Development of chemical separation processes for the treatment and monitoring of metallic cations and oxoanions in polluted waters

The chemical contamination of natural waters is a global problem with a worldwide impact. Considering the relevance of this problem, this thesis is intended, on one hand, to develop different separation/preconcentration techniques based on membranes ability to permeate anions for the transport of toxic oxyanions of chromium(VI) and arsenic contained in aqueous matrices. In particular, we have investigated supported liquid membranes and polymer inclusion membranes, both of which contain the commercial quaternary ammonium salt Aliquat 336 as a carrier, as well as commercial anion exchange membranes. On the other hand, we have focused on the development of chemical sensors to facilitate the monitoring of several metals from different aqueous matrices. Thus, a selective optical sensor for Cr(VI) based on polymeric membranes containing Aliquat 336 as an ionophore has been designed. Additionally, mercury-based screen-printed electrodes have been evaluated for for cadmium, lead, copper and zinc detection.

Influence of time on the plant availability of Cd, Ni and Zn after sewage sludge has been applied to soils

A pot experiment was conducted to test the hypothesis that decomposition of organic matter in sewage sludge and the consequent formation of dissolved organic compounds (DOC) would lead to an increase in the bioavailability of the heavy metals. Two Brown Earth soils, one with clayey loam texture (CL) and the other a loamy sand (LS) were mixed with sewage sludge at rates equivalent to 0, 10 and 50 1 dry sludge ha(-1) and the pots were sown with ryegrass (Lolium perenne L.). The organic matter content and heavy metal availability assessed with soil extractions with 0.05 M CaCl2 were monitored over a residual time of two years, while plant uptake over one year, after addition of the sludge. It was found that the concentrations of Cd and Ni in both the ryegrass and the soil extracts increased slightly but significantly during the first year. In most cases, this increase was most evident especially at the higher sludge application rate (50 t ha(-1)). However, in the second year metal availability reached a plateau. Zinc concentrations in the ryegrass did not show an increase but the CaCl2 extracts increased during the first year. In contrast, organic matter content decreased rapidly in the first months of the first year and much more slowly in the second (total decrease of 16%). The concentrations of DOC increased significantly in the more organic rich CL soil in the course of two years. The pattern followed by the decomposition of organic matter with time and the production of DOC may provide at least a partial explanation for trend towards increased metal availability.

Phylogenetic variation in the tolerance and uptake of organic contaminants

An investigation into the phylogenetic variation of plant tolerance and the root and shoot uptake of organic contaminants was undertaken. The aim was to determine if particular families or genera were tolerant of, or accumulated organic pollutants. Data were collected from sixty-nine studies. The variation between experiments was accounted for using a residual maximum likelihood analysis to approximate means for individual taxa. A nested ANOVA was subsequently used to determine differences at a number of differing phylogenetic levels. Significant differences were observed at a number of phylogenetic levels for the tolerance to TPH, the root concentration factor and the shoot concentration factor. There was no correlation between the uptake of organic pollutants and that of heavy metals. The data indicate that plant phylogeny is an important influence on both the plant tolerance and uptake of organic pollutants. If this study can be expanded, such information can be used when designing plantings for phytoremediation or risk reduction during the restoration of contaminated sites.

Enhanced phytoextraction: In search of EDTA alternatives

Enhanced phytoextraction proposes the use of soil amendments to increase the heavy-metal content of above-ground harvestable plant tissues. This study compares the effect of synthetic aminopolycarboxylic acids [ethylenediamine tetraacetatic acid (EDTA), nitriloacetic acid (NTA), and diethylenetriamine pentaacetic acid (DTPA)] with a number of biodegradable, low-molecular weight, organic acids (citric acid, ascorbic acid, oxalic acid, salicylic acid, and NH4 acetate) as potential soil amendments for enhancing phytoextraction of heavy metals (Cu, Zn, Cd, Pb, and Ni) by Zea mays. The treatments in this study were applied at a dose of 2 mmol/kg(-1) 1 d before sowing. To compare possible effects between presow and postgermination treatments, a second smaller experiment was conducted in which EDTA, citric acid, and NH4 acetate were added 10 d after germination as opposed to 1 d before sowing. The soil used in this screening was a moderately contaminated topsoil derived from a dredged sediment disposal site. This site has been in an oxidized state for more than 8 years before being used in this research. The high carbonate, high organic matter, and high clay content characteristic to this type of sediment are thought to suppress heavy-metal phytoavailability. Both EDTA and DTPA resulted in increased levels of heavy metals in the above-ground biomass. However, the observed increases in uptake were not as large as reported in the literature. Neither the NTA nor organic acid treatments had any significant effect on uptake when applied prior to sowing. This was attributed to the rapid mineralization of these substances and the relatively low doses applied. The generally low extraction observed in this experiment restricts the use of phytoextraction as an effective remediation alternative under the current conditions, with regard to amendments used, applied dose (2 mmol/kg(-1) soil), application time (presow), plant species (Zea mays), and sediment (calcareous clayey soil) under study.

Investigation of tin-based alternatives for cadmium in optoelectronic thin-films materials

Increasing legislation has steadily been introduced throughout the world to restrict the use of heavy metals, particularly cadmium (Cd) and lead (Pb) in high temperature pigments, ceramics, and optoelectronic material applications. Removal of cadmium from thin-film optical and semiconductor device applications has been hampered by the absence of viable alternatives that exhibit similar properties with stability and durability. We describe a range of tin-based compounds that have been deposited and characterized in terms of their optical and mechanical properties and compare them with existing cadmium-based films that currently find widespread use in the optoelectronic and semiconductor industries. (c) 2008 Optical Society of America.

Sediment fingerprinting as an environmental forensics tool explaining cyanobacteria blooms in lakes

Cyanobacteria (blue-green algae) blooms in water bodies present serious public health issues with attendant economic and ecological impacts. Llyn Tegid (Lake Bala) is an important conservation and amenity asset within Snowdonia National Park, Wales which since the mid-1990s has experienced multiple toxic cyanobacteria blooms threatening the ecology and tourism-dependent local economy. Multiple working hypotheses explain the emergence of this problem, including climate change, land management linked to increased nutrient flux, hydromorphological alterations or changing trophic structure - any of which may operate individually or cumulatively to impair lake function. This paper reports the findings of a sedimentfingerprinting study using dated lake cores to explore the linkages between catchment and lake management practices and the emergence of the algal blooms problem. Since 1900 AD lake bed sedimentation rates have varied from 0.06 to 1.07 g cm−2 yr−1, with a pronounced acceleration since the early 1980s. Geochemical analysis revealed increases in the concentrations of total phosphorus (TP), calcium and heavy metals such as zinc and lead consistent with eutrophication and a rising pollution burden, particularly since the late 1970s. An uncertainty-inclusive sedimentfingerprinting approach was used to apportion the relative fluxes from the major catchment land cover types of improved pasture, rough grazing, forestry and channel banks. This showed improved pasture and channel banks are the dominant diffuse sources of sediment in the catchment, though forestry sources were important historically. Conversion of rough grazing to improved grassland, coupled with intensified land management and year-round livestock grazing, is concluded to provide the principal source of rising TP levels. Lake Habitat Survey and particle size analysis of lake cores demonstrate the hydromorphological impact of the River Dee Regulation Scheme, which controls water level and periodically diverts flow into Llyn Tegid from the adjacent Afon Tryweryn catchment. This hydromorphological impact has also been most pronounced since the late 1970s. It is concluded that an integrated approach combining land management to reduce agricultural runoff allied to improved water level regulation enabling recovery of littoral macrophytes offers the greatest chance halting the on-going cyanobacteria issue in Llyn Tegid.

Effect of impurities in biodiesel-derived waste glycerol on the performance and feasibility of biotechnological processes

The rapid development of biodiesel production technology has led to the generation of tremendous quantities of glycerol wastes, as the main by-product of the process. Stoichiometrically, it has been calculated that for every 100 kg of biodiesel, 10 kg of glycerol are produced. Based on the technology imposed by various biodiesel plants, glycerol wastes may contain numerous kinds of impurities such as methanol, salts, soaps, heavy metals and residual fatty acids. This fact often renders biodiesel-derived glycerol unprofitable for further purification. Therefore, the utilization of crude glycerol though biotechnological means represents a promising alternative for the effective management of this industrial waste. This review summarizes the effect of various impurities-contaminants that are found in biodiesel-derived crude glycerol upon its conversion by microbial strains in biotechnological processes. Insights are given concerning the technologies that are currently applied in biodiesel production, with emphasis to the impurities that are added in the composition of crude glycerol, through each step of the production process. Moreover, extensive discussion is made in relation with the impact of the nature of impurities upon the performances of prokaryotic and eukaryotic microorganisms, during crude glycerol bioconversions into a variety of high added-value metabolic products. Finally, aspects concerning ways of crude glycerol treatment for the removal of inhibitory contaminants as reported in the literature are given and comprehensively discussed

A study of the chemical and physical properties of cashew nut shell ash for use in cement materials.

A study of the chemical and physical properties of cashew nut shell ash for use in cement materials. Ash occupies a prominent place among agro-industrial wastes, as it is derived from energy generation processes. Several types of ash have pozzolanic reactivity, and might be used as replacement material for cement, resulting in less energy waste and lower cost. This work aimed to investigate the physical and chemical properties of the cashew nut shell ash (CNSA), by performing the following measurement tests: chemical analysis, bulk density, specific mass, leaching and solubilization process, X-ray diffraction (XrD), specific surface area (BET) and pozzolanicity analysis with cement and lime. The results indicate a low reactivity of CNSA and the presence of heavy metals, alkalis and phenol.

Sub-tropical urban environment affecting content and composition of non-structural carbohydrates of Lolium multiflorum ssp italicum cv. Lema

This study analyzed the relationship between environmental factors, especially air pollution and climatic conditions, and non-structural carbohydrates (NSC) in plants of Lolium multiflorum exposed during 10 consecutive periods of 28 days at a polluted site (Congonhas) and at a reference site in Sao Paulo city (Brazil). After exposure, NSC composition and leaf concentrations of Al, Fe. Cu, Zn, Pb and Cd were measured. The seasonal pattern of NSC accumulation was quite similar in both sites, but plants at Congonhas showed higher concentrations of these compounds, especially fructans of low and medium degree of polymerization. Regression analysis showed that NSC in plants growing at the polluted site were explained by variations on temperature and leaf concentration of Fe (positive effect), as well as relative humidity and particulate material (negative effect). NSC in the standardized grass culture, in addition to heavy metal accumulation, may indicate stressing conditions in a sub-tropical polluted environment. (C) 2008 Elsevier Ltd. All rights reserved.

A Metal-Repressed Promoter From Gram-Positive Bacillus subtilis Is Highly Active and Metal-Induced in Gram-Negative Cupriavidus metallidurans

A synthetic version of the metal-regulated gene A (mrgA) promoter from Bacillus subtilis, which in this Gram-positive bacterium is negatively regulated by manganese, iron, cobalt, or copper turned out to promote high level of basal gene expression that is further enhanced by Co(II), Cd(II), Mn(II), Zn(II), Cu(II), or Ni(II), when cloned in the Gram-negative bacterium Cupriavidus metallidurans. Promoter activity was monitored by expression of the reporter gene coding for the enhanced green fluorescent protein (EGFP), and cellular intensity fluorescence was quantified by flow cytometry. Expression levels in C. metallidurans driven by the heterologous promoter, here called pan, ranged from 20- to 53-fold the expression level driven by the Escherichia coli lac promoter (which is constitutively expressed in C. metallidurans), whether in the absence or presence of metal ions, respectively. The pan promoter did also function in E. coli in a constitutive pattern, regardless of the presence of Mn(II) or Fe(II). In conclusion, the pan promoter proved to be a powerful tool to express heterologous proteins in Gram-negative bacteria, especially in C. metallidurans grown upon high levels of toxic metals, with potential applications in bioremediation. Biotechnol. Bioeng. 2010; 107: 469-477. (C) 2010 Wiley Periodicals, Inc.

Evaluation of trace element levels in muscles, liver and gonad of fish species from Sao Francisco River of the Parana Brazilian state by using SR-TXRF technique

This study is focused on the analysis of an accumulation of inorganic elements in muscles, liver and gonad of seven fish species from Sao Francisco River located in the Parana state of Brazil. Concentrations of the elements were determined using the SR-TXRF technique. In the muscles of fish species, negative length dependent relationships were observed for chromium and zinc ion absorption. The obtained results showed that accumulated Cr ions values are above the limits defined in the Brazilian legislative norm on food. (C) 2010 Elsevier Ltd All rights reserved.

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-K beta 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-K beta(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-K beta"" 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-K beta spectra of root tissue species were compared, the peak energies and lineshape patterns of the Cr-K beta(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. (C) 2009 Elsevier Ltd. All rights reserved.

PIXE analysis of chromium phytoaccumulation by the aquatic macrophytes Eicchornia crassipes

The uptake of hexavalent chromium in free living floating aquatic macrophytes Eicchornia crassipes cultivated in non-toxic chromium-doped hydroponic solutions is presented. A Cr-uptake bioaccumulation experiment was carried out using healthy macrophytes grown in a temperature controlled greenhouse. Six samples of nutrient media and plants were collected during the 23 day experiment. Roots and leaves were acid digested with the addition of an internal Gallium standard, for thin film sample preparation and quantitative Cr analysis by PIXE method. The Cr(6+) mass uptake by the macrophytes reached up to 70% of the initial concentration, comparable to former results and literature data. The Cr-uptake data were described using a non-structural first order kinetic model. Due to low cost and high removal efficiency, living aquatic macrophytes E. crassipes are a viable biosorbent in an artificial wetland of a water effluent treatment plant. (c) 2009 Elsevier B.V. All rights reserved.

Metal contamination in urban park soils of SA o pound Paulo

There has been little research on metal concentration levels in urban soils of SA o pound Paulo, a city with 19 million inhabitants with severe pollution problems. In the present study, the concentration of As, Ba, Cr, Cu, Pb, Sb and Zn, were determined by INAA and XRF in surface soil samples from 7 public parks located within SA o pound Paulo city. The results obtained showed that soils of SA o pound Paulo public parks present concentration levels of the studied elements higher than the reference values for soils in SA o pound Paulo State. Traffic related elements such as Cu, Pb and Zn presented high concentrations in parks located near avenues of highly dense traffic and may be associated to vehicular sources.

Ecosystem health of Montevideo coastal zone: A multi approach using some different benthic indicators to improve a ten-year-ago assessment

A study on the benthic ecosystem health was performed to assess the environmental quality of Montevideo coastal zone, in view of the construction of a new sanitation system. Data were compared to previous research undertaken 10 years ago, and biochemical composition of organic matter, heavy metals, organic matter, phytopigments, benthic diatoms, macrofauna community structure and a biotic index (AMBI) were used as proxies. Results indicate an environmental quality-gradient, with the worst conditions within the inner stations of Montevideo Bay and an improvement towards the adjacent coastal zone. Higher levels of chromium, lead, phaeopigments, organic biopolymers and poor benthic macrofauna and diatom communities, characterised the hypertrophic innermost portion of Montevideo Bay. Data indicated a clear deterioration of the adjacent coastal zone comparatively to that observed 10 years ago. The complementary use of approaches not applied before (benthic diatoms and organic biopolymers) with those formerly applied improve our assessment of the trophic status and the environmental health of the area. (C) 2010 Elsevier B.V. All rights reserved.