Assessment of cation exchange as conditioning processes of water chemistry in freshwater lenses.

Freshwater lenses are groundwater sources of limited dimensions that can be usually found in a variety of climates worldwide. These aquifers' quality is important for socioeconomic development, being cation exchange one of the most important geochemical processes that can change the water geochemistry. This study aims to assess the cation exchange processes that determine the chemistry of freshwater lenses in a multilayer aquifer type, considering the center-east of the Pampean Region (Argentina) as a case study. Water samples were taken from the freshwater lenses at different depths to analyze major ions in the laboratory. In addition, geological profiles were made along with the extraction of sediment samples for X-ray diffractometry (XRD) and laboratory tests to analyze the cation exchange capacity. The results show that water stored in the lenses has a vertical facies variation from Ca-HCO3 to Na-HCO3 . According to the laboratory results, the change of water facies mainly occurs in the clayey sediments that divide the carbonate bioclastic material above and the loessic sediment below, being cation exchange the most important process. PRACTITIONER POINTS: Cation exchange is the main geochemical process regulating groundwater chemistry. Hydrochemical changes determine the quality of freshwater lenses. Na/Ca exchange is mainly regulated by the groundwater flow into the bioturbated clay. Batch exchange tests were also carried out to quantify the Na/Ca exchange processes.

Bacterial Synthesis of Ternary CdSAg Quantum Dots through Cation Exchange: Tuning the Composition and Properties of Biological Nanoparticles for Bioimaging and Photovoltaic Applications.

In this study, we introduce a biological method for the production of ternary Quantum Dots (QDs): complex nanostructures with tunable optical and structural properties that utilizes post-synthesis modifications through cation exchange. This versatile in-situ cation exchange method being reported for the first time shows great potential for extending the scope of microbial synthesis. By using this bacterial-based method, we easily synthesize and purify CdS, CdSAg, and Ag2S nanocrystals of a size below 15 nm and with variable morphologies that exhibit fluorescence emissions covering a broad spectral range (from 400 to 800 nm). Energy-dispersive X-ray spectroscopy (EDS) results indicate the partial replacement of Cd2+ by Ag+ when AgNO3 concentration is increased. This replacement produces CdSAg ternary QDs hetero-structures with high stability, fluorescence in the NIR-I (700 - 800 nm), and 36.13% quantum yield. Furthermore, this reaction can be extended for the production of soluble Ag2S nanoparticles (NPs) without any traces of Cd. QDs biosynthesized through this cation exchange process display very low toxicity when tested in bacterial or human cell lines. Biosynthesized ternary hetero-structures were used as red fluorescent dyes to label HeLa cells in confocal microscopy studies, which validates its use in bioimaging applications in the near infrared region. In addition, the application of biologically-produced cadmium NPs in solar cells is reported for the first time. The three biosynthesized QDs were successfully used as photosensitizers, where the CdSAg QDs show the best photovoltaic parameters. Altogether, obtained results validate the use of bacterial cells for the controlled production of nanomaterials with properties that allow their application in diverse technologies. We developed a simple biological process for obtaining tunable Quantum Dots (QDs) with different metal compositions through a cation exchange process. Nanoparticles (NPs) are produced in the extracellular space of bacterial cells exposed to cysteine and CdCl2 in a reaction that depends on S2- generation mediated by cysteine desulfhydrase enzymes and uses cellular biomolecules to stabilize the nanoparticle. Using this extracellular approach, water-soluble fluorescent CdS, CdSAg, and Ag2S Quantum Dots with a tunable emission ranging from 400 to 800 nm were generated. This is the first study reporting the use of microorganisms to produce tunable ternary QDs and the first time that a cation exchange process mediated by cells is described. Obtained results validate the use of biological synthesis to produce NPs with new characteristics and opens a completely new research field related to the use of microorganisms to synthesize complex NPs that are difficult to obtain with regular chemical methods.

Strategies for the one-step immobilization-purification of enzymes as industrial biocatalysts.

In this review, we detail the efforts performed to couple the purification and the immobilization of industrial enzymes in a single step. The use of antibodies, the development of specific domains with affinity for some specific supports will be revised. Moreover, we will discuss the use of domains that increase the affinity for standard matrices (ionic exchangers, silicates). We will show how the control of the immobilization conditions may convert some unspecific supports in largely specific ones. The development of tailor-made heterofunctional supports as a tool to immobilize-stabilize-purify some proteins will be discussed in deep, using low concentration of adsorbent groups and a dense layer of groups able to give an intense multipoint covalent attachment. The final coupling of mutagenesis and tailor made supports will be the last part of the review.

Remoción de níqeel presente en aguas efluentes ndustriales mediante utilizacióón de sustratos de aserrín de pino / Removal of nickll from industrial waste water using pine sawdust / Eliminação de nqquel de águas residuais industriais usando serragem do pinheiro

Se evaluaron dos variedades de aserrín de pino (Pinus cupresus, Pinus caribeae) para la remoción de Ni2+ presente en efluentes industriales. Un estudio comparativo a través de operaciones batch permitió establecer la influencia de la concentración inicial del metal, la relación adsorbente a efluente y la velocidad de agitación en el proceso de remoción. La variedad Pinus cupresus arrojó la mayor adsorción, 0,53 mgNi/g, y esto, sumado a su fácil adquisición y bajo costo, lo hacen un adsorbente con gran potencial. Se ajustó un modelo cinético para la adsorción del metal y de modo paralelo se demostró que el fenómeno se da principalmente por intercambio iónico con Ca2+ y Mg2+ presentes en el aserrín. La torta húmeda residual puede disponerse por incineración ya que aproximadamente el 44% del níquel queda depositado en las cenizas. Finalmente se implementó una columna de adsorción piloto y se alcanzó una eficiencia de remoción del 57%.

Sawdust of two varieties of pine (Pinus cupresus, Pinus caribeae) have been studied for the removal Ni2+ from industrial wastes. A comparative study using batch operations allowed establishing the influence of initial metal concentration, amount of adsorbent and stirring rate in the removal process. Pinus cupresus variety shows the biggest adsorption, 0,53 mgNi/g; and considering its availability and low cost, it becomes a potential commercial adsorbent. A kinetic model was fitted for the metal adsorption. The experimental results provided evidence for ionic exchange with Ca2+ and Mg2+ as the major adsorption mechanism. The residual wet cake can be disposed by incineration, because about 44% of nickel is deposited in the ashes. Finally an adsorption column was developed achieving an efficiency of 57% in the removing process.

Duas variedades da serragem de pinheiro (Pinus cupresus, Pinus caribeae) foram investigadas para a remoção de Ni2+ de resíduos industriais.Umestudo comparativo usando operações de lote permitiu estabelecer a influência da concentração metálica inicial, a quantidade de adsorvente e a velocidade de agitação no processo de eliminaçao. A variedade Pinus cupresus mostra a adsorção maior, 0,53 mgNi/g. Considerando a sua disponibilidade e baixo preço, ele vira um adsorvente comercial potencial. Um modelo cinético foi ajustado para a adsorção metálica. Os resultados experimentais forneceram evidência da troca iônica com principalmente Ca2+eMg2+ como o mecanismo de adsorção principal. O bolo úmido residual pode ser disposto pela incineração, porque aproximadamente 44% de níquel é depositado nas cinzas. Finalmente, uma coluna de adsorção foi desenvolvida logrando uma eficiência de 57% no processo de remoção.

Electrochemical attributes and availability of nutrients, toxic elements, and heavy metals in tropical soils

Electrochemical properties of soils are very important for the understanding of the physico-chemical phenomena which affect soil fertility and the availability of nutrients for plants. This review highlights the electrochemical properties of tropical soils, the behavior and the availability of nutrients, toxic elements and heavy metals in the soil, especially for soils with predominant variable charge minerals. Availability of the elements is related to ionic exchange, solution speciation, and electrostatic and specific adsorptive soil properties. Empirical and surface complexation models are briefly described, and some results of their application in tropical soils are presented. A better understanding of the role of the double diffuse layer of charges and CEC on nutrient cation availability for highly weathered soils is required, as well as a solid comprehension of surface complexation models, in order to improve the knowledge regarding the behavior of anions in soils. More studies have to be conducted to generate results that enable the use of chemical speciation concepts and calculation of several constants used in surface complexation models, especially for highly weathered soils from the humid tropics. There has to be a continuing development and use of computer softwares that have already incorporated the concepts of chemical speciation and adsorption models in the study of nutrients, toxic elements and heavy metal availability in the soil-plant system.

As propriedades eletroquímicas dos solos tropicais são muito importantes para entendimento dos fenômenos físico-químicos que afetam a fertilidade do solo e a disponibilidade dos nutrientes das plantas. Essa revisão destaca os atributos eletroquímicos de solos e o comportamento e a disponibilidade de nutrientes, elementos tóxicos e metais pesados no solo, especialmente aqueles com predominância de minerais com cargas variáveis. A disponibilidade dos elementos é relacionada com a troca iônica, especiação da solução e propriedades adsortivas eletrostáticas e específicas do solo. Modelos empíricos e de complexação de superfície são brevemente descritos, e são apresentados resultados de sua aplicação em solos tropicais. É necessário um melhor entendimento do papel da dupla camada difusa de cargas e da CTC na disponibildade de nutrientes em solos altamente intemperizados, assim como uma melhor compreensão dos modelos de complexação de superfície, a fim de melhorar o entendimento do comportamento dos ânions no solo. Mais estudos devem ser conduzidos para gerar resultados que tornem possível o uso de conceitos de especiação química e o cálculo de diversas constantes usadas em modelos de complexação, especialmente para solos altamente intemperizados do trópico úmido. Deve haver um contínuo desenvolvimento de programas computacionais que já tenham incorporado os conceitos de especiação e modelos de adsorção no estudo da disponibilidade de nutrientes, elementos tóxicos e metais pesados no sistema solo-planta.

Electrochemical attributes and availability of nutrients, toxic elements, and heavy metals in tropical soils

Electrochemical properties of soils are very important for the understanding of the physico-chemical phenomena which affect soil fertility and the availability of nutrients for plants. This review highlights the electrochemical properties of tropical soils, the behavior and the availability of nutrients, toxic elements and heavy metals in the soil, especially for soils with predominant variable charge minerals. Availability of the elements is related to ionic exchange, solution speciation, and electrostatic and specific adsorptive soil properties. Empirical and surface complexation models are briefly described, and some results of their application in tropical soils are presented. A better understanding of the role of the double diffuse layer of charges and CEC on nutrient cation availability for highly weathered soils is required, as well as a solid comprehension of surface complexation models, in order to improve the knowledge regarding the behavior of anions in soils. More studies have to be conducted to generate results that enable the use of chemical speciation concepts and calculation of several constants used in surface complexation models, especially for highly weathered soils from the humid tropics. There has to be a continuing development and use of computer softwares that have already incorporated the concepts of chemical speciation and adsorption models in the study of nutrients, toxic elements and heavy metal availability in the soil-plant system.

As propriedades eletroquímicas dos solos tropicais são muito importantes para entendimento dos fenômenos físico-químicos que afetam a fertilidade do solo e a disponibilidade dos nutrientes das plantas. Essa revisão destaca os atributos eletroquímicos de solos e o comportamento e a disponibilidade de nutrientes, elementos tóxicos e metais pesados no solo, especialmente aqueles com predominância de minerais com cargas variáveis. A disponibilidade dos elementos é relacionada com a troca iônica, especiação da solução e propriedades adsortivas eletrostáticas e específicas do solo. Modelos empíricos e de complexação de superfície são brevemente descritos, e são apresentados resultados de sua aplicação em solos tropicais. É necessário um melhor entendimento do papel da dupla camada difusa de cargas e da CTC na disponibildade de nutrientes em solos altamente intemperizados, assim como uma melhor compreensão dos modelos de complexação de superfície, a fim de melhorar o entendimento do comportamento dos ânions no solo. Mais estudos devem ser conduzidos para gerar resultados que tornem possível o uso de conceitos de especiação química e o cálculo de diversas constantes usadas em modelos de complexação, especialmente para solos altamente intemperizados do trópico úmido. Deve haver um contínuo desenvolvimento de programas computacionais que já tenham incorporado os conceitos de especiação e modelos de adsorção no estudo da disponibilidade de nutrientes, elementos tóxicos e metais pesados no sistema solo-planta.