The effects of metamorphism on O and Fe isotope compositions in the Biwabik Iron Formation, northern Minnesota

The Biwabik Iron Formation of Minnesota (1.9 Ga) underwent contact metamorphism by intrusion of the Duluth Complex (1.1 Ga). Apparent quartz–magnetite oxygen isotope temperatures decrease from ∼700°C at the contact to ∼375°C at 2.6 km distance (normal to the contact in 3D). Metamorphic pigeonite at the contact, however, indicates that peak temperatures were greater than 825°C. The apparent O isotope temperatures, therefore, reflect cooling, and not peak metamorphic conditions. Magnetite was reset in δ¹⁸O as a function of grain size, indicating that isotopic exchange was controlled by diffusion of oxygen in magnetite for samples from above the grunerite isograd. Apparent quartz–magnetite O isotope temperatures are similar to calculated closure temperatures for oxygen diffusion in magnetite at a cooling rate of ∼5.6°C/kyr, which suggests that the Biwabik Iron Formation cooled from ∼825 to 400°C in ∼75 kyr at the contact with the Duluth Complex. Isotopic exchange during metamorphism also occurred for Fe, where magnetite–Fe silicate fractionations decrease with increasing metamorphic grade. Correlations between quartz–magnetite O isotope fractionations and magnetite–iron silicate Fe isotope fractionations suggest that both reflect cooling, where the closure temperature for Fe was higher than for O. The net effect of metamorphism on δ¹⁸O–δ⁵⁶Fe variations in magnetite is a strong increase in δ¹⁸O_Mt and a mild decrease in δ⁵⁶Fe with increasing metamorphic grade, relative to the isotopic compositions that are expected at the low temperatures of initial magnetite formation. If metamorphism of Iron Formations occurs in a closed system, bulk O and Fe isotope compositions may be preserved, although re-equilibration among the minerals may occur for both O and Fe isotopes. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

The Fe-C system at 5 GPa and implications for Earth’s core

Earth’s core may contain C, and it has been suggested that C in the core could stabilize the formation of a solid inner core composed of Fe₃C. We experimentally examined the Fe-C system at a pressure of 5 GPa and determined the Fe-C phase diagram at this pressure. In addition, we measured solid metal/liquid metal partition coefficients for 17 trace elements and examined the partitioning behavior between Fe₃C and liquid metal for 14 trace elements. Solid metal/liquid metal partition coefficients are similar to those found in one atmosphere studies, indicating that the effect of pressure to 5 GPa is negligible. All measured Fe₃C/liquid metal partition coefficients investigated are less than one, such that all trace elements prefer the C-rich liquid to Fe₃C. Fe₃C/liquid metal partition coefficients tend to decrease with decreasing atomic radii within a given period. Of particular interest, our 5 GPa Fe-C phase diagram does not show any evidence that the Fe-Fe₃C eutectic composition shifts to lower C contents with increasing pressure, which is central to the previous reasoning that the inner core may be composed of Fe₃C.     

Comparison of arsenic concentrations in simultaneously-collected groundwater and aquifer particles from Bangladesh,India, Vietnam,and Nepal

One of the reasons the processes resulting in As release to groundwater in southern Asia remain poorly understood is the high degree of spatial variability of physical and chemical properties in shallow aquifers. In an attempt to overcome this difficulty, a simple device that collects groundwater and sediment as a slurry from precisely the same interval was developed in Bangladesh. Recently published results from Bangladesh and India relying on the needle-sampler are augmented here with new data from 37 intervals of grey aquifer material of likely Holocene age in Vietnam and Nepal. A total of 145 samples of filtered groundwater ranging in depth from 3 to 36 m that were analyzed for As (1–1000 μg/L), Fe (0.01–40 mg/L), Mn (0.2–4 mg/L) and S (0.04–14 mg/L) are compared. The P-extractable (0.01–36 mg/kg) and HCl-extractable As (0.04–36 mg/kg) content of the particulate phase was determined in the same suite of samples, in addition to Fe(II)/Fe ratios (0.2–1.0) in the acid-leachable fraction of the particulate phase. Needle-sampler data from Bangladesh indicated a relationship between dissolved As in groundwater and P-extractable As in the particulate phase that was interpreted as an indication of adsorptive equilibrium, under sufficiently reducing conditions, across 3 orders of magnitude in concentrations according to a distribution coefficient of 4 mL/g. The more recent observations from India, Vietnam and Nepal show groundwater As concentrations that are often an order of magnitude lower at a given level of P-extractable As compared to Bangladesh, even if only the subset of particularly reducing intervals characterized by leachable Fe(II)/Fe >0.5 and dissolved Fe >0.2 mg/L are considered. Without attempting to explain why As appears to be particularly mobile in reducing aquifers of Bangladesh compared to the other regions, the consequences of increasing the distribution coefficient for As between the particulate and dissolved phase to 40 mL/g for the flushing of shallow aquifers of their initial As content are explored.     

Measurement of the redox speciation of iron in seawater by catalytic cathodic stripping voltammetry

Catalytic cathodic stripping voltammetry (CSV) preceded by adsorptive collection of complexes of 1-nitroso-2-napthol (NN) can be used to determine iron in seawater. It is shown here that iron(II) is effectively masked in the presence of 2,2-dipyridyl (Dp) so that iron(III) is measured selectively. The concentration of iron(II) is then calculated as the difference between the concentrations of reactive iron (Fe_R) in the absence and presence of 2 μM Dp, Fe_R being defined as that which was complexed by 20 μM NN at pH 6.9 in the presence of 1.8 mM H₂O₂ and 5 ppm sodium dodecyl sulphate. A 30 min reaction time was allowed for Dp to react with iron(II) in seawater prior to the determination of reactive iron(III) using the same conditions as used for Fe_R. Detection limits of 0.08 nM, 0.077 nM and 0.12 nM were obtained for Fe_R, iron(III) and iron(II), respectively, using a 60 s deposition time.The method was utilised to determine the redox speciation of iron in the northern North Sea. Concentrations of Fe_R ranged between 0.8 and 3.5 nM with nutrient-like depth profiles. Iron(II) was found to be present at concentrations up to 1.2 nM, the highest concentrations occurring in the upper 20 m of the water column.     

Voracious planktonic hydroids: unexpected predatory impact on a coastal marine ecosystem

Hydroids are typically attached, benthic cnidarians that feed on a variety of small prey. During sampling on Georges Bank in spring 1994, we found huge numbers of hydroids suspended in the plankton. They fed on young stages of copepods that are an important prey for fish, as well as on young fish themselves. Two independent methods were used to estimate feeding rates of the hydroids; both indicate that the hydroids are capable of consuming from 50% to over 100% of the daily production of young copepods. These results suggest that hydroids can have a profound effect on the population dynamics of zooplankton and young fish on Georges Bank.     

Offshore marine conservation policies in the North East Atlantic: Emerging tensions and opportunities

An inherent tension exists between legal approaches to nature conservation and fisheries management in the European Union, as the former remains the remit of Member States while the latter is under the exclusive legislative jurisdiction of the European Community (EC). This tension is of particular importance when addressing the conservation of habitats or species that are under threat from fishing activities. This article examines recent developments in offshore marine conservation in the North-East Atlantic in light of the legislative developments and political frameworks that are currently evolving. By analysing the emergency closure of the Darwin Mounds area of cold-water corals and the UK pair-trawl ban, it becomes evident that the precautionary principle is a key factor in the tension between fisheries management and marine nature conservation, and is not always taken into account.     

Community turnover provides insight into variable invertebrate recovery between restored streams with different integrated catchment management plans

ABSTRACT

Understanding temporal patterns in restored environments is important for identifying potential barriers to recovery and improved management of degraded habitats. In this paper, we use temporal beta diversity analyses to compare invertebrate community recovery trajectories in three restored agricultural stream sites under different integrated catchment plans, a native forest reference site, and two unmodified pasture control stream sites over 24 years. The restored sites diverged from their initial community composition over time and became more similar to the reference site community, which was relatively stable over time. Variation partitioning showed that prior to restoration beta diversity was primarily associated with environmental and spatial drivers, whereas post-restoration beta diversity was more influenced by temporal and environmental drivers, including changes in substrate size, fine sediments, water clarity, and nutrients, as well as temperature and flow regime. Species’ contributions to beta diversity varied between sites and years, with sensitive EPT taxa contributing more in reference and control sites. However, contributions of some EPT species, particularly mayflies, increased in restored sites post-ICM. In summary, after nearly two decades of ICM, restored stream sites show recovery towards reference conditions, yet differences persist, indicating that rehabilitation may take longer, depending on the restoration goals.     

Effect of native and invasive cordgrass on Macoma petalum density, growth, and isotopic signatures

Ecosystem engineers can influence community and ecosystem dynamics by controlling resources, modifying the flow of energy or biomass, or changing physical characteristics of the habitat. Invasive hybrid cordgrass (Spartina alterniflora × Spartina foliosa) is an ecosystem engineer in salt marshes in San Francisco Bay, California, U.S.A. that raises intertidal elevations and may be either increasing C₄ plant carbon input into food webs or tying up carbon in a form that is not usable by consumers. A manipulative experiment compared abundance, growth, and stable isotope (δ¹³C and δ¹⁵N) composition of the clam Macoma petalum (=M. balthica) among native marsh, hybrid Spartina, and mudflats in central San Francisco Bay. We found higher densities (individuals m⁻²) of M. petalum on mudflats compared to either native or hybrid Spartina (p < 0.001). Macoma petalum shell growth was significantly greater in mudflats than in either vegetation type in 2002 (p = 0.005) but not 2003. Differences in shell growth between native and hybrid Spartina were not significant. Stable isotope results showed differences between habitats in δ¹³C but not δ¹⁵N. Carbon signatures of M. petalum placed in Spartina were much more depleted than the isotopic signature of Spartina. Neither native nor hybrid Spartina appears to be a significant carbon source for M. petalum in San Francisco Bay, and we found no evidence that hybrid Spartina contributes carbon to M. petalum beyond what is provided by S. foliosa, despite the hybrid's much greater biomass. Our results show that loss of mudflat habitat, rather than increased input of C₄ carbon, is the greatest effect of the invasion of hybrid Spartina on M. petalum.