Incorporation of dithiooxamide as a complexing agent into cellulose for the removal and pre-concentration of Cu(II) and Cd(II) ions from natural water samples

The present study describes the incorporation of a complexing agent, dithiooxamide, into microcrystalline cellulose for use in the pre-concentration of Cu(II) and Cd(II) ions from aqueous samples. The FTIR spectrum of the adsorbent exhibited an absorption band in the region of 800 cm-1, which confirmed the binding of the silylating agent to the matrix. Elemental analysis indicated the amount of 0.150 mmol g-1 of the complexing agent. The adsorption data were fit to the modified Langmuir equation, and the maximum amount of metal species extracted from the solution, Ns, was determined to be 0.058 and 0.072 mmol g-1 for Cu(II) and Cd(II), respectively. The covering fraction φ, which was 0.39 and 0.48 for Cu(II) and Cd(II), respectively, was used to estimate a 1:2 (metal:ligand) ratio in the formed complex, and a binding model was proposed based on this information. The adsorbent was applied in the pre-concentration of natural water samples and exhibited an enrichment factor of approximately 50-fold for the species studied, which enabled its use in the analysis of trace metals in aqueous samples. The system was validated by the analysis of certified standard (1643e), and the adsorbent was stable for more than 20 cycles, thus enabling its safe reutilization. © 2012 Elsevier B.V. All rights reserved.

Integrated quality assessment of sediments from harbour areas in Santos-São Vicente Estuarine System, Southern Brazil

Santos-São Vicente Estuarine System is a highly populated coastal zone in Brazil and where it is located the major port of Latin America. Historically, port activities, industrial and domestic effluents discharges have constituted the main sources of contaminants to estuarine system. This study aimed to assess the recent status of sediment quality from 5 zones of Port of Santos by applying a lines-of-evidence approach through integrating results of: (1) acute toxicity of whole sediment and chronic toxicity of liquid phases; (2) grain size, organic matter, organic carbon, nitrogen, phosphorus, trace metals, polycyclic aromatic hydrocarbons, linear alkylbenzenes and butyltins; (3) benthic community descriptors. Results revealed a gradient of increasing contamination for metals and organic compounds, alongside with their geochemical carriers. Sediment liquid phases were more toxic compared to whole sediment. Low number of species and individuals indicated the impoverishment of benthic community. The use of site-specific sediment quality guidelines was more appropriate to predict sediment toxicity. The integration of results through Sediment Quality Triad approach and principal component analysis allowed observing the effects of natural stressors and dredging on sediment quality and benthic distribution. Even with recent governmental efforts to control, pollution is still relevant in Port of Santos and a threat to local ecosystems. © 2013 Elsevier Ltd.

Mineralogia e geoquímica de sedimentos de manguezais da costa amazônica: o exemplo do estuário do rio Marapanim (Pará)

Os manguezais do estado do Pará representam importante segmento da costa norte brasileira sobre os quais pouco se conhece das características geológicas e as relações com área(s)-fonte. A pesquisa foi realizada no estuário do rio Marapanim, na costa paraense, para demonstrar a contribuição de sedimentos continentais para a formação dos sedimentos dos manguezais. Foram coletados sedimentos da Formação Barreiras e solos dela derivados (principais fontes terrígenas), e os sedimentos de manguezal. Nos sedimentos de manguezal foram realizadas análises granulométricas, determinação dos teores de carbono (C %) e medidas de pH, Eh e salinidade intersticial. A determinação mineralógica e a geoquímica multi-elementar foi feita nos sedimentos lamosos e nos sedimentos continentais adjacentes, para comparações. Os sedimentos de manguezal são sílticoargilosos (> 90 %), com teores de carbono entre 0,75 a 3,5 %. A mineralogia principal é composta por quartzo, goethita, hematita, caulinita, illita, além de zircão, turmalina, estaurolita e cianita como acessórios, assinatura mineralógica típica dos sedimentos da Formação Barreiras e dos solos. De ocorrência comum nesses manguezais, os minerais neoformados são: esmectita, feldspato potássico, pirita, halita, gipso e a jarosita. O enriquecimento em SiO₂, Al₂O₃, Fe₂O₃, e TiO₂ nos manguezais e os níveis crustais dos metais-traço refletem o clima tropical e a composição mineralógica da área-fonte, rica em quartzo e caulinita e a ausência de influência antrópica. A composição química associada à matéria orgânica, abundantes diatomáceas além de Fe, S e os aportes de Cl^-, Na⁺, K⁺, Ca⁺⁺ e Mg⁺⁺ da água do mar, identificam o ambiente deposicional e os minerais autigênicos. O padrão de fracionamento dos elementos-traço nos manguezais também corrobora a marcante contribuição da área-fonte continental. Esses sedimentos apresentam o predomínio dos Elementos Terras Rara Leves (ETRL) sobre os Elementos Terras Raras Pesados (ETRP) com elevadas razões de Th/Co; La/Th; La/Sc; La/Co e Zr/Sc e Th/ Sc e Ba/Co, elementos presentes nas rochas ígneas félsicas que originaram os sedimentos terrígenos.

Síntese e caracterização de hidróxidos duplos a partir da lama vermelha

O resíduo do refino da bauxita, comumente conhecido como lama vermelha, tem mostrado ser capaz de ligar metais traços tais como o cobre, cádmio, zinco, cromo, níquel e chumbo sob condições apropriadas. A neutralização da lama vermelha é necessária porque essa lama é tipicamente cáustica, com pH em torno de 13. Muitas pesquisas têm sido desenvolvidas envolvendo a utilização da lama vermelha, porque contem uma série de elementos valiosos. Assim a utilização da lama vermelha como material de construção e como adsorvente é atrativa porque ela é utilizada em grande quantidade. Nada pode ser feito sem descartar componentes valiosos como titânio, zircônio e principalmente ferro. A síntese de hidrotalcita conectada com a reciclagem de soluções alcalinas representa uma maneira efetiva de uso dessa solução considerando a forte demanda por proteção ambiental no mundo. Os compostos tipo hidrotalcita, precipitados durante a neutralização da lama, também removem oxi-ânions de metais de transição através da combinação de intercalações e adsorção de espécies aniônicas na sua superfície externa. Os hidróxidos duplos lamelares (HDL) vêm sendo investigados à muitos anos como materiais hospedeiros para uma variedade de reações de intercalação de anions. A estrutura lamelar dos HDLs pode ser usada para controlar a adição ou remoção de uma variedade de espécies químicas, tanto orgânicas quanto inorgânicas. Isto é alcançado através de sua habilidade de adaptar a separação das lamelas de hidróxidos, e da reatividade da região interlamelar. O material resultante adsorve anions quando colocado em soluções e reverte a estrutura da hidrotalcita. Avanços significativos têm sido alcançados recentemente na caracterização desses materiais, incluindo estudos estruturais sobre o mecanismo de intercalação. O objetivo desse trabalho foi a síntese e caracterização de HDLs a partir da lama vermelha, e testar esses materiais como adsorventes de metais pesados.

Evaluation of diffusive gradients in thin films technique (DGT) for measuring Al, Cd, Co, Cu, Mn, Ni, and Zn in Amazonian rivers

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Avaliação da membrana de troca aniônica DE 81 como ligante ba técnica de difusão em filmes finos por gradientes de concentração (DGT) para a determinação de Cromo VI

It is known that there is a wide variety of bioavailable trace metals in aquatic systems, and its determination is fundamental to predict impacts to organisms in these environments. However, the determination of the total concentration of chemicals in aquatic systems, despite its importance, does not provide necessary information for decision making or even may lead to misinterpretation of the procedures and potential risks to the system in question. This study aimed to use the technique of diffusion in thin films by concentration gradients (DGT) to evaluate the anion exchange membrane Whatman DE 81 as binder alternative in determining Cr (VI). Experiments were carried out to determine the diffusion coefficients for the material used diffusion (agarose gel). The behaviors of the binders were analyzed before the main variables of the systems, immersion time, pH and ionic strength. Then was made the assessment of potential interferences, to finally proceed with testing using actual samples in the laboratory and in situ

Cassava wastewater as carbon source for the polyhydroxybutyrate production by Azotobacter vinelandii CCT 2841

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Constructed Wetland for Treating Effluent from Subtropical Aquaculture Farm

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Influência do manejo do solo em atributos químicos, físicos e microbiológicos dos córregos Jaboticabal e Cerradinho

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Integrated sediment quality assessment in Paranagua Estuarine System, Southern Brazil

Sediment quality from Paranagua Estuarine System (PES), a highly important port and ecological zone, was evaluated by assessing three lines of evidence: (1) sediment physical-chemical characteristics; (2) sediment toxicity (elutriates, sediment-water interface, and whole sediment); and (3) benthic community structure. Results revealed a gradient of increasing degradation of sediments (i.e. higher concentrations of trace metals, higher toxicity, and impoverishment of benthic community structure) towards inner PES. Data integration by principal component analysis (PCA) showed positive correlation between some contaminants (mainly As, Cr, Ni, and Pb) and toxicity in samples collected from stations located in upper estuary and one station placed away from contamination sources. Benthic community structure seems to be affected by both pollution and natural fine characteristics of the sediments, which reinforces the importance of a weight-of-evidence approach to evaluate sediments of PES. (C) 2008 Elsevier Inc. All rights reserved.

Determination of labile barium in petroleum-produced formation water using paper-based DGT samplers

A polyacrylamide hydrogel containing the Chelex-100 resin has traditionally been used as the binding agent for the diffusion gradients in thin films (DGT) technique. The Chelex-100 resin, although important for the determination of various transition metals, is unsatisfactory for the determination of alkaline earth metals, particularly Ba. In this paper, a cellulose membrane, treated with phosphate (P81 membrane), was evaluated as a binding agent for DGT devices for the determination of Ba in produced formation water (PEW) samples. In addition, diffusive layers of filter paper (cellulose) were tested to diffuse Ba through the DGT devices. Experiments to evaluate the key variables of the technique (pH, deployment time, and ionic strength/salinity) were performed. The Ba sampled by these DGT devices was measured using inductively coupled plasma optical emission spectrometry. Aiming to generate information (related to bioavailability of Ba) on the reuse of PEW for irrigation, the determination of Ba in onshore and offshore samples was performed. The new approach was effective for determination of Ba in onshore samples. To determine Ba in offshore samples, it was necessary to use an alternative calibration procedure due to the high NaCl concentration in these samples. (C) 2012 Elsevier B.V. All rights reserved.

Evaluation of tropical water sources and mollusks in southern Brazil using microbiological, biochemical, and chemical parameters

Florianopolis, a city located in the Santa Catarina State in southern Brazil, is the national leading producer of bivalve mollusks. The quality of bivalve mollusks is closely related to the sanitary conditions of surrounding waters where they are cultivated. Presently, cultivation areas receive large amounts of effluents derived mainly from treated and non-treated domestic, rural, and urban sewage. This contributes to the contamination of mollusks with trace metals, pesticides, other organic compounds, and human pathogens such as viruses, bacteria, and protozoan. The aim of this study was to perform a thorough diagnosis of the shellfish growing areas in Florianopolis, on the coast of Santa Catarina. The contamination levels of seawater, sediments, and oysters were evaluated for their microbiological, biochemical, and chemical parameters at five sea sites in Florianopolis, namely three regular oyster cultivation areas (Sites 1, 2, and oyster supplier), a polluted site (Site 3), and a heavily polluted site (Site 4). Samples were evaluated at day zero and after 14 days. Seawater and sediment samples were collected just once, at the end of the experiment. Antioxidant defenses, which may occur in contaminated environments in response to the increased production of reactive oxygen species (ROS) by organisms, were analyzed in oysters, as well as organic compounds (in oysters and sediment samples) and microbiological contamination (in oysters and seawater samples). The results showed the presence of the following contaminants: fecal coliforms in seawater samples (four sites), human adenovirus (all sites), human noroviruses GI and GII (two sites), Hepatitis A viruses (one site), JC Polyomavirus in an oyster sample from the oyster supplier, Giardia duodenalis cysts, and Cryptosporidium sp oocysts (one site). Among organochlorine pesticides, only DDT (dichlorodiphenyltrichloroethane) and HCH (hexachlorocyclohexane) were detected in some sediment and oysters samples in very low levels; site 4 had the highest concentrations of total aliphatic hydrocarbons. PAHs, and linear alkylbenzenes (LABs) found either in oysters or in sediment samples. The major concentration of fecal sterol coprostanol was found at site 4, followed by site 3. After 14 days of allocation in the four selected sites, there was a significant difference in the enzymes analyzed at the monitored spots. The detection of different contaminants in oysters, seawater, and sediment samples in the present study shows the impact untreated or inadequately treated effluents have on coastal areas. These results highlight the need for public investment in adequate wastewater treatment and adequate treatment of oysters, ensuring safe areas for shellfish production as well as healthier bivalve mollusks for consumption.

Cylindrospermopsis raciborskii exudate-Cu complexes: impact on copper dynamics and bioavailability in an aquatic food chain

The increasing contamination of aquatic environments motivates studies on the interactions among natural dissolved organic matter, metals, and the biota. This investigation focused on the organic exudates of the toxic cyanobacteria Cylindrospermopsis raciborskii as a Cu carrier through a three-level aquatic trophic chain (bacteria, protozoa, and copepod). The effects of bacteria activity and growth on the metal-organic complexes were evaluated through changes in free Cu2+ ions, total dissolved, and total particulate Cu. To be sure that the added copper would be complexed to the exudates, its complexing properties were previously determined. The cyanobacteria exudate-Cu complexes were furnished to bacteria that were further used as a food source to the protozoan Paramercium caudatum. This was then furnished as food to the copepod Mesocyclops sp. The results showed that, in general, the cyanobacterial exudates decreased Cu bioavailability and toxicity to the first trophic level (bacteria), but because the heterotrophic bacteria accumulated Cu, they were responsible for the transference for the otherwise low availability metal form. Both the bacteria and protozoan organisms accumulated Cu, but no metal accumulation was detected in the copepods.

Chemical and physical factors influencing lead and copper contamination in drinking water: approach for a case study in analytical chemistry

CHEMICAL AND PHYSICAL FACTORS INFLUENCING LEAD AND COPPER CONTAMINATION IN DRINKING WATER: APPROACH FOR A CASE STUDY IN ANALYTICAL CHEMISTRY. Lead and copper concentrations in drinking water increase considerably on going from municipality reservoirs to the households sampled in Ribeirao Preto (SP-Brazil). Flushing of only 3 liters of water reduced metal concentrations by more than 50%. Relatively small changes in water pH rapidly affected corrosion processes in lead pipes, while water hardness appeared to have a long-term effect. This approach aims to encourage University teachers to use its content as a case study in disciplines of Instrumental Analytical Chemistry and consequently increase knowledge about drinking water contamination in locations where no public monitoring of trace metals is in place.

CHEMICAL CHANGES AND ZINC PHYTOAVAILABILITY IN SEWAGE SLUDGE-AMENDED SOIL ESTIMATED BY THE ISOTOPIC METHOD

CHEMICAL CHANGES AND ZINC PHYTOAVAILABILITY IN SEWAGE SLUDGE-AMENDED SOIL ESTIMATED BY THE ISOTOPIC METHOD. Zn availability in Red Latossol (Rhodic Ferralsol) of different pH amended with different rates of sewage sludge was studied by the isotopic Zn-65 L value method. Soil chemical properties were found to be altered by SS addition. Zn concentration and Zn derived from SS (ZnpfSS) in plant, and Zn phytoavailability (L value), were increased with increasing SS rates. The linear correlation coefficient of plant Zn with SS rates and with L value was significant at 1% probability. The L value proved an efficient method for predicting Zn phytoavailability in sewage sludge-amended soil with different pH under the soil conditions studied.