Impact of river runoff into the ocean on Indian summer monsoon

Rivers of the world discharge about 36000 km 3 of freshwater into the ocean every year. To investigate the impact of river discharge on climate, we have carried out two 100 year simulations using the Community Climate System Model (CCSM3), one including the river runoff into the ocean and the other excluding it. When the river discharge is shut off, global average sea surface temperature (SST) rises by about 0.5 degrees C and the Indian Summer Monsoon Rainfall (ISMR) increases by about 10% of the seasonal total with large increase in the eastern Bay of Bengal and along the west coast of India. In addition, the frequency of occurrence of La Nina-like cooling events in the equatorial Pacific increases and the correlation between ISMR and Pacific SST anomalies become stronger. The teleconnection between the SST anomalies in the Pacific and monsoon is effected via upper tropospheric meridional temperature gradient and the North African-Asian Jet axis.

A comparison of the fine-scale structure of the diurnal cycle of tropical rain and lightning

In this study, the fine-scale structure of the diurnal variability of ground-based lightning is systematically compared with satellite-based rain. At the outset, it is shown that tropical variability of lightning exhibits a prominent diurnal mode, much like rain. A comparison of the geographical distribution of the timing of the diurnal maximum shows that there is very good agreement between the two observables over continental and coastal regions throughout the tropics. Following this global tropical comparison, we focus on two regions, Borneo and equatorial South America, both of which show the interplay between oceanward and landward propagations of the phase of the diurnal maximum. Over Borneo, both rain and lightning clearly show a climatological cycle of ``breathing in'' (afternoon to early morning) and ``breathing out'' (morning to early afternoon). Over the equatorial east coast of South America, landward propagation is noticed in rain and lightning from early afternoon to early morning. Along the Pacific coast of South America, both rain and lightning show oceanward propagation. Though qualitatively consistent, over both regions the propagation is seen to extend further in rainfall. Additionally, given that lightning highlights vigorous convection, the timing of its diurnal maximum often precedes that of rainfall in the convective life cycle. (C) 2015 Elsevier B.V. All rights reserved.

Isotopic disequilibrium in Globigerina bulloides and carbon isotope response to productivity increase in Southern Ocean

Oxygen and carbon isotope ratios in planktonic foraminifera Globigerina bulloides collected from tow samples along a transect from the equatorial Indian ocean to the Southern Ocean (45 degrees E and 80 degrees E and 10 degrees N to 53 degrees S) were analysed and compared with the equilibrium delta O-18 and delta C-13 values of calcite calculated using the temperature and isotopic composition of the water column. The results agree within similar to 0.25% for the region between 10 degrees N and 40 degrees S and 75-200 m water depth which is considered to be the habitat of Globigerina bulloides. Further south (from 40 degrees S to 55 degrees S), however, the measured delta O-18 and delta C-13 values are higher than the expected values by similar to 2% and similar to 1% respectively. These enrichments can be attributed to either a `vital effect' or a higher calcification rate. An interesting pattern of increase in the delta C-13(DIC) value of the surface water with latitude is observed between 35 degrees S and similar to 60 degrees S, with a peak at similar to 42 degrees S. This can be caused by increased organic matter production and associated removal. A simple model accounting for the increase in the delta C-13(DIC) values is proposed which fits well with the observed chlorophyll abundance as a function of latitude.

El Nino and the Indian rainfall in June

We have addressed the question of whether the massive deficit of 42% in rainfall over the Indian region in June 2014 can be attributed primarily to the El Nino. We have shown that the variation of convection over the Northern part of the Tropical West Pacific (NWTP: 120-150E, 20-30N) plays a major role in determining the all-India rainfall in June with deficit (excess) in rainfall associated with enhancement (suppression) of convection over NWTP. In June 2014, the outgoing long wave radiation (OLR) anomaly over this region was unfavourable, whereas in June 2015, the OLR anomaly over NWTP was favourable and the all-India rainfall was 16% higher than the long-term average. We find that during El Nino, when the convection over the equatorial central Pacific intensifies, there is a high propensity for intensification of convection over NWTP. Thus, El Nino appears to have an impact on the rainfall over the Indian region via its impact on the convection over the West Pacific, particularly over NWTP. This occurred in June 2014, which suggests that the large deficit in June 2014, could be primarily attributed to the El Nino acting via intensification of convection over NWTP.

Numerical study of bifurcation solutions of spherical Taylor-Couette flow

The steady bifurcation flows in a spherical gap (gap ratio sigma=0.18) with rotating inner and stationary outer spheres are simulated numerically for Re(c1)less than or equal to Re less than or equal to 1 500 by solving steady axisymmetric incompressible Navier-Stokes equations using a finite difference method. The simulation shows that there exist two steady stable flows with 1 or 2 vortices per hemisphere for 775 less than or equal to Re less than or equal to 1 220 and three steady stable flows with 0, 1, or 2 vortices for 1 220equatorial symmetry. The mechanism of development of a saddle point in the meridional plane at higher Re number and its role in the formation of two-vortex flow are analyzed.

“El Niño” study based on analysis of ocean surface temperatures 1935-57

ENGLISH: The following report describes the findings of an "El Niño" project carried out at the Department of Meteorology of the University of California, Los Angeles, at the request of, and with funds provided from, the Inter-American Tropical Tuna Commission. The project was, in its early stages, supervised by Professor M. Neiburger, but was in June 1959 transferred to Professor J. Bjerknes, who thereby became the sole author of this final report. Readers who may be interested in the general background of knowledge of the maritime meteorology of the Eastern Pacific are herewith referred to Professor Neiburger's final report of the "Subtropical Pacific Meteorology Project." That report, submitted in September 1958 to the Office of Naval Research, summarizes the results of all the meteorological soundings released at sea since 1949 from California in the north to Peru in the south. The soundings off Ecuador and Peru were all taken by the "Shellback" expedition during July 1952. Important as this first exploration of the atmosphere over the Eastern Equatorial Pacific was, it did not even begin to explore " El Niño " itself, which is confined to the southern summer season and, moreover, only reaches catastrophic proportions in a few exceptional years. SPANISH: Este estudio da a conocer los resultados de una investigación que, bajo el nombre de Proyecto "El Niño", ha sido efectuada en el Departamento de Meteorología de la Universidad de California, Los Angeles, a solicitud de la Comisión Interamericana del Atún Tropical y con fondos provistos por ésta. En sus primeras etapas, el proyecto fué supervisado por el Profesor M. Neiburger, pero en junio de 1959 fué transferido al Profesor J. Bjerknes, quien de este modo vino a ser el solo autor de este informe final. A los lectores interesados en los conocimientos de fondo de la meteorología marítima del Pacífico Oriental se les recomienda consultar el informe final del Profesor Neiburger intitulado "Subtropical Pacific Meteorology Project". Este informe, sometido a la "Office of Naval Research" en septiembre de 1958 sumariza los resultados de todos los sondeos meteorológicos efectuados en el mar desde 1949 en el área entre California en el norte y Perú en el sur. Todos los sondeos frente al Ecuador y el Perú fueron hechos por la Expedición "Shellback" durante el mes de julio de 1952. Importante como fué esta primera exploración de la atmósfera sobre el Pacífico Ecuatorial del Este, ni siquiera comenzó a explorar "El Niño" en sí, que se confina a la estación de verano en el sur y, más aún, sólo alcanza proporciones catastróficas en unos pocos años excepcionales.

Seasonal Climatologies and Variability of Eastern Tropical Pacific Surface Waters

Interannual variability caused by the El Nino-Southern Oscillation in the eastern tropical Pacific Ocean (ETP) is analogous to seasonal variability of comparable magnitude. Climatological spatial patterns and seasonal variability of physical variables that may affect the ETP ecosystem are presented and discussed. Surface temperature, surface salinity, mixed layer depth, thermocline depth, thermocline strength, and surface dynamic height were derived from bathythermograph, hydrocast, and CTD data. Surface current velocity, divergence, and upwelling velocity were derived from ship drift reports. Surface wind velocity, wind stress, wind divergence, wind stress curl, and Ekman pumping velocity were derived from gridded pseudostress data obtained from Florida State University. Seasonal maps of these variables, and their deviations from the annual mean, show different patterns of variation in Equatorial (S°S-SON) and Tropical Surface Water (SOlS0N). Seasonal shifts in the trade winds, which affect the strength of equatorial upwelling and the North Equatorial Countercurrent, cause seasonal variations in most variables. Seasonal and interannual variability of surface temperature, mixed layer depth, thermocline depth and wind stress were quantified. Surface temperature, mixed layer depth and thermocline depth, but not local wind stress, are less variable in Tropical Surface Water than in Equatorial Surface Water. Seasonal and interannual variability are close to equal in most of the ETP, within factors of 2 or less. (PDF file contains 70 pages.)

Distribution of skipjack in the Pacific Ocean, based on records of incidental catches of the Japanese longline tuna fishery

ENGLISH: All available longline data on skipjack captured in the Pacific Ocean by Japanese research vessels (1949-1965) and from incidental skipjack catches by Japanese commercial vessels (1956-1964) were analyzed. As skipjack are not specifically sought by longline vessels, the data are limited. Considering this it was found that: longline gear captures skipjack of wider size-range and is more selective for larger skipjack than conventional fishing methods, i.e. pole-and-line and purse-seine; skipjack are widely and almost continuously distributed across the Pacific; throughout the year average hook-rates are greater in the southeastern Pacific than in the northwestern Pacific; areas of high hook-rate shift south during the second and third quarters and north during the first and fourth quarters; in the western Pacific the north-south range of the catch distribution was greatest in the first and fourth quarters; skipjack hook-rates are relatively high in the northwestern Pacific east of Japan only during the first and fourth quarters; the highest hook-rates were recorded in extensive areas along the equator (from lO°N to 20°8 between approximately 155°W-100°W); generally more skipjack were captured by research longline gear in water temperature ranges approaching both the upper and lower temperature limits of skipjack distribution (18-21C and 26-28C), than is the case in surface skipjack fisheries; tentative comparisons of longline skipjack catch distributions with Pacific current systems, suggests low skipjack abundance in both North Pacific Central and North Pacific Equatorial water; the sex ratio was 95 males : 63 females in a small sample of skipjack examined; longlines capture skipjack of three, and possibly more, age groups; in skipjack size-composition samples studied, the smaller modal group (65 cm) observed in January-March in the northwestern Pacific (1600E-180oE and 20oN-45°N) corresponds in size to the larger modal group appearing in the late-summer surface fishery off the Izu-Bonin Islands southeast of Japan, and also compares in modal size to the skipjack taken in the Hawaiian fishery in spring time; the analysis of skipjack catches by hook position on the longline and by death-rate studies, indicates that part of the catch is made while the gear is in motion near the surface, and a lesser part of the catch is made when the gear is stabilized at a depth of 70 to 140 m. A brief discussion is given, in the light of new information presented, on several hypotheses by other authors concerning the population structure and migration of skipjack in the Pacific Ocean. SPANISH: Se analizaron todos los datos disponibles de la pesca con palangre de barriletes capturados en el Océano Pacífico por barcos japoneses de investigación (1949-1965) y por las capturas incidentales de los barcos comerciales japoneses (1956-1964). Como los barcos palangreros específicamente, no persiguen al barrilete, los datos son limitados. Considerando ésto, se encontró: que el arte palangrero obtiene barriletes con una distribución más amplia de tallas, y es más selectivo en cuanto a los barriletes de mayor talla, que los métodos convencionales de pesca, Le. cañas de pescar y redes de cerco; el barrilete se encuentra amplia y casi continuamente distribuido a través del Pacífico; en todo el año, las tasas promedio de captura por anzuelo son superiores en el Pacífico sudoriental que las del Pacífico noroeste; las áreas con una tasa alta de captura por anzuelo, se cambian hacia el sur durante los trimestres segundo y tercero, y durante los trimestres primero y cuarto hacia el norte; en el Pacífico occidental la amplitud de la distribución de captura norte-sur, fue superior en los trimestres primero y cuarto; las tasas de captura por anzuelo de barrilete, son relativamente altas en el Pacífico noroeste al este del Japón, únicamente durante los trimestres primero y cuarto; las tasas de captura por anzuelo más altas fueron registradas en extensas áreas a lo largo del ecuador (desde los 10°N hasta los 20°S, aproximadamente entre los 155°W-100°W) ; generalmente las artes palangreras de investigación capturaron más barrilete en aguas en las que la temperatura se aproximaba a los límites más altos o bajos de la temperatura en la distribución del barrilete (18-21 C y 26-28 C), que en el caso de la pesca superficial de barrilete; las comparaciones tentativas de la captura de barrilete con palangre, con el sistema de las corrientes del Pacífico, sugieren una abundancia inferior de barrilete tanto en las aguas del Pacífico central del norte como en las del Pacífico ecuatorial del norte; la proporcíon sexual examinada en una pequeña muestra de barriletes, fue de 95 machos y 63 hembras; los palangreros capturan barriletes de tres grupos de edad y posiblemente de más; en las muestras estudiadas de la composición de las tallas de barrilete, el grupo modal más pequeño (65 cm), observado en enero-marzo en el Pacífico noroeste (160 0E-180° y 20 oN-45°N), corresponde en talla al grupo modal más grande que aparece en la pesca de superficie a fines del verano frente a las Islas Izu-Bonín al sudeste del Japón, y se compara también con la talla modal del barrilete obtenido en la pesca hawaiana en la época de primavera; el análisis de las capturas de barrilete por medio del estudio de la posición de los anzuelos en el palangre y por la tasa de mortalidad, indica que parte de la captura se efectúa cuando el equipo está en movimiento cerca a la superficie y una parte inferior de la captura se realiza, cuando las artes se estabilizan a una profundidad de 70 a 140 m. Se ofrece una breve discusión sobre varias hipótesis de otros autores, en vista de la nueva información presentada referente a la estructura poblacional y a la migración del barrilete en el Océano Pacífico. (PDF contains 100 pages.)

The Japanese longline fishery for tunas and billfishes in the Eastern Pacific Ocean east of 130°W, 1964-1966

ENGLISH: Catch and effort statistics from the Japanese longline fishery operating in the eastern Pacific Ocean east of 130°W, from 1964 through 1966, were examined to study the geographic distribution, trends in apparent abundance, sexual maturity, and size composition of the tunas and billfishes. Yellowfin and bigeye tuna are generally most abundant in the equatorial regions of the high seas between about 10°N and 20°S, but west of 95°W. The marlins are more coastal in distribution, usually occurring to the east, and to the north and south of the heavy concentration of tropical tunas. Sailfish tend to be associated with coastal areas also, whereas shortbill spearfish are more frequently captured on the high seas. Swordfish are found most abundantly in the coastal regions off northern Mexico, and off northern Peru and southern Ecuador. The albacore, a temperate-water species of tuna, is most abundant in the high-seas area of the southeastern Pacific, Trends in apparent abundance were measured by the hook-rate (i.e. catch per 100 hooks). Hook-rates for bigeye tuna have decreased from about 3.5 fish per 100 hooks in 1958 to about 1.1 fish per 100 hooks in 1966. During the same period, effort was increased substantially and total catch has decreased since 1963. It does not appear that increased effort will result in sustained increased catches of bigeye. Hook-rates for yellowfin tuna in recent years have decreased to about one third of their initial levels. The surface fishery for yellowfin in the eastern Pacific apparently affects recruitment to the longline fishery. Assuming that present conditions in the surface fishery do not change appreciably, increased effort in the longline fishery probably would not produce sustained increased catches, but might in fact result in reduced catch rates. Unlike the situation for the other tunas of the eastern Pacific, it appears that the albacore fishery east of 130°W is not having a marked effect on their abundance. Although a high degree of variability was observed in the hookrates for striped marlin, no obvious trends are evident. Catches have decreased slightly from 13,500 tons in 1964 to about 11,000 tons in 1966. Heavy fishing for sailfish began in 1964 with a hook-rate of 10.6 fish per 100 hooks; by 1966 it had dropped to 5.8. Catches of this species in the area of major concentration dropped from 329,900 fish in 1965 to 173,600 fish in 1966. This fishery has operated for too short a period of time to enable one to determine its effect on the sustainable yield. Length-frequency measurements and gonad samples from yellowfin and bigeye tunas collected in the eastern Pacific were analyzed to determine sexual maturity and growth characteristics. The results corroborate the findings of earlier investigators. SPANISH: Las estadísticas de captura y del esfuerzo de la pesca japonesa con palangre que maniobra en el Océano Pacífico oriental al este de los 130°W, desde 1964 hasta 1966, fueron examinadas para estudiar la distribución geográfica, las tendencias de la abundancia aparente, la madurez sexual y la composición de talla de los atunes y de los peces espada. Los atunes aleta amarilla y ojo grande son generalmente más abundantes en las regiones ecuatoriales de alta entre unos 10°N y 20°S, pero al oeste de los 95°W. Los marlines son costaneros en distribución, apareciendo habitualmente hacia el y hacia el norte y sur de la densa concentración de atunes tropicales. pez vela tiende a asociarse también con las áreas costaneras, mientras el pez aguja corta es capturado con más frecuencia en alta mar. Los peces espada se encuentran más abundantemente en las regiones costaneras de México septentrional y frente al norte del Perú y del Ecuador meridional. La albacora, una especie de atún de aguas templadas, es más abundante en el área de alta mar del Pacífico sudoriental. Las tendencias en la abundancia aparente fueron evaluadas por la tasa de captura por anzuelo (i.e., captura por 100 anzuelos). Las tasas de captura por anzuelo del atún ojo grande, disminuyeron en 1958, de unos 3.5 peces por 100 anzuelos a cerca de 1.1 pez por 100 anzuelos en 1966. Durante el mismo período, el esfuerzo fue aumentado substancialmente y, desde 1963, la captura total disminuyó. No parece que el aumento del esfuerzo resultara en un aumento sostenido de las capturas del atún ojo grande. Las tasas de captura por anzuelo de atún aleta amarilla han disminuido en un tercio de los niveles iniciales, en años recientes. La pesca de superficie de esta especie en el Pacífico oriental afectó aparentemente el reclutamiento en la pesca con palangre. Suponiendo que las condiciones actuales de la pesquería no cambien apreciablemente, un aumento del esfuerzo en la pesquería palangrera probablemente no produciría un aumento sostenido de las capturas, pero en realidad podría resultar en tasas de captura reducidas. A diferencia de la situación de otros túnidos del Pacífico oriental, parece que la pesca de la albacora al este de los 130°W no ha tenido un efecto marcado en su abundancia. Aunque se observó un alto grado de variabilidad en las tasas de captura por anzuelo correspondientes al marlin rayado, no fueron evidentes tendencias obvias. Las capturas han mermado ligeramente de 13,500 toneladas en 1964 a unas 11,000 toneladas en 1966. La fuerte pesca por peces vela empezó en 1964 con una tasa por anzuelo de 10.6 peces por 100 anzuelos; en 1966 había mermado a 5.8. Las capturas de esta especie en el área de mayor concentración disminuyeron de 329,000 peces en 1965, a 173,600 peces en 1966. Esta pesquería ha maniobrado por un período demasiado corto de tiempo para que pueda determinarse su efecto en el rendimiento sostenible. Las mediciones frecuencia-longitud, y las muestras de las gónadas de los atunes aleta amarilla y ojo grande, obtenidas en el Pacífico oriental, fueron analizadas para determinar la madurez sexual y las características del crecimiento. Los resultados corroboraron los hallazgos anteriores de investigadores. (PDF contains 144 pages.)

The El Nino of 1972-1973 in the Eastern Tropical Pacific Ocean

ENGLISH: Beginning in February 1972 the usual seasonal cooling of the surface water of the eastern Pacific Ocean in the region of the Peru Current and along the equator failed to develop. By July tropical coastal and equatorial island stations and ships crossing the equator were recording sea-surface temperatures which were 6° to 8°F (3.3°-4.4°C) above the long-term mean. The anomalies spread over most of the eastern tropical Pacific and westward into the central equatorial Pacific through September. During October surface temperatures at coastal stations along South America were returning to normal, but in November and December 1972 temperatures rose rapidly again, with a near-record temperature anomaly of 8.1°F (4.2°C) above the long-term mean recorded at Puerto Chieama, Peru (7°42'S-79°27'W). After January 1973 sea-surface temperatures began returning to normal over most of the eastern tropical Pacific, and by March 1973 the El Nino had completed its cycle. Monthly sea-surface temperature anomalies over the eastern tropical Pacific are discussed to show the extent and magnitude of warming. Annual temperature profiles at several South American coastal and equatorial island stations are compared with temperature profiles for the 1957-1958 and 1965 EI Nino years. Characteristics of the temperature anomaly profiles at Puerto Chicama during several very warm years for the 1925-1972 period are also compared. Finally, meteorological factors contributing to a relaxation of the southeast trade winds and to the decreased unwilling along the coast of South America in 1972-1973 are examined. SPANISH: A comienzos de febrero de 1972, no se registró el enfriamiento común estacional del agua superficial del Océano Pacífico oriental en la región de la Corriente del Perú y a lo largo del ecuador. En julio las estaciones tropicales, costeras y de las islas ecuatoriales, y los barcos que cruzaban la linea ecuatorial registraron temperaturas superficiales del mar de 6° a 8°F (3.3°-4.4°C) más altas que la media a largo plazo. Las anomalías se esparcieron sobre la mayoría del Pacífico oriental tropical, y al oeste en el Pacífico central ecuatorial. En octubre, las temperaturas superficiales de las estaciones costaneras a lo largo de Sudamérica volvieron a la normalidad, pero en noviembre y diciembre de 1972, las temperaturas de nuevo ascendieron rápidamente con una anomalía de temperatura que alcanzó 8.1°F (4.2°C) sobre la media a largo plazo registrada en Puerto Chicama, Perú (7°42'S-79°27'W). Después de enero 1973 las temperaturas de la superficie del mar volvieron rápidamente a la normalidad en la mayoría del Pacífico oriental tropical y en marzo de 1973 el Niño había completado su ciclo. Se discuten las anomalías mensuales de las temperaturas de la superficie del mar en el Pacífico oriental tropical para indicar la extensión y magnitud del calentamiento. Los perfiles anuales de temperatura en varias estaciones costeras y de las islas ecuatoriales sudamericanas se comparan con los perfiles de temperatura de los años en que ocurrió el Niño en 1957-1958 y 1965. Se comparan también las características de los perfiles de las anomalías de temperatura en Puerto Chicama durante varios años muy cálidos para el período de 1925-1972. Finalmente, se examinan los factores meteorológicos que contribuyen al debilitamiento de los vientos alisios del sudeste y a la reducción del afloramiento a lo largo de la costa sudamericana en 1972-1973. (PDF contains 48 pages.)

Investment prospects in marine capture fisheries

An examination is made of investment prospects in the Nigerian marine fisheries, considering the following sectors: inshore demersal fishery; inshore pelagic fishery; and the offshore pelagic fishery. The marine fisheries resources of countries with which Nigeria has bilateral fishing rights agreements are discussed, considering Equatorial Guinea, Guinea Conakry, Guinea Bissau, Senegal and Mauritania. Fishing gear and methods for the marine fishery sectors are outlined. Market potentials for fish products and profitability are also examined

The influence of some environmental variables on the apparent abundance of skipjack tuna, Katsuwonus pelamis, in the Eastern Pacific Ocean

ENGLISH: The abundance of skipjack larvae in the central and western Pacific approximately doubled for every 1°C increase in sea-surface temperature (SST) from 23°C to a maximum of about 29°C, and then usually decreased with further increases in SST. Skipjack larvae are scarce in the eastern Pacific Ocean (EPO), so most skipjack recruits and adults in this area are believed to have originated in the central and, possibly, the western Pacific. The catch per unit of effort (CPUE), in short tons per day's fishing, and the catch rate, in number of fish per day's fishing, are estimates of apparent abundance in a fishery. The logarithm of the annual CPUE for skipjack for international baitboats in the EPO for the 1934-1960 period was positively correlated with SST in the spawning area in the central Pacific 18 months earlier (r2 0.31), during the July-June period when most of the recruits in each cohort were presumed to have been spawned. Adequate data for other environmental variables were not available for testing with the baitboat data. The other environmental variables available and selected for testing for correlation with estimates of skipjack abundance for purse seiners for the 1961-1984 period and the reasons for their selection are as follows. 1)Wind-mixing index (WMI). The degree of mixing in the upper layers of the ocean is proportional to the cube of the wind speed, called WMI. The degree of mixing in the spawning areas of the central and the western Pacific may affect the concentration of organisms that skipjack larvae feed upon, thereby influencing their survival, and ultimately determining cohort strength and the number of recruits to the eastern Pacific fishery. 2) SST in the fishing areas at the time of fishing (SST). The CPUE for yellowfin tuna has been shown to be inversely related to SST in the fishing areas, and there are indications that skipjack CPUE is lower during EI Nino events when SST is higher than normal. 3) North-south SST gradient across the thermal front off the Gulf of Guayaquil. This is a measure of the degree of upwelling and nutrient enrichment of the upper waters south of the front and ultimately of the production of food for tunas. 4) Speed of the North Equatorial Countercurrent (NECC). Young skipjack may migrate from the central Pacific to the EPO in the eastward flowing NECC; if so, the number of recruits might be affected by variations in the speed of the current. The logarithm of the annual catch rate of skipjack recruits by international purse seiners in the EPO for the 1961-1984 period was positively correlated with SST in the spawning area of the central Pacific 18 months earlier (r2 = 0.21),and inversely correlated with WMI in the spawning area 18 months earlier (r2 0.46). The logarithm of CPUE for purse seiners in the area off the Gulf of Guayaquil was not correlated with SST in the spawning area 18 months earlier, but was inversely correlated with WMI in the spawning area 18 months earlier (r2 = 0.19), and inversely correlated with the north-south SST gradient in the fishing area at the time of fishing (r2 0.32). Neither of these estimates of apparent abundance from purse seiners were correlated with SST in the fishing areas, or with the speed of the NECC at earlier times. SPANISH: La abundancia de larvas de barrilete en el Pacífico central y occidental se multiplicó por dos, aproximadamente, por cada aumento de 1°Cen la temperatura de la superficie del mar (TSM) entre 23°C y un máximo de unos 29°C, y luego generalmente disminuyó con más aumentos en la TSM. Las larvas de barrilete son escasas en el Océano Pacífico oriental (OPO), y por lo tanto se cree que la mayoría de los reclutas y adultos en esta zona surgieron del Pacífico central, y posiblemente también del Pacífico occidental. La captura por unidad de esfuerzo (CPUE), en toneladas cortas por día de pesca, y la tasa de captura, en número de peces por día de pesca, son estimaciones de la abundancia aparente en una pesquería. El logaritmo de la CPUE anual de barrilete lograda por barcos de carnada en el OPO en el período 1934-1960 se correlacionó positivamente con la TSM en la zona de desove en el Pacífico central de 18 meses antes (r2 = 0.31), durante el período de junio-julio en el cual se cree que nació la mayoría de los reclutas en cada cohorte. No se dispuso de datos suficientes sobre otras variables ambientales para comprobarlos con los datos de los barcos de carnada. Las demás variables ambientales disponibles y seleccionadas para someterlas a pruebas de correlación con las estimaciones de la abundancia del barrilete de barcos cerqueros en el período 1961-1984, y las razones por su selección, son las siguientes: 1) Indice de mezcla por el viento (IMV). El grado de mezcla en las capas superiores del océano es proporcional al cubo de la velocidad del viento, llamado IMV. Es posible que el grado de mezcla en las zonas de desove del Pacífico central y occidental afecte la concentración de los organismos que alimentan a las larvas del barrilete, afectando así la supervivencia de éstas, y finalmente determinando el tamaño de las cohortes y el número de reclutas a la pesquería del OPO. 2) TSM en la zona de pesca al realizarse la pesca (TSM). Se ha mostrado que la relación de la CPUE del atún aleta amarilla a la TSM en la zona de pesca es inversa, y existen indicaciones que la CPUE de barrilete es inferior durante eventos del Niño, cuando las TSM son superiores a lo normal. 3) Gradiente norte-sur de las TSM a través del frente térmico frente al Golfo de Guayaquil. Esto es una medida del grado de afloramiento y enriquecimiento nutritivo del nivel superior de las aguas al sur de dicho frente, y finalmente de la producción de alimento para los atunes. 4) La velocidad de la Contracorriente Ecuatorial del Norte (CCEN). Es posible que los bariletes juveniles migren del Pacífico central al Pacífico oriental en la CCEN, que fluye hacia el este; de ser así, es posible que la cantidad de reclutas se vea afectada por variaciones en la velocidad de la corriente. El logaritmo de la tasa anual de captura de reclutas de barrilete por cerqueros de varias banderas en el OPO en el período 1961-1964 estuvo correlacionado de forma positiva con las TSM en la zona de desove del Pacífico central de 18meses antes (r2 0.21),y de forma inversa con el IMV de la zona de desove de 18 meses antes (r2 0.46). El logaritmo de la CPUE de los cerqueros en la zona frente al Golfo de Guayaquil no estuvo correlacionado con las TSM en la zona de desove de 18 meses antes, pero sí estuvo correlacionado de forma inversa con el IMV en la zona de desove de 18 meses antes (r2 0.19),y con el gradiente norte-sur de las TSM en la zona de pesca al realizarse la pesca (r2 0.32). Ninguna de estas estimaciones de abundancia aparente provenientes de barcos cerqueros estuvo correlacionada con las TSM en las zonas de pesca o con la velocidad de la CCEN en épocas anteriores. (PDF contains 140 pages.)

Synthetic, structural and mechanistic studies of interactions of carbon, nitrogen, and oxygen nucleophiles with bis-pentamethylcyclopentadienyl zirconium and hafnium derivatives

The reactivity of permethylzirconocene and permethylhafnocene complexes with various nucleophiles has been investigated. Permethylzirconocene reacts with sterically hindered ketenes and allenes to afford metallacycle products. Reaction of these cummulenes with permethylzirconocene hydride complexes affords enolate and σ-allyl species, respectively. Reactions which afford enolate products are nonstereospecific, whereas reactions which afford allyl products initially give a cis-σ-allyl complex which rearranges to its trans isomer. The mechanism of these reactions is proposed to occur either by a Lewis Acid-Lewis Base interaction (ketenes) or by formation of a π-olefin intermediate (allenes).

Permethylzirconocene haloacyl complexes react with strong bases such as lithium diisopropylamide or methylene trimethylphosphorane to afford ketene compounds. Depending on the size of the alkyl ketene substituent, the hydrogenation of these compounds affords enolate-hydride products with varying degrees of stereoselectivity. The larger the substituent, the greater is the selectivity for cis hydrogenation products.

The reaction of permethylzirconocene dihydride and permethylhafnocene dihydride with methylene trimethylphosphorane affords methyl-hydride and dimethyl derivatives. Under appropriate conditions, the metallated-ylide complex 1, (η^5-C_5(CH_3)_5)_2 Zr(H)CH_2PMe_2CH_2, is also obtained and has been structurally characterized by X-ray diffraction techniques. Reaction of 1 with CO affords (η^5-C_5(CH_3)_5)_2 Zr(C,O-η^2 -(PMe_3)HC=CO)H which exists in solution as an equilibrium mixture of isomers. In one isomer (2), the η^2-acyl oxygen atom occupies a lateral equatorial coordination position about zirconium, whereas in the other isomer (3), the η-acyl oxygen atom occupies the central equatorial position. The equilibrium kinetics of the 2→3 isomerization have been studied and the structures of both complexes confirmed by X-ray diffraction methods. These studies suggest a mechanism for CO insertion into metal-carbon bonds of the early transition metals.

Permethylhafnocene dihydride and permethylzirconocene hydride complexes react with diazoalkanes to afford η^2-N, N' -hydrazonido species in which the terminal nitrogen atom of the diazoalkane molecule has inserted into a metal-hydride or metal-carbon bond. The structure of one of these compounds, Cp*_2Zr(NMeNCTol_2)OH, has been determined by X-ray diffraction techniques. Under appropriate conditions, the hydrazonido-hydride complexes react with a second equivalent of diazoalkene to afford η' -N-hydrazonido-η^2-N, N' -hydrazonido species.

Capturing protein dynamics with time-resolved luminescence spectroscopy

The presented doctoral research utilizes time-resolved spectroscopy to characterize protein dynamics and folding mechanisms. We resolve millisecond-timescale folding by coupling time-resolved fluorescence energy transfer (trFRET) to a continuous flow microfluidic mixer to obtain intramolecular distance distributions throughout the folding process. We have elucidated the folding mechanisms of two cytochromes---one that exhibits two-state folding (cytochrome cb₅₆₂) and one that has both a kinetic refolding intermediate ensemble and a distinct equilibrium unfolding intermediate (cytochrome c₅₅₂). Our data reveal that the distinct structural features of cytochrome c₅₅₂ contribute to its thermostability.

We have also investigated intrachain contact dynamics in unfolded cytochrome cb₅₆₂ by monitoring electron transfer, which occurs as the heme collides with a ruthenium photosensitizer, covalently bound to residues along the polypeptide. Intrachain diffusion for chemically denatured proteins proceeds on the microsecond timescale with an upper limit of 0.1 microseconds. The power-law dependence (slope = -1.5) of the rate constants on the number of peptide bonds between the heme and Ru complex indicate that cytochrome cb₅₆₂ is minimally frustrated.

In addition, we have explored the pathway dependence of electron tunneling rates between metal sites in proteins. Our research group has converted cytochrome b₅₆₂ to a c-type cytochrome with the porphyrin covalently bound to cysteine sidechains. We have investigated the effects of the changes to the protein structure (i.e., increased rigidity and potential new equatorial tunneling pathways) on the electron transfer rates, measured by transient absorption, in a series of ruthenium photosensitizer-modified proteins.

Constraints on the carbon cycle and climate during the early evolution of animals

One of the greatest challenges in science lies in disentangling causality in complex, coupled systems. This is illustrated no better than in the dynamic interplay between the Earth and life. The early evolution and diversification of animals occurred within a backdrop of global change, yet reconstructing the potential role of the environment in this evolutionary transition is challenging. In the 200 million years from the end-Cryogenian to the Ordovician, enigmatic Ediacaran fauna explored body plans, animals diversified and began to biomineralize, forever changing the ocean's chemical cycles, and the biological community in shallow marine ecosystems transitioned from a microbial one to an animal one.

In the following dissertation, a multi-faceted approach combining macro- and micro-scale analyses is presented that draws on the sedimentology, geochemistry and paleontology of the rocks that span this transition to better constrain the potential environmental changes during this interval.

In Chapter 1, the potential of clumped isotope thermometry in deep time is explored by assessing the importance of burial and diagenesis on the thermometer. Eocene- to Precambrian-aged carbonates from the Sultanate of Oman were analyzed from current burial depths of 350-5850 meters. Two end-member styles of diagenesis independent of burial depth were observed.

Chapters 2, 3 and 4 explore the fallibility of the Ediacaran carbon isotope record and aspects of the sedimentology and geochemistry of the rocks preserving the largest negative carbon isotope excursion on record---the Shuram Excursion. Chapter 2 documents the importance of temperature, fluid composition and mineralogy on the delta 18-O min record and interrogates the bulk trace metal signal. Chapter 3 explores the spatial variability in delta 13-C recorded in the transgressive Johnnie Oolite and finds a north-to-south trend recording the onset of the excursion. Chapter 4 investigates the nature of seafloor precipitation during this excursion and more broadly. We document the potential importance of microbial respiratory reactions on the carbonate chemistry of the sediment-water interface through time.

Chapter 5 investigates the latest Precambrian sedimentary record in carbonates from the Sultanate of Oman, including how delta 13-C and delta 34-S CAS vary across depositional and depth gradients. A new model for the correlation of the Buah and Ara formations across Oman is presented. Isotopic results indicate delta 13-C varies with relative eustatic change and delta 34-S CAS may vary in absolute magnitude across Oman.

Chapter 6 investigates the secular rise in delta 18-Omin in the early Paleozoic by using clumped isotope geochemistry on calcitic and phosphatic fossils from the Cambrian and Ordovician. Results do not indicate extreme delta 18-O seawater depletion and instead suggest warmer equatorial temperatures across the early Paleozoic.