The Distribution and Redox Chemistry of Iron in the Pettaquamscutt Estuary

A series of high resolution (10 cm) vertical profiles of iron were determined across the oxic/anoxic boundary in the Lower Pond of the Pettaquamscutt Estuary. Selective chemical treatments and multiple analytical methods were used to detemine the oxidation state and lability of iron across the oxic/anoxic boundary. The vertical distributions of dissolved and total iron were determined by atomic absorption spectroscopy, and dissolved Fe(II) and reducible iron were determined using a modified Ferrozine spectrophotometric method. Well-developed maxima of total dissolved iron ≈7·5 μM occurred within the oxic/anoxic transition zone. Analysis of Fe(II) by the FZ method indicates that more than 95% of the dissolved iron determined by atomic absorption spectroscopy within the maximum is in the form of Fe(II). The concentration of dissolved Fe(II) ranged from <4 nM in oxygenated surface waters to between 7 and 8 μM at the total dissolved iron maximum.Both dissolved and total iron samples were treated with ascorbic acid to quantify the fraction of iron that was reducible in this system. Dissolved iron is quantitatively reduced to Fe(II) by 3·5 m depth, and particulate iron was almost completely dissolved by 6 m. Thermodynamic speciation calculations indicate that the dominant species of Fe(II) in the anoxic waters is the Fe(HS)⁺complex. In addition, the concentration of Fe(II) in the anoxic zone appears to be controlled by precipitation of a sulfide phase, the ion activity product for waters below 7 m is in good agreement with the solubility product of mackinawite.The vertical distribution of oxidation states of the metals indicates non-equilibrium conditions due to microbiological and chemical processes occurring in the redox transition zone. A one-dimensional vertical, eddy diffusion model is presented that incorporates redox reactions of iron, sulfide and oxygen. The modeling suggests the maximum in Fe(II) can be achieved through inorganic oxidation and reduction reactions, however the depth at which the maximum occurs is sensitive to sulfide oxidation, which appears to be dominated by biological oxidation. The magnitude of the Fe(II) maximum depends on the flux of iron into the basin, and reductive dissolution of particulate iron.     

Effects of age, sex and reproductive status on persistent organic pollutant concentrations in “Southern Resident” killer whales

“Southern Resident” killer whales (Orcinus orca) that comprise three fish-eating “pods” (J, K and L) were listed as “endangered” in the US and Canada following a 20% population decline between 1996 and 2001. Blubber biopsy samples from Southern Resident juveniles had statistically higher concentrations of certain persistent organic pollutants than were found for adults. Most Southern Resident killer whales, including the four juveniles, exceeded the health-effects threshold for total PCBs in marine mammal blubber. Maternal transfer of contaminants to the juveniles during rapid development of their biological systems may put these young whales at greater risk than adults for adverse health effects (e.g., immune and endocrine system dysfunction). Pollutant ratios and field observations established that two of the pods (K- and L-pod) travel to California to forage. Nitrogen stable isotope values, supported by field observations, indicated possible changes in the diet of L-pod over the last decade.     

The Fundamental Challenge in Measuring Sprawl: Which Land Should Be Considered?*

Lack of agreement on how to define and measure sprawl has hampered development of policy related to its causes and consequences. We question previous work for two reasons: the use of study areas that overbound or underbound sprawl landscapes, and the failure to account for land unavailable for development. We formulate “extended urban areas,” based on housing density and commuting patterns and argue that they represent a preferable geographic basis for measuring sprawl. We operationalize with satellite imagery a way for measuring land unavailable for development in these areas. We then compute five measures of urban development using the National Land Cover Data Base and decennial census data to assess the extent of sprawl in the extended urban areas of Atlanta, Baltimore, Boston, Los Angeles, and Washington. Our sensitivity analyses reveal that the measurement of sprawl critically depends on which land area forms the basis of the analysis, and, to a lesser degree, how one accounts for land unavailable for development.     

Modelling the impact of climate extremes: an overview of the MICE project

This paper provides an overview of the aims, objectives, research activities undertaken, and a selection of results generated in the European Commission-funded project entitled “Modelling the Impact of Climate Extremes” (MICE) – a pan-European end-to-end assessment, from climate model to impact model, of the potential impacts of climate change on a range of economic sectors important to the region. MICE focussed on changes in temperature, precipitation and wind extremes. The research programme had three main themes – the evaluation of climate model performance, an assessment of the potential future changes in the occurrence of extremes, and an examination of the impacts of changes in extremes on six activity sectors using a blend of quantitative modelling and expert judgement techniques. MICE culminated in a large stakeholder-orientated workshop, the aim of which was not only to disseminate project results but also to develop new stakeholder networks, whose expertise can be drawn on in future projects such as ENSEMBLES. MICE is part of a cluster of three projects, all related to European climate change and its impacts. The other projects in the cluster are PRUDENCE (Prediction of Regional Scenarios and Uncertainties for Defining European Climate Change Risks and Effects) and STARDEX (Statistical and Regional Dynamical Downscaling of Extremes for European Regions).     

Temporal changes in the vertical distribution of flow and chloride in deep wells

The combination of flowmeter and depth-dependent water-quality data was used to evaluate the quantity and source of high-chloride water yielded from different depths to eight production wells in the Pleasant Valley area of southern California. The wells were screened from 117 to 437 m below land surface, and in most cases, flow from the aquifer into the wells was not uniformly distributed throughout the well screen. Wells having as little as 6 m of screen in the overlying upper aquifer system yielded as much as 50% of their water from the upper system during drought periods, while the deeper parts of the well screens yielded 15% or less of the total yield of the wells. Mixing of water within wells during pumping degraded higher-quality water with poorer-quality water from deeper depths, and in some cases with poorer-quality water from the overlying upper aquifer system. Changes in the mixture of water within a well, resulting from changes in the distribution of flow into the well, changed the quality of water from the surface discharge of wells over time. The combination of flowmeter and depth-dependent water quality data yielded information about sources of high-chloride water to wells that was not available on the basis of samples collected from nearby observation wells. Changing well design to eliminate small quantities of poor-quality water from deeper parts of the well may improve the quality of water from some wells without greatly reducing well yield.     

Climatological and hydrographic influences on nearshore food webs off the southeastern United States: bacterioplankton dynamics

Bacterioplankton productivity, numbers, and cell specific activity were studied in nearshore waters of the southeastern U.S. continental shelf during seasons of maximum freshwater discharge. In April 1984, coastal waters were stratified from normal spring discharge and typical northeastward wind stress. In April 1985, shelf waters were vertically homogeneous due to below normal runoff and southwestward wind stress. In 1984, nearshore bacterial productivity ranged from 7.0 to 14.7 × 10⁶ cells l⁻¹ h⁻¹ and midshelf rates were 40–50% less. In 1985, nearshore productivity ranged from 0.9 to 2.4 × 10⁶ cells 1⁻¹ h⁻¹, and productivity was extremely patchy over the entire shelf. The cell-specific activity (thymidine incorporation per cell) suggests that although productivity was high in 1984, only a fraction of the bacterioplankton was actively growing or incorporating thymidine (0.9–2.9 × 10⁻²¹ mol cell⁻¹ h⁻¹). In 1985, a higher percentage of cells appeared to be active and incorporating thymidine (5–13 × 10⁻²¹mol cell⁻¹h⁻¹) even though productivity was low. Hydrographic conditions along the southeastern coastline may have had a significant impact on the overall community structure and carbon flow through the microbial food web. When coastal waters were stratified in 1984, bacterial biomass was a significant percentage (35–320%) of the phytoplankton biomass. During vertically homogeneous conditions of 1985, bacterial production and biomass were a small percentage (2–13%) of the phytoplankton production and biomass across the shelf. The interannual variation in the microbial food web was attributed to the interannual variability of the southeastern U.S. hydrology due to changes in freshwater discharge and wind direction and intensity. The ecological implications of these results extend to the potential impact of seasonal microbial food webs on nearshore allochothonous and autochothonous organics before removal from the southeastern U.S. coastline.     

Trace element constraints on pegmatite genesis: Tin Mountain pegmatite,Black Hills,South Dakota

The Tin Mountain pegmatite is a small, zoned granitic body that is extremely enriched in Rb and Li, but has moderate concentrations of Sr and Ba. These trace elements are modelled using granitic distribution coefficients in order to test the potentials of partial melting of metasedimentary rocks and fractionation of a less-evolved granitic melt to have produced the parental liquid to the Tin Mountain pegmatite. Batch melting of any reasonable metasedimentary source rock would likely have yielded melts that were either insufficiently enriched in Rb and Li to be the parental liquid, or that had Sr and Ba concentrations that were much higher than those estimated for the parental liquid. The modelling of simple fractional crystallization and equilibrium crystallization of a granitic melt within the compositional range of the spatially associated Harney Peak Granite gives calculated melt compositions with either lower Sr and Ba concentrations or inadequate Rb and Li enrichments, to be the parent liquid of the pegmatite. At least two variants from simple crystal-liquid fractionation models can, however, successfully account for the derivation of the parent liquid: 1) generation of a Rb-, Li-, Ba- and Sr-rich granitic melt (outside of the compositional range of the sampled portions of the Harney Peak Granite complex) by low degrees of partial melting of metasedimentary rocks found in the Black Hills, followed by moderate extents of fractional or equilibrium crystallization, 2) derivation from Harney Peak granite via a complex, multi-stage crystal-liquid fractionation process, such as progressive equilibrium crystallization.     

Rare earth element evidence concerning the origin of voluminous mid-Tertiary rhyolitic ignimbrites and related volcanic rocks,Sierra Madre Occidental,Chihuahua, Mexico

The mid-Tertiary volcanic sequence of the central Sierra Madre Occidental in Chihuahua, Mexico, is about one kilometer thick and is composed predominantly of rhyolitic ignimbrites. Basaltic andesite to dacitic lavas are interbedded with the rhyolites, but they are of minor volumetric importance. Rare earth element (REE) data are used to constrain a crustal anatexis model for the origin of the voluminous ignimbrites and to test a fractional crystallization model. The REE patterns indicate that if the rhyolites were formed by direct crustal anatexis, the residue from partial melting could contain no more than a few percent garnet or about 20% hornblende. This eliminates residues with the mineralogy of amphibolite, eclogite, or garnet granulite, but melting of a garnet-free granulite source is permitted. The crustal anatexis model is difficult to evaluate critically because of a lack of knowledge concerning the mid-Tertiary geothermal gradient and the composition of the crust beneath the Sierra Madre Occidental.In contrast, the fractional crystallization model can be tested rigorously. Rayleigh fractionation calculations are used to closely model REE patterns in the basaltic andesite to rhyolite series. The minerals involved are those occurring as phenocryst phases, and the mineral proportions were generated by leastsquares major element calculations. The results of the calculations are consistent with the hypothesis that the voluminous rhyolites originated by plagioclase-dominated crystal fractionation.