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.

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.

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) (BC) modification to be used for removal of As(III) from waters. The BC and BC produced at different pyrolysis temperatures were characterised using FTIR and SEM/EDS. Adsorption capacities of BC and BC 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 BC and BC 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 BC and 50 mg/g for BC. The adsorption kinetics of BC 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 BC and BC attractive for in situ and commercial (filters) use, since time and efficiency are required in new technologies.