Support for Integrated Ecosystem Assessments of NOAA’s National Estuarine Research Reserves System (NERRS), Volume II: Assessment of Ecological Condition and Stressor Impacts in Subtidal Waters of the North Carolina NERRS

A study was conducted to assess the status of ecological condition and potential human-health risks in subtidal estuarine waters throughout the North Carolina National Estuarine Research Reserve System (NERRS) (Currituck Sound, Rachel Carson, Masonboro Island, and Zeke’s Island). Field work was conducted in September 2006 and incorporated multiple indicators of ecosystem condition including measures of water quality (dissolved oxygen, salinity, temperature, pH, nutrients and chlorophyll, suspended solids), sediment quality (granulometry, organic matter content, chemical contaminant concentrations), biological condition (diversity and abundances of benthic fauna, fish contaminant levels and pathologies), and human dimensions (fish-tissue contaminant levels relative to human-health consumption limits, various aesthetic properties). A probabilistic sampling design permitted statistical estimation of the spatial extent of degraded versus non-degraded condition across these estuaries relative to specified threshold levels of the various indicators (where possible). With some exceptions, the status of these reserves appeared to be in relatively good to fair ecological condition overall, with the majority of the area (about 54%) having various water quality, sediment quality, and biological (benthic) condition indicators rated in the healthy to intermediate range of corresponding guideline thresholds. Only three stations, representing 10.5% of the area, had one or more of these indicators rated as poor/degraded in all three categories. While such a conclusion is encouraging from a coastal management perspective, it should be viewed with some caution. For example, although co-occurrences of adverse biological and abiotic environmental conditions were limited, at least one indicator of ecological condition rated in the poor/degraded range was observed over a broader area (35.5%) represented by 11 of the 30 stations sampled. In addition, the fish-tissue contaminant data were not included in these overall spatial estimates; however, the majority of samples (77% of fish that were analyzed, from 79%, of stations where fish were caught) contained inorganic arsenic above the consumption limits for human cancer risks, though most likely derived from natural sources. Similarly, aesthetic indicators are not reflected in these spatial estimates of ecological condition, though there was evidence of noxious odors in sediments at many of the stations. Such symptoms reflect a growing realization that North Carolina estuaries are under multiple pressures from a variety of natural and human influences. These data also suggest that, while the current status of overall ecological condition appears to be good to fair, long-term monitoring is warranted to track potential changes in the future. This study establishes an important baseline of overall ecological condition within NC NERRS that can be used to evaluate any such future changes and to trigger appropriate management actions in this rapidly evolving coastal environment. (PDF contains 76 pages)

Determinación de arsénico total e inorgánico en carnes y víceras de camélidos (Lamma glama) autóctonos de la provincia de Jujuy, Argentina

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Accumulation or production of arsenobetaine in humans?

Arsenobetaine has always been referred to as a non-toxic but readily bioavailable compound and the available data would suggest that it is neither metabolised by nor accumulated in humans. Here this study investigates the urine of five volunteers on an arsenobetaine exclusive diet for twelve days and shows that arsenobetaine was consistently excreted by three of the five volunteers. From the expected elimination pattern of arsenobetaine in rodents, no significant amount of arsenobetaine should have been detectable after 5 days of the trial period. The arsenobetaine concentration found in the urine was constant after 5 days and varied between 0.2 and 12.2 microg As per L for three of the volunteers. Contrary to the established belief that arsenobetaine is neither accumulated nor generated by humans, the presented results would suggest that either accumulated arsenobetaine in the tissues is slowly released over time or that arsenobetaine is a human metabolite of dimethylarsinic acid or inorganic arsenic from the trial food, or both. Either possibility is intriguing and raises fundamental questions about human arsenic metabolism and the toxicological and environmental inertness of arsenobetaine.

Profiling the ionome of rice and its use in discriminating geographical origins at the regional scale, China

Element profile was investigated for their use to trace the geographical origin of rice (Oryza sativa L.) samples. The concentrations of 13 elements (calcium (Ca), potassium (K), magnesium (Mg), phosphorus (P), boron (B), manganese (Mn), iron (Fe), nickel (Ni), copper (Cu), arsenic (As), selenium (Se), molybdenum (Mo), and cadmium (Cd)) were determined in the rice samples by inductively coupled plasma optical emission and mass spectrometry. Most of the essential elements for human health in rice were within normal ranges except for Mo and Se. Mo concentrations were twice as high as those in rice from Vietnam and Spain. Meanwhile, Se concentrations were three times lower in the whole province compared to the Chinese average level of 0.088 mg/kg. About 12% of the rice samples failed the Chinese national food safety standard of 0.2 mg/kg for Cd. Combined with the multi-elemental profile in rice, the principal component analysis (PCA), discriminant function analysis (DFA) and Fibonacci index analysis (FIA) were applied to discriminate geographical origins of the samples. Results indicated that the FIA method could achieve a more effective geographical origin classification compared with PCA and DFA, due to its efficiency in making the grouping even when the elemental variability was so high that PCA and DFA showed little discriminatory power. Furthermore, some elements were identified as the most powerful indicators of geographical origin: Ca, Ni, Fe and Cd. This suggests that the newly established methodology of FIA based on the ionome profile can be applied to determine the geographical origin of rice.

Silicon, the silver bullet for mitigating biotic and abiotic stress, and improving grain quality, in rice?

Adequate silicon fertilization greatly boosts rice yield and mitigates biotic and abiotic stress, and improves grain quality through lowering the content of cadmium and inorganic arsenic. This review on silicon dynamics in rice considers recent advances in our understanding of the role of silicon in rice, and the challenges of maintaining adequate silicon fertility within rice paddy systems. Silicon is increasingly considered as an element required for optimal plant performance, particularly in rice. Plants can survive with very low silicon under laboratory/glasshouse conditions, but this is highly artificial and, thus, silicon can be considered as essential for proper plant function in its environment. Silicon is incorporated into structural components of rice cell walls were it increases cell and tissue rigidity in the plant. Structural silicon provides physical protection to plants against microbial infection and insect attack as well as reducing the quality of the tissue to the predating organisms. The abiotic benefits are due to silicon's effect on overall organ strength. This helps protect against lodging, drought stress, high temperature (through efficient maintenance of transpiration), and photosynthesis by protecting against high UV. Furthermore, silicon also protects the plant from saline stress and against a range of toxic metal stresses (arsenic, cadmium, chromium, copper, nickel and zinc). Added to this, silicon application decreases grain concentrations of various human carcinogens, in particular arsenic, antimony and cadmium. As rice is efficient at stripping bioavailable silicon from the soil, recycling of silicon rich rice straw biomass or addition of inorganic silicon fertilizer, primarily obtained from iron and steel slag, needs careful management. Silicon in the soil may be lost if the silicon-cycle, traditionally achieved via composting of rice straw and returning it to the land, is being broken. As composting of rice straw and incorporation of composted or non-composted straw back to land are resource intensive activities, these activities are declining due to population shifts from the countryside to cities. Processes that accelerate rice straw composting, therefore, need to be identified to aid more efficient use of this resource. In addition, rice genetics may help address declining available silicon in paddy soils: for example by selecting for characteristics during breeding that lead to an increased ability of roots to access recalcitrant silicon sources from soil and/or via selection for traits that aid the maintenance of a high silicon status in shoots. Recent advances in understanding the genetic regulation of silicon uptake and transport by rice plants will aid these goals.

Análise de especiação redox de arsênio in situ usando a técnica de difusão de filmes finos por gradiente de concentração

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

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.

Uptake and translocation of inorganic and methylated arsenic species by plants

The uptake and translocation into shoots of arsenate, methylarsonate (MA), and dimethylarsinate (DMA) by 46 different plant species were studied. The plants (n = 3 per As species) were exposed for 24 h to 1 mg of As per litre under identical conditions. Total arsenic was measured in the roots and the shoots by acid digestion and inductively coupled plasma mass spectrometry from which, besides total As values, root absorption factors and shoot-to-root transfer factors were calculated. As uptake into the root for the different plant species ranged from 1.2 to 95 (mu g of As per g of dry weight) for As-V, from 0.9 to 44 for MA(V) and from 0.8 to 13 for DMA(V), whereas in shoots the As concentration ranged from 0.10 to 17 for As-V, 0.1 to 13 for MA(V), and 0.2 to 17 for DMA(V). The mean root absorption factor for As-V (1.2 to 95%) was five times higher than for DMA(V) (0.8 to 13%) and 2.5 times higher than for MA(V) (0.9 to 44%). Although the uptake of arsenic in the form of As-V was significantly higher than that of MA(V) and DMA(V), the translocation of the methylated species was more efficient in most plant species studied. Thus, an exposure of plants to DMA(V) or MA(V) can result in higher arsenic concentrations in the shoots than when exposed to As-V. Shoot-to-root transfer factors (TFs) for all plants varied with plant and arsenic species. While As-V had a median TF of 0.09, the TF of DMA(V) was nearly a factor of 10 higher (0.81). The median TF for MA(V) was in between (0.30). Although the TF for MA(V) correlates well with the TF for DMA(V), the plants can be separated into two groups according to their TF of DMA(V) in relation to their TF of As-V. One group can immobilise DMA(V) in the roots, while the other group translocates DMA(V) very efficiently into the shoot. The reason for this is as yet unknown.

Arsenic and selenium mobilisation from organic matter treated mine spoil with and without inorganic fertilisation

Organic matter amendments are applied to contaminated soil to provide a better habitat for revegetation and remediation, and olive mill waste compost (OMWC) has been described as a promising material for this aim. We report here the results of an incubation experiment carried out in flooded conditions to study its influence in As and metal solubility in a trace elements contaminated soil. NPK fertilisation and especially organic amendment application resulted in increased As, Se and Cu concentrations in pore water. Independent of the amendment, dimethylarsenic acid (DMA) was the most abundant As species in solution. The application of OMWC increased pore water dissolved organic-carbon (DOC) concentrations, which may explain the observed mobilisation of As, Cu and Se; phosphate added in NPK could also be in part responsible of the mobilisation caused in As. Therefore, the application of soil amendments in mine soils may be particularly problematic in flooded systems. (C) 2012 Elsevier Ltd. All rights reserved.

Inorganic species of arsenic in soil solution determined by microcartridges and ferrihydrite-based diffusive gradient in thin films

The bioavailability of soil arsenic (As) is determined by its speciation in soil solution, i.e., arsenite [As(III)] or arsenate [As(V)]. Soil bioavailability studies require suitable methods to cope with small volumes of soil solution that can be speciated directly after sampling, and thereby minimise any As speciation change during sample collection. In this study, we tested a self-made microcartridge to separate both As species and compared it to a commercially available cartridge. In addition, the diffusive gradient in thin films technique (DGT), in combination with the microcartridges, was applied to synthetic solutions and to a soil spiked with As. This combination was used to improve the assessment of available inorganic As species with ferrihydrite(FH)-DGT, in order to validate the technique for environmental analysis, mainly in soils. The self-made microcartridge was effective in separating As(III) from As(V) in solution with detection by inductively coupled plasma optical emission spectrometry (ICP-OES) in volumes of only 3 ml. The DGT study also showed that the FH-based binding gels are effective for As(III) and As(V) assessment, in solutions with As and P concentrations and ionic strength commonly found in soils. The FH-DGT was tested on flooded and unflooded As spiked soils and recoveries of As(III) and As(V) were 85–104% of the total dissolved As. This study shows that the DGT with FH-based binding gel is robust for assessing inorganic species of As in soils.

Arsenic and selenium mobilisation from organic matter treated mine spoil with and without inorganic fertilisation

Organic matter amendments are applied to contaminated soil to provide a better habitat for re-vegetation and remediation, and olive mill waste compost (OMWC) has been described as a promising material for this aim. We report here the results of an incubation experiment carried out in flooded conditions to study its influence in As and metal solubility in a trace elements contaminated soil. NPK fertilisation and especially organic amendment application resulted in increased As, Se and Cu concentrations in pore water. Independent of the amendment, dimethylarsenic acid (DMA) was the most abundant As species in solution. The application of OMWC increased pore water dissolved organic-carbon (DOC) concentrations, which may explain the observed mobilisation of As, Cu and Se; phosphate added in NPK could also be in part responsible of the mobilisation caused in As. Therefore, the application of soil amendments in mine soils may be particularly problematic in flooded systems.

In-situ formation of graphene-lead oxide composite and its use in trace arsenic detection

Reduced graphene oxide-lead dioxide composite is formed when EGO coated surface is electrochemically reduced along with lead ions in the solution. This composite has been shown to be an excellent material for low level detection of arsenic. Various functional groups present on EGO, in a wide pH range of 2-11, are responsible for the favorable interaction between metal ion and the modified electrode surface and subsequent trace level detection. X-ray photoelectron spectroscopy and Raman spectroscopic techniques confirm the formation of composite and its composition. Thin layer of lead dioxide along with reduced exfoliated graphene oxide has been shown to be responsible for the enhanced activity of the surface. The detection limit of arsenic is found to be 10 nM. This study opens up the possibility of using the composites for sensing applications and possibly simultaneous detection of arsenic and lead. (C) 2011 Elsevier B.V. All rights reserved.

Cyclodextrin functionalized magnetic iron oxide nanocrystals: a host-carrier for magnetic separation of non-polar molecules and arsenic from aqueous media

A single-step magnetic separation procedure that can remove both organic pollutants and arsenic from contaminated water is clearly a desirable goal. Here we show that water dispersible magnetite nanoparticles prepared by anchoring carboxymethyl-beta-cyclodextrin (CMCD) cavities to the surface of magnetic nanoparticles are suitable host carriers for such a process. Monodisperse, 10 nm, spherical magnetite, Fe3O4, nanocrystals were prepared by the thermal decomposition of FeOOH. Trace amounts of antiferromagnet, FeO, present in the particles provides an exchange bias field that results in a high superparamagnetic blocking temperature and appreciable magnetization values that facilitate easy separation of the nanocrystals from aqueous dispersions on application of modest magnetic fields. We show here that small molecules like naphthalene and naphthol can be removed from aqueous media by forming inclusion complexes with the anchored cavities of the CMCD-Fe3O4 nanocrystals followed by separation of the nanocrystals by application of a magnetic field. The adsorption properties of the iron oxide surface towards As ions are unaffected by the CMCD capping so it too can be simultaneously removed in the separation process. The CMCD-Fe3O4 nanocrystals provide a versatile platform for magnetic separation with potential applications in water remediation.

Multilayer assemblies of polyelectrolyte-gold nanoparticles for the electrocatalytic oxidation and detection of arsenic(III)

Multilayers of poly(diallyldimethylammonium chloride) (PDDA) and citrate capped Au nanoparticles (AuNPs) anchored on sodium 3-mercapto-1-propanesulfonate modified gold electrode by electrostatic layer-by-layer assembly (LbL) technique are shown to be an excellent architecture for the direct electrochemical oxidation of As(III) species. The growth of successive layers in the proposed LbL architecture is followed by atomic force microscopy, UV-vis spectroscopy, quartz crystal microbalance with energy dissipation, and electrochemistry. The first bilayer is found to show rather different physico-chemical characteristics as compared to the subsequent bilayers, and this is attributed to the difference in the adsorption environments. The analytical utility of the architecture with five bilayers is exploited for arsenic sensing via the direct electrocatalytic oxidation of As(III), and the detection limit is found to be well below the WHO guidelines of 10 ppb. When the non-redox active PDDA is replaced by the redoxactive Os(2,2'-bipyridine)(2)Cl-poly(4-vinylpyridine) polyelectrolyte (PVPOs) in the LbL assembly, the performance is found to be inferior, demonstrating that the redox activity of the polyelectrolyte is futile as far as the direct electro-oxidation of As(III) is concerned. (C) 2012 Elsevier Inc. All rights reserved.

Voltammetric detection of arsenic on a bismuth modified exfoliated graphite electrode

We present the application of a bismuth modified exfoliated graphite electrode in the detection of arsenic in water. Bismuth film was electrodeposited onto an exfoliated graphite (EG) electrode at a potential of -600 mV. The modification of EG resulted in an increase in the electroactive surface area of the electrode and consequently peak current enhancement in Ru(NH3)(6)(2+/13+) redox probe. Square wave anodic stripping voltammetry was performed with the modified electrode (EG-Bi) in As (III) solutions at the optimum conditions of pH 6, deposition potential of -600 mV and pre-concentration time of 180s. The EG-Bi was able to detect As (III) to the limit of 5 mu g L-1 and was not susceptible to many interfering cations except Cu (II). The EG-Bi is low cost and easy to prepare. (C) 2013 Elsevier Ltd. All rights reserved.