Thermodynamic controls on element partitioning between titanomagnetite and andesitic–dacitic silicate melts

Titanomagnetite–melt partitioning of Mg, Mn, Al, Ti, Sc, V, Co, Ni, Cu, Zn, Ga, Zr, Nb, Mo, Hf and Ta was investigated experimentally as a function of oxygen fugacity (fO₂) and temperature (T) in an andesitic–dacitic bulk-chemical compositional range. In these bulk systems, at constant T, there are strong increases in the titanomagnetite–melt partitioning of the divalent cations (Mg²⁺, Mn²⁺, Co²⁺, Ni²⁺, Zn²⁺) and Cu²⁺/Cu⁺ with increasing fO₂ between 0.2 and 3.7 log units above the fayalite–magnetite–quartz buffer. This is attributed to a coupling between magnetite crystallisation and melt composition. Although melt structure has been invoked to explain the patterns of mineral–melt partitioning of divalent cations, a more rigorous justification of magnetite–melt partitioning can be derived from thermodynamic principles, which accounts for much of the supposed influence ascribed to melt structure. The presence of magnetite-rich spinel in equilibrium with melt over a range of fO₂ implies a reciprocal relationship between a(Fe²⁺O) and a(Fe³⁺O_1.5) in the melt. We show that this relationship accounts for the observed dependence of titanomagnetite–melt partitioning of divalent cations with fO₂ in magnetite-rich spinel. As a result of this, titanomagnetite–melt partitioning of divalent cations is indirectly sensitive to changes in fO₂ in silicic, but less so in mafic bulk systems.     

Stratospheric methane and nitrogen dioxide from infrared spectra

Values of the mixing ratio by volume of stratospheric NO₂ and CH₄ deduced from infrared spectra taken by means of balloon-borne spectrometers are presented. Possible evidence for the presence of formaldehyde in the stratosphere is also given.     

Tropospheric Ozone in a Global-Scale Three-Dimensional Lagrangian Model and Its Response to NOX Emission Controls

A three-dimensional Lagrangian tropospheric chemistry modelis used toinvestigate the impact of human activities on the tropospheric distributionofozone and hydroxyl radicals. The model describes the behaviour of 50 speciesincluding methane, carbon monoxide, oxides of nitrogen, sulphur dioxide andnineorganic compounds emitted from human activities and a range of other sources.Thechemical mechanism involves about 100 chemical reactions of which 16 arephotochemical reactions whose diurnal dependence is treated in full. The modelutilises a five minute chemistry time step and a three hour advection timestepfor the 50,000 air parcels. Meteorological data for the winds, temperatures,clouds and so on are taken from the UK Meteorological Office global model for1994 onwards. The impacts of a 50% reduction in European NO_Xemissions onglobal ozone concentrations are assessed. Surface ozoneconcentrations decrease in summertime and rise in wintertime, but to differentextents.     

Multi-decadal synthesis of benthic–pelagic coupling in the western arctic: Role of cross-shelf advective processes

Using geographic information systems (GIS) software and geostatistical techniques, we utilized three decades of water-column chlorophyll a data to examine the relative importance of autochthonous versus allochthonous sources of reduced carbon to benthic communities that occur from the northern Bering to the eastern Beaufort Sea shelf. Spatial trend analyses revealed areas of high benthic biomass (>300 g m⁻²) and chlorophyll (>150 mg m⁻²) on both the southern and northern Chukchi shelf; both areas are known as depositional centers for reduced organic matter that originates on the Bering Sea shelf and is advected northward in Anadyr and Bering shelf water masses. We found a significant correlation between biomass and chlorophyll a in the Chukchi Sea, reflective of the strong benthic–pelagic coupling in a system that is utilized heavily by benthic-feeding marine mammals. In contrast, there was no significant correlation between biomass and chlorophyll in the Beaufort Sea, which by comparison, is considerably less productive (biomass and chlorophyll, <75 g m⁻² and <50 mg m⁻², respectively). One notable exception is an area of relatively high biomass (50–100 g m⁻²) and chlorophyll (80 mg m⁻²) near Barter Island in the eastern Beaufort Sea. Compared to other adjacent areas in the Beaufort Sea, the chlorophyll values in the vicinity of Barter Island were considerably higher and likely reflect a long-hypothesized upwelling in that area and close coupling between the benthos and autochthonous production. In the Bering Sea, a drop in benthic biomass in 1994 compared with previous measurements (1974–1993) may support earlier observations that document a decline in biomass that began between the 1980s and 1990s in the Chirikov Basin and south of St. Lawrence Island. The results of this study indicate that the benthos is an excellent long-term indicator of both local and physical advective processes. In addition, this work provides further evidence that secondary production on arctic shelves can be significantly augmented by reduced carbon advected from highly productive adjacent shelves.     

Stable carbon isotope variations in northwest Europe during the last glacial–interglacial transition

Stable carbon isotope data that span part of the last glacial–interglacial transition (ca. 14-9 ka ¹⁴C BP; ca. 15–11 ka cal. BP), and which derive from organ-specific plant macrofossils recovered from two lake sediment profiles in the UK and one in Norway, are compared. The recorded temporal variations show similar trends, which, over a millennial time-scale appear to parallel the main drift in δ¹⁸O as determined for the GRIP ice-core. It is postulated that some smaller scale variations in the δ¹³C profiles may reflect the shorter term oscillations in δ¹⁸O values evident in the GRIP record, although this is less certain. Overall, however, the results suggest that stable carbon isotope measurements based on organ-specific terrestrial plant macrofossils may provide (i) a means for establishing correlations between terrestrial successions and (ii) additional paleoenvironmental information, as the apparent ‘shadowing’ of the GRIP record indicates a common forcing mechanism for both Greenland δ¹⁸O and northwest European δ¹³C variations. From the evidence available we suggest that the recorded δ¹³C variations reflect fluctuations in air temperature and/or changes in water vapour pressure in the atmosphere. © 1997 John Wiley & Sons, Ltd.     

Resolving mechanisms of toxicity while pursuing ecotoxicological relevance?

In this age of modern biology, aquatic toxicological research has pursued mechanisms of action of toxicants. This has provided potential tools for ecotoxicologic investigations. However, problems of biocomplexity and issues at higher levels of biological organization remain a challenge. In the 1980s and 1990s and continuing to a lesser extent today, organisms residing in highly contaminated field sites or exposed in the laboratory to calibrated concentrations of individual compounds were carefully analyzed for their responses to priority pollutants. Correlation of biochemical and structural analyses in cultured cells and tissues, as well as the in vivo exposures led to the production and application of biomarkers of exposure and effect and to our awareness of genotoxicity and its chronic manifestations, such as neoplasms, in wild fishes. To gain acceptance of these findings in the greater environmental toxicology community, “validation of the model” versus other, better-established often rodent models, was necessary and became a major focus. Resultant biomarkers were applied to heavily contaminated and reference field sites as part of effects assessment and with investigations following large-scale disasters such as oil spills or industrial accidents.

Over the past 15 years, in the laboratory, small aquarium fish models such as medaka (Oryzias latipes), zebrafish (Danio rerio), platyfish (Xiphophorus species), fathead minnow (Pimephales promelas), and sheepshead minnow (Cyprinodon variegatus) were increasingly used establishing mechanisms of toxicants. Today, the same organisms provide reliable information at higher levels of biological organization relevant to ecotoxicology. We review studies resolving mechanisms of toxicity and discuss ways to address biocomplexity, mixtures of contaminants, and the need to relate individual level responses to populations and communities.     

Low induction number, ground conductivity meters: A correction procedure in the absence of magnetic effects

Ground conductivity meters, comprising a variety of coil–coil configurations, are intended to operate within the limits provided by a low induction number (LIN), electromagnetic condition. They are now routinely used across a wide range of application areas and the measured apparent conductivity data may be spatially assembled and examined/correlated alongside information obtained from many other earth science, environmental, soil and land use assessments. The theoretical behaviour of the common systems is examined in relation to both the prevailing level of subsurface conductivity and the instrument elevation. It is demonstrated that, given the inherent high level of accuracy of modern instruments, the prevailing LIN condition may require operation in environments restricted to very low (< 12 mS/m) conductivities. Beyond this limit, non-linear departures from the apparent conductivity that would be associated with a LIN condition occur and are a function of the coil configuration, the instrument height and the prevailing conductivity. Using both theory and experimental data, it is demonstrated that this has the potential to provide biased and spatially distorted measurements. A simple correction procedure that can be applied to the measured data obtained from any of the LIN instruments is developed. The correction procedure would, in the limit of a uniform subsurface, return the same (correct) conductivity, irrespective of the ground conductivity meter used, the prevailing conductivity or the measurement height.