An investigation of the kinetics of CO2 uptake by a synthetic calcium based sorbent

This study examines the kinetics of carbonation by CO2 at temperatures of ca. 750 °C of a synthetic sorbent composed of 15 wt% mayenite (Ca12Al14O33) and CaO, designated HA-85-850, and draws comparisons with the carbonation of a calcined limestone. In-situ XRD has verified the inertness of mayenite, which neither interacts with the active CaO nor does it significantly alter the CaO carbonation–calcination equilibrium. An overlapping grain model was developed to predict the rate and extent of carbonation of HA-85-850 and limestone. In the model, the initial microstructure of the sorbent was defined by a discretised grain size distribution, assuming spherical grains. The initial input to the model – the size distribution of grains – was a fitted parameter, which was in good agreement with measurements made with mercury porosimetry and by the analysis of SEM images of sectioned particles. It was found that the randomly overlapping spherical grain assumption offered great simplicity to the model, despite its approximation to the actual porous structure within a particle. The model was able to predict the performance of the materials well and, particularly, was able to account for changes in rate and extent of reaction as the structure evolved after various numbers of cycles of calcination and carbonation.

An investigation of the kinetics of CO 2 uptake by a synthetic calcium based sorbent

This study examines the kinetics of carbonation by CO 2 at temperatures of ca. 750°C of a synthetic sorbent composed of 15wt% mayenite (Ca 12Al 14O 33) and CaO, designated HA-85-850, and draws comparisons with the carbonation of a calcined limestone. In-situ XRD has verified the inertness of mayenite, which neither interacts with the active CaO nor does it significantly alter the CaO carbonation-calcination equilibrium. An overlapping grain model was developed to predict the rate and extent of carbonation of HA-85-850 and limestone. In the model, the initial microstructure of the sorbent was defined by a discretised grain size distribution, assuming spherical grains. The initial input to the model - the size distribution of grains - was a fitted parameter, which was in good agreement with measurements made with mercury porosimetry and by the analysis of SEM images of sectioned particles. It was found that the randomly overlapping spherical grain assumption offered great simplicity to the model, despite its approximation to the actual porous structure within a particle. The model was able to predict the performance of the materials well and, particularly, was able to account for changes in rate and extent of reaction as the structure evolved after various numbers of cycles of calcination and carbonation. © 2011 Elsevier Ltd.

In situ observations of the atomistic mechanisms of Ni catalyzed low temperature graphene growth.

The key atomistic mechanisms of graphene formation on Ni for technologically relevant hydrocarbon exposures below 600 °C are directly revealed via complementary in situ scanning tunneling microscopy and X-ray photoelectron spectroscopy. For clean Ni(111) below 500 °C, two different surface carbide (Ni2C) conversion mechanisms are dominant which both yield epitaxial graphene, whereas above 500 °C, graphene predominantly grows directly on Ni(111) via replacement mechanisms leading to embedded epitaxial and/or rotated graphene domains. Upon cooling, additional carbon structures form exclusively underneath rotated graphene domains. The dominant graphene growth mechanism also critically depends on the near-surface carbon concentration and hence is intimately linked to the full history of the catalyst and all possible sources of contamination. The detailed XPS fingerprinting of these processes allows a direct link to high pressure XPS measurements of a wide range of growth conditions, including polycrystalline Ni catalysts and recipes commonly used in industrial reactors for graphene and carbon nanotube CVD. This enables an unambiguous and consistent interpretation of prior literature and an assessment of how the quality/structure of as-grown carbon nanostructures relates to the growth modes.

Combined effects of polyfluorinated and perfluorinated compounds on primary cultured hepatocytes from rare minnow (Gobiocypris rarus) using toxicogenomic analysis

Polyfluorinated and perfluorinated compounds (PFCs) are used in numerous commercial products and have been ubiquitously detected in the environment as well as in the blood of humans and wildlife. To assess the combined effects caused by PFCs in mixtures, gene expression profiles were generated using a custom cDNA microarray to detect changes in primary cultured hepatocytes of rare minnows exposed to six individual PFCs (perfluorooctanoic acid, perfluorononanoic acid, perfluorodecanoic acid, perfluorododecanoic acid, perfluorooctane sulfonate, and 8:2 fluorotelomer alcohol) and four formulations of the PFCs mixtures. Mixtures as well as individual compounds consistently regulated a particular gene set, which suggests that these conserved genes may play a central role in the toxicity mediated by PFCs. Specifically, a number of genes regulated by the mixtures were identified in this study, which were not affected by exposure to any single component. These genes are implicated in multiple biological functions and processes, including fatty acid metabolism and transport, xenobiotic metabolism, immune responses, and oxidative stress. More than 80% of the altered genes in the PFOA- and PFOS-dominant mixture groups were of the same gene set, while the gene expression profiles from single PFOA and PFOS exposures were not as similar. This work contributes to the development of toxicogenomic approaches in combined toxicity assessment and allows for comprehensive insights into the combined action of PFCs mixtures in multiple environmental matrices. (C) 2009 Elsevier B.V. All rights reserved.

Hexabromocyclododecane-induced developmental toxicity and apoptosis in zebrafish embryos

Hexabromocyclododecane (HBCD) is widely used as a brominated flame retardant, and has been detected in the aquatic environment, wild animals, and humans. However, details of the environmental health risk of HBCD are not well known. In this study, zebrafish embryos were used to assess the developmental toxicity of the chemical. Four-hour post-fertilization (hpf) zebrafish embryos were exposed to various concentrations of HBCD (0, 0.05, 0.1, 0.5, and 1.0 mg L-1) until 96 h. Exposure to 0.1, 0.5, and 1.0 mg L-1 HBCD significantly increased the malformation rate and reduced survival in the 0.5 and 1.0 mg L-1 HBCD exposure groups. Acridine orange (AO) staining showed that HBCD exposure resulted in cell apoptosis. Reactive oxygen species (ROS) was significantly induced at exposures of 0.1, 0.5, and 1.0 mg L-1 HBCD. To test the apoptotic pathway, several genes related to cell apoptosis, such as p53, Puma, Apaf-1, caspase-9, and caspase-3, were examined using real-time PCR. The expression patterns of these genes were up-regulated to some extent. Two anti-apoptotic genes, Mdm2 (antagonist of p53) and Bcl-2 (inhibitor of Bax), were down-regulated, and the activity of capspase-9 and caspase-3 was significantly increased. The overall results demonstrate that waterborne HBCD is able to produce oxidative stress and induce apoptosis through the involvement of caspases in zebrafish embryos. The results also indicate that zebrafish embryos can serve as a reliable model for the developmental toxicity of HBCD. (C) 2009 Elsevier B.V. All rights reserved.

Light histories influence the impacts of solar ultraviolet radiation on photosynthesis and growth in a marine diatom, Skeletonema costatum

Phytoplanktonic species acclimated to high light are known to show less photoinhibition. However, little has been documented on how cells grown under indoor conditions for decades without exposure to UV radiation (UVR, 280-400 nm) would respond differently to solar UVR compared to those in situ grown under natural solar radiation. Here, we have shown the comparative photosynthetic and growth responses to solar UVR in an indoor-(IS) and a naturally grown (WS) Skeletonema costatum type. In short-term experiment (<1 day), phi(PSII) and photosynthetic carbon fixation rate were more inhibited by UVR in the IS than in the WS cells. The rate of UVR-induced damages of PSII was faster and their repair was significantly slower in IS than in WS. Even under changing solar radiation simulated for vertical mixing, solar UVR-induced higher inhibition of photosynthetic rate in IS than in WS cells. During long-term (10 days) exposures to solar radiation, the specific growth rate was much lower in IS than WS at the beginning, then increased 3 days later to reach an equivalent level as that of WS. UVR-induced inhibition of photosynthetic carbon fixation in the IS was identical with that of WS at the end of the long-term exposure. The photosynthetic acclimation was not accompanied with increased contents of UV-absorbing compounds, indicating that repair processes for UVR-induced damages must have been accelerated or upgraded. (C) 2008 Elsevier B.V. All rights reserved.

Photosynthesis and growth of Arthrospira (Spirulina) platensis (Cyanophyta) in response to solar UV radiation, with special reference to its minor variant

The minor variant of the economically important cyanobacterium, Arthrospira platensis, usually appears in commercial production ponds under solar radiation. However, how sensitive the minor variant to solar UVR and whether its occurrence relates to the solar exposures are not known. We investigated the photochemical efficiency of PSII and growth rate of D-0083 strain and its minor variant in semi-continuous cultures under PAR (400-700 nm) alone, PAR + UV-A (320-400 nm) and PAR + UV-A + UV-B (280-700 nm) of solar radiation. The effective quantum yield of D-0083 at 14:00 p.m. decreased by about 86% under PAR, 87% under PAR + UV-A and 92% under PAR + UV-A + UV-B (280-315 nm), respectively. That of the minor variant was reduced by 93% under PAR and to undetectable values in the presence of UV-A or UV-A + UV-B. Diurnal change of the yield showed constant pattern during long-term (10 days) exposures, high in the early morning and late afternoon but the lowest at noontime in both strains, with the UVR-related inhibition being always higher in the variant than D-0083. During the long-term exposures, cells of D-0083 acclimated faster to solar UV radiation and showed paralleled growth rates among the treatments with or without UVR at the end of the experiment; however, growth of the minor variant was significantly reduced by UV-A and UV-B throughout the period. Comparing to the major strain D-0083, the minor variant was more sensitive to UVR in terms of its growth, quantum yield and acclimation to solar radiation. (c) 2007 Elsevier B.V. All rights reserved.

Daily timing of emersion and elevated atmospheric CO2 concentration affect photosynthetic performance of the intertidal macroalga Ulva lactuca (Chlorophyta) in sunlight

The lunar day differs in length from the solar day so that times of low tide vary from day to day. Thus, aerial exposure of intertidal seaweeds may be during the day or during the night. We measured photosynthetic CO, assimilation rates of the intertidal green macroalga Ulva lactuca during exposures of varied daily timings during sunny days of summer to establish how photosynthetic performance responds to emersion timing under varied CO2 levels [at ambient (360 ppmv) and 2x ambient (720 ppmv) atmospheric CO2 concentrations]. There was an increase in net photosynthetic rates following some duration of exposure when the initial timing of exposure occurred during early morning (06.30 h) and late afternoon (17.15 h). In contrast, net rates exhibited a sharp decline with exposure duration when the initial timing of exposure occurred at 09.30 h, 15.30 h and especially at noon (12.30 h), implying the occurrence of a severe photoinhibition resulting from mid-day insolation. Doubled atmospheric CO2 concentration significantly enhanced the emersed photosynthetic rates, indicating that the emersed photosynthesis is CO2-limited at ambient CO2 levels. However, increasing CO2 barely stimulates the emersed photosynthetic rates during mid-day insolation.

Photodegradation of 2-naphthol in aqueous solutions in the presence of humic acid and ferric ions

In this work, the photodegradation of the carcinogenic pollutant 2-naphthol in aqueous solution containing Aldrich humic acid (HA) and ferric ions (Fe(III)) under 125 W and 250 W high pressure mercury lamp (HPML, lambda >= 365 nm) irradiation was investigated. The photooxidation efficiencies were dependent on the pH values, light intensities and Fe(III)/HA concentration in the water, with higher efficiency at pHs 3-4, and 50 mu mol l(-1) Fe(III) with 20 mg l(-1) HA under 250 W HPML. The initial rate of photooxidation increases with increasing, the initial concentration of 2-naphthol from 10 mu mol l(-1) to 100 mu mol l(-1), while do not change at 50 and 100 mu mol l(-1). However, higher removal efficiency of 2-naphthol is achieved at its lower initial concentration of 10 mu mol l(-1), and initial rate of photooxidation is 0.193 mu mol l(-1) min(-1). Dissolved oxygen (DO) plays an important role in the system containing Fe(III)-HA complexes in which Fenton and photo-Fenton reactions were enhanced in the environment. Hydroxyl radicals produced in HA solution with or without ferric ions were determined by using benzene as free radical scavenger and phenol as scavenging products proportional to hydroxyl radicals. By using UV-Vis and excited fluorescence spectrum techniques, the main photooxidation products, which have higher absorption in the region of 240-340 nm, were found, and the mechanisms for the oxidative degradation is proposed.

Photoreduction of mercuric salt in UV/Fe (III)-oxalate complex system

In this paper, the photochemical reduction process of Hg (II) in aqueous solution containing ferric iron and oxalate (Ox) has been studied. Under the radiation of a low-pressure mercury lamp (lambda = 253.7 nm, 8W), Fe(III)-oxalate complexes undergo photolysis to produce ferrous ions and other organic reductive species, which reduce Hg(II) subsequently. For 0.1 mg/L Hg (II), the photoreduction efficiency is comparatively higher in the solution at pH 5.0 than that over the range of 3.0 similar to 8.0. The photoreduction efficiency of Ho (II) in aqueous solution increases with increasing, initial concentration of ferric ions from 0.02 mmol/L to 0.2 mmol/L and initial concentration of oxalate from 0.96 mmol/L to 4.8 mmol/L and then gradually approaches to a steady state. CH3OH also contributes the reduction of Hg (II). We investigate the increase of the ferric, oxalate and CH3OH concentrations resulting from the increase of reduction efficiency of Hg (II). It can be seen that ferrous ions and other reactive species are reductants of Hg (II), and the reaction product with oxalate is mainly volatile metallic mercury.

Ecophysiological characteristics of four intertidal marine macroalgae during emersion along Shantou coast of China, with a special reference to the relationship of photosynthesis and CO2

Intertidal marine macroalgae experience periodical exposures during low tide due to their zonational distribution. The duration of such emersion leads to different exposures of the plants to light and aerial CO2, which then affect the physiology of them to different extents. The ecophysiological responses to light and CO2 were investigated during emersion in two red algae Gloiopeltis furcata and Gigartina intermedia, and two brown algae Petalonia fascia and Sargassum hemiphyllum, growing along the Shantou coast of China. The light-saturated net photosynthesis in G. furcata and P. fascia showed an increase followed by slightly desiccation, whereas that in G. intermedia and S. hemiphyllum exhibited a continuous decrease with water loss. In addition, the upper-zonated G. furcata and P. fascia, exhibited higher photosynthetic tolerance to desiccation and required higher light level to saturate their photosynthesis than the lower-zonated G. intemedia and S. hemiphyllum. Desiccation had less effect on dark respiration in these four algae compared with photosynthesis. The light-saturated net photosynthesis increased with increased CO2 concentrations, being saturated at CO2 concentrations higher than the present atmospheric level in G. furcata, G. intermedia and S. hemiphyllum during emersion. It was evident that the relative enhancement of photosynthesis by elevated CO, in those three algae increased, though the absolute values of photosynthetic enhancement owing to CO2 increase were reduced when the desiccation statuses became more severe. However, in the case of desiccated P. fascia (water loss being greater than 20 %), light saturated net photosynthesis was saturated with current ambient atmospheric CO2 level. It is proposed that increasing atmospheric CO2 will enhance the daily photosynthetic production in intertidal macroalgae by varied extents that were related to the species and zonation.

Comparative mechanisms of photosynthetic carbon acquisition in Hizikia fusiforme under submersed and emersed conditions

The economic seaweed Hizikia fusiforme (Harv.) Okamura (Sargassaceae, Phaeophyta) usually experiences periodical exposures to air at low tide. Photosynthetic carbon acquisition mechanisms were comparatively studied under submersed and emersed conditions in order to establish a general understanding of its photosynthetic characteristics associated with tidal cycles. When submersed in seawater, H fusiforme was capable of acquiring HCO3- as a source of inorganic carbon (Ci) to drive photosynthesis, while emersed and exposed to air, it used atmospheric CO2 for photosynthesis. The pH changes surrounding the H fusiforme fronds had less influence on the photosynthetic rates under emersed condition than under submersed condition. When the pH was as high as 10.0, emersed H fusiforme could photosynthesize efficiently, but the submersed alga exhibited very poor photosynthesis. Extracellular carbonic anhydrase (CA) played an important role in the photosynthetic acquisitions of exogenous Ci in water as well as in air. Both the concentrations of dissolved inorganic carbon in general seawater and CO2 in air were demonstrated to limit the photosynthesis of H fusiforme, which was sensitive to O-2. It appeared that the exogenous carbon acquisition system, being dependent of external CA activity, operates in a way not enough to raise intracellular CO2 level to prevent photorespiration. The inability of H fusiforme to achieve its maximum photosynthetic rate at the current ambient Ci levels under both submersed and emersed conditions suggested that the yield of aquaculture for this economic species would respond profitably to future increases in CO2 concentration in the sea and air.

Environmental threats to children's health in Southeast Asia and the Western Pacific

The Southeast Asia and Western Pacific regions contain half of the world's children and are among the most rapidly industrializing regions of the globe. Environmental threats to children's health are widespread and are multiplying as nations in the area undergo industrial development and pass through the epidemiologic transition. These environmental hazards range from traditional threats such as bacterial contamination of drinking water and wood smoke in poorly ventilated dwellings to more recently introduced chemical threats such as asbestos construction materials; arsenic in groundwater; methyl isocyanate in Bhopal, India; untreated manufacturing wastes released to landfills; chlorinated hydrocarbon and organophosphorous pesticides; and atmospheric lead emissions from the combustion of leaded gasoline. To address these problems, pediatricians, environmental health scientists, and public health workers throughout Southeast Asia and the Western Pacific have begun to build local and national research and prevention programs in children's environmental health. Successes have been achieved as a result of these efforts: A cost-effective system for producing safe drinking water at the village level has been devised in India; many nations have launched aggressive antismoking campaigns; and Thailand, the Philippines, India, and Pakistan have all begun to reduce their use of lead in gasoline, with resultant declines in children's blood lead levels. The International Conference on Environmental Threats to the Health of Children, held in Bangkok, Thailand, in March 2002, brought together more than 300 representatives from 35 countries and organizations to increase awareness on environmental health hazards affecting children in these regions and throughout the world. The conference, a direct result of the Environmental Threats to the Health of Children meeting held in Manila in April 2000, provided participants with the latest scientific data on children's vulnerability to environmental hazards and models for future policy and public health discussions on ways to improve children's health. The Bangkok Statement, a pledge resulting from the conference proceedings, is an important first step in creating a global alliance committed to developing active and innovative national and international networks to promote and protect children's environmental health.

Distribution, transformation, and long-term accumulation of polychlorinated dibenzo-p-dioxins and dibenzofurans in different tissues of fish and piscivorous birds

The present study monitored 10-year-old fish and piscivorous birds from sites contaminated for many Stars. The data reflected the results of actual, long-term environmental exposures, The results demonstrate that different tissues of fish have quite different concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F), The concentration order of PCDD/F within fish is liver congruent to egg congruent to intestines kidney congruent to hearts gill congruent to bladders > muscle > brain. The concentration order of PCDD/F within piscivorous birds was livers egg congruent to hearts muscle congruent to stomachs brain, The results obtained also demonstrate that the accumulation patterns of piscivorous birds and fish are quite different. The tissues of fish and piscivorous birds have different capacities for bioaccumulation and biotransformation of PCDD/F; variable proportions of TEQs were also found throughout their bodies. In fish, toxic equivalency quotient (TEQ): PCDD/F ratios in various tissues ranged from 0.01 to 0.07, whereas in birds the ratios ranged from 0.07 to 0.43. If the concentrations are normalized with lipid content, the results vary less. The effect of different lipid properties is obvious in the case of brain tissue, which is richer in phospholipids. (C) 2000 Academic Press.

A phototaxis inhibition assay using barnacle larvae

The effects of sublethal concentrations of phenol and cadmium on the phototactic responses of the stage II nauplii of the barnacle Balanus amphitrite were investigated. Increased toxicant concentrations caused a reduction in phototactic responses. Balanus amphitrite nauplii exposed to nominal phenol concentrations of 100 ppm and higher for 1-12 h failed to exhibit phototactic responses, while longer exposure times of 24 and 48 h reduced the lowest observable effect concentration (LOECs) to 80 and 60 ppm, respectively. For cadmium, the LOECs, based on nominal concentrations, for B. amphitrite following 1, 6, 12, 24, and 48 h exposures were 20, 4.5, 4.0, 1, and 0.75 ppm, respectively. The LOECs can be significantly reduced by increasing the duration of exposure to the toxicants. A good relationship exists between the phototactic response and toxicant concentration as well as exposure time. Results of this study indicate that the toxicant-induced reduction in phototactic responses of barnacle larvae can be used in a sensitive, rapid screening test for ecotoxicological assessments. (C) 1997 by John Wiley & Sons, Inc.