Aqueous geochemistry and oxygen isotope compositions of acid mine drainage from the Río Tinto, SW Spain, highlight inconsistencies in current models

The Rio Tinto river in SW Spain is a classic example of acid mine drainage and the focus of an increasing amount of research including environmental geochemistry, extremophile microbiology and Mars-analogue studies. Its 5000-year mining legacy has resulted in a wide range of point inputs including spoil heaps and tunnels draining underground workings. The variety of inputs and importance of the river as a research site make it an ideal location for investigating sulphide oxidation mechanisms at the field scale. Mass balance calculations showed that pyrite oxidation accounts for over 93% of the dissolved sulphate derived from sulphide oxidation in the Rio Tinto point inputs. Oxygen isotopes in water and sulphate were analysed from a variety of drainage sources and displayed delta O-18((SO4-H2O)) values from 3.9 to 13.6 parts per thousand, indicating that different oxidation pathways occurred at different sites within the catchment. The most commonly used approach to interpreting field oxygen isotope data applies water and oxygen fractionation factors derived from laboratory experiments. We demonstrate that this approach cannot explain high delta O-18((SO4-H2O)) values in a manner that is consistent with recent models of pyrite and sulphoxyanion oxidation. In the Rio Tinto, high delta O-18((SO4-H2O)) values (11.2-13.6 parts per thousand) occur in concentrated (Fe = 172-829 mM), low pH (0.88-1.4), ferrous iron (68-91% of total Fe) waters and are most simply explained by a mechanism involving a dissolved sulphite intermediate, sulphite-water oxygen equilibrium exchange and finally sulphite oxidation to sulphate with O-2. In contrast, drainage from large waste blocks of acid volcanic tuff with pyritiferous veins also had low pH (1.7). but had a low delta O-18((SO4-H2O)) value of 4.0 parts per thousand and high concentrations of ferric iron (Fe(III) = 185 mM, total Fe = 186 mM), suggesting a pathway where ferric iron is the primary oxidant, water is the primary source of oxygen in the sulphate and where sulphate is released directly from the pyrite surface. However, problems remain with the sulphite-water oxygen exchange model and recommendations are therefore made for future experiments to refine our understanding of oxygen isotopes in pyrite oxidation. (C) 2009 Elsevier B.V. All rights reserved.

Current intakes of EPA and DHA in European populations and the potential of animal-derived foods to increase them

The beneficial effects of long-chain (C chain >= 20) n-3 PUFA are well documented and, overall, increased intake reduces risk of CVD. Recent evidence also points to a role in reducing, age-related decline in cognitive function. The two key fatty acids are EPA (20:5) and DHA (22:6), with current UK recommendation for adults being 450 mg EPA + DHA/d. Whilst some EPA and DHA can be synthesised in vivo from alpha-linolenic acid, recent data indicate this source to be very limited, Suggesting that EPA and DHA should be classified as dietary essentials. In many parts of Europe the daily intake of EPA + DHA by adults and especially young adults (18-24 years) is < 100 mg/d, since many never eat oily fish. Poultry meat contributes small but worthwhile amounts of EPA+DHA. Studies to enrich the EPA+DHA content of animal-derived foods mainly use fish oil in the diet of the animal. Recent work has shown that such enrichment has the potential to provide to the UK adult diet a daily intake of EPA+DHA of about 230 mg, with poultry meat providing the largest amount (74 mg). There are. however. concerns that the Continued and possibly increased use of fish oils in animals diets is not Sustainable and alternative approaches are being examined, including the genetic modification of certain plants to allow them to synthesise EPA and DHA from shorter-chain precursors.

Current intakes of EPA and DHA in European populations and the potential of animal-derived foods to increase them

The beneficial effects of long-chain (C chain >= 20) n-3 PUFA are well documented and, overall, increased intake reduces risk of CVD. Recent evidence also points to a role in reducing, age-related decline in cognitive function. The two key fatty acids are EPA (20:5) and DHA (22:6), with current UK recommendation for adults being 450 mg EPA + DHA/d. Whilst some EPA and DHA can be synthesised in vivo from alpha-linolenic acid, recent data indicate this source to be very limited, Suggesting that EPA and DHA should be classified as dietary essentials. In many parts of Europe the daily intake of EPA + DHA by adults and especially young adults (18-24 years) is < 100 mg/d, since many never eat oily fish. Poultry meat contributes small but worthwhile amounts of EPA+DHA. Studies to enrich the EPA+DHA content of animal-derived foods mainly use fish oil in the diet of the animal. Recent work has shown that such enrichment has the potential to provide to the UK adult diet a daily intake of EPA+DHA of about 230 mg, with poultry meat providing the largest amount (74 mg). There are. however. concerns that the Continued and possibly increased use of fish oils in animals diets is not Sustainable and alternative approaches are being examined, including the genetic modification of certain plants to allow them to synthesise EPA and DHA from shorter-chain precursors.

The role of meat as a source of n-3 polyunsaturated fatty acids in the human diet

It is considered that consumption of very long chain (VLC, carbon chain length >= 20) n - 3 PUFAs in most Western populations is sub-optimal and benefits in relation to chronic disease would be gained from increased consumption. This review examines the current contribution that meat makes to dietary intake of VLC n - 3 PUFA and given its current low contribution, how ruminant meat may be enriched. Enrichment both directly with VLC n - 3 fatty acids and indirectly by increasing intake by the animals of alpha-linolenic acid (ALNA; C 18:3 n - 3) are considered. Since it now appears that dietary ALNA is a very limited source of VLC n - 3 PUFA in humans, the indirect route is controversial but since some forages-are rich sources of ALNA this route has many sustainability and environmental attractions. Consideration is also given to the increased concentrations of trans and conjugated fatty acids that will arise from enriching ruminant meat with PUFA.

The role of meat as a source of n-3 polyunsaturated fatty acids in the human diet

It is considered that consumption of very long chain (VLC, carbon chain length >= 20) n - 3 PUFAs in most Western populations is sub-optimal and benefits in relation to chronic disease would be gained from increased consumption. This review examines the current contribution that meat makes to dietary intake of VLC n - 3 PUFA and given its current low contribution, how ruminant meat may be enriched. Enrichment both directly with VLC n - 3 fatty acids and indirectly by increasing intake by the animals of alpha-linolenic acid (ALNA; C 18:3 n - 3) are considered. Since it now appears that dietary ALNA is a very limited source of VLC n - 3 PUFA in humans, the indirect route is controversial but since some forages-are rich sources of ALNA this route has many sustainability and environmental attractions. Consideration is also given to the increased concentrations of trans and conjugated fatty acids that will arise from enriching ruminant meat with PUFA.

Cyclic loss of open solar flux since 1868: the link to heliospheric current sheet tilt and implications for the Maunder Minimum

Open solar flux (OSF) variations can be described by the imbalance between source and loss terms. We use spacecraft and geomagnetic observations of OSF from 1868 to present and assume the OSF source, S, varies with the observed sunspot number, R. Computing the required fractional OSF loss, χ, reveals a clear solar cycle variation, in approximate phase with R. While peak R varies significantly from cycle to cycle, χ is surprisingly constant in both amplitude and waveform. Comparisons of χ with measures of heliospheric current sheet (HCS) orientation reveal a strong correlation. The cyclic nature of χ is exploited to reconstruct OSF back to the start of sunspot records in 1610. This agrees well with the available spacecraft, geomagnetic, and cosmogenic isotope observations. Assuming S is proportional to R yields near-zero OSF throughout the Maunder Minimum. However, χ becomes negative during periods of low R, particularly the most recent solar minimum, meaning OSF production is underestimated. This is related to continued coronal mass ejection (CME) activity, and therefore OSF production, throughout solar minimum, despite R falling to zero. Correcting S for this produces a better match to the recent solar minimum OSF observations. It also results in a cycling, nonzero OSF during the Maunder Minimum, in agreement with cosmogenic isotope observations. These results suggest that during the Maunder Minimum, HCS tilt cycled as over recent solar cycles, and the CME rate was roughly constant at the levels measured during the most recent two solar minima.

Dust sources and deposition during the last glacial maximum and current climate: a comparison of model results with paleodata from ice cores and marine sediments

Mineral dust aerosols in the atmosphere have the potential to affect the global climate by influencing the radiative balance of the atmosphere and the supply of micronutrients to the ocean. Ice and marine sediment cores indicate that dust deposition from the atmosphere was at some locations 2–20 times greater during glacial periods, raising the possibility that mineral aerosols might have contributed to climate change on glacial-interglacial time scales. To address this question, we have used linked terrestrial biosphere, dust source, and atmospheric transport models to simulate the dust cycle in the atmosphere for current and last glacial maximum (LGM) climates. We obtain a 2.5-fold higher dust loading in the entire atmosphere and a twenty-fold higher loading in high latitudes, in LGM relative to present. Comparisons to a compilation of atmospheric dust deposition flux estimates for LGM and present in marine sediment and ice cores show that the simulated flux ratios are broadly in agreement with observations; differences suggest where further improvements in the simple dust model could be made. The simulated increase in high-latitude dustiness depends on the expansion of unvegetated areas, especially in the high latitudes and in central Asia, caused by a combination of increased aridity and low atmospheric [CO2]. The existence of these dust source areas at the LGM is supported by pollen data and loess distribution in the northern continents. These results point to a role for vegetation feedbacks, including climate effects and physiological effects of low [CO2], in modulating the atmospheric distribution of dust.

Relationship between the near-Earth interplanetary field and the coronal source flux: dependence on timescale

The Ulysses spacecraft has shown that the radial component of the heliospheric magnetic field is approximately independent of latitude. This has allowed quantification of the total open solar flux from near-Earth observations of the interplanetary magnetic field. The open flux can also be estimated from photospheric magnetograms by mapping the fields up to the ‘‘coronal source surface’’ where the field is assumed to be radial and which is usually assumed to be at a heliocentric distance r = 2.5R_{S} (a mean solar radius, 1R_{S} = 6.96x10^{8} m). These two classes of open flux estimate will differ by the open flux that threads the heliospheric current sheet(s) inside Earth’s orbit at 2.5R_{S} < r < 1R{1} (where the mean Earth-Sun distance, 1R_{1} = 1 AU = 1.5 x 10^{11} m). We here use near-Earth measurements to estimate this flux and show that at sunspot minimum it causes only a very small (approximately 0.5%) systematic difference between the two types of open flux estimate, with an uncertainty that is of order ±24% in hourly values, ±16% in monthly averages, and between -6% and +2% in annual values. These fractions may be somewhat larger for sunspot maximum because of flux emerging at higher heliographic latitudes.

High-latitude particle precipitation and its relationship to magnetospheric source regions

Two central issues in magnetospheric research are understanding the mapping of the low-altitude ionosphere to the distant regions of the magnetsphere, and understanding the relationship between the small-scale features detected in the various regions of the ionosphere and the global properties of the magnetosphere. The high-latitude ionosphere, through its magnetic connection to the outer magnetosphere, provides an important view of magnetospheric boundaries and the physical processes occurring there. All physical manifestations of this magnetic connectivity (waves, particle precipitation, etc.), however, have non-zero propagation times during which they are convected by the large-scale magnetospheric electric field, with phenomena undergoing different convection distances depending on their propagation times. Identification of the ionospheric signatures of magnetospheric regions and phenomena, therefore, can be difficult. Considerable progress has recently been made in identifying these convection signatures in data from low- and high-altitude satellites. This work has allowed us to learn much about issues such as: the rates of magnetic reconnection, both at the dayside magnetopause and in the magnetotail; particle transport across the open magnetopause; and particle acceleration at the magnetopause and the magnetotail current sheets.

A new source of suprathermal O+ions near the dayside polar cap boundary

A new dayside source of O+ ions for the polar magnetosphere is described, and a statistical survey presented of upward flows of O+ ions using 2 years of data from the retarding ion mass spectrometer (RIMS) experiment on board DE 1, at geocentric distances below 3 RE and invariant latitudes above 40°. The flows are classified according to their spin angle distributions. It is believed that the spacecraft potential near perigee is generally less than +2 V, in which case the entire O+ population at energies below about 60 eV is sampled. Examples are given of field-aligned flow and of transversely accelerated “core” O+ ions; in the latter events a large fraction of the total O+ ion population has been transversely accelerated, and in some extreme cases all the observed ions (of all ion species) have been accelerated, and no residual cold population is observed (“toroidal” distributions). However, by far the most common type of O+ upflow seen by DE RIMS lies near the dayside polar cap boundary (particularly in the prenoon sector) and displays an asymmetric spin angle distribution. In such events the ions carry an upward heat flux, and strong upflow of all species is present (H+, He+, O+, O++, and N+ have all been observed with energies up to about 30 eV, but with the majority of ions below about 2 eV); hence, these have been termed upwelling ion events. The upwelling ions are embedded in larger regions of classical light ion polar wind and are persistently found under the following conditions: at geocentric distances greater than 1.4 RE; at all Kp in summer, but only at high Kp in winter. Low-energy conical ions (<30 eV) are only found near the equatorial edge of the events, the latitude of which moves equatorward with increasing Kp and is highly correlated with the location of field-aligned currents. The RIMS data are fully consistent with a “mass spectrometer effect,” whereby light ions and the more energetic O+ ions flow into the lobes and mantle and hence the far-tail plasma sheet, but lower-energy O+ is swept across the polar cap by the convection electric field, potentially acting as a source for the nightside auroral acceleration regions. The occurrence probability of upwelling ion events, as compared to those of low-altitude transversely accelerated core ions and of field-aligned flow, suggests this could be the dominant mechanism for supplying the nightside auroral acceleration region, and subsequently the ring current and near-earth plasma sheet, with ionospheric O+ ions. It is shown that the total rate of O+ outflow in upwelling ion events (greater than 10^25 s^{−1}) is sufficient for the region near the dayside polar cap boundary to be an important ionospheric heavy ion source.

Thermospheric Control of the Auroral Source of O+Ions for the Magnetosphere

Linear theory, model ion-density profiles and MSIS neutral thermospheric predictions are used to investigate the stability of the auroral, topside ionosphere to oxygen cyclotron waves: variations of the critical height, above which the plasma is unstable, with field-aligned current, thermal ion density and exospheric temperature are considered. In addition, probabilities are assessed that interactions with neutral atomic gases prevent O+ ions from escaping into the magnetosphere after they have been transversely accelerated by these waves. The two studies are combined to give a rough estimate of the total O+ escape flux as a function of the field-aligned current density for an assumed rise in the perpendicular ion temperature. Charge exchange with neutral oxygen, not hydrogen, is shown to be the principle limitation to the escape of O+ ions, which occurs when the waves are driven unstable down to low altitudes. It is found that the largest observed field-aligned current densities can heat a maximum of about 5×1014 O+ ions m−2 to a threshold above which they are subsequently able to escape into the magnetosphere in the following 500s. Averaged over this period, this would constitute a flux of 1012 m−2 s−1 and in steady-state the peak outflow would then be limited to about 1013 m−2 s−1 by frictional drag on thermal O+ at lower altitudes. Maximum escape is at low plasma density unless the O+ scale height is very large. The outflow decreases with decreasing field-aligned current density and, to a lesser extent, with increasing exospheric temperature. Upward flowing ion events are evaluated as a source of O+ ions for the magnetosphere and as an explanation of the observed solar cycle variation of ring current O+ abundance.

The role of root exuded low molecular weight organic anions in facilitating petroleum hydrocarbon degradation: current knowledge and future directions

Rhizoremediation is a bioremediation technique whereby enhanced microbial degradation of organic contaminants occurs within the plant root zone (rhizosphere). It is considered an effective and affordable ‘green technology’ for remediating soils contaminated with petroleum hydrocarbons (PHCs). This paper critically reviews the potential role of root exuded compounds in rhizoremediation, with emphasis on commonly exuded low molecular weight aliphatic organic acid anions (carboxylates). The extent to which remediation is achieved shows wide disparity among plant species. Therefore, plant selection is crucial for the advancement and widespread adoption of this technology. Root exudation is speculated to be one of the predominant factors leading to microbial changes in the rhizosphere and thus the potential driver behind enhanced petroleum biodegradation. Carboxylates can form a significant component of the root exudate mixture and are hypothesised to enhance petroleum biodegradation by: i) providing an easily degradable energy source; ii) increasing phosphorus supply; and/or iii) enhancing the contaminant bioavailability. These differing hypotheses, which are not mutually exclusive, require further investigation to progress our understanding of plant–microbe interactions with the aim to improve plant species selection and the efficacy of rhizoremediation.

The water vapour continuum in near-infrared windows – current understanding and prospects for its inclusion in spectroscopic databases

Spectroscopic catalogues, such as GEISA and HITRAN, do not yet include information on the water vapour continuum that pervades visible, infrared and microwave spectral regions. This is partly because, in some spectral regions, there are rather few laboratory measurements in conditions close to those in the Earth’s atmosphere; hence understanding of the characteristics of the continuum absorption is still emerging. This is particularly so in the near-infrared and visible, where there has been renewed interest and activity in recent years. In this paper we present a critical review focusing on recent laboratory measurements in two near-infrared window regions (centred on 4700 and 6300 cm−1) and include reference to the window centred on 2600 cm−1 where more measurements have been reported. The rather few available measurements, have used Fourier transform spectroscopy (FTS), cavity ring down spectroscopy, optical-feedback – cavity enhanced laser spectroscopy and, in very narrow regions, calorimetric interferometry. These systems have different advantages and disadvantages. Fourier Transform Spectroscopy can measure the continuum across both these and neighbouring windows; by contrast, the cavity laser techniques are limited to fewer wavenumbers, but have a much higher inherent sensitivity. The available results present a diverse view of the characteristics of continuum absorption, with differences in continuum strength exceeding a factor of 10 in the cores of these windows. In individual windows, the temperature dependence of the water vapour self-continuum differs significantly in the few sets of measurements that allow an analysis. The available data also indicate that the temperature dependence differs significantly between different near-infrared windows. These pioneering measurements provide an impetus for further measurements. Improvements and/or extensions in existing techniques would aid progress to a full characterisation of the continuum – as an example, we report pilot measurements of the water vapour self-continuum using a supercontinuum laser source coupled to an FTS. Such improvements, as well as additional measurements and analyses in other laboratories, would enable the inclusion of the water vapour continuum in future spectroscopic databases, and therefore allow for a more reliable forward modelling of the radiative properties of the atmosphere. It would also allow a more confident assessment of different theoretical descriptions of the underlying cause or causes of continuum absorption.

Review of current in vivo measurement techniques for quantifying enteric methane emission from ruminants

Ruminant husbandry is a major source of anthropogenic greenhouse gases (GHG). Filling knowledge gaps and providing expert recommendation are important for defining future research priorities, improving methodologies and establishing science-based GHG mitigation solutions to government and non-governmental organisations, advisory/extension networks, and the ruminant livestock sector. The objectives of this review is to summarize published literature to provide a detailed assessment of the methodologies currently in use for measuring enteric methane (CH4) emission from individual animals under specific conditions, and give recommendations regarding their application. The methods described include respiration chambers and enclosures, sulphur hexafluoride tracer (SF6) technique, and techniques based on short-term measurements of gas concentrations in samples of exhaled air. This includes automated head chambers (e.g. the GreenFeed system), the use of carbon dioxide (CO2) as a marker, and (handheld) laser CH4 detection. Each of the techniques are compared and assessed on their capability and limitations, followed by methodology recommendations. It is concluded that there is no ‘one size fits all’ method for measuring CH4 emission by individual animals. Ultimately, the decision as to which method to use should be based on the experimental objectives and resources available. However, the need for high throughput methodology e.g. for screening large numbers of animals for genomic studies, does not justify the use of methods that are inaccurate. All CH4 measurement techniques are subject to experimental variation and random errors. Many sources of variation must be considered when measuring CH4 concentration in exhaled air samples without a quantitative or at least regular collection rate, or use of a marker to indicate (or adjust) for the proportion of exhaled CH4 sampled. Consideration of the number and timing of measurements relative to diurnal patterns of CH4 emission and respiratory exchange are important, as well as consideration of feeding patterns and associated patterns of rumen fermentation rate and other aspects of animal behaviour. Regardless of the method chosen, appropriate calibrations and recovery tests are required for both method establishment and routine operation. Successful and correct use of methods requires careful attention to detail, rigour, and routine self-assessment of the quality of the data they provide.

Nd and Pb isotope signatures on the Southeastern South American upper margin: Implications for sediment transport and source rocks

Neodymium and lead isotope values in sediment samples were used to interpret sediment transport and source rocks on the Southeastern South American upper margin. The sediments of the Argentinian margin exhibit an average epsilon(Nd) value of -1.9, indicating the influence of the Andean rocks as sediment sources. Sediments from the Rio de La Plata estuary show an average epsilon(Nd) value of -9.6 which is similar to that of the Southern Brazilian Upper Margin. Finally, sediments of Southeastern Brazil, which are associated with the transport of the Brazil Current exhibit an average epsilon(Nd) of -13.0. The Pb isotope signatures also confirm the differentiation of source rocks in the sedimentation of the study area. In addition, Pb isotopes helped to establish the extent of the influence of the Rio de La Plata on the sedimentation of the Southern Brazilian margin. In terms of Pb isotopes the sediments from the Rio de La Plata estuary and Southern Brazil are more radiogenic than those of Southeastem Brazil and the Argentinian margin. (c) 2007 Elsevier B.V. All rights reserved.