Effect of elemental composition assigned to antrotopic pollution on the quality of the water and sediment of the Marrecas river (PR, Brazil) as highlighted by multivariate statistical analyses.

In recent years, several environmental pollutants have been monitored in surface waters and sediments. However, few studies apply multivariate statistics to identify the main components and correlate them temporally and spatially. In this sense, the present study sought to monitor the quality of water and sediments in the Rio Marrecas/Brazil, through the analysis of physicochemical parameters and trace elements, as well as to identifying sources of contamination, using multivariate statistics. For this purpose, sampling was carried out in nine locations for a period of 12 months. The Total Reflection X-ray Fluorescence (TXRF) technique was used to quantify the 15 elements identified in water and sediment samples. Through multivariate statistical analyses, the most significant elements, their correlations and possible pollutant sources were defined, and the pollution index (HPI) and assessment index (HEI) of heavy metals were applied. The parameters pH and BOD5 do not comply with Brazilian legislation. Based on PCA and Spearman correlation, there was strong evidence of contamination of the water naturally, composed of the elements Ti, V, Mn, Fe, and of anthropogenic origin composed of the elements Ca, Ni, Cu, Zn. These findings provide insights to determine the impacts of heavy metals on human health and the environment.

Study of the involved sorption mechanisms of Cr(VI) and Cr(III) species onto dried Salvinia auriculata biomass.

Removal of Cr(VI) species by dried biomass of the aquatic macrophyte Salvinia auriculata was studied in order to understand the involved sorption mechanisms. Kinetic tests were carried out under the conditions such as concentration range of Cr(VI) from 50 to 250 mg L-1 and a temperature of 30 °C. Modification of the biosorbent by the presence of Cr(VI) species was assessed by analysis of its porosity, density and infrared molecular absorption spectrum. A series of experimental approaches involving directed chemical modifications on the biosorbent surface was performed. The main functional groups involved in the sorption mechanisms were identified. The gas sorption analyser was applied and proved that a strong chemical effect of Cr(VI) species on the surface took place, resulting in a leaching organic matter with an obvious and significant increase in the porosity parameters. The intra-particle diffusion model revealed different mass transfer zones into the adsorbent during Cr(VI) removal. New combined Langmuir and Dubinin-Radushkevich isotherm was the best to fit the equilibrium data of Cr(VI) species removal. Finally, Cr(VI) removal was mainly mediated by a redox process where Cr(III) species were formed.

Potential of Salvinia auriculata biomass as biosorbent of the Cr(III): directed chemical treatment, modeling and sorption mechanism study.

In this work, the mechanism of the Cr(III) sorption by Salvinia auriculata biosorbent was studied in two stages. To understand the influence of the sorption parameters on the Cr(III) uptake, preliminary tests were performed. First, S. auriculata biomass was separately treated with base and acid solutions. Second, acid and base treatment of samples was performed based on the knowledge data base of our group. It was achieved a higher Cr(III) sorption capacity above 15 mg g-1 as associated to an increase of the micro-pores specific area and biosorbent volume. The obtained kinetic data of raw and treated biosorbents were well described by the intra-particle diffusion model. In this model, Cr(III) adsorption onto treated biomass is progressively improved with appearing of different mass transfer zones from out layer up to micro-porous layers. The equilibrium data of raw biomass were best described by the Langmuir isotherm, whereas the equilibrium data of the treated biomass were best fit by a combination of both Langmuir and Dubinin-Radushkevich isotherms. At low concentrations the adsorption most likely occurred on the outer monolayer, as proposed by the Langmuir model, followed by the adsorption on the micro-porous layers, as validated by the Dubinin-Radushkevich isotherm.

Improvement on the concentrated grape juice physico-chemical characteristics by an enzymatic treatment and Membrane Separation Processes.

In this work, the improvement on the concentrated grape juice physico-chemical characteristics by using an enzymatic treatment followed by Membrane Separation Process (MSP) has been investigated. By using Novozym 33095(r) and Ultrazym AFP L(r) enzymes varying three operating parameters, the best result on the grape pulp characteristics was attained for the Novozym 33095(r) performed at 35oC, 15 min. and 50 mgL-1. In micro/ultra filtration processes after enzymatic pretreatment, the best performance of the MSP with high permeate flux value and suitable grape juice characteristics was attained using 0.05 mm membrane pore size, 1 bar pressure and 40 oC treatment temperature. When reverse osmosis process is operated at 40 bar and 40oC, high soluble solid and low turbidity values are attained. An enzymatic treatment along with MSP has shown an alternative and efficient grape juice processing system, being possible to extend to other foods.

Assessment of the banana pseudostem as a low-cost biosorbent for the removal of reactive blue 5G dye.

In this work, the removal of reactive blue 5G (RB5G) dye using the drying biomass of banana pseudostem (BPS) was investigated. The characterization of BPS particles was performed. Improvement in the RB5G dye removal performance at the following sorption conditions was evidenced: pH 1, 30°C sorption temperature and 40 rpm shaking, regardless of the particle size range. Kinetic RB5G dye sorption data obtained at better conditions fit well in an Elovich model. A combined Langmuir-BET isotherm model provides a good representation of the RB5G dye equilibrium sorption data, which shows the evidence of a physical sorption process on the BPS surface. Based on the results, the removal of RB5G dye molecules by BPS is based on a physical sorption process.

Inhibitory effect on the uptake and diffusion of Cd(2+) onto soybean hull sorbent in Cd-Pb binary sorption systems.

The uptake of Cd(2+) and Pb(2+) ions by a soybean hull (SH) biosorbent in single and binary systems has been investigated. Sorption tests regarding SH in natura and chemically treated were carried out testing a suitable value range of solution pH, sorption temperature and shaking velocity. Sorption capacity is improved at pH 4, 30 °C temperature and 100 rpm. When a strong base is applied, a related-to-untreated SH increasing of 20% in the sorption capacity of Pb(2+) ions was observed, but with poor results for Cd(2+) uptake. Additionally, a relatively strong decreasing in both sorption capacities of Pb(2+) and Cd(2+) ions was evidenced for all acidic treatments. Regarding untreated SH, kinetic sorption data of both metals were well-interpreted by a pseudo second-order model and a rate-limiting step on the basis of an intra-particle diffusion model was suggested to occur. An inhibitory effect of Pb(2+) diffusion over Cd(2+) one was observed, limiting to reach the obtained maximum sorption capacity in single system. Maximum adsorption capacities of 0.49 and 0.67mequivg(-1) for Cd(2+) and Pb(2+), respectively, were predicted by the Langmuir isotherm model that reproduced well the equilibrium sorption data for single systems. The inhibitory effect of one metal over the other one was verified in equilibrium sorption data for binary systems interpreted on the basis of a modified extended Langmuir isotherm model, predicting changes in metal affinity onto the SH surface. Finally, SH is an alternative biosorbent with a great potential for the wastewater treatment containing cadmium and lead ions.

Performance evaluation of different solar advanced oxidation processes applied to the treatment of a real textile dyeing wastewater.

The performance of different solar-driven advanced oxidation processes (AOPs), such as TiO2/UV, TiO2/H2O2/UV, and Fe(2+)/H2O2/UV-visible in the treatment of a real textile effluent using a pilot plant with compound parabolic collectors (CPCs), was investigated. The influence of the main photo-Fenton reaction variables such as iron concentration (20-100 mg Fe(2+) L(-1)), pH (2.4-4.5), temperature (10-50 °C), and irradiance (22-68 WUV m(-2)) was evaluated in a lab-scale prototype using artificial solar radiation. The real textile wastewater presented a beige color, with a maximum absorbance peak at 641 nm, alkaline pH (8.1), moderate organic content (dissolved organic carbon (DOC) = 129 mg C L(-1) and chemical oxygen demand (COD) = 496 mg O2 L(-1)), and high conductivity mainly associated to the high concentration of chloride (1.1 g Cl(-) L(-1)), sulfate (0.4 g SO 4 (2 -) L(- 1)), and sodium (1.2 g Na(+) L(-1)) ions. Although all the processes tested contributed to complete decolorization and effective mineralization, the most efficient process was the solar photo-Fenton with an optimum catalyst concentration of 60 mg Fe(2+) L(-1), leading to 70 % mineralization (DOCfinal = 41 mg C L(-1); CODfinal < 150 mg O2 L(-1)) at pH 3.6, requiring a UV energy dose of 3.5 kJUV L(-1) (t 30 W = 22.4 min; [Formula: see text]; [Formula: see text]) and consuming 18.5 mM of H2O2.

Biodegradability and toxicity assessment of a real textile wastewater effluent treated by an optimized electrocoagulation process.

In this work, the application of an iron electrode-based electrocoagulation (EC) process on the treatment of a real textile wastewater (RTW) was investigated. In order to perform an efficient integration of the EC process with a biological oxidation one, an enhancement in the biodegradability and low toxicity of final compounds was sought. Optimal values of EC reactor operation parameters (pH, current density and electrolysis time) were achieved by applying a full factorial 3(3) experimental design. Biodegradability and toxicity assays were performed on treated RTW samples obtained at the optimal values of: pH of the solution (7.0), current density (142.9 A m(-2)) and different electrolysis times. As response variables for the biodegradability and toxicity assessment, the Zahn-Wellens test (Dt), the ratio values of dissolved organic carbon (DOC) relative to low-molecular-weight carboxylates anions (LMCA) and lethal concentration 50 (LC50) were used. According to the Dt, the DOC/LMCA ratio and LC50, an electrolysis time of 15 min along with the optimal values of pH and current density were suggested as suitable for a next stage of treatment based on a biological oxidation process.

Determination of the mass transfer limiting step of dye adsorption onto commercial adsorbent by using mathematical models.

Reactive blue 5G dye removal in a fixed-bed column packed with Dowex Optipore SD-2 adsorbent was modelled. Three mathematical models were tested in order to determine the limiting step of the mass transfer of the dye adsorption process onto the adsorbent. The mass transfer resistance was considered to be a criterion for the determination of the difference between models. The models contained information about the external, internal, or surface adsorption limiting step. In the model development procedure, two hypotheses were applied to describe the internal mass transfer resistance. First, the mass transfer coefficient constant was considered. Second, the mass transfer coefficient was considered as a function of the dye concentration in the adsorbent. The experimental breakthrough curves were obtained for different particle diameters of the adsorbent, flow rates, and feed dye concentrations in order to evaluate the predictive power of the models. The values of the mass transfer parameters of the mathematical models were estimated by using the downhill simplex optimization method. The results showed that the model that considered internal resistance with a variable mass transfer coefficient was more flexible than the other ones and this model described the dynamics of the adsorption process of the dye in the fixed-bed column better. Hence, this model can be used for optimization and column design purposes for the investigated systems and similar ones.

Influence of lead-doped hydroponic medium on the adsorption/bioaccumulation processes of lead and phosphorus in roots and leaves of the aquatic macrophyte Eicchornia crassipes.

In this study, lead bioaccumulation by the living free-floating aquatic macrophyte Eicchornia crassipes in different hydroponic conditions with variations in phosphorus and lead concentrations was investigated. A set of growth experiments in hydroponic media doped with lead and phosphorus within a wide concentration range was performed for 32 days in a greenhouse. All experiments were carried out with periodic replacement of all nutrients and lead. The concentration of lead and nutrients in biomass was determined by synchrotron radiation-excited total reflection X-ray fluorescence. By increasing the lead concentration in the medium, a reduction in biomass growth was observed, but a higher phosphorus retention in roots and leaves was shown at lower lead concentrations. In addition, an increase in the amount of bioaccumulated lead and phosphorus in roots was observed for higher lead and phosphorus concentrations in the medium, reaching saturation values of 4 mg Pb g(-1) and 7 mg P g(-1), respectively. Four non-structural kinetic models were tested, to represent the bioaccumulation of lead and phosphorus in roots. Pseudo-second order and irreversible kinetic models described the lead bioaccumulation data well, however, an irreversible kinetic model better fitted phosphorus uptake in roots.

Elements concentration analysis in groundwater from the North Serra Geral aquifer in Santa Helena-Brazil using SR-TXRF spectrometer.

In this work the analysis of elements concentration in groundwater was performed using the synchrotron radiation total-reflection X-ray fluorescence (SR-TXRF) technique. A set of nine tube-wells with serious risk of contamination was chosen to monitor the mean concentration of elements in groundwater from the North Serra Geral aquifer in Santa Helena, Brazil, during 1 year. Element concentrations were determined applying a SR-TXRF methodology. The accuracy of SR-TXRF technique was validated by analysis of a certified reference material. As the groundwater composition in the North Serra Geral aquifer showed heterogeneity in the spatial distribution of eight major elements, a hierarchical clustering to the data was performed. By a similarity in their compositions, two of the nine wells were grouped in a first cluster, while the other seven were grouped in a second cluster. Calcium was the major element in all wells, with higher Ca concentration in the second cluster than in the first cluster. However, concentrations of Ti, V, Cr in the first cluster are slightly higher than those in the second cluster. The findings of this study within a monitoring program of tube-wells could provide a useful assessment of controls over groundwater composition and support management at regional level.

Application of high resolution X-ray emission spectroscopy on the study of Cr ion adsorption by activated carbon.

In this work granular activated carbon has been chosen as an absorbent in order to investigate the Cr(VI) reduced by adsorption experiments. Several batch chromium-sorption experiments were carried out using 0.25 g of granular activated carbon in 50 mL aqueous solution containing approximately 70 and 140 mg L(-1) of Cr(VI) and Cr(III), respectively. Cr-Kbeta fluorescence spectra of Cr adsorbed in a carbon matrix and Cr reference materials were measured using a high-resolution Johann-type spectrometer. Based on evidence from the Cr-Kb satellite lines, the Cr(VI) reduction process has actually happened during metal adsorption by the activated carbon.

Electrocoagulation efficiency of the tannery effluent treatment using aluminium electrodes.

An electro-coagulation laboratory scale system using aluminium plates electrodes was studied for the removal of organic and inorganic pollutants as a by-product from leather finishing industrial process. A fractional factorial 2(3) experimental design was applied in order to obtain optimal values of the system state variables. The electro-coagulation (EC) process efficiency was based on the chemical oxygen demand (COD), turbidity, total suspended solid, total fixed solid, total volatile solid, and chemical element concentration values. Analysis of variance (ANOVA) for final pH, total fixed solid (TFS), turbidity and Ca concentration have confirmed the predicted models by the experimental design within a 95% confidence level. The reactor working conditions close to real effluent pH (7.6) and electrolysis time in the range 30-45 min were enough to achieve the cost effective reduction factors of organic and inorganic pollutants' concentrations. An appreciable improvement in COD removal efficiency was obtained for electro-coagulation treatment. Finally, the technical-economical analysis results have clearly shown that the electro-coagulation method is very promising for industrial application.

Toxicity assessment from electro-coagulation treated-textile dye wastewaters by bioassays.

In this study the pollutant removal from a textile dyeing wastewater has been investigated by using the electro-coagulation technique with iron electrodes. In order to obtain optimal values of the system state variables, a 3(3) full factorial experimental design was applied. The electro-coagulation (EC) process response was evaluated on the basis of COD removal and decolourization values. The electrolysis time and density current were statistically significant for the COD removal and decolourization. Based on the lettuce seeds (Lactuca sativa) and brine shrimp (Artemia salina), the lowest toxicity level was achieved in 5 min of electrolysis time. Due to the remaining high toxicity level above 30 min of electrolysis time, the EC process is not adequate to be used in a single effluent treatment, suggesting that this electrochemical process of up to 5 min could be used as part of a complete effluent treatment system.

Root uptake and reduction of hexavalent chromium by aquatic macrophytes as assessed by high-resolution X-ray emission.

Aquatic macrophytes Salvinia auriculata, Pistia stratiotes and Eichhornia crassipes were chosen to investigate the Cr(VI) reduced by root-based biosorption in a chromium uptake experiment, using a high-resolution XRF technique. These plants were grown in hydroponics medium supplied with non-toxic Cr concentrations during a 27-day metal uptake experiment. The high-resolution Cr-Kbeta fluorescence spectra for dried root tissues and Cr reference material (100% Cr, Cr(2)O(3), and CrO(3)) were measured using an XRF spectrometer. For all species of aquatic plant treated with Cr(VI), the energy of the Cr-Kbeta(2,5) line was shifted around 8 eV below the same spectral line identified for the Cr(VI) reference, but it was also near to the line identified for the Cr(III) reference. Moreover, there was a lack of the strong Cr-Kbeta'' line assigned to the Cr(VI) reference material within the Cr(VI)-treated plant spectra, suggesting the reduction of Cr(VI) for other less toxic oxidation states of Cr. As all Cr-Kbeta spectra of root tissue species were compared, the peak energies and lineshape patterns of the Cr-Kbeta(2,5) line are coincident for the same aquatic plant species, when they were treated with Cr(III) and Cr(VI). Based on the experimental evidence, the Cr(VI) reduction process has happened during metal biosorption by these plants.