Natural iron fertilization of the Atlantic sector of the Southern Ocean by continental shelf sources of the Antarctic Peninsula

In large parts of the Southern Ocean, primary production is limited due to shortage of iron (Fe). We measured vertical Fe profiles in the western Weddell Sea, Weddell-Scotia Confluence, and Antarctic Circumpolar Current (ACC), showing that Fe is derived from benthic Fe diffusion and sediment resuspension in areas characterized by high turbulence due to rugged bottom topography. Our data together with literature data reveal an exponential decrease of dissolved Fe (DFe) concentrations with increasing distance from the continental shelves of the Antarctic Peninsula and the western Weddell Sea. This decrease can be observed 3500 km eastward of the Antarctic Peninsula area, downstream the ACC. We estimated DFe summer fluxes into the upper mixed layer of the Atlantic sector of the Southern Ocean and found that horizontal advection dominates DFe supply, representing 54 ± 15% of the total flux, with significant vertical advection second most important at 29 ± 13%. Horizontal and vertical diffusion are weak with 1 ± 2% and 1 ± 1%, respectively. The atmospheric contribution is insignificant close to the Antarctic continent but increases to 15 ± 10% in the remotest waters (>1500 km offshore) of the ACC. Translating Southern Ocean carbon fixation by primary producers into biogenic Fe fixation shows a twofold excess of new DFe input close to the Antarctic continent and a one-third shortage in the open ocean. Fe recycling, with an estimated “fe” ratio of 0.59, is the likely pathway to balance new DFe supply and Fe fixation.

Chemical interaction of atmospheric mineral dust-derived nanoparticles with natural seawater — EPS and sunlight-mediated changes

Laboratory studies were conducted to investigate the interactions of nanoparticles (NPs) formed via simulated cloud processing of mineral dust with seawater under environmentally relevant conditions. The effect of sunlight and the presence of exopolymeric substances (EPS) were assessed on the: (1) colloidal stability of the nanoparticle aggregates (i.e. size distribution, zeta potential, polydispersity); (2) micromorphology and (3) Fe dissolution from particles. We have demonstrated that: (i) synthetic nano-ferrihydrite has distinct aggregation behaviour from NPs formed from mineral dusts in that the average hydrodynamic diameter remained unaltered upon dispersion in seawater (~1500 nm), whilst all dust derived NPs increased about three fold in aggregate size; (ii) relatively stable and monodisperse aggregates of NPs formed during simulated cloud processing of mineral dust become more polydisperse and unstable in contact with seawater; (iii) EPS forms stable aggregates with both the ferrihydrite and the dust derived NPs whose hydrodynamic diameter remains unchanged in seawater over 24h; (iv) dissolved Fe concentration from NPs, measured here as <3 kDa filter-fraction, is consistently >30% higher in seawater in the presence of EPS and the effect is even more pronounced in the absence of light; (v) micromorphology of nanoparticles from mineral dusts closely resemble that of synthetic ferrihydrite in MQ water, but in seawater with EPS they form less compact aggregates, highly variable in size, possibly due to EPS-mediated steric and electrostatic interactions. The larger scale implications on real systems of the EPS solubilising effect on Fe and other metals with the additional enhancement of colloidal stability of the resulting aggregates are discussed.

Nitrogen-15 and Oxygen-18 Natural Abundance of Potassium Chloride Extractable Soil Nitrate Using the Denitrifier Method

In agroecosystems, most isotopic investigations of NO3- involve the use of tracers that are artificially enriched in 15N. Although the dual isotope composition of NO3-— d15N and d18O is especially beneficial for understanding the origin and fate of NO3-, its use for KCl-extractable soil NO3- has been hampered by the lack of a suitable analytical technique. Our objective was to test whether the denitrifier method, whereby NO3- is reduced to N2O before mass spectrometric analysis, can be used to determine the N and O isotopic composition of NO3- from 2 M KCl soil extracts. Several internationally accepted NO3- standards were dissolved in 2 M KCl, the conventional extractant for soil inorganic N, and inoculated with the bacterial strain Pseudomonas aureofaciens (ATCC no. 13985). The standard deviation of the NO3- standards analyzed did not exceed 0.2‰ for d15N and 0.3‰ for d18O values. After appropriate corrections, differences between our measured and consensus d15N and d18O values of standard NO3- generally were within the standard deviations given for the consensus values. Both d15N and d18O values were reproducible among separate analytical runs. The method was also tested on genuine 2 M KCl extracts from unfertilized and fertilized soils. Depending on N fertilization, the soils had distinct d15N and d18O values, which were attributed to amendment with NH4NO3 fertilizer. Hence, our data indicate that the denitrifier method provides a fast, reliable, precise, and accurate way of simultaneously analyzing the natural abundances of 15N and 18O in KCl-extractable soil NO3-.

A commentary on climate change, stone decay dynamics and the ‘greening’ of natural stone buildings: new perspectives on ‘deep wetting’

Environmental controls on stone decay processes are rapidly changing as a result of changing climate. UKCP09 projections for the 2020s (2010–2039) indicate that over much of the UK seasonality of precipitation will increase. Summer dryness and winter wetness are both set to increase, the latter linked to projected precipitation increases in autumn and spring months. If so, this could increase the time that stone structures remain wet and possibly the depth of moisture penetration, and it appears that building stone in Northern Ireland has already responded through an increased incidence of algal ‘greening’.This paper highlights the need for understanding the effects of climate change through a series of studies of largely sandstone structures. Current and projected climatic trends are therefore considered to have aesthetic, physical and chemical implications that are not currently built into our models of sandstone decay, especially with respect to the role played by deep-seated wetness on sandstone deterioration and decay progression and the feedbacks associated with, for example surface algal growth. In particular,it is proposed that algal biofilms will aid moisture retention and further facilitate moisture and dissolved salt penetration to depth. Thus, whilst the outer surface of stone may continue to experience frequent wetting and drying associated with individual precipitation events, the latter is less likely to be complete, and the interiors of building blocks may only experience wetting/drying in response to seasonal cycling. A possible consequence of deeper salt penetration could be a delay in the onset of surface deterioration,but more rapid and effective retreat once it commences as decay mechanisms ‘tap into a reservoir of deep salt’.

Modeling radionuclides dispersion and deposition downwind of a coal-fired power plant

In this study the inhalation doses and respective risk are calculated for the population living within a 20 km radius of a coal-fired power plant. The dispersion and deposition of natural radionuclides were simulated by a Gaussian dispersion model estimating the ground level activity concentration. The annual effective dose and total risk were 0.03205 mSv/y and 1.25 x 10-8, respectively. The effective dose is lower than the limit established by the ICRP and the risk is lower than the limit proposed by the U.S. EPA, which means that the considered exposure does not pose any risk for the public health.

Effect of dissolved NaCl, MgCl2, and Na2SO4 in seawater on the optical attenuation in the region from 430 to 630 nm

The split-pulse laser method is used to reinvestigate the optical attenuation of distilled water in the region from 430 to 630 nm. The studies are then extended to ionic solutions of NaCl, MgCl2, and Na2SO4, these salts forming the major constituents of seawater. The effect of the concentration of these constituents on optical attenuation is investigated. Further, optical attenuation studies are carried out for the region from 430 to 630 nm for an aqueous solution prepared with all the major constituents in the same proportions as in natural seawater. These values are then compared with values obtained for natural seawater. The relative role of dissolved salts and suspended particles on optical attenuation in seawater is discussed. The lowest attenuation is observed at ~450 nm for all solutions and is found to coincide with that for distilled water.

Modeling the mechanisms that control in-stream dissolved organic carbon dynamics in upland and forested catchments

[1] We present a new, process-based model of soil and stream water dissolved organic carbon (DOC): the Integrated Catchments Model for Carbon (INCA-C). INCA-C is the first model of DOC cycling to explicitly include effects of different land cover types, hydrological flow paths, in-soil carbon biogeochemistry, and surface water processes on in-stream DOC concentrations. It can be calibrated using only routinely available monitoring data. INCA-C simulates daily DOC concentrations over a period of years to decades. Sources, sinks, and transformation of solid and dissolved organic carbon in peat and forest soils, wetlands, and streams as well as organic carbon mineralization in stream waters are modeled. INCA-C is designed to be applied to natural and seminatural forested and peat-dominated catchments in boreal and temperate regions. Simulations at two forested catchments showed that seasonal and interannual patterns of DOC concentration could be modeled using climate-related parameters alone. A sensitivity analysis showed that model predictions were dependent on the mass of organic carbon in the soil and that in-soil process rates were dependent on soil moisture status. Sensitive rate coefficients in the model included those for organic carbon sorption and desorption and DOC mineralization in the soil. The model was also sensitive to the amount of litter fall. Our results show the importance of climate variability in controlling surface water DOC concentrations and suggest the need for further research on the mechanisms controlling production and consumption of DOC in soils.

Record of natural and anthropogenic changes in reef environments (Barbados West Indies) using laser ablation ICP-MS and sclerochronology on coral cores

Coral growth rate can be affected by environmental parameters such as seawater temperature, depth, and light intensity. The natural reef environment is also disturbed by human influences such as anthropogenic pollutants, which in Barbados are released close to the reefs. Here we describe a relatively new method of assessing the history of pollution and explain how these effects have influenced the coral communities off the west coast of Barbados. We evaluate the relative impact of both anthropogenic pollutants and natural stresses. Sclerochronology documents framework and skeletal growth rate and records pollution history (recorded as reduced growth) for a suite of sampled Montastraea annularis coral cores. X-radiography shows annual growth band patterns of the corals extending back over several decades and indicates significantly lower growth rate in polluted sites. Results using laser-ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) on the whole sample (aragonite, organic matter, trapped particulate matter, etc.), have shown contrasting concentrations of the trace elements (Cu, Sn, Zn, and Pb) between corals at different locations and within a single coral. Deepwater corals 7 km apart, record different levels of Pb and Sn, suggesting that a current transported the metal pollution in the water. In addition, the 1995 hurricanes are associated with anomalous values for Sn and Cu from most sites. These are believed to result from dispersion of nearshore polluted water. We compared the concentrations of trace elements in the coral growth of particular years to those in the relevant contemporaneous seawater. Mean values for the concentration factor in the coral, relative to the water, ranged from 10 for Cu and Ni to 2.4 and 0.7 for Cd and Zn, respectively. Although the uncertainties are large (60-80%), the coral record enabled us to demonstrate the possibility of calculating a history of seawater pollution for these elements from the 1940s to 1997. Our values were much higher than those obtained from analysis of carefully cleaned coral aragonite; they demonstrate the incorporation of more contamination including that from particulate material as well as dissolved metals.

Acidity controls on dissolved organic carbon mobility in organic soils

Dissolved organic carbon (DOC) concentrations in surface waters have increased across much of Europe and North America, with implications for the terrestrial carbon balance, aquatic ecosystem functioning, water treatment costs and human health. Over the past decade, many hypotheses have been put forward to explain this phenomenon, from changing climate and land-management to eutrophication and acid deposition. Resolution of this debate has been hindered by a reliance on correlative analyses of time-series data, and a lack of robust experimental testing of proposed mechanisms. In a four-year, four-site replicated field experiment involving both acidifying and de-acidifying treatments, we tested the hypothesis that DOC leaching was previously suppressed by high levels of soil acidity in peat and organo-mineral soils, and therefore that observed DOC increases a consequence of decreasing soil acidity. We observed a consistent, positive relationship between DOC and acidity change at all sites. Responses were described by similar hyperbolic relationships between standardised changes in DOC and hydrogen ion concentrations at all sites, suggesting potentially general applicability. These relationships explained a substantial proportion of observed changes in peak DOC concentrations in nearby monitoring streams, and application to a UK-wide upland soil pH dataset suggests that recovery from acidification alone could have led to soil solution DOC increases in the range 46-126% by habitat type since 1978. Our findings raise the possibility that changing soil acidity may have wider impacts on ecosystem carbon balances. Decreasing sulphur deposition may be accelerating terrestrial carbon loss, and returning surface waters to a natural, high-DOC condition.

Separation of natural colorants from the fermented broth of filamentous fungi using colloidal gas aphrons

There is a worldwide interest in the development of processes for producing colorants from natural sources. Microorganisms provide an alternative source of natural colorants produced by cultivation technology and extracted from the fermented broth. The aim of the present work was to study the recovery of red colorants from the fermented broth of Talaromyces amestolkiae using the technique of colloidal gas aphrons (CGA) comprising surfactant-stabilized microbubbles. Preliminary experiments were performed to evaluate the red colorants’ solubility in different organic solvents, octanol/water partitioning, and their stability in surfactant solutions, namely hexadecyl trimethylammonium bromide (CTAB), sodium dodecyl sulfate (SDS), and polyoxyethylenesorbitan monolaurate (Tween 20), which are cationic, anionic and nonionic surfactants, respectively. The first recovery experiments were carried out using CGA generated by these surfactants at different volumetric ratios (VR, 3–18). Subsequently, two different approaches to generate CGA were investigated at VR values of 6 and 12: the first involved the use of CTAB at pH 6.9–10.0, and the second involved the use of Tween 20 using red colorants partially dissolved in ethanol and Tween 20. The characterization results showed that red colorants have a hydrophilic nature. The highest recoveries were obtained with Tween 20 (78%) and CTAB (70%). These results demonstrated that the recovery of the colorants was driven by both electrostatic and hydrophobic interactions. The VR was found to be an important operating parameter and at VR 12 with CTAB (at pH 9) maximum recovery, partitioning coefficient (K = 5.39) and selectivity in relation to protein and sugar (SP = 3.75 and SS = 7.20 respectively) were achieved. Furthermore, with Tween 20, the separation was driven mainly by hydrophobic interactions. Overall CGA show promise for the recovery of red colorants from a fermented broth. Although better results were obtained with CTAB than with Tween 20 the latter may be more suitable for some application due to its lower toxicity.

Uranium series disequilibria in ground waters from a fractured bedrock aquifer (Morungaba Granitoids-Southern Brazil): Implications to the hydrochemical behavior of dissolved U and Ra

Activity concentrations of dissolved U-234, U-238, Ra-226 and Ra-228 were determined in ground waters fromtwo deep wells drilled in Morungaba Granitoids (Southern Brazil). Sampling was done monthly for little longer than 1 year. Significant disequilibrium between U-238, U-234 and Ra-226 were observed in all samples. The variation of U-238 and U-234 activity concentrations and U-234/U-238 activity ratios is related to seasonal changes. Although the distance between the two wells is short (about 900m), systematic differences of activity concentrations of U isotopes, as well as of U-234/U-238, Ra-226/U-234 and Ra-228/Ra-226 activity ratios were noticed, indicating distinct host rock-water interactions. Slightly acidic ground water percolation through heterogeneous host rock, associated with different recharge processes, may explain uranium and radium isotope behavior. (c) 2008 Elsevier Ltd. All rights reserved.

Occupational exposure to radon and natural gamma radiation in the La Carolina, a former gold mine in San Luis Province, Argentina

Radon and gamma radiation level measurements were carried out inside the La Carolina mine, one of the oldest gold mining camps of southern South America, which is open for touristic visits nowadays. CR-39 track-etch detectors and thermoluminescent dosimeters of natural CaF(2) and LiF TLD-100 were exposed at 14 points along the mine tunnels in order to estimate the mean (222)Rn concentration and the ambient dose equivalent during the summer season (November 2008 to February 2009). The values for the (222)Rn concentration at each monitoring site ranged from 1.8 +/- 0.1 kBq m(-3) to 6.0 +/- 0.5 kBq m(-3), with a mean value of 4.8 kBq m(-3), indicating that these measurements exceed in about three times the upper action level recommended by ICRP for workplaces. The correlations between radon and gamma radiation levels inside the mine were also investigated. Effective doses due to (222)Rn and gamma rays inside the mine were determined, resulting in negligible values to tourists. Considering the effective dose to the mine tourist guides, values exceeding 20 mSv of internal contribution to the effective doses can be reached, depending on the number of working hours inside the mine. (C) 2009 Elsevier Ltd. All rights reserved.

Estrutura e dinâmica do fitoplânctone bacterioplâncton em cultivos de camarão no Rio Grande do Norte-Brasil: impacto sobre o ambiente natural

This work aimed to study the structure and dynamic of Phytoplankton and Bacterioplankton in a complete cycle of shrimp cultivation (Litopenaeus vannamei) and determine the environmental factors responsible for the structural changes of these communities. The study was realized in a saltwater shrimp farm (Macaíba, RN), between September/2005 and February/2006, and in a freshwater shrimp farm (Ceará Mirim, RN), between May/2007 and September 2007. The samplings were collected weekly in saltwater farm and every fifteen days in freshwater farm. Total phosphorus, chlorophyll a and environmental parameters (pH, dissolved oxygen, salinity, temperature, depth and water transparency) were measured. Qualitative and quantitative analysis of the phytoplankton and bacterioplankton were carried out. The Shannon-Wiener ecologic indexes of diversity and the Pielou equitability indexes were calculated to the phytoplankton. Bacterial density was determined by epifluorescence microscopy. The data were statistically analyzed by Pearson correlation and t-Test. Chlorophycea were predominat in salt water and in the captation/drainage point (24 to 99%). Diatoms had higher wealth. The species Choricystis minor had the highest occurrence (100%) and dominance (90-100%), thus showing its adaptation to the high temperatures, salinity and low water transparency conditions. Filamentous Cyanobacteria like Oscillatoria sp., Pseudoanabaena sp. and Phormidium sp. had constant levels. The negative correlation between chlorophycea and water transparency, and the positive correlation between chlorophyll a and salinity, showed that the phytoplankton was well adapted to the low transparency and to the high salinity. The bacterioplankton was negatively correlated with the total phosphorus and salinity. In freshwater, Cyanobacteria were predominant (>80%), presenting some producers of toxins species like Microcystis sp., Aphanizomenon sp., Cylindrospermopsis raciborskii e Anabaena circinalis. Cyanobacterial density and total phosphorus and chlorophyll a concentrations exceeded the maximum value allowed by legislation. The means of total phosphorus varied from 264 to 627 Wg.L-1 and the means of chlorophyll a oscillated between 22 and 182 Wg.L-1. The phytoplankton species were selected by low availability of the light, high pH, temperature and high availability of total phosphorus. The bacterioplankton showed high densities (5,13 x 107 to 8,50 x107 Bac.mL-1). The studied environments (ponds and rivers) presented a high level of trophic state based on the high concentrations of chlorophyll a and total phosphorus and cyanobacteria dominance. The composition of species in the ponds and rivers was similar, as well as high concentrations of total phosphorus and chlorophyll a, highlighting the pollution caused by the discharges of the farms in natural environment

Dependence of the electrical conductivity and elastomeric properties on sample preparation of blends of polyaniline and natural rubber

Blend films (free-standing) containing 20% in volume of polyaniline (PANI) in 80% of natural rubber (NR) were fabricated by casting in three different ways: (1) adding PANI-EB (emeraldine base) dissolved in N-methyl-2-pyrrolidone (NMP) to the latex (NRL), (2) adding PANI-EB dissolved in in-cresol to NR dissolved in xylol (NRD), (3) overlaying the surface of a pure NR cast film with a PANI layer grown by in situ polymerization (NRO). All the films were immersed into HCl solution to achieve the primary doping (protonation) of PANI before the characterization. The main goal here was to investigate the elastomeric and electrical conductivity properties for each blend, which may be applied as pressure and deformation sensors in the future. The characterization was carried out by optical microscopy, dc conductivity, vibrational spectroscopy (infrared absorption and Raman scattering), thermogravimetry analysis (TGA), differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMTA), and tensile stress-strain curves. The results suggest that the NRL blend is the most suitable in terms of mechanical and electrical properties required for applications in pressure and deformation sensors: a gain of conductivity without losing the elastomeric property of the rubber. (c) 2005 Wiley Periodicals, Inc.

Implications of groundwater weathered profile interactions to the mobilization of radionuclides

This study reports the nature and extent of open-system interaction between groundwater and a weathered profile developed in the high grade thorium and REE ore body in Morro do Ferro, Pocos de Caldas plateau. The radioelement mobility in the shallow oxidizing environment was considered by using chemical data in conjunction with U-234/U-238, Ra-226/Th-230, Th-230/U-234, Th-228/Th-232, Ra-228/Th-232 and Th-230/Ra-228 activity ratios (AR's) for borehole spoil and groundwater samples.Recharging groundwater from the studied borehole has low salinity values, with total dissolved solids content of 14.7 mg/l and total ionic strength of 0.00018. The ratio of the weight of dissolved radioelement per unit volume of solution to the weight of radioelement in solid phase per unit weight of solid phase showed that the radioelement solubility in the studied waters varied according to the following order: radium> uranium >thorium.U-234/U-238 AR's less than 1 were measured in solid phase and can justify the enhancement of U-234 in solution. Ra-226/Th-230 AR's greater than 1 and Th-230/U-234 AR'S less than 1 were evaluated between 20 and 27 m in depth, where a 2.1-m thick magnetite dike was intersected. These ratios could be justified by deposition of U and Ra associated with Fe-Mn oxides and kaolinite, where mineral saturation indices evaluated from the available data confirm this possibility. Covariations among disequilibria involving Th-228/(228) Ra and Ra-228/Th-232 AR's showed the preferential removal of Ra-228 relative to Tn isotopes, Th-228 and Th-232. The recent deposition of radium within the timescale of at least the last 35 years also is suggested. (C) 1998 Elsevier B.V. Ltd. All rights reserved.