Seawater carbonate chemistry and community calcification during Miyako Island (Japan) coral reef studies, 1994

Coral reefs are characterized by enormous carbonate production of the organisms. It is known that rapid calcification is linked to photosynthesis under control of the carbonate equilibrium in seawater. We have established a model simulating the coexisting states of photosynthesis and calcification in order to examine the effects of photosynthesis and calcification on the carbonate system in seawater. Supposing that the rates of photosynthesis and calcification are proportional to concentrations of their inorganic carbon source, the model calculations indicate that three kinds of unique interactions of the organic and inorganic carbon productions are expected. These are photosynthetic enhancement of calcification, calcification which benefits photosynthesis and carbonate dissolution induced by respiration. The first effect appears when the photosynthetic rate is more than approximately 1.2 larger than that of calcification. This effect is caused by the increase of CO3 content and carbonate saturation degree in seawater. If photosynthesis use molecular carbon dioxide, the second effect occurs when the calcification rate is more than approximately 1.6 times larger than that of photosynthesis. Time series model experiments indicate that photosynthesis and calcification potentially enhance each other and that organic and inorganic carbon is produced more efficiently in the coexisting system than in the isolated reactions. These coexisting effects on production enhancement of photosynthesis and calcification are expected to appear not only in the internal pool of organisms but also in a reef environment which is isolated from the outer ocean during low tide. According to the measurements on the fringing type Shiraho Reef in the Ryukyu Islands, the diurnal change of water properties (pH, total alkalinity, total carbon dioxide and carbonate saturation degree) were conspicuous. This environment offers an appropriate condition for the appearance of these coexisting effects. The photosynthetic enhancement of calcification and the respiratory inducement of decalcification were observed during day-time and night-time slack-water periods, respectively. These coexisting effects, especially the photosynthetic enhancement of calcification, appear to play important roles for fluorishing coral reef communities.

Avaliação da radioatividade natural em tintas de uso comercial no Brasil

A radioatividade natural presente em solos, rochas e materiais de construção, devida ao 40K e às séries radioativas do 232Th e 238U é a principal contribuição à exposição externa aos seres humanos. Neste trabalho, determinou-se as concentrações de atividade de 226Ra (da série do 238U), 232Th e 40K presentes em 50 amostras de tintas látex de cor branca comercializadas no Brasil, especificamente, 15 do tipo econômico, 15 do tipo standard, 20 do tipo premium e em uma amostra de dióxido de titânio. As amostras foram seladas e armazenadas por um período mínimo de 30 dias para se alcançar o equilíbrio radioativo secular nas séries do 238U e do 232Th e medidas pela técnica analítica de espectrometria gama de alta resolução. As concentrações de atividade foram calculadas utilizando-se as médias ponderadas pelas incertezas do 214Pb e 214Bi para o 226Ra e médias ponderadas pelas incertezas do 228Ac, 212Pb e 212Bi para o 232Th. A concentração de atividade do 40K foi determinada pela sua transição única de 1460,8 keV. Fatores de autoatenuação gama foram calculados e utilizados para correção da concentração de atividade das amostras com densidade maior que 1,0 g.cm-3. Os índices radiológicos equivalente em rádio (Raeq), índice de concentração de atividade (Iγ), índice de risco à exposição gama interna (Hin), o índice de risco à exposição gama externa (Hex) e a taxa de dose (D) e dose efetiva anual (Def) foram calculados a partir das concentrações de atividade do 226Ra, 232Th e 40K. As concentrações de atividade de 226Ra das tintas variaram entre valores abaixo da atividade mínima detectável e 38,7 Bq.kg-1, as de 232Th variaram entre valores abaixo da atividade mínima detectável e 101,2 Bq.kg-1 e as de 40K variaram entre valores abaixo da atividade mínima detectável e 256 Bq.kg-1. O Raeq variou entre 1,41 Bq.kg-1 e 203 Bq.kg-1, o Iγ variou entre 0,0047 e 0,720, o Hin variou entre 0,0076 e 0,653 e o Hex variou entre 0,0038 e 0,549. A taxa de dose variou de 0,170 nGy.h-1 a 21,3 nGy.h-1 e a dose efetiva anual variou entre 0,83 μSv.a-1 e 104,2 μSv.a-1. Estes resultados mostram que as concentrações de atividades das tintas utilizadas neste estudo estão abaixo dos limites recomendados por Hassan et al. para Raeq (370 Bq.kg-1), pela Comissão Européia para o Iγ (limite de 2 para materiais superficiais) e pela Organização para Cooperação Econômica e Desenvolvimento para Hin e para Hex (ambos com limite de 1), para todas as 50 amostras estudadas, mostrando assim a segurança destas tintas com relação a proteção radiológica.

A systematic study on the influence of carbon on the behavior of hard-to-ionize elements in inductively coupled plasma–mass spectrometry

A systematic study on the influence of carbon on the signal of a large number of hard-to-ionize elements (i.e. B, Be, P, S, Zn, As, Se, Pd, Cd, Sb, I, Te, Os, Ir, Pt, Au, and Hg) in inductively coupled plasma–mass spectrometry has been carried out. To this end, carbon matrix effects have been evaluated considering different plasma parameters (i.e. nebulizer gas flow rate, r.f. power and sample uptake rate), sample introduction systems, concentration and type of carbon matrix (i.e. glycerol, citric acid, potassium citrate and ammonium carbonate) and type of mass spectrometer (i.e. quadrupole filter vs. double-focusing sector field mass spectrometer). Experimental results show that P, As, Se, Sb, Te, I, Au and Hg sensitivities are always higher for carbon-containing solutions than those obtained without carbon. The other hard-to-ionize elements (Be, B, S, Zn, Pd, Cd, Os, Ir and Pt) show no matrix effect, signal enhancement or signal suppression depending on the experimental conditions selected. The matrix effects caused by the presence of carbon are explained by changes in the plasma characteristics and the corresponding changes in ion distribution in the plasma (as reflected in the signal behavior plot, i.e. the signal intensity as a function of the nebulizer gas flow rate). However, the matrix effects for P, As, Se, Sb, Te, I, Au and Hg are also related to an increase in analyte ion population caused as a result of charge transfer reactions involving carbon-containing charged species in the plasma. The predominant specie is C+, but other species such as CO+, CO2+, C2+ and ArC+ could also play a role. Theoretical data suggest that B, Be, S, Pd, Cd, Os, Ir and Pt could also be involved in carbon based charge transfer reactions, but no experimental evidence substantiating this view has been found.

Non-spectral interferences due to the presence of sulfuric acid in inductively coupled plasma mass spectrometry

Results of a systematic study concerning non-spectral interferences from sulfuric acid containing matrices on a large number of elements in inductively coupled plasma–mass spectrometry (ICP-MS) are presented in this work. The signals obtained with sulfuric acid solutions of different concentrations (up to 5% w w− 1) have been compared with the corresponding signals for a 1% w w− 1− nitric acid solution at different experimental conditions (i.e., sample uptake rates, nebulizer gas flows and r.f. powers). The signals observed for 128Te+, 78Se+ and 75As+ were significantly higher when using sulfuric acid matrices (up to 2.2-fold for 128Te+ and 78Se+ and 1.8-fold for 75As+ in the presence of 5 w w-1 sulfuric acid) for the whole range of experimental conditions tested. This is in agreement with previously reported observations. The signal for 31P+ is also higher (1.1-fold) in the presence of sulfuric acid. The signal enhancements for 128Te+, 78Se+, 75As+ and 31P+ are explained in relation to an increase in the analyte ion population as a result of charge transfer reactions involving S+ species in the plasma. Theoretical data suggest that Os, Sb, Pt, Ir, Zn and Hg could also be involved in sulfur-based charge transfer reactions, but no experimental evidence has been found. The presence of sulfuric acid gives rise to lower ion signals (about 10–20% lower) for the other nuclides tested, thus indicating the negative matrix effect caused by changes in the amount of analyte loading of the plasma. The elemental composition of a certified low-density polyethylene sample (ERM-EC681K) was determined by ICP-MS after two different sample digestion procedures, one of them including sulfuric acid. Element concentrations were in agreement with the certified values, irrespective of the acids used for the digestion. These results demonstrate that the use of matrix-matched standards allows the accurate determination of the tested elements in a sulfuric acid matrix.

Use of novel biomarkers (Homocysteine, vitamin B6, B9 and B12) on the assessing the progression of cardiovascular disease

A large number of evidences correlate elevated levels of homocysteine (Hcys) with a higher cardiovascular diseases (CVDs) risk, especially, atherosclerosis. Similarly, abnormal low levels of the vitamins B6, B9 and B12 are associated to an instability in the methionine cycle with an over production of Hcys. Thus, biomedical sciences are looking forward for a cheaper, faster, precise and accurate analytical methodology to quantify these compounds in a suitable format for the clinical environment. Therefore the objective of this study was the development of a simple, inexpensive and appropriate methodology to use at the clinical level. To achieve this goal, a procedure integrating a digitally controlled (eVol®) microextraction by packed sorbent (MEPS) and an ultra performance liquid chromatography (UPLC) coupled to a photodiode array detector (PDA) was developed to identify and quantify Hcys vitamins B6, B9 and B12. Although different conditions were assayed, we were not able to combine Hcys with the vitamins in the same analytical procedure, and so we proceeded to the optimization of two methods differing only in the composition of the gradient of the mobile phase and the injected volume. It was found that MEPS did not bring any benefit to the quantification of the Hcys in the plasma. Therefore, we developed and validate an alternative method that uses the direct injection of treated plasma (reduced and precipitated). This same method was evaluated in terms of selectivity, linearity, limit of detection (LOD), limit of quantification (LOQ), matrix effect and precision (intra-and inter-day) and applied to the determination of Hcys in a group composed by patients presenting augmented CVD risk. Good results in terms of selectivity and linearity (R2> 0.9968) were obtained, being the values of LOD and LOQ 0.007 and 0.21 mol / L, respectively. The intra-day precision (1.23-3.32%), inter-day precision (5.43-6.99%) and the recovery rate (82.5 to 93.1%) of this method were satisfactory. The matrix effect (>120%) was, however, higher than we were waiting for. Using this methodology it was possible to determine the amount of Hcys in real plasma samples from individuals presenting augmented CVD risk. Regarding the methodology developed for vitamins, despite the optimization of the extraction technique and the chromatographic conditions, it was found that the levels usually present in plasma are far below the sensitivity we obtained. Therefore, further optimizations of the methodology developed are needed. As conclusion, part of the objectives of this study was achieved with the development of a quick, simple and cheaper method for the quantification of Hcys.

A Two-Step Sol–Gel Method for Synthesis of Nanoporous TiO2

This article reports a study of the effects of synthesis parameters on the preparation and formation of mesoporous titania nanopowders by employing a two-step sol-gel method. These materials displayed crystalline domains characteristic of anatase. The first step of the process involved the hydrolysis of titanium isopropoxide in a basic aqueous solution mediated by neutral surfactant. The solid product obtained from step 1 was then treated in an acidified ethanol solution containing the same titanium precursor to thicken the pore walls. Low pH and higher loading of the Ti precursor in step 2 produced better mesoporosity and crystallinity of titanium dioxide polymorphs. The resultant powder exhibited a high surface area (73.8 m(2)/g) and large pore volume (0.17 cm(3)/g) with uniform mesopores. These materials are envisaged to be used as precursors for mesoporous titania films as a wide band gap semiconductor in dye-sensitized nanocrystalline TiO2 solar cells.

Development of a co-culture model of the human lungs for toxicity testing and identification of biomarkers of inhalation toxicity

The airway epithelium is the first point of contact in the lung for inhaled material, including infectious pathogens and particulate matter, and protects against toxicity from these substances by trapping and clearance via the mucociliary escalator, presence of a protective barrier with tight junctions and initiation of a local inflammatory response. The inflammatory response involves recruitment of phagocytic cells to neutralise and remove and invading materials and is oftern modelled using rodents. However, development of valid in vitro airway epithelial models is of great importance due to the restrictions on animal studies for cosmetic compound testing implicit in the 7th amendment to the European Union Cosmetics Directive. Further, rodent innate immune responses have fundamental differences to human. Pulmonary endothelial cells and leukocytes are also involved in the innate response initiated during pulmonary inflammation. Co-culture models of the airways, in particular where epithelial cells are cultured at air liquid interface with the presence of tight junctions and differentiated mucociliary cells, offer a solution to this problem. Ideally validated models will allow for detection of early biomarkers of response to exposure and investigation into inflammatory response during exposure. This thesis describes the approaches taken towards developing an in vitro epithelial/endothelial cell model of the human airways and identification biomarkers of response to exposure to xenobiotics. The model comprised normal human primary microvascular endothelial cells and the bronchial epithelial cell line BEAS-2B or normal human bronchial epithelial cells. BEAS-2B were chosen as their characterisation at air liquid interface is limited but they are robust in culture, thereby predicted to provide a more reliable test system. Proteomics analysis was undertaken on challenged cells to investigate biomarkers of exposure. BEAS-2B morphology was characterised at air liquid interface compared with normal human bronchial epithelial cells. The results indicate that BEAS-2B cells at an air liquid interface form tight junctions as shown by expression of the tight junction protein zonula occludens-1. To this author’s knowledge this is the first time this result has been reported. The inflammatory response of BEAS-2B (measured as secretion of the inflammatory mediators interleukin-8 and -6) air liquid interface mono-cultures to Escherichia coli lipopolysaccharide or particulate matter (fine and ultrafine titanium dioxide) was comparable to published data for epithelial cells. Cells were also exposed to polymers of “commercial interest” which were in the nanoparticle range (and referred to particles hereafter). BEAS-2B mono-cultures showed an increased secretion of inflammatory mediators after challenge. Inclusion of microvascular endothelial cells resulted in protection against LPS- and particle- induced epithelial toxicity, measured as cell viability and inflammatory response, indicating the importance of co-cultures for investigations into toxicity. Two-dimensional proteomic analysis of lysates from particle-challenged cells failed to identify biomarkers of toxicity due to assay interference and experimental variability. Separately, decreased plasma concentrations of serine protease inhibitors, and the negative acute phase proteins transthyretin, histidine-rich glycoprotein and alpha2-HS glycoprotein were identified as potential biomarkers of methyl methacrylate/ethyl methacrylate/butylacrylate treatment in rats.