Iron and Sulfur Chemistry in a Stratified Lake: Evidence for Iron-Rich Sulfide Complexes

A four month study of a man-made lake used for hydroelectric power generation in northeastern Pennsylvania USA was conducted to investigate seasonal anoxia and the effects of sulfide species being transported downstream of the power generation equipment. Water column analyses show that the system is iron-rich compared to sulfide. Total Fe(II) concentrations in the hypolimnion are typically at least twice the total sulfide levels. In situ voltammetric analyses show that free Fe(II) as [Fe(H₂O)₆]²⁺ or free H₂S as H₂S/HS^- are either not present or at trace levels and that iron-rich sulfide complexes are present. From the in situ data and total Fe(II) and H₂S measurements, we infer that these iron-rich sulfide complexes may have stoichiometries such as Fe₂SH³⁺ (or polymeric forms of this and other stoichiometries). These iron-rich sulfide complexes appear related to dissolution of the iron-rich FeS mineral, mackinawite, because IAP calculations on data from discrete bottle samples obtained from bottom waters are similar to the pK_sp of mackinawite. Soluble iron-sulfide species are stable in the absence of O₂ (both in lake waters and the pipeline) and transported several miles during power generation. However, iron-sulfide complexes can react with O₂ to oxidize sulfide and can also dissociate releasing volatile H₂S when the waters containing them are exposed to the atmosphere downstream of the powerplant. Sediment analyses show that the lake is rich in oxidized iron solids (both crystalline and amorphous). Fe concentrations in FeS solids are low (<5 μmole/gr_{dry wt}) and the pyrite concentration ranges from about equal to the solid FeS to 30 times the solid FeS concentration. The degree of pyritization is below 0.12 indicating that pyrite formation is limited by free sulfide, which can react with the iron-rich sulfide complexes.     

Analysis of the surface temperature and wind forecast errors of the NCAR-AirDat operational CONUS 4-km WRF forecasting system

Investigating the characteristics of model-forecast errors using various statistical and object-oriented methods is necessary for providing useful guidance to end-users and model developers as well. To this end, the random and systematic errors (i.e., biases) of the 2-m temperature and 10-m wind predictions of the NCAR-AirDat weather research and forecasting (WRF)-based real-time four-dimensional data assimilation (RTFDDA) and forecasting system are analyzed. This system has been running operationally over a contiguous United States (CONUS) domain at a 4-km grid spacing with four forecast cycles daily from June 2009 to September 2010. In the result an exceptionally useful forecast dataset was generated and used for studying the error properties of the model forecasts, in terms of both a longer time period and a broader coverage of geographic regions than previously studied. Spatiotemporal characteristics of the errors are investigated based on the 24-h forecasts between June 2009 and April 2010, and the 72-h forecasts between May and September 2010. It was found that the biases of both wind and temperature forecasts vary greatly seasonally and diurnally, with dependency on the forecast length, station elevation, geographical location, and meteorological conditions. The temperature showed systematic cold biases during the daytime at all station elevations and warm biases during the nighttime above 1,000 m above sea level (ASL), while below 600 m ASL cold biases occurred during the nighttime. The forecasts of surface wind speed exhibited strong positive biases during the nighttime, while the negative biases were observed in the spring and summer afternoons. The surface wind speed was mostly over-predicted except for the stations located between 1,000 and 2,100 m ASL, for which negative biases were identified for most forecast cycles. The highest wind-speed errors were found over the high terrain and near sea-level stations. The wind-direction errors were relatively large at the high-terrain elevation in the Rocky and Appalachian mountain ranges and the western coastal areas and the error structure exhibited notable diurnal variability.     

The effect of El Niño Southern Oscillation cycles on the decadal scale suspended sediment behavior of a coastal dry‐summer subtropical catchment

Rivers display temporal dependence in suspended sediment–water discharge relationships. Although most work has focused on multi‐decadal trends, river sediment behavior often displays sub‐decadal scale fluctuations that have received little attention. The objectives of this study were to identify inter‐annual to decadal scale fluctuations in the suspended sediment–discharge relationship of a dry‐summer subtropical river, infer the mechanisms behind these fluctuations, and examine the role of El Niño Southern Oscillation climate cycles. The Salinas River (California) is a moderate sized (11 000 km²), coastal dry‐summer subtropical catchment with a mean discharge (Q_mean) of 11.6 m³ s^?1. This watershed is located at the northern most extent of the Pacific coastal North America region that experiences increased storm frequency during El Niño years. Event to inter‐annual scale suspended sediment behavior in this system was known to be influenced by antecedent hydrologic conditions, whereby previous hydrologic activity regulates the suspended sediment concentration–water discharge relationship. Fine and sand suspended sediment in the lower Salinas River exhibited persistent, decadal scale periods of positive and negative discharge corrected concentrations. The decadal scale variability in suspended sediment behavior was influenced by inter‐annual to decadal scale fluctuations in hydrologic characteristics, including: elapsed time since small (~0.1 × Q_mean), and moderate (~10 × Q_mean) threshold discharge values, the number of preceding days that low/no flow occurred, and annual water yield. El Niño climatic activity was found to have little effect on decadal‐scale fluctuations in the fine suspended sediment–discharge relationship due to low or no effect on the frequency of moderate to low discharge magnitudes, annual precipitation, and water yield. However, sand concentrations generally increased in El Niño years due to the increased frequency of moderate to high magnitude discharge events, which generally increase sand supply. Copyright © 2014 John Wiley & Sons, Ltd.     

Vertical heat transports in the ocean and their effect on time-dependent climate change

In response to increasing atmospheric concentrations of greenhouse gases, the rate of time-dependent climate change is determined jointly by the strength of climate feedbacks and the efficiency of processes which remove heat from the surface into the deep ocean. This work examines the vertical heat transport processes in the ocean of the HADCM2 atmosphere–ocean general circulation model (AOGCM) in experiments with CO₂ held constant (control) and increasing at 1 per year (anomaly). The control experiment shows that global average heat exchanges between the upper and lower ocean are dominated by the Southern Ocean, where heat is pumped downwards by the wind-driven circulation and diffuses upwards along sloping isopycnals. This is the reverse of the low-latitude balance used in upwelling–diffusion ocean models, the global average upward diffusive transport being against the temperature gradient. In the anomaly experiment, weakened convection at high latitudes leads to reduced diffusive and convective heat loss from the deep ocean, and hence to net heat uptake, since the advective heat input is less affected. Reduction of deep water production at high latitudes results in reduced upwelling of cold water at low latitudes, giving a further contribution to net heat uptake. On the global average, high-latitude processes thus have a controlling influence. The important role of diffusion highlights the need to ensure that the schemes employed in AOGCMs give an accurate representation of the relevant sub-grid-scale processes. Received: 8 July 1999 / Accepted: 17 November 1999     

A Review of High-Performance Computational Strategies for Modeling and Imaging of Electromagnetic Induction Data

Many geoscientific applications exploit electrostatic and electromagnetic fields to interrogate and map subsurface electrical resistivity—an important geophysical attribute for characterizing mineral, energy, and water resources. In complex three-dimensional geologies, where many of these resources remain to be found, resistivity mapping requires large-scale modeling and imaging capabilities, as well as the ability to treat significant data volumes, which can easily overwhelm single-core and modest multicore computing hardware. To treat such problems requires large-scale parallel computational resources, necessary for reducing the time to solution to a time frame acceptable to the exploration process. The recognition that significant parallel computing processes must be brought to bear on these problems gives rise to choices that must be made in parallel computing hardware and software. In this review, some of these choices are presented, along with the resulting trade-offs. We also discuss future trends in high-performance computing and the anticipated impact on electromagnetic (EM) geophysics. Topics discussed in this review article include a survey of parallel computing platforms, graphics processing units to multicore CPUs with a fast interconnect, along with effective parallel solvers and associated solver libraries effective for inductive EM modeling and imaging.     

Sedimentary architecture of a glaciolacustrine braidplain delta: proxy evidence of a pre‐Middle Wisconsinan glaciation (Grimshaw gravels,Interior Plains,Canada)

The erosional nature of glacial systems commonly results in removal of direct evidence of previous glaciation (e.g. till and moraine). Therefore, reconstruction of former ice‐margin positions may rely, in part, on indirect (proxy) evidence from the sedimentary record. This study examines the facies and sedimentary architecture of a pre‐Middle Wisconsinan sand and gravel deposit (the ‘Grimshaw gravels’), which is positioned between areas where previous stratigraphical investigations have identified single (Late Wisconsinan) and multiple (pre‐Middle to Late Wisconsinan) glaciation by the Laurentide Ice Sheet. Five facies associations (FAs) are characterized within the deposit, which, together with the sedimentary architecture, record a transition from a braided river environment in the west (FA1‐3) to a gravelly braidplain delta front in the east (FA4 and 5). We propose that the Grimshaw gravels braid delta formed at the margin of a body of water that occupied the ancestral Peace River valley, probably impounded by the LIS; hence, the Grimshaw braid delta provides proxy evidence of the presence of an ice margin (previously unrecognized) in the Peace River lowland prior to the Middle Wisconsinan. This study provides further understanding of the origin of the Grimshaw gravels deposit, allowing re‐evaluation of previous models of formation. These findings offer insight into the glacial history of the southwestern margin of the LIS, and may help to refine ice‐sheet reconstructions spanning the Wisconsinan glaciation.     

Constraints on formation processes of two coarse-grained calcium- aluminum-rich inclusions: A study of mantles,islands and cores

Abstract— Many coarse-grained calcium- aluminum-rich inclusions (CAIs) contain features that are inconsistent with equilibrium liquid crystallization models of origin. Spinel-free islands (SFIs) in spinel-rich cores of Type B CAIs are examples of such features. One model previously proposed for the origin of Allende 5241, a Type B1 CAI containing SFIs, involves the capture and assimilation of xenoliths by a liquid droplet in the solar nebula (El Goresy et al., 1985; MacPherson et al., 1989). This study reports new textural and chemical zoning data from 5241 and identifies previously unrecognized chemical zoning patterns in the melilite mantle and in a SFI. These zoning patterns are identified by large-scale elemental mapping techniques. The compositional zoning is completely independent of, and cross-cuts individual melilite crystals in the mantle, a relation that suggests the mantle was deposited or accreted onto a preexisting core of the inclusion. Lack of correlation with individual mantle crystals also suggests that the mantle totally recrystallized at subsolidus temperatures. Sodium distribution maps demonstrate that most of the Na in 5241 was introduced during the secondary alteration process. Major- and trace-element data from the SFI boundary in a second type B1 CAI, Allende 3529Z, were obtained. The boundary bisects a large fassaite crystal. If the SFI is a relict xenolith, then chemical differences are likely to be present across the boundary. Electron microprobe analysis of the fassaite crystal reveals concentric zoning of Ti, which is unrelated to the SFI boundary, as well as distinct zones enriched in Al and depleted in Ti⁺³. Ion microprobe analyses at the SFI boundary show no significant variation in Ba, Sc, V, Cr, Sr, Zr, Nb and REE in fassaite. There is no evidence that requires the capture of a xenolith in 3529Z. Based on chemical zoning and textural arguments, it is suggested that both of these CAIs formed by a process of partial melting of precursors, which contained either vesicles or spinel-free grains. Allende 5241 shows evidence for vapor condensation and accretion and/or introduction of a second liquid to form the melilite mantle. Chemical zoning patterns in the mantles of the inclusions indicate that 3529Z experienced a higher degree of partial melting than 5241, but it was not high enough to melt spinel or completely melt and homogenize relict fassaite components.     

The effects of reduced land fraction and solar forcing on the general circulation: results from the NCAR CCM

Land fraction and the solar energy at the top of the atmosphere (solar constant) may have been significantly lower early in Earth's history. It is likely that both of these factors played some important role in the climate of the early earth. The climate changes associated with a global ocean(i.e. no continents) and reduced solar constant are examined with a general circulation model and compared with the present-day climate simulation. The general circulation model used in the study is the NCAR CCM with a swamp ocean surface. First, all land points are removed in the model and then the solar constant is reduced by 10% for this global ocean case.Results indicate that a 4 K increase in air temperature occurs with global ocean simulation compared to the control. When solar constant is reduced by 10% under global ocean conditions a 23 K decrease in air temperature is noted. The global ocean warms much of the troposphere and stratosphere, while a reduction in the solar constant cools the troposphere and stratosphere. The largest cooling occurs near the surface with the lower solar constant.Global mean values of evaporation, water vapor amounts, absorbed solar radiation and the downward longwave radiation are increased under global ocean conditions, while all are reduced when the solar constant is lowered. The global ocean simulation produces sea ice only in the highest latitudes. A frozen planet does not occur when the solar constant is reduced—rather, the ice line settles near 30° of latitude. It is near this latitude that transient eddies transport large amounts of sensible heat across the ice line acting as a negative feedback under lower solar constant conditions keeping sea ice from migrating to even lower latitudes.Clouds, under lower solar forcing, also act as a negative feedback because they are reduced in higher latitudes with colder atmospheric temperatures allowing additional solar radiation to reach the surface. The overall effect of clouds in the global ocean is to act as a positive feedback because they are slightly reduced thereby allowing additional solar radiation to reach the surface and increase the warming caused by the removal of land. The relevance of the results to the “Faint-Young Sun Paradox” indicates that reduced land fraction and solar forcing affect dynamics, heat transport, and clouds. Therefore the associated feedbacks should be taken into account in order to understand their roles in resolving the “Faint-Young Sun Paradox”.     

Coolidge and Loongana 001: A new carbonaceous chondrite grouplet

Abstract— Petrographic and bulk compositional data suggest the existence of a new grouplet of carbonaceous chondrites consisting of Coolidge and Loongana 001. Coolidge is a carbonaceous chondrite find from Kansas, USA, previously considered a metamorphosed CV chondrite. Loongana 001 is a recent find from Western Australia. It has a high matrix/chondrule modal abundance ratio, 1–2 vol% refractory inclusions and high refractory lithophile abundance ratios (～1.35x CI), indicating that it is a carbonaceous chondrite. Coolidge and Loongana 001 have many compositional and petrographic similarities. They have refractory element abundances in the range of CV chondrites, significantly higher than those in the CR chondrites. They have similar volatile element abundance patterns showing low volatile element abundances relative to both CR and CV chondrites. Coolidge and Loongana 001 have similar chondrule dimensions and shapes, oxidation states and opaque mineral assemblages. They are also similar in petrologic type (3.8–4) and shock stage (S2). Although both Coolidge and Loongana 001 may be related to the CV clan, they are not CV chondrites, nor are they formed by metamorphism of a CV precursor. They are distinctly different in composition from CV chondrites and their chondrules are smaller and have a much lower abundance of coarse-grained chondrule rims. Coolidge and Loongana 001 constitute a distinct carbonaceous chondrite grouplet.     

INFORMATION SOURCES FOR NINETEENTH CENTURY MIDWESTERN MIGRATION*

A variety of sources provides different levels of information about the origins of nineteenth century migrants to the Midwest. The advantages and disadvantages of four of the most common records, the federal census, land office records, genealogical collections, and county histories/biographies/atlases, are examined. Characteristics considered are the specific types of data provided, extent of coverage, level of detail, statistical reliability, and accessibility. Examples of studies using each record type are cited.