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.

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.

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.

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.

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.

Interaction of arsenic species with tropical river aquatic humic substances enriched with aluminum and iron.

The mobility and bioavailability of arsenic (As) are strongly controlled by adsorption/precipitation processes involving metal oxides. However, the organic matter present in the environment, in combination with these oxides, can also play an important role in the cycle of arsenic. This work concerns the interaction between As and two samples of aquatic humic substances (AHS) from tropical rivers. The AHS were extracted as proposed by IHSS, and were characterized by (13)C NMR. The experiments were conducted with the AHS in natura and enriched with metal cations, with different concentrations of As, and complexation capacity was evaluated at three different pH levels (5.0, 7.0, and 9.0). The AHS samples showed similar chemical compositions. The results suggested that there was no interaction between As(III) and AHS in natura or enriched with Al. Low concentrations of As(V) were bound to AHS in natura. For As(III), the complexation capacity of the AHS enriched with Fe was approximately 48 µmol per g of C, while the values for As(V) were in the range 69-80 µmol per grams of C. Fluorescence spectra showed that changes in Eh affected the complexation reactions of As(V) species with AHS.

Application of orange peel waste in the production of solid biofuels and biosorbents.

This work aimed to study the potential use of pyrolyzed orange peels as solid biofuels and biosorption of heavy metals. The dry biomass and the biofuel showed moderate levels of carbon (44-62%), high levels of oxygen (30-47%), lower levels of hydrogen (3-6%), nitrogen (1-2.6%), sulfur (0.4-0.8%) and ash with a maximum of 7.8%. The activation energy was calculated using Kissinger method, involving a 3 step process: volatilization of water, biomass degradation and volatilization of the degradation products. The calorific value obtained was 19.3MJ/kg. The studies of metal biosorption based on the Langmuir model obtained the best possible data fits. The results obtained in this work indicated that the potential use of waste orange peel as a biosorbent and as a solid biofuel are feasible, this product could be used in industrial processes, favoring the world economy.

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.

Development of hydrophilic nanocarriers for the charged form of the local anesthetic articaine.

One of the current challenges in drug encapsulation concerns the development of carrier systems for hydrophilic compounds. Potential carriers include nanocapsules prepared with amphiphilic polymers, which consist of a polymeric coating surrounding an aqueous nucleus, or dense matrices such as nanospheres of alginate/chitosan, where the drug may be dispersed in the matrix or adsorbed on the surface. The development of new formulations of nanocarriers, for example the poly(ethylene glycol)-poly(ɛ-caprolactone) (PEG-PCL) nanocapsules and alginate/chitosan (AG/CS) nanospheres described in this work, is needed in the case of ionized drugs such as articaine. This amino amide local anesthetic is the drug of choice in dentistry for regional anesthesia as well as the relief of acute and chronic pain. Here, the physico-chemical properties of suspensions of the nanoparticles (considering diameter, polydispersion, and zeta potential) were determined as a function of time, in order to establish the stability of the systems. The formulations did not show any substantial changes in these parameters, and were stable for up to 120 days of storage at ambient temperature. Satisfactory encapsulation efficiencies were obtained for the PEG-PCL nanocapsules (60%) and the AG/CS nanospheres (45%). Cytotoxicity assays confirmed that the encapsulation of articaine reduced its toxicity, relative to the free drug. The most promising results were obtained using the vesicular system (PEG-PCL nanocapsules), which not only altered the release profile of the drug, but also resulted in the lowest toxicity. This carrier system therefore holds promise for use in future practical applications.

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.

Preparation and characterization of poly(ε-caprolactone) nanospheres containing the local anesthetic lidocaine.

The objective of this work was to develop a modified release system for the local anesthetic lidocaine (LDC), using poly(ε-caprolactone) (PCL) nanospheres (NSs), to improve the pharmacological properties of the drug when administered by the infiltration route. In vitro experiments were used to characterize the system and investigate the release mechanism. The NSs presented a polydispersion index of 0.072, an average diameter of 449.6 nm, a zeta potential of -20.1 mV, and an association efficiency of 93.3%. The release profiles showed that the release of associated LDC was slower than that of the free drug. Atomic force microscopy analyses showed that the spherical structure of the particles was preserved as a function of time, as well as after the release experiments. Cytotoxicity and pharmacological tests confirmed that association with the NSs reduced the toxicity of LDC, and prolonged its anesthetic action. This new formulation could potentially be used in applications requiring gradual anesthetic release, especially dental procedures.

Poly(ε-caprolactone)nanocapsules as carrier systems for herbicides: physico-chemical characterization and genotoxicity evaluation.

The toxicity of herbicides used in agriculture is influenced by their chemical stability, solubility, bioavailability, photodecomposition, and soil sorption. Possible solutions designed to minimize toxicity include the development of carrier systems able to modify the properties of the compounds and allow their controlled release. Polymeric poly(ε-caprolactone) (PCL) nanocapsules containing three triazine herbicides (ametryn, atrazine, and simazine) were prepared and characterized in order to assess their suitability as controlled release systems that could reduce environmental impacts. The association efficiencies of the herbicides in the nanocapsules were better than 84%. Assessment of stability (considering particle diameter, zeta potential, polydispersity, and pH) was conducted over a period of 270 days, and the particles were found to be stable in solution. In vitro release kinetics experiments revealed controlled release of the herbicides from the nanocapsules, governed mainly by relaxation of the polymer chains. Microscopy analyses showed that the nanocapsules were spherical, dense, and without aggregates. In the infrared spectra of the PCL nanocapsules containing herbicides, there were no bands related to the herbicides, indicating that interactions between the compounds had occurred. Genotoxicity tests showed that formulations of nanocapsules containing the herbicides were less toxic than the free herbicides. The results indicate that the use of PCL nanocapsules is a promising technique that could improve the behavior of herbicides in environmental systems.