iron and aluminium.

The objective of this work was to investigate the interaction of arsenic species (As(III) and As(V)) with tropical peat. Peat samples collected in Brazil were characterized using elemental analysis and 13C NMR. Adsorption experiments were performed using different concentrations of As with peat in natura and enriched with Fe or Al, at three different pH levels. Peat samples, in natura or enriched with metals, were analysed before and after adsorption processes using Fourier transform infrared spectroscopy (FTIR) spectroscopy. The adsorption kinetics was evaluated, and the data were fitted using the Langmuir and Freundlich models. The results showed that interaction between As and peat was dependent on the levels of organic matter (OM) and the metals (Fe and Al). As(III) was not adsorbed by in natura peat or Al-enriched peat, although small amounts of As(III) were adsorbed by Fe-enriched peat. Adsorption of As(V) by the different peat samples ranged from 21.3 to 52.7 µg g(-1). The best fit to the results was obtained using the pseudo-second-order kinetic model, and the adsorption of As(V) could be described by the Freundlich isotherm model. The results showed that Fe-enriched peat was most effective in immobilizing As(V). FTIR analysis revealed the formation of ternary complexes involving As(V) and peat enriched with metals, suggesting that As(V) was associated with Al or Fe-OM complexes by metal bridging.

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.

Polybrominated diphenyl ethers in indoor dust from Brazil: assessing demographic differences and human health exposure.

Indoor house dust is considered an important human exposure route to polybrominated diphenyl ethers (PBDEs), which has raised concern about their environmental persistence and toxicity properties. In this study, eight PBDEs (BDE-28, -47, -99, -100, -153, -154, -183, and -209) were determined in house dust from two cities with different socio-demographic characteristics from Brazil, examining possible relationships with factors that potentially influence contamination (population density, economic activities, presence of electronic equipment, and so on) and also estimating the risk of human exposure through oral ingestion and dermal contact. The Σ8PBDE concentration in Sorocaba city ranged between 380 and 4269 ng/g dw, while in Itapetininga city ranged from 106 to 1000 ng/g dw. In both regions, BDE-209 was the most abundantly found congener, followed by BDE-99. House dust from Sorocaba presented significantly greater concentrations of BDE-183 and BDE-209 than Itapetininga. Regarding risk exposure assessment, the estimated daily intake (EDI) of PBDEs was much lower than their respective reference doses (RfDs) in all pathways estimated (non-dietary ingestion and dermal contact). This study provided valuable data to improve the knowledge about the presence and exposure to PBDEs in Brazilian house dust in comparison to other developing countries and the need to control environmental pollution and protect human health.

Study of adsorption and preconcentration by using a new silica organomodified with [3-(2,2'-dipyridylamine)propyl] groups.

In this work, a silica surface chemically modified with [3-(2,2'-dipyridylamine)propyl] groups, named [3-(2,2'-dipyridylamine)propyl]silica (Si-Pr-DPA) was prepared, characterized, and evaluated for its heavy metal adsorption characteristics from aqueous solution. To our knowledge, we are the first authors who have reported the present modification. The material was characterized using infrared spectroscopy, SEM, and NMR (29) Si and (13) C solid state. Batch and column experiments were conducted to investigate for heavy metal removal from dilute aqueous solution by sorption onto Si-Pr-DPA. From a number of studies the affinity of various metal ions for the Si-Pr-DPA sorbent was determined to follow the order Fe(III) > Cr(III) >> Cu(II) > Cd(II) > Pb(II) > Ni(II). Two standard reference materials were used for checking the accuracy and precision of the method. The proposed method was successfully applied to the analysis of environmental samples. This ligand material has great advantage for adsorption of transition-metal ions from aqueous medium due to its high degree of organofunctionalization associated with the large adsorption capacity, reutilization possibility, and rapidity in reaching the equilibrium.

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.

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.

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.

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.

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.

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.

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.

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.

Dynamics and heterogeneity of Pb(II) binding by SiO2 nanoparticles in an aqueous dispersion.

Pb(II) binding by SiO(2) nanoparticles in an aqueous dispersion was investigated under conditions where the concentrations of Pb(2+) ions and nanoparticles are of similar magnitude. Conditional stability constants (log K) obtained at different values of pH and ionic strength varied from 4.4 at pH 5.5 and I = 0.1 M to 6.4 at pH 6.5 and I = 0.0015 M. In the range of metal to nanoparticle ratios from 1.6 to 0.3, log K strongly increases, which is shown to be due to heterogeneity in Pb(II) binding. For an ionic strength of 0.1 M the Pb(2+)/SiO(2) nanoparticle system is labile, whereas for lower ionic strengths there is loss of lability with increasing pH and decreasing ionic strength. Theoretical calculations on the basis of Eigen-type complex formation kinetics seem to support the loss of lability. This is related to the nanoparticulate nature of the system, where complexation rate constants become increasingly diffusion controlled. The ion binding heterogeneity and chemodynamics of oxidic nanoparticles clearly need further detailed research.