Distinct weather conditions and human mobility impacts on the SARS-CoV-2 outbreak in Colombia: Application of an artificial neural network approach.

The coronavirus disease 2019 (COVID-19) is still spreading fast in several tropical countries after more than one year of pandemic. In this scenario, the effects of weather conditions that can influence the spread of the virus are not clearly understood. This study aimed to analyse the influence of meteorological (temperature, wind speed, humidity and specific enthalpy) and human mobility variables in six cities (Barranquilla, Bogota, Cali, Cartagena, Leticia and Medellin) from different biomes in Colombia on the coronavirus dissemination from March 25, 2020, to January 15, 2021. Rank correlation tests and a neural network named self-organising map (SOM) were used to investigate similarities in the dynamics of the disease in the cities and check possible relationships among the variables. Two periods were analysed (quarantine and post-quarantine) for all cities together and individually. The data were classified in seven groups based on city, date and biome using SOM. The virus transmission was most affected by mobility variables, especially in the post-quarantine. The meteorological variables presented different behaviours on the virus transmission in different biogeographical regions. The wind speed was one of the factors connected with the highest contamination rate recorded in Leticia. The highest new daily cases were recorded in Bogota where cold/dry conditions (average temperature <14 °C and absolute humidity >9 g/m3) favoured the contagions. In contrast, Barranquilla, Cartagena and Leticia presented an opposite trend, especially with the absolute humidity >22 g/m3. The results support the implementation of better local control measures based on the particularities of tropical regions.

Dominance of in situ produced particulate organic carbon in a subtropical reservoir inferred from carbon stable isotopes.

Sources of particulate organic carbon (POC) play important roles in aqueous carbon cycling because internal production can provide labile material that can easily be turned into CO2. On the other hand, more recalcitrant external POC inputs can cause increased loads to sedimentary organic matter that may ultimately cause CH4 release. In order to differentiate sources, stable isotopes offer a useful tool. We present a study on the Itupararanga Reservoir (Brazil) where origins of POC were explored by comparing its isotope ratios (δ13CPOC) to those of dissolved inorganic carbon (δ13CDIC). The δ13CPOC averaged around - 25.1‰ in near-surface waters, which indicates higher primary production inferred from a fractionation model that takes into account carbon transfer with a combined evaluation of δ13CPOC, δ13CDIC and aqueous CO2. However, δ13CPOC values for water depths from 3 to 15 m decreased to - 35.6‰ and indicated different carbon sources. Accordingly, the δ13CDIC values of the reservoir averaged around + 0.6‰ in the top 3 m of the water column. This indicates CO2 degassing and photosynthesis. Below this depth, DIC isotope values of as low as - 10.1‰ showed stronger influences of respiration. A fractionation model with both isotope parameters revealed that 24% of the POC in the reservoir originated from detritus outside the reservoir and 76% of it was produced internally by aqueous CO2 fixation.

Taxonomic and non-taxonomic responses of benthic macroinvertebrates to metal toxicity in tropical reservoirs. The case of Cantareira Complex, São Paulo, Brazil.

Benthic macroinvertebrates are organisms that are recognized as water quality bio-indicators. A wide variety of indices and metrics have been shown to respond to a variety of anthropogenic impacts, usually under a general condition of environmental impairment. The absence of a clear distinction in the relations between specific pollutants and biotic variables is very common and can lead to biased interpretation of biomonitoring. The aims of this research were to test taxonomic and non-taxonomic responses to specific environmental conditions instead to general conditions. For this purpose, we estimated the theoretical toxicity by comparing toxicity values published by EPA with metal concentrations in water and sediments. Then we tested the responses of biological variables to toxicity and other environmental conditions using the linear mixed effects models approach. We generated 32 models considering 24 different biological metrics and indices that were grouped in five levels. Taxonomic and abundance metrics were best predictor than functional or tolerance-based indexes. The strongest model was that which considered subfamily taxonomic resolution responding to Al_w and Cr_s.

Application of chitosan film as a binding phase in the diffusive gradients in thin films technique (DGT) for measurement of metal ions in aqueous solution.

Diffusive gradients in thin films technique (DGT) allows in situ determination of labile metal in water, soils, and sediments. This paper aims to evaluate the performance of a new proposal of DGT to measure Cu2+ and Cd2+ in aqueous solution using chitosan films as binding agent. These films were prepared and characterized (Fourier transform infrared spectroscopy, scanning electron microscopy, atomic force microscope, and elemental analysis). The maximum adsorption rates onto chitosan films at initial concentrations of 0.5 and 1.0 mg L-1 for Cu2+ and Cd2+ were 97%, 98% and 60%, 62%, respectively. Effects of main DGT parameters were evaluated and the results obtained suggest that the pH between 4.0 and 6.0 and ionic strength from 0.0008 to 0.1 mol L-1 presented the best ranges for the application of DGT-Chitosan. The results suggest that chitosan films prepared in this work can be an effective binding agent for DGT technique in aqueous solution. Graphical abstract.

High efficiency removal of As(III) from waters using a new and friendly adsorbent based on sugarcane bagasse and corncob husk Fe-coated biochars.

Water contamination of As is a big issue in many areas around the globe. Therefore, cheap and efficient techniques are essential facing traditional treatment methods. Then, biochars (BC) emerged recently as material that can be used for As removal. However, research about efficiency of BC produced from local feedstock is still needed. The purpose of this study is to assess the efficiency of BC produced from sugarcane bagasse (SB) together with corncob husk (CH) with and without Fe(III) (BCFe) modification to be used for removal of As(III) from waters. The BC and BCFe produced at different pyrolysis temperatures were characterised using FTIR and SEM/EDS. Adsorption capacities of BC and BCFe were evaluated via batch adsorption, desorption and column tests and their performance was compared with adsorption using activated carbon. The results showed that Fe modification improve substantially the As(III) adsorption in a way that both BCFe-SB and BCFe-CH removed from 85% to 99.9% from 1000 µg/L As(III) solutions. Both materials fitted well in Langmuir model and the maximum adsorption capacity was 20 mg/g for BCFe-SB and 50 mg/g for BCFe-CH. The adsorption kinetics of BCFe was fast (≤ 30 min) and it had a better performance than activated carbon. The column tests showed that the process is efficient even at high As(III) concentrations. The fast removal process and good removal results make the BCFe-SB and BCFe-CH attractive for in situ and commercial (filters) use, since time and efficiency are required in new technologies.

Aquatic Humic Substances: Relationship Between Origin and Complexing Capacity.

Aiming to determine the relationship between source and complexing capacity, humic substances obtained from three sites (Sorocaba and Itapanhau Brasilian rivers, and Xochimilco Lake in Mexico) were studied. Copper, manganese, zinc and arsenic complexing capacity were determined for the three substances under various pH conditions. Results showed similar complexing capacity for the three elements depending on the chemistry of each one and on the physico-chemical conditions. Speciation diagrams showed that these conditions affect both, the humic substances, and the transition metals and arsenic.

Effects of Fe(III) and quality of humic substances on As(V) distribution in freshwater: Use of ultrafiltration and Kohonen neural network.

Humic substances (HS) are ubiquitous organic compounds able to affect mobility and availability of arsenic (As) in aquatic systems. Although it is known that associations between HS and As occur mainly via iron (Fe)-cationic bridges, the behaviour and distribution of this metalloid in HS- and Fe-rich environments is still not fully understood. In this paper, the quality of HS from different rivers in Brazil and Germany and its influence on the behaviour of As(V) under different Fe(III) concentrations were investigated. HS were extracted from four different rivers (Cascatinha, Holtemme, Selke and Warme Bode), characterised and fractionated into different molecular weight sizes (10, 5 and 1 kDa). Complexation tests were performed using an ultrafiltration system and 1 kDa membranes. All data was analysed using the Kohonen neural network (SOM - Self organising maps). All samples, except Selke, exhibited similar results of free As (<1 kDa). The results suggested that associations between HS, Fe and As were dependent on nitrogen (N)-aromatic carbon (C), amount of sulphur (S) and the molecular size of the HS. Although all HS appeared to be similar after looking at most variables analysed, the SOM could discriminate them into three different groups. Characterisation of the HS indicated that they had terrestrial material (from C3 plants) as precursor material. Most of the As and Fe was distributed in the fractions of higher (>10 kDa) and lower (<1 kDa) size. HS quality is an important factor to take into account when studying the behaviour of As in HS-rich environments.

Distribution and bioavailability of arsenic in natural waters of a mining area studied by ultrafiltration and diffusive gradients in thin films.

The distribution of metals and metalloids among particulate, dissolved, colloidal, free, and labile forms in natural waters is of great environmental concern since it determines their transportation behaviour and bioavailability. Organic matter can have an important role for this distribution process, since it is an important complexing agent and ubiquitous in the aquatic environment. We studied the distribution, mobility and bioavailability of Al, As and Fe in natural waters of a mining area (Quadrilátero Ferrífero, Brazil) and the influence of organic matter in these processes. Water samples were taken from 12 points during the dry and rainy seasons, filtrated at 0.45 µm and ultrafiltrated (<1 kDa) to separate the particulate, colloidal and free fractions. Diffusive gradients in thin films (DGT) were deployed at 5 sampling points to study the labile part of the elements. Total and dissolved organic carbon and the physicochemical parameters were measured along with the sampling. The results of ultrafiltration (UF) and DGT were compared. The relationship among the variables was studied through multivariate analysis (Kohonen neural network), which showed that the seasonality did not impact most of the samples. Fe and Al occurred mainly in the particulate fraction whereas As appeared more in the free fraction. Most of the dissolved Fe and Al were inert (colloidal form) while As was more labile and bioavailable. The results showed that sampling points with a higher quantity of complexed Fe (colloidal fraction) showed less labile As, which may indicate formation of ternary complexes among organic matter, As and Fe.

Chitosan nanoparticles loaded the herbicide paraquat: the influence of the aquatic humic substances on the colloidal stability and toxicity.

Polymeric nanoparticles have been developed for several applications, among them as carrier system of pesticides. However, few studies have investigated the fate of these materials in the environment in relation to colloidal stability and toxicity. In nature, humic substances are the main agents responsible for complexation with metals and organic compounds, as well as responsible for the dynamics of these nanoparticles in aquatic and terrestrial environments. In this context, the evaluation of the influence of aquatic humic substances (AHS) on the colloidal stability and toxicity of polymeric nanoparticles of chitosan/tripolyphosphate with or without paraquat was performed. In this study, the nanoparticles were prepared by the ionic gelation method and characterized by size distribution measurements (DLS and NTA), zeta potential, infrared and fluorescence spectroscopy. Allium cepa genotoxicity studies and ecotoxicity assays with the alga Pseudokirchneriella subcapitata were used to investigate the effect of aquatic humic substances (AHS) on the toxicity of this delivery system. No changes were observed in the physical-chemical stability of the nanoparticles due to the presence of AHS using DLS and NTA techniques. However some evidence of interaction between the nanoparticles and AHS was observed by infrared and fluorescence spectroscopies. The ecotoxicity and genotoxicity assays showed that humic substances can decrease the toxic effects of nanoparticles containing paraquat. These results are interesting because they are important for understanding the interaction of these nanostructured carrier systems with species present in aquatic ecosystems such as humic substances, and in this way, opening new perspectives for studies on the dynamics of these carrier systems in the ecosystem.

Engineered nanoparticles and organic matter: a review of the state-of-the-art.

Growth in the development and production of engineered nanoparticles (ENPs) in recent years has increased the potential for interactions of these nanomaterials with aquatic and terrestrial environments. Carefully designed studies are therefore required in order to understand the fate, transport, stability, and toxicity of nanoparticles. Natural organic matter (NOM), such as the humic substances found in water, sediment, and soil, is one of the substances capable of interacting with ENPs. This review presents the findings of studies of the interaction of ENPs and NOM, and the possible effects on nanoparticle stability and the toxicity of these materials in the environment. In addition, ENPs and NOM are utilized for many different purposes, including the removal of metals and organic compounds from effluents, and the development of new electronic sensors and other devices for the detection of active substances. Discussion is therefore provided of some of the ways in which NOM can be used in the production of nanoparticles. Although there has been an increase in the number of studies in this area, further progress is needed to improve understanding of the dynamic interactions between ENPs and NOM.

Application of poly(epsilon-caprolactone) nanoparticles containing atrazine herbicide as an alternative technique to control weeds and reduce damage to the environment.

Nanoparticles of poly(epsilon-caprolactone) containing the herbicide atrazine were prepared, characterized, and evaluated in terms of their herbicidal activity and genotoxicity. The stability of the nanoparticles was evaluated over a period of three months, considering the variables: size, polydispersion index, pH, and encapsulation efficiency. Tests on plants were performed with target (Brassica sp.) and non-target (Zea mays) organisms, and the nanoparticle formulations were shown to be effective for the control of the target species. Experiments using soil columns revealed that the use of nanoparticles reduced the mobility of atrazine in the soil. Application of the Allium cepa chromosome aberration assay demonstrated that the nanoparticle systems were able to reduce the genotoxicity of the herbicide. The formulations developed offer a useful means of controlling agricultural weeds, while at the same time reducing the risk of harm to the environment and human health.

Preconcentration and determination of metal ions from fuel ethanol with a new 2,2'-dipyridylamine bonded silica.

A silica surface chemically modified with [3-(2,2'-dipyridylamine) propyl] groups was prepared, characterized, and evaluated for its metal ion preconcentration in fuel ethanol. To our knowledge, we are the first authors who have reported the present modification on silica gel surface. The material was characterized using infrared spectra, scanning electronic microscopy, and (13)C and (29)Si solid-state NMR spectra. Batch and column experiments were conducted to investigate for metal ion removal from fuel ethanol. The results showed that the Langmuir model describes the sorption equilibrium data of the metal ions in a satisfactory way. From the Langmuir isotherms, the following maximum adsorption capacities (in mmol g(-1)) were determined: 1.81 for Fe(III), 1.75 for Cr(III), 1.30 for Cu(II), 1.25 for Co(II), 1.15 for Pb(II), 0.95 for Ni(II), and 0.87 for Zn(II). Thermodynamic functions, the change of free energy (ΔG), enthalpy (ΔH), and entropy (ΔS) showed that the adsorption of metal ions onto Si-Pr-DPA was feasible, spontaneous, and endothermic. The sorption-desorption of the metal ions made possible the development of a preconcentration and quantification method of metal ions in fuel ethanol.

Removal of a combination of endocrine disruptors from aqueous systems by seedlings of radish and ryegrass.

Endocrine disruptors (EDs) are widespread in the environment, especially aquatic systems, and cause dangerous effects on wildlife and humans. This work was aimed to assess the capacity of radish (Raphanus sativus L.) and ryegrass (Lolium perenne L.) seedlings to tolerate and remove two combinations of EDs containing bisphenol A (BPA), 17alpha-ethynilestradiol (EE2), and linuron from four aqueous media: distilled water, a solution of natural organic matter (NOM), a lake water and a river water. Seeds of the two species were germinated in each contaminated medium and, at the end of germination, the seedling growth was evaluated by biometric measurements and residual EDs were quantified by chromatographic analysis. Biometric measurements revealed that the phytotoxicity of the two combinations of EDs depended on the medium used. Radish showed a discrete tolerance in distilled water and lake water but was inhibited in the solution of NOM and river water. Ryegrass was negatively affected mainly in river water. The concentration of each ED appeared significantly reduced in all media in the presence of seedlings of both species, but not in the blanks without plants. In 5 days, radish removed up to 88% of BPA, 100% of EE2 and 42% of linuron, and in 6 days ryegrass removed up to 92% of BPA, 74% of EE2 and 16% of linuron. The considerable removal capacity of radish and ryegrass in all media tested encourages the use of phytoremediation to remove EDs from waters.

Study on soluble heavy metals with preconcentration by using a new modified oligosilsesquioxane sorbent.

In this work, a new modified oligosilsesquioxane was prepared, characterized and evaluated for its heavy metal adsorption characteristics from aqueous solution. The material was characterized using infrared spectroscopy, X-ray diffractometry, solid-state (29)Si and (13)C nuclear magnetic resonance. Batch and column experiments were conducted to investigate for Fe (III), Cr (III), Cu (II), Cd (II), Pb (II) and Ni (II) removal from dilute aqueous solution by sorption onto modified oligosilsesquioxane. The results obtained in the flow experiments, showed a recovery of ca. 100% of the metal ions adsorbed in a column packed with 2.0 g of nanomaterial, using 3 mL of 1.0 mol L(-1) HCl solution as eluent. The detection limits for Fe, Cr, Cu, Cd, Pb, and Ni were 0.26, 0.33, 0.38, 0.41, 0.47 and 0.55 µg L(-1), respectively. The relative standard deviation values (n=12) were <4.82% for Fe, <4.12% for Cr, <3.79% for Cu, <3.03% for Cd, <4.02% for Pb and <2.65% for Ni. The proposed method was successfully applied to the analysis of environmental samples.

Use of diffusive gradients in thin films and tangential flow ultrafiltration for fractionation of Al(III) and Cu(II) in organic-rich river waters.

Diffusive gradients in thin films (DGT) and tangential-flow ultrafiltration (TF-UF) were combined for fractionation of Al and Cu in river water containing high content of dissolved organic carbon. A procedure based on ultrafiltration data is proposed to determine diffusion coefficients of the analytes in water samples and model solutions containing both free metal (M) and complex (metal-humic substance). Aiming to evaluate the accuracy of the proposed approach, the DGT results were compared with those from a protocol for determination of labile Al and Cu based on solid phase extraction (SPE). Good agreement between data from DGT and SPE were attained for model solutions. For analysis of real organic-rich water samples, differences between DGT and SPE measurements were consistent with the time-scales of the techniques. The concentration of labile Al determined by DGT were lower than the total dissolved concentrations (determined by inductively coupled plasma mass spectrometry) and exceeded the ultrafiltered concentration, indicating that inorganic Al species (species small enough to pass through 1 kDa membrane) were minor species as compared with Al organic complexes. For both Al and Cu, there were species not measured by DGT as they are not sufficiently labile.

Preparation of a clay-modified carbon paste electrode based on 2-thiazoline-2-thiol-hexadecylammonium sorption for the sensitive determination of mercury.

A montmorillonite from Wyoming-USA was used to prepare an organo-clay complex, named 2-thiazoline-2-thiol-hexadecyltrimethylammonium-clay (TZT-HDTA-clay), for the purpose of the selective adsorption of the heavy metals ions and possible use as a chemically modified carbon paste electrode (CMCPE). Adsorption isotherms of Hg2+, Pb2+, Cd2+, Cu2+, and Zn2+ from aqueous solutions as a function of the pH were studied at 298 K. Conditions for quantitative retention and elution were established for each metal by batch and column methods. The organo-clay complex was very selective to Hg(II) in aqueous solution in which other metals and ions were also present. The accumulation voltammetry of Hg(II) was studied at a carbon paste electrode chemically modified with this material. The mercury response was evaluated with respect to the pH, electrode composition, preconcentration time, mercury concentration, "cleaning" solution, possible interferences and other variables. A carbon paste electrode modified by TZT-HDTA-clay showed two peaks: one cathodic peak at about 0.0 V and an anodic peak at 0.25 V, scanning the potential from -0.2 to 0.8 V (0.05 M KNO3 vs. Ag/AgCl). The anodic peak at 0.25 V presents excellent selectivity for Hg(II) ions in the presence of foreign ions. The detection limit was estimated as 0.1 microg L(-1). The precision of determination was satisfactory for the respective concentration level.

Preconcentration and determination of mercury(II) at a chemically modified electrode containing 3-(2-thioimidazolyl)propyl silica gel.

A mercury-sensitive chemically modified graphite paste electrode was constructed by incorporating modified silica gel into a conventional graphite paste electrode. The functional group attached to the (3-chloropropyl) silica gel surface was 2-mercaptoimidazole, giving a new product denoted by 3-(2-thioimidazolyl)propyl silica gel, which is able to complex mercury ions. Mercury was chemically adsorbed on the modified graphite paste electrode containing 3-(2-thioimidazolyl)propyl silica (TIPSG GPE) by immersion in a Hg(II) solution, and the resultant surface was characterized by cyclic and differential pulse anodic stripping voltammetry. One cathodic peak at 0.1 V and other anodic peak at 0.34 V were observed on scanning the potential from -0.1 to 0.8 V (0.01 M KNO3; v = 2.0 mV s(-1) vs. Ag/AgCl). The anodic peak at 0.34 V show an excellent sensitivity for Hg(II) ions in the presence of several foreign ions. A calibration graph covering the concentration range from 0.02 to 2 mg L(-1) was obtained. The detection limit was estimated to be 5 microg L(-1). The precision for six determinations of 0.05 and 0.26 mg L(-1) Hg(II) was 3.0 and 2.5% (relative standard deviation), respectively. The method can be used to determine the concentration of mercury(II) in natural waters contaminated by this metal.