Seawater carbonate chemistry and buffer capacity of the coelomic fluid in echinoderms in a laboratory experiment

The increase in atmospheric CO2 due to anthropogenic activity results in an acidification of the surface waters of the oceans. The impact of these chemical changes depends on the considered organisms. In particular, it depends on the ability of the organism to control the pH of its inner fluids. Among echinoderms, this ability seems to differ significantly according to species or taxa. In the present paper, we investigated the buffer capacity of the coelomic fluid in different echinoderm taxa as well as factors modifying this capacity. Euechinoidea (sea urchins except Cidaroidea) present a very high buffer capacity of the coelomic fluid (from 0.8 to 1.8 mmol/kg SW above that of seawater), while Cidaroidea (other sea urchins), starfish and holothurians have a significantly lower one (from -0.1 to 0.4 mmol/kg SW compared to seawater). We hypothesize that this is linked to the more efficient gas exchange structures present in the three last taxa, whereas Euechinoidea evolved specific buffer systems to compensate lower gas exchange abilities. The constituents of the buffer capacity and the factors influencing it were investigated in the sea urchin Paracentrotus lividus and the starfish Asterias rubens. Buffer capacity is primarily due to the bicarbonate buffer system of seawater (representing about 63% for sea urchins and 92% for starfish). It is also partly due to coelomocytes present in the coelomic fluid (around 8% for both) and, in P. lividus only, a compound of an apparent size larger than 3 kDa is involved (about 15%). Feeding increased the buffer capacity in P. lividus (to a difference with seawater of about 2.3 mmol/kg SW compared to unfed ones who showed a difference of about 0.5 mmol/kg SW) but not in A. rubens (difference with seawater of about 0.2 for both conditions). In P. lividus, decreased seawater pH induced an increase of the buffer capacity of individuals maintained at pH 7.7 to about twice that of the control individuals and, for those at pH 7.4, about three times. This allowed a partial compensation of the coelomic fluid pH for individuals maintained at pH 7.7 but not for those at pH 7.4.

Estudios de especiación de arsénico y acumulación de metales en muestras de interés medioambiental : Arsenic speciation and metal accumulation studies in environmental samples

Se ha estudiado la determinación de especies de arsénico y de contenidos totales de arsénico y metales pesados, específicamente cadmio, cromo, cobre, níquel, plomo y cinc, en muestras de interés medioambiental por su elevada capacidad acumuladora de metales, concretamente algas marinas comestibles y plantas terrestres procedentes de suelos contaminados por la actividad minera. La determinación de contenidos totales se ha llevado a cabo mediante espectrometría de emisión atómica con plasma de acoplamiento inductivo (ICP‐AES), así como por espectrometría de fluorescencia atómica con generación de hidruros (HG‐AFS), para bajos contenidos de arsénico. Las muestras fueron mineralizadas en medio ácido y calentamiento en horno de microondas. Los métodos fueron validados a través de su aplicación a materiales de referencia de matriz similar a la de las muestras, certificados en contenidos totales de los elementos seleccionados. Los resultados obtenidos mostraron su elevada capacidad de bioabsorción, especialmente en relación a los elevados contenidos de arsénico encontrados en algunas especies de algas pardas (Phaeophytas). En las plantas, se calcularon los factores de translocación, acumulación y biodisponibilidad de los elementos estudiados, permitiendo identificar a la especie Corrigiola telephiifolia como posible acumuladora de plomo e hiperacumuladora de arsénico. La determinación de especies de arsénico hidrosolubles en las muestras objeto de estudio, se llevó a cabo por cromatografía líquida de alta eficacia (HPLC) acoplado a ICP‐AES, HG‐ICP‐AES y HG‐AFS, incluyendo una etapa previa de foto‐oxidación. Los métodos desarrollados, mediante intercambio aniónico y catiónico, permitieron la diferenciación de hasta once especies de arsénico. Para el análisis de las muestras, fue necesaria la optimización de métodos de extracción, seleccionándose la extracción asistida por microondas (MAE) con agua desionizada. Asimismo, se realizaron estudios de estabilidad de arsénico total y de las especies hidrosolubles presentes en las algas, tanto sobre la muestra sólida como en sus extractos acuosos, evaluando las condiciones de almacenamiento adecuadas. En el caso de las plantas, la aplicación del diseño factorial de experimentos permitió optimizar el método de extracción y diferenciar entre las especies de arsénico presentes en forma de iones sencillos de mayor movilidad y el arsénico más fuertemente enlazado a componentes estructurales. Los resultados obtenidos permitieron identificar la presencia de arseniato (As(V)) y arsenito (As(III)) en las plantas, así como de ácido monometilarsónico (MMA) y óxido de trimetilarsina (TMAO) en algunas especies. En la mayoría de las algas se encontraron especies tóxicas, tanto mayoritarias (arseniato) como minoritarias (ácido dimetilarsínico (DMA)), así como hasta cuatro arsenoazúcares. Los resultados obtenidos y su estudio a través de la legislación vigente, mostraron la necesidad de desarrollar una reglamentación específica para el control de este tipo de alimentos. La determinación de especies de arsénico liposolubles en las muestras de algas se llevó a cabo mediante HPLC, en modo fase inversa, acoplado a espectrometría de masas con plasma de acoplamiento inductivo (ICP‐MS) y con ionización por electrospray (ESI‐MS), permitiendo la elucidación estructural de estos compuestos a través de la determinación de sus masas moleculares. Para ello, fue necesaria la puesta a punto de métodos extracción y purificación de los extractos. La metodología desarrollada permitió identificar hasta catorce especies de arsénico liposolubles en las algas, tres de ellas correspondientes a hidrocarburos que contienen arsénico, y once a arsenofosfolípidos, además de dos especies desconocidas. Las masas moleculares de las especies identificadas fueron confirmadas mediante cromatografía de gases acoplada a espectrometría de masas (GC‐MS) y espectrometría de masas de alta resolución (HR‐MS). ABSTRACT The determination of arsenic species and total arsenic and heavy metal contents (cadmium, chromium, cooper, nickel, lead and zinc) in environmental samples, with high metal accumulator capacity, has been studied. The samples studied were edible marine algae and terrestrial plants from soils polluted by mining activities. The determination of total element contents was performed by inductively coupled plasma atomic emission spectrometry (ICP‐AES), as well as by hydride generation atomic fluorescence spectrometry (HG‐AFS) for low arsenic contents. The samples studied were digested in an acidic medium by heating in a microwave oven. The digestion methods were validated against reference materials, with matrix similar to sample matrix and certified in total contents of the elements studied. The results showed the high biosorption capacity of the samples studied, especially regarding the high arsenic contents in some species of brown algae (Phaeophyta division). In terrestrial plants, the translocation, accumulation and bioavailability factors of the elements studied were calculated. Thus, the plant species Corrigiola telephiifolia was identified as possible lead accumulator and arsenic hyperaccumulator. The determination of water‐soluble arsenic species in the samples studied was carried out by high performance liquid chromatography (HPLC) coupled to ICP‐AES, HG‐ICP‐AES and HG‐AFS, including a prior photo‐oxidation step. The chromatographic methods developed, by anion and cation exchange, allowed us to differentiate up to eleven arsenic species. The sample analysis required the optimization of extraction methods, choosing the microwave assisted extraction (MAE) with deionized water. On the other hand, the stability of total arsenic and water‐soluble arsenic species in algae, both in the solid samples and in the water extracts, was studied, assessing the suitable storage conditions. In the case of plant samples, the application of a multivariate experimental design allowed us to optimize the extraction method and differentiate between the arsenic species present as simple ions of higher mobility and the arsenic more strongly bound to structural components. The presence of arsenite (As(III)) and arsenate (As(V)) was identified in plant samples, as well as monomethylarsonic acid (MMA) and trimethylarsine oxide (TMAO) in some cases. Regarding algae, toxic arsenic species were found in most of them, both As(V) and dimethylarsinic acid (DMA), as well as up to four arsenosugars. These results were discussed according to the current legislation, showing the need to develop specific regulations to control this kind of food products. The determination of lipid‐soluble arsenic species in alga samples was performed by reversed‐phase HPLC coupled to inductively coupled plasma and electrospray mass spectrometry (ICP‐MS and ESI‐MS), in order to establish the structure of these compounds by determining the corresponding molecular masses. For this purpose, it was necessary to develop an extraction method, as well as a clean‐up method of the extracts. The method developed permitted the identification of fourteen lipid‐soluble arsenic compounds in algae, corresponding to three arsenic‐hydrocarbons and eleven arsenosugarphospholipids, as well as two unknown compounds. Accurate mass measurements of the identified compounds were performed by gas chromatography coupled to mass spectrometry (GC‐MS) and high resolution mass spectrometry (HR‐MS).

Building sustainable capacity for health research in africa through cloud computing applications

Access to information and continuous education represent critical factors for physicians and researchers over the world. For African professionals, this situation is even more problematic due to the frequently difficult access to technological infrastructures and basic information. Both education and information technologies (e.g., including hardware, software or networking) are expensive and unaffordable for many African professionals. Thus, the use of e-learning and an open approach to information exchange and software use have been already proposed to improve medical informatics issues in Africa. In this context, the AFRICA BUILD project, supported by the European Commission, aims to develop a virtual platform to provide access to a wide range of biomedical informatics and learning resources to professionals and researchers in Africa. A consortium of four African and four European partners work together in this initiative. In this framework, we have developed a prototype of a cloud-computing infrastructure to demonstrate, as a proof of concept, the feasibility of this approach. We have conducted the experiment in two different locations in Africa: Burundi and Egypt. As shown in this paper, technologies such as cloud computing and the use of open source medical software for a large range of case present significant challenges and opportunities for developing countries, such as many in Africa.

Electrochemical anion recognition with ferrocene functionalised macrocycles

The syntheses and characterization of two new redox active cyclam ligands ferrocenylmethyl-(6-methyl-1,4,8,11-tetraazacyclotetradec-6-yl)-amine(L-3) and 1, 1'-ferrocenylmethyl-bis(6-methyl-1,4,8,11-tetraazacyclotetradec-6-yl)-amine (L-4) are reported. The compounds each possess a ferrocenyl group bearing one (L-3) or two (L-4) appended macrocycles linked by their exocyclic amino groups and the crystal structures of both compounds have been determined. Anion binding of L-3 and L-4 was investigated by electrochemical titrations where H-bonding to each macrocycle causing a shift in the Fc(+/0) redox potential was used as a reporter of guest binding. The Zn-II complex of L-3 has also been isolated and characterized structurally. These compounds were analysed for their capacity to electrochemically recognize anions in both aqueous and non-aqueous solution. We have found that L-3, L-4 and [ZnL3-](2+) sense Cl- and AcO- anions in MeCN-CH2Cl2, a function that is lost in aqueous solution.

The genetic structure of Australasian green turtles (Chelonia mydas): exploring the geographical scale of genetic exchange

Ecological and genetic studies of marine turtles generally support the hypothesis of natal homing, but leave open the question of the geographical scale of genetic exchange and the capacity of turtles to shift breeding sites. Here we combine analyses of mitochondrial DNA (mtDNA) variation and recapture data to assess the geographical scale of individual breeding populations and the distribution of such populations through Australasia. We conducted multiscale assessments of mtDNA variation among 714 samples from 27 green turtle rookeries and of adult female dispersal among nesting sites in eastern Australia. Many of these rookeries are on shelves that were flooded by rising sea levels less than 10 000 years (c. 450 generations) ago. Analyses of sequence variation among the mtDNA control region revealed 25 haplotypes, and their frequency distributions indicated 17 genetically distinct breeding stocks (Management Units) consisting either of individual rookeries or groups of rookeries in general that are separated by more than 500 km. The population structure inferred from mtDNA was consistent with the scale of movements observed in long-term mark-recapture studies of east Australian rookeries. Phylogenetic analysis of the haplotypes revealed five clades with significant partitioning of sequence diversity (Phi = 68.4) between Pacific Ocean and Southeast Asian/Indian Ocean rookeries. Isolation by distance was indicated for rookeries separated by up to 2000 km but explained only 12% of the genetic structure. The emerging general picture is one of dynamic population structure influenced by the capacity of females to relocate among proximal breeding sites, although this may be conditional on large population sizes as existed historically across this region.

The effect of caudal block on functional residual capacity and ventilation homogeneity in healthy children

Caudal block results in a motor blockade that can reduce abdominal wall tension. This could interact with the balance between chest wall and lung recoil pressure and tension of the diaphragm, which determines the static resting volume of the lung. On this rationale, we hypothesised that caudal block causes an increase in functional residual capacity and ventilation distribution in anaesthetised children. Fifty-two healthy children (15-30 kg, 3-8 years of age) undergoing elective surgery with general anaesthesia and caudal block were studied and randomly allocated to two groups: caudal block or control. Following induction of anaesthesia, the first measurement was obtained in the supine position (baseline). All children were then turned to the left lateral position and patients in the caudal block group received a caudal block with bupivacaine. No intervention took place in the control group. After 15 nun in the supine position, the second assessment was performed. Functional residual capacity and parameters of ventilation distribution were calculated by a blinded reviewer. Functional residual capacity was similar at baseline in both groups. In the caudal block group, the capacity increased significantly (p < 0.0001) following caudal block, while in the control group, it remained unchanged. In both groups, parameters of ventilation distribution were consistent with the changes in functional residual capacity. Caudal block resulted in a significant increase in functional residual capacity and improvement in ventilation homogeneity in comparison with the control group. This indicates that caudal block might have a beneficial effect on gas exchange in anaesthetised, spontaneously breathing preschool-aged children with healthy lungs.

Computational modeling of intermediate temperature proton exchange membrane (PEM) fuel cells

A two-phase three-dimensional computational model of an intermediate temperature (120--190°C) proton exchange membrane (PEM) fuel cell is presented. This represents the first attempt to model PEM fuel cells employing intermediate temperature membranes, in this case, phosphoric acid doped polybenzimidazole (PBI). To date, mathematical modeling of PEM fuel cells has been restricted to low temperature operation, especially to those employing Nafion ® membranes; while research on PBI as an intermediate temperature membrane has been solely at the experimental level. This work is an advancement in the state of the art of both these fields of research. With a growing trend toward higher temperature operation of PEM fuel cells, mathematical modeling of such systems is necessary to help hasten the development of the technology and highlight areas where research should be focused.^ This mathematical model accounted for all the major transport and polarization processes occurring inside the fuel cell, including the two phase phenomenon of gas dissolution in the polymer electrolyte. Results were presented for polarization performance, flux distributions, concentration variations in both the gaseous and aqueous phases, and temperature variations for various heat management strategies. The model predictions matched well with published experimental data, and were self-consistent.^ The major finding of this research was that, due to the transport limitations imposed by the use of phosphoric acid as a doping agent, namely low solubility and diffusivity of dissolved gases and anion adsorption onto catalyst sites, the catalyst utilization is very low (∼1--2%). Significant cost savings were predicted with the use of advanced catalyst deposition techniques that would greatly reduce the eventual thickness of the catalyst layer, and subsequently improve catalyst utilization. The model also predicted that an increase in power output in the order of 50% is expected if alternative doping agents to phosphoric acid can be found, which afford better transport properties of dissolved gases, reduced anion adsorption onto catalyst sites, and which maintain stability and conductive properties at elevated temperatures.^

Benthic Exchange of C, N, and P Along the Estuarine Ecotone of Lower Taylor Slough, Florida (USA): Effect of Seasonal Flows and Phosphorus Availability

The southern Everglades and Florida Bay have experienced a nearly 50 % reduction in freshwater flow resulting in increased salinity and landward expansion of mangrove forest. Given the marine end-member is a natural source of P to this region, it is necessary to understand the interactions between inflows and P availability in controlling the exchange of materials across the mangrove ecotone. From 2007 to 2008, we used sediment core incubations to quantify fluxes of dissolved inorganic N and P and dissolved organic carbon (DOC) in three ecotone areas (dwarf mangrove, pond, and bay). Experiments were repeated seasonally over 2 years involving P-enriched surface water as a factor. We saw consistent uptake of soluble reactive P (SRP), DOC, and nitrate + nitrite (N+N) by the soils/sediments and release of ammonium (NH4 +) from soils/sediments to the water column across all sites and seasons. P enrichment had no discernible effect on DIN or DOC flux, suggesting that rapid P uptake may have been more geochemically mediated. However, uptake of added P occurred across all sites and seasons, reflecting high uptake capacity in this carbonate system and the potential of the mangrove ecotone to sequester P as it becomes more available.

Learning from one another: evaluating the impact of horizontal knowledge exchange for environmental management and governance

There is increasing advocacy for inclusive community-based approaches to environmental management, and growing evidence that involving communities improves the sustainability of social-ecological systems. Most community-based approaches rely on partnerships and knowledge exchange between communities, civil society organizations, and professionals such as practitioners and/or scientists. However, few models have actively integrated more horizontal knowledge exchange from community to community. We reflect on the transferability of community owned solutions between indigenous communities by exploring challenges and achievements of community peer-to-peer knowledge exchange as a way of empowering communities to face up to local environmental and social challenges. Using participatory visual methods, indigenous communities of the North Rupununi (Guyana) identified and documented their community owned solutions through films and photostories. Indigenous researchers from this community then shared their solutions with six other communities that faced similar challenges within Guyana, Suriname, Venezuela, Colombia, French Guiana, and Brazil. They were supported by in-country civil society organizations and academics. We analyzed the impact of the knowledge exchange through interviews, field reports, and observations. Our results show that indigenous community members were significantly more receptive to solutions emerging from, and communicated by, other indigenous peoples, and that this approach was a significant motivating force for galvanizing communities to make changes in their community. We identified a range of enabling factors, such as building capacity for a shared conceptual and technical understanding, that strengthens the exchange between communities and contributes to a lasting impact. With national and international policy-makers mobilizing significant financial resources for biodiversity conservation and climate change mitigation, we argue that the promotion of community owned solutions through community peer-to-peer exchange may deliver more long-lasting, socially and ecologically integrated, and investment-effective strategies compared to top-down, expert led, and/or foreign-led initiatives.

Wastewater treatment by novel hybrid biological – ion exchange processes

This study presents two novel methods for treating important environmental contaminants from two different wastewater streams. One process utilizes the kinetic advantages and reliability of ion exchanging clinoptilolite in combination with biological treatment to remove ammonium from municipal sewage. A second process, HAMBgR (Hybrid Adsorption Membrane Biological Reactor), combines both ion exchange resin and bacteria into a single reactor to treat perchlorate contaminated waters. Combining physicochemical adsorptive treatment with biological treatment can provide synergistic benefits to the overall removal processes. Ion exchange removal solves some of the common operational reliability limitations of biological treatment, like slow response to environmental changes and leaching. Biological activity can in turn help reduce the economic and environmental challenges of ion exchange processes, like regenerant cost and brine disposal. The second section of this study presents continuous flow column experiments, used to demonstrate the ability of clinoptilolite to remove wastewater ammonium, as well as the effectiveness of salt regeneration using highly concentrated sea salt solutions. The working capacity of clinoptilolite more than doubled over the first few loading cycles, while regeneration recovered more than 98% of ammonium. Using the regenerant brine for subsequent halotolerant algae growth allowed for its repeated use, which could lead to cost savings and production of valuable algal biomass. The algae were able to uptake all ammonium in solution, and the brine was able to be used again with no loss in regeneration efficiency. This process has significant advantages over conventional biological nitrification; shorter retention times, wider range of operational conditions, and higher quality effluent free of nitrate. Also, since the clinoptilolite is continually regenerated and the regenerant is rejuvenated by algae, overall input costs are expected to be low. The third section of this study introduces the HAMBgR process for the elimination of perchlorate and presents batch isotherm experiments and pilot reactor tests. Results showed that a variety of ion-exchange resins can be effectively and repeatedly regenerated biologically, and maintain an acceptable working capacity. The presence of an adsorbent in the HAMBgR process improved bioreactor performance during operational fluctuations by providing a physicochemical backup to the biological process. Pilot reactor tests showed that the HAMBgR process reduced effluent perchlorate spikes by up to 97% in comparison to a conventional membrane bio-reactor (MBR) that was subject to sudden changes in influent conditions. Also, the HAMBgR process stimulated biological activity and lead to higher biomass concentrations during increased contaminant loading conditions. Conventional MBR systems can be converted into HAMBgR’s at a low cost, easily justifiable by the realized benefits. The concepts employed in the HAMBgR process can be adapted to treat other target contaminants, not just perchlorate.

A comparative study of alginate beads and an ion-exchange resin for the removal of heavy metals from a metal plating effluent

The capacity of dry protonated calcium alginate beads to sorb metals from an industrial effluent was studied and compared with a commercial ion-exchange resin (Lewatit TP 207). Both sorbents decreased zinc, nickel, iron and calcium concentrations in the effluent, and released sodium during treatment. Alginate beads removed lower amounts of heavy metals than the resin, but exhibited faster uptake kinetics. Zinc desorption from the sorbents was achieved in 30 minutes using 0.1 M HCl or 0.1 M H(2)SO(4). Desorption ratios with these acids varied between 90 and 100% for alginate, and 98 to 100% for the ion-exchange resin. Reusability tests with HCl showed that alginate beads can stand acid desorption and recover binding capacity. Overall, the comparison of dry protonated alginate beads with the resin supports the potential of the biosorbent for the treatment of industrial effluents.

The Coming of Post-reflexive Society: Commodification and Language in Digital Capitalism

Language is a unique aspect of human communication because it can be used to discuss itself in its own terms. For this reason, human societies potentially have superior capacities of co-ordination, reflexive self-correction, and innovation than other animal, physical or cybernetic systems. However, this analysis also reveals that language is interconnected with the economically and technologically mediated social sphere and hence is vulnerable to abstraction, objectification, reification, and therefore ideology – all of which are antithetical to its reflexive function, whilst paradoxically being a fundamental part of it. In particular, in capitalism, language is increasingly commodified within the social domains created and affected by ubiquitous communication technologies. The advent of the so-called ‘knowledge economy’ implicates exchangeable forms of thought (language) as the fundamental commodities of this emerging system. The historical point at which a ‘knowledge economy’ emerges, then, is the critical point at which thought itself becomes a commodified ‘thing’, and language becomes its “objective” means of exchange. However, the processes by which such commodification and objectification occurs obscures the unique social relations within which these language commodities are produced. The latest economic phase of capitalism – the knowledge economy – and the obfuscating trajectory which accompanies it, we argue, is destroying the reflexive capacity of language particularly through the process of commodification. This can be seen in that the language practices that have emerged in conjunction with digital technologies are increasingly non-reflexive and therefore less capable of self-critical, conscious change.