Global cooling during the Eocene Oligocene Transition

About 34 million years ago, Earth's climate shifted from a relatively ice-free world to one with glacial conditions on Antarctica characterized by substantial ice sheets. How Earth's temperature changed during this climate transition remains poorly understood, and evidence for Northern Hemisphere polar ice is controversial. Here, we report proxy records of sea surface temperatures from multiple ocean localities and show that the high-latitude temperature decrease was substantial and heterogeneous. High-latitude (45 degrees to 70 degrees in both hemispheres) temperatures before the climate transition were ~20°C and cooled an average of ~5°C. Our results, combined with ocean and ice-sheet model simulations and benthic oxygen isotope records, indicate that Northern Hemisphere glaciation was not required to accommodate the magnitude of continental ice growth during this time.

Cenozoic radiolarians from the Bahamas

Radiolarians from two sites north of Little Bahama Bank (Sites 627 and 628) are correlated with assemblages from sites on the southeastern U.S. coastal plain and continental shelf and from DSDP Sites 391 and 534 in the Blake-Bahama Basin. Results show that deposition of biogenic silica-rich sediments occurred in this region from the late Oligocene through middle Miocene, although the record is interrupted by unconformities. Radiolarians help constrain the age of a mass-transported deposit at Site 627 that appears to be coeval with the Great Abaco Member of the Blake Ridge Formation.

Oligocene planktonic foraminifera from the Ontong Java Plateau

Ocean Drilling Program Hole 803D (Leg 130) from the western tropical Pacific (Ontong Java Plateau) and Hole 628A (Leg 101) from the western subtropical North Atlantic (Little Bahama Bank) contain rich assemblages of planktonic foraminifers. The uppermost Eocene-basal Miocene section of Hole 803D is apparently complete, whereas the Oligocene section of Hole 628A contains three unconformities based on planktonic foraminiferal evidence. Anomalous ranges are recorded for Chiloguembelina cubensis and Globigerinoides primordius. C. cubensis is found to range throughout the upper Oligocene of both sites, and G. primordius first occurs near the base of upper Oligocene Zone P22 in Hole 628A. Paleomagnetic stratigraphy provides constraints on the last occurrence (LO) of Subbotina angiporoides, the first occurrence (FO) of Globigerina angulisuturalis, the FO of Globigerinoides primordius, the FO of Paragloborotalia pseudokugleri, and the LO of Chiloguembelina cubensis. In general, taxon ranges, total diversity, and the composition of the planktonic foraminiferal assemblages from Holes 628A and 803D are similar. Differences in the composition of planktonic foraminiferal assemblages between the two sites are interpreted to be primarily the result of enhanced dissolution at Site 803 (e.g., paucity of Globigerina angulisuturalis and absence of G. ciperoensis). However, the greater abundances of Subbotina angiporoides in subtropical Hole 628A and Paragloborotalia opima in tropical Hole 803D are probably related to oceanographic differences between the two low-latitude sites. Comparison between the low and southern high latitudes illustrates some similarities in the composition of Oligocene planktonic foraminiferal assemblages as well as some important differences. Species such as Pseudohastigerina spp., Turborotalia increbescens, "Turborotalia" ampliapertura, Paragloborotalia opima, P. pseudokugleri, P. semivera/mayeri, Globigerinella obesa, Globigerina angulisuturalis, G. gortanii, G. ouachitaensis, G. sellii, G. tapuriensis, G. tripartita, G. pseudovenezuelana, Subbotina? eocaena and S.? yeguaensis are absent or have rare occurrences in the subantarctic Oligocene assemblages. Biogeographic gradients, although not as pronounced as during the late Neogene, were nonetheless significant during the Oligocene.

Carbonate preservation of sediment cores from the Great Bahama Bank

The oceanic carbon cycle mainly comprises the production and dissolution/ preservation of carbonate particles in the water column or within the sediment. Carbon dioxide is one of the major controlling factors for the production and dissolution of carbonate. There is a steady exchange between the ocean and atmosphere in order to achieve an equilibrium of CO2; an anthropogenic rise of CO2 in the atmosphere would therefore also increase the amount of CO2 in the ocean. The increased amount of CO2 in the ocean, due to increasing CO2-emissions into the atmosphere since the industrial revolution, has been interpreted as "ocean acidification" (Caldeira and Wickett, 2003). Its alarming effects, such as dissolution and reduced CaCO3 formation, on reefs and other carbonate shell producing organisms form the topic of current discussions (Kolbert, 2006). Decreasing temperatures and increasing pressure and CO2 enhance the dissolution of carbonate particles at the sediment-water interface in the deep sea. Moreover, dissolution processes are dependent of the saturation state of the surrounding water with respect to calcite or aragonite. Significantly increased dissolution has been observed below the aragonite or calcite chemical lysocline; below the aragonite compensation depth (ACD), or calcite compensation depth (CCD), all aragonite or calcite particles, respectively, are dissolved. Aragonite, which is more prone to dissolution than calcite, features a shallower lysocline and compensation depth than calcite. In the 1980's it was suggested that significant dissolution also occurs in the water column or at the sediment-water interface above the lysocline. Unknown quantities of carbonate produced at the sea surface, would be dissolved due to this process. This would affect the calculation of the carbonate production and the entire carbonate budget of the world's ocean. Following this assumption, a number of studies have been carried out to monitor supralysoclinal dissolution at various locations: at Ceara Rise in the western equatorial Atlantic (Martin and Sayles, 1996), in the Arabian Sea (Milliman et al., 1999), in the equatorial Indian Ocean (Peterson and Prell, 1985; Schulte and Bard, 2003), and in the equatorial Pacific (Kimoto et al., 2003). Despite the evidence for supralysoclinal dissolution in some areas of the world's ocean, the question still exists whether dissolution occurs above the lysocline in the entire ocean. The first part of this thesis seeks answers to this question, based on the global budget model of Milliman et al. (1999). As study area the Bahamas and Florida Straits are most suitable because of the high production of carbonate, and because there the depth of the lysocline is the deepest worldwide. To monitor the occurrence of supralysoclinal dissolution, the preservation of aragonitic pteropod shells was determined, using the Limacina inflata Dissolution Index (LDX; Gerhardt and Henrich, 2001). Analyses of the grain-size distribution, the mineralogy, and the foraminifera assemblage revealed further aspects concerning the preservation state of the sediment. All samples located at the Bahamian platform are well preserved. In contrast, the samples from the Florida Straits show dissolution in 800 to 1000 m and below 1500 m water depth. Degradation of organic material and the subsequent release of CO2 probably causes supralysoclinal dissolution. A northward extension of the corrosive Antarctic Intermediate Water (AAIW) flows through the Caribbean Sea into the Gulf of Mexico and might enhance dissolution processes at around 1000 m water depth. The second part of this study deals with the preservation of Pliocene to Holocene carbonate sediments from both the windward and leeward basins adjacent to Great Bahama Bank (Ocean Drilling Program Sites 632, 633, and 1006). Detailed census counts of the sand fraction (250-500 µm) show the general composition of the coarse grained sediment. Further methods used to examine the preservation state of carbonates include the amount of organic carbon and various dissolution indices, such as the LDX and the Fragmentation Index. Carbonate concretions (nodules) have been observed in the sand fraction. They are similar to the concretions or aggregates previously mentioned by Mullins et al. (1980a) and Droxler et al. (1988a), respectively. Nonetheless, a detailed study of such grains has not been made to date, although they form an important part of periplatform sediments. Stable isotopemeasurements of the nodules' matrix confirm previous suggestions that the nodules have formed in situ as a result of early diagenetic processes (Mullins et al., 1980a). The two cores, which are located in Exuma Sound (Sites 632 and 633), at the eastern margin of Great Bahama Bank (GBB), show an increasing amount of nodules with increasing core depth. In Pliocene sediments, the amount of nodules might rise up to 100%. In contrast, nodules only occur within glacial stages in the deeper part of the studied core interval (between 30 and 70 mbsf) at Site 1006 on the western margin of GBB. Above this level the sediment is constantly being flushed by bottom water, that might also contain corrosive AAIW, which would hinder cementation. Fine carbonate particles (<63 µm) form the matrix of the nodules and do therefore not contribute to the fine fraction. At the same time, the amount of the coarse fraction (>63 µm) increases due to the nodule formation. The formation of nodules might therefore significantly alter the grain-size distribution of the sediment. A direct comparison of the amount of nodules with the grain-size distribution shows that core intervals with high amounts of nodules are indeed coarser than the intervals with low amounts of nodules. On the other hand, an initially coarser sediment might facilitate the formation of nodules, as a high porosity and permeability enhances early diagenetic processes (Westphal et al., 1999). This suggestion was also confirmed: the glacial intervals at Site 1006 are interpreted to have already been rather coarse prior to the formation of nodules. This assumption is based on the grain-size distribution in the upper part of the core, which is not yet affected by diagenesis, but also shows coarser sediment during the glacial stages. As expected, the coarser, glacial deposits in the lower part of the core show the highest amounts of nodules. The same effect was observed at Site 632, where turbidites cause distinct coarse layers and reveal higher amounts of nodules than non-turbiditic sequences. Site 633 shows a different pattern: both the amount of nodules and the coarseness of the sediment steadily increase with increasing core depth. Based on these sedimentological findings, the following model has been developed: a grain-size pattern characterised by prominent coarse peaks (as observed at Sites 632 and 1006) is barely altered. The greatest coarsening effect due to the nodule formation will occur in those layers, which have initially been coarser than the adjacent sediment intervals. In this case, the overall trend of the grain-size pattern before and after formation of the nodules is similar to each other. Although the sediment is altered due to diagenetic processes, grain size could be used as a proxy for e.g. changes in the bottom-water current. The other case described in the model is based on a consistent initial grain-size distribution, as observed at Site 633. In this case, the nodule reflects the increasing diagenetic alteration with increasing core depth rather than the initial grain-size pattern. In the latter scenario, the overall grain-size trend is significantly changed which makes grain size unreliable as a proxy for any palaeoenvironmental changes. The results of this study contribute to the understanding of general sedimentation processes in the periplatform realm: the preservation state of surface samples shows the influence of supralysoclinal dissolution due to the degradation of organic matter and due to the presence of corrosive water masses; the composition of the sand fraction shows the alteration of the carbonate sediment due to early diagenetic processes. However, open questions are how and when the alteration processes occur and how geochemical parameters, such as the rise in alkalinity or the amount of strontium, are linked to them. These geochemical parameters might reveal more information about the depth in the sediment column, where dissolution and cementation processes occur.

Evaluation of the Scottsdale Loop 101 automated speed enforcement demonstration program

Speeding is recognized as a major contributing factor in traffic crashes. In order to reduce speed-related crashes, the city of Scottsdale, Arizona implemented the first fixed-camera photo speed enforcement program (SEP) on a limited access freeway in the US. The 9-month demonstration program spanning from January 2006 to October 2006 was implemented on a 6.5 mile urban freeway segment of Arizona State Route 101 running through Scottsdale. This paper presents the results of a comprehensive analysis of the impact of the SEP on speeding behavior, crashes, and the economic impact of crashes. The impact on speeding behavior was estimated using generalized least square estimation, in which the observed speeds and the speeding frequencies during the program period were compared to those during other periods. The impact of the SEP on crashes was estimated using 3 evaluation methods: a before-and-after (BA) analysis using a comparison group, a BA analysis with traffic flow correction, and an empirical Bayes BA analysis with time-variant safety. The analysis results reveal that speeding detection frequencies (speeds> or =76 mph) increased by a factor of 10.5 after the SEP was (temporarily) terminated. Average speeds in the enforcement zone were reduced by about 9 mph when the SEP was implemented, after accounting for the influence of traffic flow. All crash types were reduced except rear-end crashes, although the estimated magnitude of impact varies across estimation methods (and their corresponding assumptions). When considering Arizona-specific crash related injury costs, the SEP is estimated to yield about $17 million in annual safety benefits.

How automated speed enforcement may reduce travel time variability and result in travel time savings : the case study of the loop 101 speed enforcement program in Scottsdale, Arizona

The city of Scottsdale Arizona implemented the first fixed photo Speed Enforcement camera demonstration Program (SEP) on a US freeway in 2006. A comprehensive before-and-after analysis of the impact of the SEP on safety revealed significant reductions in crash frequency and severity, which indicates that the SEP is a promising countermeasure for improving safety. However, there is often a trade off between safety and mobility when safety investments are considered. As a result, identifying safety countermeasures that both improve safety and reduce Travel Time Variability (TTV) is a desirable goal for traffic safety engineers. This paper reports on the analysis of the mobility impacts of the SEP by simulating the traffic network with and without the SEP, calibrated to real world conditions. The simulation results show that the SEP decreased the TTV: the risk of unreliable travel was at least 23% higher in the ‘without SEP’ scenario than in the ‘with SEP’ scenario. In addition, the total Travel Time Savings (TTS) from the SEP was estimated to be at least ‘569 vehicle-hours/year.’ Consequently, the SEP is an efficient countermeasure not only for reducing crashes but also for improving mobility through TTS and reduced TTV.

ZnO nanocones with high-index {101̅1} facets for enhanced energy conversion efficiency of dye-sensitized solar cells

ZnO is a promising photoanode material for dye-sensitized solar cells (DSCs) due to its high bulk electron mobility and because different geometrical structures can easily be tailored. Although various strategies have been taken to improve ZnO-based DSC efficiencies, their performances are still far lower than TiO2 counterparts, mainly because low conductivity Zn2+–dye complexes form on the ZnO surfaces. Here, cone-shaped ZnO nanocrystals with exposed reactive O-terminated {101̅1} facets were synthesized and applied in DSC devices. The devices were compared with DSCs made from more commonly used rod-shaped ZnO nanocrystals where {101̅0} facets are predominantly exposed. When cone-shaped ZnO nanocrystals were used, DSCs sensitized with C218, N719, and D205 dyes universally displayed better power conversion efficiency, with the highest photoconversion efficiency of 4.36% observed with the C218 dye. First-principles calculations indicated that the enhanced DSCs performance with ZnO nanocone photoanodes could be attributed to the strength of binding between the dye molecules and reactive O-terminated {101̅1} ZnO facets and that more effective use of dye molecules occurred due to a significantly less dye aggregation on these ZnO surfaces compared to other ZnO facets.