Análise do enxofre corrosivo em óleo mineral isolante e remoção do dibenzil dissulfeto com nanotubos de carbono baseados em matriz metálica

Falhas inesperadas em transformadores levaram a identificação da formação de sulfeto de cobre, depositado sobre os condutores, avaliando-se da presença qualitativa de enxofre corrosivo resultando na alteração da norma brasileira ABNT NBR 10505, que avalia a presença de enxofre corrosivo em óleo mineral, alterando-se o tempo e a temperatura de ensaio para 150 °C por 48 horas. Realizando-se a especiação química de compostos organosulfurados via cromatografia gasosa acoplada a espectrometria de massas, onde foram encontrados 13 compostos sulfurados no óleo Nynas e 9 compostos no óleo da Petrobras, sendo o dibenzil dissulfeto (DBDS) o de maior concentração, encontrado apenas no óleo Nynas. Para realizar a determinação da presença do DBDS em óleo mineral isolante foi desenvolvido um método através de cromatografia gasosa acoplada a espectrometria de massas, e por este método foi possível quantificar o teor de DBDS em amostras de OMI oriundas de transformadores de potência. Foi avaliado o processo de passivação do cobre por benzotriazol e tolutriazol, utilizados como aditivos anticorrosivos no núcleo dos equipamentos elétricos, verificando-se que o efeito da adição agente de passivação torna-se ineficaz com o passar do tempo. A solução para a remoção de DBDS em óleo mineral foi a utilização de nanotubo de carbono baseado em matriz metálica (NTC/Al) como agente de remoção do DBDS. Verificou-se que o agente de adsorção foi capaz de efetuar a remoção total do DBDS do OMI até um volume de 4000 mL de óleo contaminado com DBDS.

Characterization and source apportionment of organic aerosol using offline aerosol mass spectrometry

Field deployments of the Aerodyne Aerosol Mass Spectrometer (AMS) have significantly advanced real-time measurements and source apportionment of non-refractory particulate matter. However, the cost and complex maintenance requirements of the AMS make its deployment at sufficient sites to determine regional characteristics impractical. Furthermore, the negligible transmission efficiency of the AMS inlet for supermicron particles significantly limits the characterization of their chemical nature and contributing sources. In this study, we utilize the AMS to characterize the water-soluble organic fingerprint of ambient particles collected onto conventional quartz filters, which are routinely sampled at many air quality sites. The method was applied to 256 particulate matter (PM) filter samples (PM1, PM2:5, and PM10, i.e., PM with aerodynamic diameters smaller than 1, 2.5, and 10 μm, respectively), collected at 16 urban and rural sites during summer and winter. We show that the results obtained by the present technique compare well with those from co-located online measurements, e.g., AMS or Aerosol Chemical Speciation Monitor (ACSM). The bulk recoveries of organic aerosol (60–91 %) achieved using this technique, together with low detection limits (0.8 μg of organic aerosol on the analyzed filter fraction) allow its application to environmental samples. We will discuss the recovery variability of individual hydrocarbon ions, ions containing oxygen, and other ions. The performance of such data in source apportionment is assessed in comparison to ACSM data. Recoveries of organic components related to different sources as traffic, wood burning, and secondary organic aerosol are presented. This technique, while subjected to the limitations inherent to filter-based measurements (e.g., filter artifacts and limited time resolution) may be used to enhance the AMS capabilities in measuring size-fractionated, spatially resolved longterm data sets.

Fossil and non-fossil source contributions to atmospheric carbonaceous aerosols during extreme spring grassland fires in Eastern Europe

In early spring the Baltic region is frequently affected by high-pollution events due to biomass burning in that area. Here we present a comprehensive study to investigate the impact of biomass/grass burning (BB) on the evolution and composition of aerosol in Preila, Lithuania, during springtime open fires. Non-refractory submicron particulate matter (NR-PM1) was measured by an Aerodyne aerosol chemical speciation monitor (ACSM) and a source apportionment with the multilinear engine (ME-2) running the positive matrix factorization (PMF) model was applied to the organic aerosol fraction to investigate the impact of biomass/grass burning. Satellite observations over regions of biomass burning activity supported the results and identification of air mass transport to the area of investigation. Sharp increases in biomass burning tracers, such as levoglucosan up to 683 ngm-3 and black carbon (BC) up to 17 μgm-3 were observed during this period. A further separation between fossil and non-fossil primary and secondary contributions was obtained by coupling ACSM PMF results and radiocarbon (14C) measurements of the elemental (EC) and organic (OC) carbon fractions. Non-fossil organic carbon (OCnf/ was the dominant fraction of PM1, with the primary (POCnf/ and secondary (SOCnf/ fractions contributing 26–44% and 13–23% to the total carbon (TC), respectively. 5–8% of the TC had a primary fossil origin (POCf/, whereas the contribution of fossil secondary organic carbon (SOCf/ was 4–13 %. Nonfossil EC (ECnf/ and fossil EC (ECf/ ranged from 13–24 and 7–13 %, respectively. Isotope ratios of stable carbon and nitrogen isotopes were used to distinguish aerosol particles associated with solid and liquid fossil fuel burning.

Enhancing non-refractory aerosol apportionment from an urban industrial site through receptor modelling of complete high time-resolution aerosol mass spectra

Receptor modelling was performed on quadrupole unit mass resolution aerosol mass spectrometer (Q-AMS) sub-micron particulate matter (PM) chemical speciation measurements from Windsor, Ontario, an industrial city situated across the Detroit River from Detroit, Michigan. Aerosol and trace gas measurements were collected on board Environment Canada’s CRUISER mobile laboratory. Positive matrix factorization (PMF) was performed on the AMS full particle-phase mass spectrum (PMFFull MS) encompassing both organic and inorganic components. This approach was compared to the more common method of analysing only the organic mass spectra (PMFOrg MS). PMF of the full mass spectrum revealed that variability in the non-refractory sub-micron aerosol concentration and composition was best explained by six factors: an amine-containing factor (Amine); an ammonium sulphate and oxygenated organic aerosol containing factor (Sulphate-OA); an ammonium nitrate and oxygenated organic aerosol containing factor (Nitrate-OA); an ammonium chloride containing factor (Chloride); a hydrocarbon like organic aerosol (HOA) factor; and a moderately oxygenated organic aerosol factor (OOA). PMF of the organic mass spectrum revealed three factors of similar composition to some of those revealed through PMFFull MS: Amine, HOA and OOA. Including both the inorganic and organic mass proved to be a beneficial approach to analysing the unit mass resolution AMS data for several reasons. First, it provided a method for potentially calculating more accurate sub-micron PM mass concentrations, particularly when unusual factors are present, in this case, an Amine factor. As this method does not rely on a priori knowledge of chemical species, it circumvents the need for any adjustments to the traditional AMS species fragmentation patterns to account for atypical species, and can thus lead to more complete factor profiles. It is expected that this method would be even more useful for HR-ToF-AMS data, due to the ability to better understand the chemical nature of atypical factors from high resolution mass spectra. Second, utilizing PMF to extract factors containing inorganic species allowed for the determination of extent of neutralization, which could have implications for aerosol parameterization. Third, subtler differences in organic aerosol components were resolved through the incorporation of inorganic mass into the PMF matrix. The additional temporal features provided by the inorganic aerosol components allowed for the resolution of more types of oxygenated organic aerosol than could be reliably re-solved from PMF of organics alone. Comparison of findings from the PMFFull MS and PMFOrg MS methods showed that for the Windsor airshed, the PMFFull MS method enabled additional conclusions to be drawn in terms of aerosol sources and chemical processes. While performing PMFOrg MS can provide important distinctions between types of organic aerosol, it is shown that including inorganic species in the PMF analysis can permit further apportionment of organics for unit mass resolution AMS mass spectra.

A comparison of in situ vs. ex situ filtration methods on the assessment of dissolved and particulate metals at hydrothermal vents

The objective of this study was to assess the impact of the filtration method (in situ vs. ex situ) on the dissolved/particulate partitioning of 12 elements in hydrothermal samples collected from the Lucky Strike vent field (Mid-Atlantic Ridge; MAR). To do so, dissolved ( <0.45 mu m) and particulate Mg, Li, Mn, U, V, As, Ba, Fe, Zn, Cd, Pb and Cu were measured using different techniques (HR-ICP-MS, ICP-AES and CCSA). Using in situ filtration as a baseline, we showed that ex situ filtration (on-board and on shore after freezing) resulted in an underestimation of the dissolved pool, which was counterbalanced by an overestimation of the particulate pool for almost all the elements studied. We also showed that on-board filtration was acceptable for the assessment of dissolved and particulate Mn, Mg, Li and U for which the measurement bias for the dissolved fraction did not exceed 3%. However, in situ filtration appeared necessary for the accurate assessment of the dissolved and particulate concentrations of V, As, Fe, Zn, Ba, Cd, Pb and Cu. In the case of Fe, on-board filtration underestimated the dissolved pool by up to 96%. Laboratory filtration (after freezing) resulted in a large bias in the dissolved and particulate concentrations, unambiguously discounting this filtration method for deep-sea chemical speciation studies. We discuss our results in light of the precipitation processes that can potentially affect the accuracy of ex situ filtration methods.

Desenvolvimento e validação de método voltamétrico para determinação de ferro e sua especiação química em água intersticial no sedimento da Lagoa dos Patos-RS

Os sedimentos podem atuar tanto como acumuladores quanto como fontes de poluentes. Em função das atividades portuárias locais estarem em ritmo de crescimento pela ampliação do porto de Rio Grande (RS), estudos que mostrem a situação do local investigado são importantes a fim de prever o aporte do ferro nesse ambiente. Neste trabalho, a especiação química do ferro e a determinação da concentração do metal total e dissolvido em amostras de águas intersticiais no sedimento do Saco do Mendanha (RS) foram avaliadas, utilizando a Voltametria Adsortiva de Redissolução Catódica com o ligante 2,3-Dihidroxinaftaleno. O objetivo principal desse trabalho foi validar a metodologia analítica para realizar a especiação química do ferro em águas intersticiais, o que englobou a faixa linear de trabalho, limites de detecção e de quantificação, a exatidão e precisão. O Limite de Detecção encontrado foi de 0,11 nmol L-1 . Foram determinadas as concentrações de ferro total, dissolvido e lábil em três frações distintas: na interface água/sedimento, entre 0 e -5 cm; e entre -15 e -20 cm de profundidade na coluna sedimentar. Nas amostras analisadas, a concentração de ferro lábil encontrada foi entre 4,64 – 135,37 µmol L-1 ; a concentração do metal dissolvido foi de 6,25 – 322,70 µmol L-1 e de ferro total entre 83,36 – 390,30 µmol L-1 . A concentração do metal lábil em comparação com a fração dissolvida e total indica a presença de complexos estáveis entre o metal e a matéria orgânica natural presente na água intersticial, tornando dessa forma, o metal menos biodisponível para a biota local. Durante os meses de amostragem do sedimento, foi observada variação da concentração do metal, onde no mês de abril ocorreu o maior aporte do metal da coluna d’água para o sedimento. Essa transferência do metal para o sedimento pode estar relacionada pela forte mudança na salinidade no local de amostragem, passando de 16 no mês de fevereiro para 33 no mês de abril e para próximo de zero nos meses de agosto e novembro de 2009.

Especiação química de arsênio inorgânico no estuário da Lagoa dos Patos-RS

A poluição das águas por metais, principalmente os metais pesados, vem chamando a atenção no mundo, pois estes poluentes aquáticos representam um risco em potencial, devido ao seu caráter acumulativo. Entre os metais, o arsênio recebe destaque pelo seu potencial tóxico. O arsênio inorgânico ocorre na natureza em quatro estados de oxidação: As5+, As3+, As0 e As3- . O estado de oxidação do arsênio tem um papel importante no seu comportamento e toxicidade nos sistemas aquáticos. Pelo fato do arsênio ser extremamente perigoso e nocivo para o meio ambiente, novos métodos analíticos de especiação química no meio ambiente têm sido publicados. Neste estudo foi otimizado e validado um método para realizar a especiação química de arsênio inorgânico presente em amostras de água coletadas nos meses de julho e outubro de 2010 no estuário da Lagoa dos Patos (RS, Brasil), como parte das atividades do Programa de Monitoramento Ambiental do Porto do Rio Grande-RS. Foi usada a técnica de espectrometria de absorção atômica com geração de hidretos e injeção em fluxo (FI-HG AAS), podendo ser quantificadas espécies de As3+ e As5+ nas amostras de água estuarina. A concentração do arsênio trivalente inorgânico foi determinada, após adição de solução tampão citrato de sódio (0,4 mol L-1 ; pH = 6,0). A concentração de arsênio inorgânico total foi determinada, após uma etapa de pré-redução da espécie pentavalente para a forma trivalente usando uma mistura de iodeto de potássio, ácido ascórbico em meio ácido clorídrico concentrado. A concentração de arsênio pentavalente foi calculada pela diferença das concentrações de arsênio inorgânico total e trivalente. A interpretação dos resultados gerados pelo método proposto usado ao analisar amostras de águas coletadas no estuário da Lagoa dos Patos foi feita pela análise dos componentes principais. Os dados tratados estatisticamente revelaram uma interação significativa neste estudo entre o arsênio, o material em suspensão (MS) e o NH4 + na superfície da coluna d’água no período da primavera.

Análise da especiação química do cromo em águas naturais e de abastecimento em Rio Grande/RS

A presença de metais traço no ambiente está associada às fontes naturais e antropogênicas. O aumento das concentrações desses elementos pode resultar em um desequilíbrio do ecossistema tornando-se um risco potencial para o meio. O metal cromo tem seus efeitos relacionados com sua concentração e com o estado de oxidação em que se apresenta, já que seu estado trivalente é considerando essencial, enquanto que seu estado hexavalente é considerado extremamente tóxico. O objetivo deste trabalho é realizar a especiação química do cromo após ter sido realizada a revalidação analítica, englobando faixa linear de trabalho, limites de detecção e quantificação, exatidão e precisão. Este estudo é essencial tanto pela questão ambiental quanto sanitária, já que a especiação foi realizada em cinco pontos do Estuário da Lagoa dos Patos - dois na Zona Portuária e três no Saco da Mangueira, entre os meses de março e setembro de 2008 e também na Estação de Tratamento de Água que ocorreram entre os meses de janeiro e setembro de 2008. Foram realizadas determinações das frações de Cr (III) ativo, Cr (VI) e Cr (III) não ativo, por Voltametria de Redissolução Catódica. A Fração de Cromo Total foi determinada por Espectrometria de Absorção Atômica. Também foram realizadas in situ determinações dos seguintes parâmetros físicoquímicos: salinidade, pH, Eh, oxigênio dissolvido e temperatura; além dos nutrientes nitrogenados. As determinações não identificaram o metal no estado de oxidação mais tóxico (cromo hexavalente), também não foi identificada a fração de Cr (III) ativo. O metal foi identificado na forma de Cr (III) não-ativo, ou seja, na forma trivalente e complexada por ligantes naturais estáveis. As concentrações de cromo total estiveram sempre abaixo do limite estabelecido pelos órgãos reguladores competentes. Portanto, mesmo com as atividades industriais e portuárias existentes na região, não foram identificadas concentrações ou espécies de cromo que caracterizam um ambiente impactado.

Chemical variability of groundwater samples collected from a Coal Seam Gas exploration well, Maramarua, New Zealand

A pilot study has produced 31 groundwater samples from a coal seam gas (CSG) exploration well located in Maramarua, New Zealand. This paper describes sources of CSG water chemistry variations, and makes sampling and analytical recommendations to minimize these variations. The hydrochemical character of these samples is studied using factor analysis, geochemical modelling, and a sparging experiment. Factor analysis unveils carbon dioxide (CO2) degassing as the principal cause of sample variation (about 33%). Geochemical modelling corroborates these results and identifies minor precipitation of carbonate minerals with degassing. The sparging experiment confirms the effect of CO2 degassing by showing a steady rise in pH while maintaining constant alkalinity. Factor analysis correlates variations in the major ion composition (about 17%) to changes in the pumping regime and to aquifer chemistry variations due to cation exchange reactions with argillaceous minerals. An effective CSG water sampling program can be put into practice by measuring pH at the well head and alkalinity at the laboratory; these data can later be used to calculate the carbonate speciation at the time the sample was collected. In addition, TDS variations can be reduced considerably if a correct drying temperature of 180°C is consistently implemented.

Species and Hybrids: Chemical and Physical Foliar Attributes and Implications for Herbivory.

Hybridization is an important biological phenomenon that can be used to understand the evolutionary process of speciation of plants and their associated pests and diseases. Interactions between hybrid plants and the herbivores of the parental taxa may be used to elucidate the various cues being used by the pests for host location or other processes. The chemical composition of plants, and their physical foliar attributes, including leaf thickness, trichome density, moisture content and specific leaf weight were compared between allopatric pure and commercial hybrid species of Corymbia, an important subtropical hardwood taxon. The leaf-eating beetle Paropsis atomaria, to which the pure taxa represented host (C. citriodora subsp. variegata) and non-host (C. torelliana) plants, was used to examine patterns of herbivory in relation to these traits. Hybrid physical foliar traits, chemical profiles, and field and laboratory beetle feeding preference, while showing some variability, were generally intermediate to those exhibited by parent taxa, thus suggesting an additive inheritance pattern. The hybrid susceptibility hypothesis was not supported by our field or laboratory studies, and there was no strong relationship between adult preference and larval performance. The most-preferred adult host was the sympatric taxon, although this species supported the lowest larval survival, while the hybrid produced significantly smaller pupae than the pure species. The results are discussed in relation to plant chemistry and physical characteristics. The findings suggest a chemical basis for host selection behavior and indicate that it may be possible to select for resistance to this insect pest in these commercially important hardwood trees.

Solubility and Diffusivity of Water in Lunar Basalt, and Chemical Zonation in Olivine-Hosted Melt Inclusions

I report the solubility and diffusivity of water in lunar basalt and an iron-free basaltic analogue at 1 atm and 1350 °C. Such parameters are critical for understanding the degassing histories of lunar pyroclastic glasses. Solubility experiments have been conducted over a range of fO₂ conditions from three log units below to five log units above the iron-wüstite buffer (IW) and over a range of pH₂/pH₂O from 0.03 to 24. Quenched experimental glasses were analyzed by Fourier transform infrared spectroscopy (FTIR) and secondary ionization mass spectrometry (SIMS) and were found to contain up to ~420 ppm water. Results demonstrate that, under the conditions of our experiments: (1) hydroxyl is the only H-bearing species detected by FTIR; (2) the solubility of water is proportional to the square root of pH₂O in the furnace atmosphere and is independent of fO₂ and pH₂/pH₂O; (3) the solubility of water is very similar in both melt compositions; (4) the concentration of H₂ in our iron-free experiments is <3 ppm, even at oxygen fugacities as low as IW-2.3 and pH₂/pH₂O as high as 24; and (5) SIMS analyses of water in iron-rich glasses equilibrated under variable fO₂ conditions can be strongly influenced by matrix effects, even when the concentrations of water in the glasses are low. Our results can be used to constrain the entrapment pressure of the lunar melt inclusions of Hauri et al. (2011).

Diffusion experiments were conducted over a range of fO₂ conditions from IW-2.2 to IW+6.7 and over a range of pH₂/pH₂O from nominally zero to ~10. The water concentrations measured in our quenched experimental glasses by SIMS and FTIR vary from a few ppm to ~430 ppm. Water concentration gradients are well described by models in which the diffusivity of water (D^*_water) is assumed to be constant. The relationship between D^*_water and water concentration is well described by a modified speciation model (Ni et al. 2012) in which both molecular water and hydroxyl are allowed to diffuse. The success of this modified speciation model for describing our results suggests that we have resolved the diffusivity of hydroxyl in basaltic melt for the first time. Best-fit values of D^*_water for our experiments on lunar basalt vary within a factor of ~2 over a range of pH₂/pH₂O from 0.007 to 9.7, a range of fO₂ from IW-2.2 to IW+4.9, and a water concentration range from ~80 ppm to ~280 ppm. The relative insensitivity of our best-fit values of D^*_water to variations in pH₂ suggests that H₂ diffusion was not significant during degassing of the lunar glasses of Saal et al. (2008). D^*_water during dehydration and hydration in H₂/CO₂ gas mixtures are approximately the same, which supports an equilibrium boundary condition for these experiments. However, dehydration experiments into CO₂ and CO/CO₂ gas mixtures leave some scope for the importance of kinetics during dehydration into H-free environments. The value of D^*_water chosen by Saal et al. (2008) for modeling the diffusive degassing of the lunar volcanic glasses is within a factor of three of our measured value in our lunar basaltic melt at 1350 °C.

In Chapter 4 of this thesis, I document significant zonation in major, minor, trace, and volatile elements in naturally glassy olivine-hosted melt inclusions from the Siqueiros Fracture Zone and the Galapagos Islands. Components with a higher concentration in the host olivine than in the melt (MgO, FeO, Cr₂O₃, and MnO) are depleted at the edges of the zoned melt inclusions relative to their centers, whereas except for CaO, H₂O, and F, components with a lower concentration in the host olivine than in the melt (Al₂O₃, SiO₂, Na₂O, K₂O, TiO₂, S, and Cl) are enriched near the melt inclusion edges. This zonation is due to formation of an olivine-depleted boundary layer in the adjacent melt in response to cooling and crystallization of olivine on the walls of the melt inclusions concurrent with diffusive propagation of the boundary layer toward the inclusion center.

Concentration profiles of some components in the melt inclusions exhibit multicomponent diffusion effects such as uphill diffusion (CaO, FeO) or slowing of the diffusion of typically rapidly diffusing components (Na₂O, K₂O) by coupling to slow diffusing components such as SiO₂ and Al₂O₃. Concentrations of H2O and F decrease towards the edges of some of the Siqueiros melt inclusions, suggesting either that these components have been lost from the inclusions into the host olivine late in their cooling histories and/or that these components are exhibiting multicomponent diffusion effects.

A model has been developed of the time-dependent evolution of MgO concentration profiles in melt inclusions due to simultaneous depletion of MgO at the inclusion walls due to olivine growth and diffusion of MgO in the melt inclusions in response to this depletion. Observed concentration profiles were fit to this model to constrain their thermal histories. Cooling rates determined by a single-stage linear cooling model are 150–13,000 °C hr^-1 from the liquidus down to ~1000 °C, consistent with previously determined cooling rates for basaltic glasses; compositional trends with melt inclusion size observed in the Siqueiros melt inclusions are described well by this simple single-stage linear cooling model. Despite the overall success of the modeling of MgO concentration profiles using a single-stage cooling history, MgO concentration profiles in some melt inclusions are better fit by a two-stage cooling history with a slower-cooling first stage followed by a faster-cooling second stage; the inferred total duration of cooling from the liquidus down to ~1000 °C is 40 s to just over one hour.

Based on our observations and models, compositions of zoned melt inclusions (even if measured at the centers of the inclusions) will typically have been diffusively fractionated relative to the initially trapped melt; for such inclusions, the initial composition cannot be simply reconstructed based on olivine-addition calculations, so caution should be exercised in application of such reconstructions to correct for post-entrapment crystallization of olivine on inclusion walls. Off-center analyses of a melt inclusion can also give results significantly fractionated relative to simple olivine crystallization.

All melt inclusions from the Siqueiros and Galapagos sample suites exhibit zoning profiles, and this feature may be nearly universal in glassy, olivine-hosted inclusions. If so, zoning profiles in melt inclusions could be widely useful to constrain late-stage syneruptive processes and as natural diffusion experiments.

Evaluation of a sequential extraction for the speciation of thorium in soils from Baotou area, Inner Mongolia

Sequential extraction procedures were widely applied for speciation of radioactive elements. In this study, the sequential extraction procedure developed by Martinez-Aguirre was employed for quantification of different chemical forms of thorium in the soil. The total amount of thorium in contaminated soil was much higher by four-fold than the local background value. The soil properties affect the amount of thoriurn and distribution of fractions in contaminated soil. Results showed that the proportion of thorium in soils from Baotou was found as the residual fraction (F5 + F6) > absorbed fraction (F3), coprecipitated fraction (F4) > carbonates fraction (172) and exchangeable fraction (F1) that could be available to plants. The recovery, calculated by ratio of the sum of the six fractions to the pseudo-total content of thorium, was in the range from 96% to 110%. A comparison was carried out between the sequential extraction and the single extraction to evaluate the selectivity of the extractants. It was found that the amount of thorium of absorbed fraction (H) was higher in the single extraction than that estimated in the sequential extraction, possibly duo to transform of the labile form. While for non-residual fraction analysis, the single extraction scheme was a desirable alternative to the sequential extraction procedure.

Computer simulation of Gd(III) speciation in human interstitial fluid

The speciation and distribution of Gd(III) in human interstitial fluid was studied by computer simulation. Meantime artificial neural network was applied to the estimation of log beta values of complexes. The results show that the precipitate species, GdPO4 and Gd-2(CO3)(3), are the predominant species. Among soluble species, the free Gd(III), [Gd(HSA)], [Gd(Ox)] and then the ternary complexes of Gd(III) with citrate arc main species and [Gd-3(OH)(4)] becomes the predominant species at the Gd(III) total concentration or 2.2x10(-2)mol/L.