ALBERT

Description: Volcanic and geothermal areas are one of the major natural sources of H2S to the atmosphere. Its environmental impact is often the main cause of the opposition to the development of geothermal energy exploitation programs. In this paper we analyze the air concentrations and dispersion pattern of naturally emitted H2S at the geothermal area of Sousaki (Corinthia, Greece). Measurements, made with a network of passive samplers, evidence a rapid decrease of concentration values away from the emission points. The fact that the decrease is more pronounced in the summer with respect to the winter indicates that it is not only due to a dilution effect, but also to redox reactions favoured by higher temperatures and intense sunlight typical of the summer period.

Description: Published

Description: 1723-1728

Description: 1.2. TTC - Sorveglianza geochimica delle aree vulcaniche attive

Description: JCR Journal

Description: reserved

Description: Large variations of the CO2 flux through the soil were observed between November 2002 and January 2006 at Mt. Etna volcano. In many cases, the CO2 flux was strongly influenced by changes in air temperature and atmospheric pressure. A new filtering method was then developed to remove the atmospheric influences on soil CO2 flux and, at the same time, to highlight the variations strictly related to volcanic activity. Successively, the CO2 corrected data were quantitatively compared with the spectral amplitude of the volcanic tremor by cross correlation function, cross-wavelet spectrum and wavelet coherence. These analyses suggested that the soil CO2 flux variations preceded those of volcanic tremor by about 50 days. Given that volcanic tremor is linked to the shallow (a few kilometer) magma dynamics and soil CO2 flux related to the deeper (*12 km b.s.l.) magma dynamics, the “delayed similarity” between the CO2 flux and the volcanic tremor amplitude was used to assess the average speed in the magma uprising into the crust, as about 170–260 m per day. Finally, the large amount of CO2 released before the onset of the 2004–2005 eruption indicated a deep ingression of new magma, which might have triggered such an eruption.

Description: In press

Description: N/A or not JCR

Description: reserved

Description: Six hundred and sixty-seven water samples were collected from public drinking water supplies in Sicily and analysed for electric conductivity and for their Cl-, Br- and F- contents. The samples were, as far as possible, collected evenly over the entire territory with an average sampling density of about one sample for every 7600 inhabitants. The contents of Cl- and Br-, ranging between 5.53 and 1302 mg/l and between 〈 0.025 and 4.76 mg/l respectively, correlated well with the electric conductivity, a parameter used as a proxy for water salinity. The highest values were found both along the NW and SE coasts, which we attributed to seawater contamination, and in the central part of Sicily, which we attributed to evaporitic rock dissolution. The fluoride concentrations ranged from 0.023 to 3.28 mg/l, while the highest values (only 3 exceeding the maximum admissible concentration of 1.5 mg/l) generally correlated either with the presence in the area of crystalline (volcanic or metamorphic) or evaporitic rocks or with contamination from hydrothermal activity. Apart from these limited cases of exceeding F- levels, the waters of public drinking water supplies in Sicily can be considered safe for human consumption for the analysed parameters. Some limited concern could arise from the intake of bromide-rich waters (about 3% exceeding 1 mg/l) because of the potential formation of dangerous disinfection by-products.

Description: Published

Description: 303-313

Description: 4.4. Scenari e mitigazione del rischio ambientale

Description: JCR Journal

Description: reserved

Description: This study presents baseline data for future geochemical monitoring of the active Tacaná volcano–hydrothermal system (Mexico–Guatemala). Seven groups of thermal springs, related to a NW/SE-oriented fault scarp cutting the summit area (4,100m a.s.l.), discharge at the northwest foot of the volcano (1,500–2,000m a.s.l.); another one on the southern ends of Tacaná (La Calera). The near-neutral (pH from 5.8 to 6.9) thermal (T from 25.7°C to 63.0°C) HCO3–SO4 waters are thought to have formed by the absorption of a H2S/SO2–CO2-enriched steam into a Cl-rich geothermal aquifer, afterwards mixed by Na/HCO3-enriched meteoric waters originating from the higher elevations of the volcano as stated by the isotopic composition (δD and δ18O) of meteoric and spring waters. Boiling temperature fumaroles (89°C at~3,600m a.s.l. NW of the summit), formed after the May 1986 phreatic explosion, emit isotopically light vapour (δD and δ18O as low as −128 and −19.9‰, respectively) resulting from steam separation from the summit aquifer. Fumarolic as well as bubbling gases at five springs are CO2-dominated. The δ13CCO2 for all gases show typical magmatic values of −3.6 ± 1.3‰ vs V-PDB. The large range in 3He/4He ratios for bubbling, dissolved and fumarolic gases [from 1.3 to 6.9 atmospheric 3He/4He ratio (RA)] is ascribed to a different degree of near-surface boiling processes inside a heterogeneous aquifer at the contact between the volcanic edifice and the crystalline basement (4He source). Tacaná volcano offers a unique opportunity to give insight into shallow hydrothermal and deep magmatic processes affecting the CO2/3He ratio of gases: bubbling springs with lower gas/water ratios show higher 3He/4He ratios and consequently lower CO2/3He ratios (e.g. Zarco spring). Typical Central American CO2/3He and 3He/4He ratios are found for the fumarolic Agua Caliente and Zarco gases (3.1 ± 1.6 × 1010 and 6.0 ± 0.9 RA, respectively). The L/S (5.9 ± 0.5)and (L + S)/M ratios (9.2 ± 0.7) for the same gases are almost identical to the ones calculated for gases in El Salvador, suggesting an enhanced slab contribution as far as the northern extreme of the Central American Volcanic Arc,Tacana

Description: In press

Description: 1.2. TTC - Sorveglianza geochimica delle aree vulcaniche attive

Description: 2.4. TTC - Laboratori di geochimica dei fluidi

Description: JCR Journal

Description: reserved

Description: Fluorine is one of the many environmental harmful elements released by volcanic activity. The content of total, oxalate extractable and water extractable fluorine was determined in 96 topsoils of three active volcanic systems of southern Italy (Mt. Etna, Stromboli and Vulcano). Total fluorine content (FTOT) ranges from 112 to 7430 mg kg-1, F extracted with oxalate (FOX) ranges from 16 to 2320 mg kg-1 (2 – 93 % of FTOT) and F extracted with distilled water (FH2O) ranges from 1.7 to 159 mg kg-1 (0.2 – 40 % of FTOT). Fluorine in the sampled topsoils derives both from the weathering of volcanic rocks and ashes and from enhanced deposition due to volcanic gas emissions either from open-conduit passive degassing (Mt. Etna and Stromboli) or from a fumarolic field (Vulcano). Fluorine accumulation in the studied soils does generally not present particular environmental issues except for a few anomalous sites at Vulcano where measured contents could be dangerous both for vegetation and for grazing animals.

Description: Published

Description: 413-423

Description: 4.5. Degassamento naturale

Description: JCR Journal

Description: reserved

Description: Submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy at the Massachusetts institute of Technology and the Woods Hole Oceanographic Institution February 1976

Description: Analytical methods have been developed for the determination of iodate, iodide and particulate iodine in sea water. Iodate is converted to tri-iodide and the absorbance of tri-iodide at 353 nm is measured. The precision of this method is ca. ±3%. Iodide is first separated from most other anions by an AG 1-x8 anion exchange column and then precipitated as palladous iodide with elemental palladium as the carrier. The precipitate is analyzed by neutron activation analysis. The precision of the method is ±5% and the reagent blank is 0.005 uM. Marine suspended matter is collected by passing sea water under pressure through a 0.6 u (37 mm diameter) Nuclepore filter. The iodine content of the particles is determined by neutron activation analysis. The method has excellent reproducibility and the filter blank is ca. 3 ng. Iodate is depleted in the surface waters of the Equatorial Atlantic. The depletion is more pronounced than in the Argentine Basin and possibly reflects the higher productivity in the equatorial area. Superimposed on this feature, a thin lens of water, of a few tens of meters thick and with high iodate concentrations, can be traced across the Atlantic. Along the equator, this lens occurs at 80 m at 33˚W and rises upwards to 55 m at 10˚W and it coincides with a core of highly saline water which is characteristic of the Equatorial Undercurrent. Longitudinal sections reflect the complexity of the equatorial current system. At least three cores of water with high iodate concentrations may be identified. These waters may be transported to the equatorial region from the highly productive areas along the north-western and western African coasts and the Amazon plume. In anoxic basins, the concentration of iodide increases rapidly in the mixing zone from 0.02 uM to 0.44 uM in the Cariaco Trench and from 0.01 uM to 0.23 uM in the Black Sea. The iodate concentration, meanwhile. decreases to zero. A maximum in the total iodine to salinity ratio is observed just above the oxygen-sulfide interface (15 to 17 nmoles/g); it is suggestive of particle dissolution in a strong pycnocline. Below the interface, the total iodine to salinity ratio is constant at 12.3 nmoles/g in the anoxic zone of the Cariaco Trench, whereas, in the Black Sea, it increases with depth from 10.0 to 19.4 nmoles/g and suggests a possible flux of iodide from the sediments. By considering the distribution of iodate and iodide in oxic and anoxic basins and our present analytical capability, the lower limit of the pE of the oceans is estimated to be 10.7. Thermodynamic considerations further suggest that the iodide-iodate couple is a poor indica tor for the pE of the oceans with a limited usable range of 10.0 to 10.7. In the Gulf of Maine during the winter of 1974 to 1975. the effect of winter mixing was conspicuous. Uniform concentrations of iodide and iodate were observed in the mixed layer above the sill. The absence of a depletion of iodate and the low iodide concentration (0.04 uM) in the surface waters reflect the low biological activity in this region during winters. Profiles of particulate iodine are characterized by high concentrations in the euphotic zone (〉5 ng/kg), and lower concentrations (〈 2 ng/kg) at greater depths. Occasionally, high concentrations have also been observed in the nepheloid layer. The iodine-containing particles are probably biogenic. A section in the Western Atlantic from 75°N to 55˚S shows evidence of the transport of particles along isopycnals and the re-suspension of surface sediments to considerable distance from the bottom. The standing crops in the top 200 m may be qualitatively correlated with the primary productivity. Thermodynamic considerations show that iodide is a metastable form at the pH of sea water. Laboratory studies fail to show the oxidation of iodide at measurable rates. Elemental iodine is unstable in sea water and undergoes hydrolysis to form hypoiodous acid in seconds. Hypoiodous acid is also unstable and has a life time of minutes to hours. It may react with organic compounds to form iodinated derivatives or it may be reduced to iodide by a reducing agent. The disproportionation of hypoiodite to form iodate seems to be a slower process. A possible chemical cycle for iodine in the marine environment is proposed.

Description: This work was supported at various phases by NSF Grant GA-13574, NSF-IDOE Grant GX 33295, NSF Grant DES 74- 22292 and by a research fellowship from the Woods Hole Oceanographic Institution.

Description: Submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy at the Massachusetts Institute of Technology and the Woods Hole Oceanographic Institution November 1980

Description: Plankton samples have been carefully collected from a variety of marine environments under the rigorous conditions necessary to prevent contamination for major and trace-chemical analysis. Immediately after collection, the samples were subjected to a series of physical and chemical leaching-decomposition experiments designed to identify the major and trace element composition of particulate carrier phases. Elements examined through some or all of these experiments were: C, N, P, Mg, Ca, Si, Fe, Mn, Ni, Cu, Cd, Al, Ba, and Zn. Emphasis was placed on the identification of trace element/major element ratios in the biogenic materials. The majority of the trace elements in the samples were directly associated with the non-skeletal organic phases of the plankton. These associations included a very labile fraction which was rapidly released into seawater and a more refractory fraction which involved specific metal-organic binding. Calcium carbonate and opal were not significant carriers for any of the trace elements studied. A refractory phase containing Al and Fe in terrigenous ratios was present in all samples, even from the more remote marine locations. The concentration of this carrier phase within the plankton samples varied in proportion to the estimated rate of supply of terrigenous matter and in opposition to the rate of production of the biogenic particulate matter. The aluminosilicates contributed insignificant amounts to the other trace elements studied. A trace concentration of particulate Al was identified which was more labile and associated with the organic fractions of the samples. Variations in the surface water concentrations of dissolved Cu, Ni, Cd, and Zn with respect to P are compared to the ratios measured in the plankton samples and their regeneration products. The trace element/major element ratios ,in the residual plankton materials can be combined with estimates of the carrier fluxes to account for the transport of trace elements required to maintain their deep enrichment. A variety of processes determining the geochemical cycles of specific trace elements were identified. As much as 50% of the Cd, Ni, Mn, and P are rapidly released from plankton and recycled within the surface ocean. During this process, the metal/P ratio in the residual particles must decrease by 10-30% for Cd and increase by a factor of 2-4 for Ni and Cu to balance their deep enrichments. Although Mn is taken up and regenerated by plankton, the magnitude of this process is small with respect to other non-biogenic Mn fluxes and has very little influence on its dissolved distribution. The Ba content of all known surface carriers is insufficient to account for the deep enrichment of Ba. A secondary concentration process results in the formation of significant particulate Ba within the upper thermocline.

Description: Portions of the data in this research have been collected under the NSF grant DES 75-03826 and ONR grant N00014-80-C-0273. I have been supported for the last three years on an NSF National Needs Graduate Traineeship to the MIT-WHOI Joint Program. Ship time was generously provided by various principal investigators of the NSF Galapagos Hydrothermal research program and the NSF-IDOE MANOP program.

Description: Submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy at the Massachusetts Institute of Philosophy and the Woods Hole Oceanographic Institution November 1980

Description: Suspended particulate matter was collected by sediment traps deployed in the Sargasso Sea (Site S2), the north equatorial Atlantic (Site E), the north equatorial Pacific (Site P), and the Panama Basin (STIE Site). Additional samples of suspended particles were obtained by in situ filtration at Site F., at the STIE Site, and in the Guatemala Basin. Concentrations of dissolved Th and Pa were determined by extraction onto manganese dioxide adsorbers at Site P, at a second site in the Sargasso Sea (Site D), at the STIE Site and in the Guatemala Basin. Sediment samples were obtained from cores taken near Sites E and P. Results have shown unequivocally that suspended particulate matter in the open ocean preferentially scavenges Th relative to Pa. This behavior could not have been predicted from the known physical chemistry of Th and Pa. Dissolved 230Th/231Pa activity ratios were 3-5 at Sites P and D and 3-8 at the STIE Site. In contrast, unsupported 230Th/231Pa ratios were 22-35 (average 29.7 for 7 samples) in sediment-trap samples from greater than 2000 m at Sites S2, E and P. Ratios were lower in particulate matter sampled at shallower depths. Particles filtered at 3600 m and 5000 m at Site E had ratios of 50 and 40. In contrast to the open ocean samples described above, samples collected by six sediment traps at depths of 667-3791 m in the Panama Basin had unsupported 230Th/231Pa ratios of 4-8, and the deepest samples had the lowest ratios. Fractionation of Th and Pa that was observed at the three open ocean sites either does not occur or occurs to a very limited extent in the Panama Basin. Particulate 230Th/231Pa ratios were negatively correlated with the concentration of suspended particles. However, variable scavenging rates, as indicated by variable particle concentration, do not completely control the ratio at which Th and Pa are scavenged from solution. Major biogenic and inorganic components of trapped material were found in approximately the same proportions in the STIE samples and in samples from Sites E and S2. Lower 230Th/231Pa ratios found in the STIE samples must therefore result from subtle changes in the chemical properties of the particles. Consideration of 230Th/23lPa ratios in several depositional environments indicates that no single factor controls the ratio at which Th and Pa are adsorbed from seawater. Fluxes of 210Th and 231Pa were less than their rates of production in the overlying water column in every trap at Sites S2, E, and P. In the Panama Basin, fluxes measured with the same traps were greater than or equal to their rates of production. These results are a strong indication that even extremely reactive elements such as Th and Pa are redistributed within the oceans. Redistribution occurs because variable scavenging rates in different environments set up horizontal concentration gradients. Horizontal mixing processes produce a net horizontal transport of Th and Pa from areas of 1ow scavenging rates to areas of high scavenging rates. Protactinium is redistributed to a greater extent than Th. Fluxes of 230Th can be used to set lower limits for horizonttal transport of Pa even when absolute trapping efficiencies of the sediment traps are not known. Less than 50% of the Pa produced at the open ocean sites is removed from the water column by scavenging to settling particles. The remainder is removed by horizontal transport to other environments. At Sites E and P, 230Th/231Pa ratios were identical in the deepest sediment trap sample and in surface sediments. However, 230Th/232Th and 231Pa/232Th ratios were 2.5 times higher in trapped particles than in surface sediments. The 230Th/232Th ratios were 5.5 times higher in particles filtered at 3600 m and 5000 m at Site E than in surface sediments. This observation is best explained by dissolution of most of the 230Th and 231Pa scavenged by settling particles during remineralization of labile biogenic phases. The behaviors of certain other radioisotopes were also studied. 232Th is present only in detrital mineral components of trapped material. Concentrations of 232Th in trapped particles correlate closely with Al and K, at ratios approaching that of average shale or crustal abundances at Site E and P and basalts at the STIE Site. High specifìc activities of 228Th and 239+240Pu were found in sediment trap samples throughout the water column at Sites E and P and in the Panama Basin. The dominant source of these isotopes is near the sea surface and also near the sea floor in the case of 228Th. Thus it appears that the bulk of the trapped material is recently derived from the sea surface where it incorporates these isotopes,with little loss during rapid transit through the water column. A bioauthigenic form of particulate uranium is produced at the sea surface and remineralized in the deep ocean along with its labile carrier phase(s). This flux of uranium to the deep ocean is 0.25-1.0 dpm/cm2103 years, which is insufficient to cause a measurable concentration gradient in the uranium distribution within the mixing time of the oceans. Increased concentrations and fluxes of particulate uranium were not found in the eastern equatorial North Pacific under areas of an intense oxygen minimum. Therefore, reduction of uranium to the tetravalent state with subsequent scavenging to settling particles in oxygen minima is not a mechanism removing uranium from the oceans.

Description: Financial support for parts of this work have come from many sources, including: National Science Foundation Grants OCE-7826318, OCE-7825724, and OCE-7727004; Department of Energy Contract EY-76-S-02-3566; a Cottrell Research Grant from the Research Corporation; the WHOI Ocean Industries Program; a fellowship from the WHOI Education Office, and the Paul Fye Fellowship

Description: Submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy at the Massachusetts Institute of Technology and the Woods Hole Oceanographic Institution February 2003

Description: The presence of aqueous organic compounds derived from sedimentary organic matter has the potential to influence a range of chemical processes in hydrothermal vent environments. For example, hydrothermal alteration experiments indicate that alteration of organic-rich sediments leads to up to an order of magnitude more metals in solution than alteration of organic-poor basalt. This result is in contrast to traditional models for the evolution of vent fluids at sediment-covered mid-ocean ridge axis environments, and indicates the fundamental importance of including the effects of organic compounds in models of crustal alteration processes. However, in order to rigorously constrain their role in crustal alteration processes, quantitative information on the abundances and distributions of organic compounds in hydrothermal vent fluids is required. This thesis was undertaken to provide quantitative information on the distributions and stable carbon isotopic compositions of several low-molecular weight organic compounds (C1-C4 alkanes, C2-C3 alkenes, benzene and toluene) in fluids collected in July, 2000, at three sites on the northern Juan de Fuca Ridge: the Dead Dog and ODP Mound fields, which are located at Middle Valley, and the Main Endeavour Field, located on the Endeavour segment. At Middle Valley, the ridge axis is covered by up to 1.5 km of hemipelagic sediment containing up to 0.5 wt.% organic carbon. The Main Endeavour Field (MEF) is located approximately 70 km south of Middle Valley in a sediment-free ridge-crest environment, but previously measured high concentrations of NH3 and isotopically light CH4 relative to other bare-rock sites suggest that the chemical composition of these fluids is affected by sub-seafloor alteration of sedimentary material (LILLEY et al., 1993). Differences in the absolute and relative concentrations of NH3 and organic compounds and the stable carbon isotopic compositions of the C1-C3 organic compounds suggest that the three fields represent a continuum in terms of the extent of secondary alteration of the aqueous organic compounds, with the Dead Dog fluids the least altered, the MEF fluids the most altered and ODP Mound fluids in an intermediate state. At the two Middle Valley sites, the greater extent of alteration in the ODP Mound fluids as compared to the Dead Dog fluids is due either to higher temperatures in the subsurface reaction zone, or a greater residence time of the fluids at high temperatures. Higher reaction zone temperatures at the ODP Mound field than at the Dead Dog field are consistent with differences in endmember C1 concentrations between the two fields. The greater extent of alteration in the MEF fluids is caused by relatively oxidizing conditions in the subsurface reaction zone that promote faster reaction kinetics. Temperatures in the subsurface reaction zones calculated by assuming equilibrium among aqueous alkanes, alkenes and hydrogen are consistent with other inorganic indicators (C1 and Si concentrations) of temperature, indicating that metastable equilibrium among these compounds may be attained in natural systems. Isotopic equilibration among CH4 and CO2 appears to have been attained in ODP Mound fluids due to the high temperatures in the subsurface reaction zone and the approach to chemical equilibrium from excess methane. However, isotopic equilibrium between CH4 and CO2 was not attained in the MEF fluids, due to a short residence time of the fluids in the crust following late-stage addition of magmatic-derived CO2 to the fluids. Time series analysis indicate that Middle Valley fluid compositions are generally characterized by stable concentrations over the last decade. However, decreases in Br concentrations in Dead Dog fluids from 1990 to 2000 suggest that either a greater proportion of the fluids interact with basalt rather than sediments or that the sediment with which hydrothermal fluids interact is becoming exhausted. In contrast, the concentrations of H2 and H2S and the δ34S of H2S are quite different in fluids sampled from vents of differing ages at the ODP Mound field, despite their close spatial proximity. The observed variations are caused by the reaction of hydrogen-rich fluids within the ODP Mound massive sulfide to reduce pyrite to pyrrhotite during upflow. The replacement of pyrite by pyrrhotite is opposite to the reaction predicted during the weathering of sulfide minerals weather on the seafloor and reflects the real-time equilibration of the reduced fluids with mound mineralogy due to the very young age (〈2 years) venting from Spire vent. The presence of aqueous organic compounds therefore affects not only the inorganic chemical speciation in vent fluids, but can also control the mineralogy of associated sulfide deposits. These results also indicate that vent fluid compositions do not necessarily reflect conditions in the deep subsurface, but can be altered by reactions occurring in the shallow subsurface.

Description: This research was supported by grants to Jeffrey Seewald from the Petroleum Research Fund (323lO-AC2), administered by the American Chemical Society, the National Science Foundation (OCE-9618179, OCE-9906752, OCE-0136954) and the WHOI Green Technology Fund.

Description: Submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy at the Massachusetts Institute of Technology and the Woods Hole Oceanographic Institution February 2003

Description: The capability of transient tracers to constrain the ocean circulation in the North Atlantic is explored. Study of an idealized tracer shows that inferences of circulation properties from transient state distributions are impacted by uncertainties in the time-varying boundary conditions and sparse data coverage. Comparison of CFC, tritium, temperature and salinity (T-S) observations with model results in the North Atlantic shows that regions of important model-data disagreements in the transient tracer fields can also be readily identified in the T-S distributions. In the model, excessive vertical penetration of convective adjustment, leads to problematic production and outflow of the NADW, again appearing in both transient tracer and T-S fields. Sensitivities of the model fields are determined using the adjoint model. In the dual solutions, CFC-ll, CFC-ll/CFC-12 ratio age, and T - (ß/α)S (α and ß are thermal and haline expansion coefficients, respectively) exhibit the major ventilation pathways and the associated timescales, in the model. High sensitivity fields are candidates for providing the most powerful constraints in the corresponding inverse problems. Assimilation of both CFC and tritium data, with different input histories, sampling distributions, and radioactive decay constants, shows that by adjusting only initial-boundary conditions of CFCs and tritium, a 1° x 1° offline model and the transient tracer data can be brought into near-consistency, in the domain between 4.5°S and 39.5°N of the North Atlantic. Constraining a GCM with transient tracers is thus fully practical. However, the large uncertainties in the time-varying boundary conditions of transient tracer concentrations, and in their interior distributions, renders the transient tracers less-effective in determining the circulation than are more conventional steady tracers, and known oceanic dynamics.

Description: This work was supported by NSF Award #OCE-9730071 (A Synthesis Of The Global WOCE Observation), #OCE-9617570 (Estimating The Climatological Annual Cycle), and by NASA Award #NAG5-7857 and #NAG5-11933 (A Synthesis Of The Global WOCE Observation).

Description: Submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy at the Massachusetts Institute of Technology and the Woods Hole Oceanographic Institution January 1983

Description: Isotope studies of nitrogen and carbon were undertaken to investigate the fate of particulate organic matter (POM) during its residence in the water column and after deposition on the seafloor. The processes focused on were water-column transformations and sedimentary diagenesis. Sampling sites were chosen to provide POM subject to different specific mineralization processes (nitrification, denitrification, and sulfate reduction), different lengths of water column (duration of the mineralization process), and differences in the size of the organic-matter flux. The δl5N and δ13C of plankton, POM, and sediments from several oceanic sites were related to biological and hydrographic processes identified from nutrient, temperature, and salinity profiles. This was done to determine what effect these processes have on the δ15N of POM. Four stations were studied in the upwelling area off the coast of Peru and one station was studied in the Gulf of Maine. Important factors controlling the δ15N of plankton appear to be the concentration and δl5N of nitrate in the surface waters, and the relative zooplankton and phytoplankton abundances. Plankton from the Peru Upwelling Area are enriched in 15N as compared to plankton from other parts of the world's oceans where denitrification is absent. This enrichment may be due to the assimilation of 15N-enriched nitrate, produced by the selective reduction of 14N during denitrification. Zooplankton are 3 to 4% enriched in 15N as compared with phytoplankton. Production of 14N -enriched fecal pellets is suggested as a mechanism for this trophic enrichment. In the surface waters, the δl5N of POM is similar to that of plankton. In the Peru Upwelling Area, the δ15N of POM from the oxygen-deficient waters decreases with increasing depth. In the Gulf of Maine, below the euphotic zone in the oxic deep waters, the δ15N of POM increases with increasing depth. The difference in isotopic alteration may be due to the effect of different redox conditions on the mechanism and sequence by which specific organic nitrogen compounds, variably enriched in 15M, undergo degradation. Furthermore, bacterial growth on nitrogen-poor particles in the deep waters of the Peru Upwelling Area may contribute to the low δ15N of POM. In contrast to the large range in δ15N (-2 to +17%) of the POM, the range of δ15N in the sediments is small (+5 to +9%). Within a core, the average variation in δ15N was only 1.8%. Temporal variability in the δ15N of sedimenting POM and benthic activity appear to be important in determining the δ15N of the sediments. The large changes in POM concentration and isotope content at the sediment/water interface as compared with the more constant values found down-core, suggest that processes occuring at the sediment/water interface are critical, although bioturbation may also be important in determining the δ15N of oxic sediments. If diagenesis causes a significant loss of organic matter, profiles of organic carbon and nitrogen contents should show decreases with increasing depth and C/N ratios should increase with increasing depth (Reimers, 1981). Since none of the sedimentary profiles exhibited such trends, it is concluded that diagenesis was insufficient to erase the percent carbon, nitrogen and C/N ratio signatures generated by the POM flux and alterations at the sediment/water interface. Temporal variability in the δ15N of bottom-water POM may be caused by changes in deep-water currents which transport POM horizontally and to changes in bacterial and possibly other biological activity in the water column. This thesis work suggests that δ15N may be a useful tool in studying the geochemistry of POM in the marine environment. In addition, this research has shown that interpretation of the sedimentary 15N record must include consideration of isotopic alteration associated with bacterial remineralization of POM and benthic activity.

Description: Funds for this research were provided by the Massachusetts Institute of Technology / Woods Hole Oceanographic Institution Joint Program in Oceanography, the National Science Foundation under Grant No. OCE-8024442, and the Andrew W. Mellon Foundation through the Center for Coastal Research of the Woods Hole Oceanographic Institution.

Description: Measurement of effusion rate is a primary objective for studies that model lava flow and magma system dynamics, as well as for monitoring efforts during on-going eruptions. However, its exact definition remains a source of confusion, and problems occur when comparing volume flux values that are averaged over different time periods or spatial scales, or measured using different approaches. Thus our aims are to: (1) define effusion rate terminology; and (2) assess the various measurement methods and their results. We first distinguish between instantaneous effusion rate, and time-averaged discharge rate. Eruption rate is next defined as the total volume of lava emplaced since the beginning of the eruption divided by the time since the eruption began. The ultimate extension of this is mean output rate, this being the final volume of erupted lava divided by total eruption duration. Whether these values are total values, i.e. the flux feeding all flow units across the entire flow field, or local, i.e. the flux feeding a single active unit within a flow field across which many units are active, also needs to be specified. No approach is without its problems, and all can have large error (up to ∼50%). However, good agreement between diverse approaches shows that reliable estimates can be made if each approach is applied carefully and takes into account the caveats we detail here. There are three important factors to consider and state when measuring, giving or using an effusion rate. First, the time-period over which the value was averaged; second, whether the measurement applies to the entire active flow field, or a single lava flow within that field; and third, the measurement technique and its accompanying assumptions.

Description: Published

Description: 1-22

Description: 1.5. TTC - Sorveglianza dell'attività eruttiva dei vulcani

Description: JCR Journal

Description: reserved

Description: Soil-temperature measurements can provide information on the distribution of degassing fissures, their relationship to the internal structure of the volcano, and the temporal evolution of the system. At Vulcano Island (Italy) heat flux from a 〈3 km-deep magma body drives a hydrothermal system which extends across the main Fossa crater. This heat flux is also associated with variable magmatic gas flow. A high density map of soil-temperatures was made in 1996 at a constant depth of 30 cm on the central and southern inner flanks of the Fossa crater. These measurements extended over an area covering about 0.04 km2, across which the heat flux is predominantly associated with a shallow boiling aquifer. The map shows that hot zones relate to structures of higher permeability, mainly associated with a fissure system dating from the last eruptive cycle (1888-90). From 1996 to January 2005, we studied the evolution of the heat flux for the high temperature part of the map, both by repeating our measurements as part of fourteen visits, during which temperatures were measured at a constant depth, and using data from permanent stations which allowed soil-temperatures to be continuously measured for selected vertical profiles. These data allowed us to calculate the heat flux, and its variation, with good precision for values lower than about 100 W m-2, which is generally the case in the study area. Above 100 W m-2 although the heat flux value is underestimated its variations are recorded with an error less than 10%. During the period 1996-2004 two increases in the thermal flux were recorded. The first one was related to the seismic crisis of November 1998 which opened existing or new fissures. The second, in November 2004, was probably due to magma migration, and was associated with minor seismic activity.

Description: Published

Description: on line first

Description: 1.2. TTC - Sorveglianza geochimica delle aree vulcaniche attive

Description: JCR Journal

Description: partially_open

Description: Hydrological and geochemical studies performed on Lake Specchio di Venere on Pantelleria island (Italy) indicate that this endorheic basin has been formed through upwelling of the water table, and that it is continuously fed by the thermal springs situated on its shores. The lake is periodically stratified both thermally and in salinity, albeit this stratification is rather unstable over time since meteorological events such as strong rain or wind can determine the mixing of its waters. Periodical analyses of the lake water chemistry show large variations of the salt content due to the yearly evaporation-rain dilution cycle. These processes are also responsible for the saline stratification during steady meteorological conditions. The mineralogical characterisation of the bottom sediments shows the almost exclusive presence of neoformation minerals, mainly carbonates, formed in response to the pH gradient between spring- (pH≈6) and lake-waters (pH≈9). Finally, the CO2 partial pressures in the lake water slightly exceeding the atmospheric one, are due to the large amounts of CO2 brought to the lake through the bubbling free gas phase of the thermal springs. Nevertheless the high pH value of the lake water, its small volume and its periodical mixing prevent dangerous built up of this gas.

Description: Published

Description: 1.2. TTC - Sorveglianza geochimica delle aree vulcaniche attive

Description: JCR Journal

Description: reserved

Description: On 22 September 2002, 1 month before the beginning of the flank eruption on the NE Rift, an M-3.7 earthquake struck the northeastern part of Mt. Etna, on the westernmost part of the Pernicana fault. In order to investigate the ground deformation pattern associated with this event, a multi-disciplinary approach is presented here. Just after the earthquake, specific GPS surveys were carried out on two small sub-networks, aimed at monitoring the eastern part of the Pernicana fault, and some baselines belonging to the northeastern EDM monitoring network of Mt. Etna were measured. The leveling route on the northeastern flank of the volcano was also surveyed. Furthermore, an investigation using SAR interferometry was performed and also the continuous tilt data recorded at a high precision sensor close to the epicenter were analyzed to constrain the coseismic deformation. The results of the geodetic surveys show a ground deformation pattern that affects the entire northeastern flank of the volcano, clearly shaped by the Pernicana fault, but too strong and wide to be related only to an M-3.7 earthquake. Leveling and DInSAR data highlight a local strong subsidence, up to 7 cm, close to the Pernicana fault. Significant displacements, up to 2 cm, were also detected on the upper part of the NE Rift and in the summit craters area, while the displacements decrease at lower altitude, suggesting that the dislocation did not continue further eastward. Three-dimensional GPS data inversions have been attempted in order to model the ground deformation source and its relationship with the volcano plumbing system. The model has also been constrained by vertical displacements measured by the leveling survey and by the deformation map obtained by SAR interferometry.

Description: Published

Description: 757-768

Description: 1.3. TTC - Sorveglianza geodetica delle aree vulcaniche attive

Description: 3.6. Fisica del vulcanismo

Description: JCR Journal

Description: partially_open

Description: The use of a hand-held thermal camera during the 2002–2003 Stromboli effusive eruption proved essential in tracking the development of flow field structures and in measuring related eruption parameters, such as the number of active vents and flow lengths. The steep underlying slope on which the flow field was emplaced resulted in a characteristic flow field morphology. This comprised a proximal shield, where flow stacking and inflation caused piling up of lava on the relatively flat ground of the vent zone, that fed a medial–distal lava flow field. This zone was characterized by the formation of lava tubes and tumuli forming a complex network of tumuli and flows linked by tubes. Most of the flow field was emplaced on extremely steep slopes and this had two effects. It caused flows to slide, as well as flow, and flow fronts to fail frequently, persistent flow front crumbling resulted in the production of an extensive debris field. Channel-fed flows were also characterized by development of excavated debris levees in this zone (Calvari et al. 2005). Collapse of lava flow fronts and inflation of the upper proximal lava shield made volume calculation very difficult. Comparison of the final field volume with that expecta by integrating the lava effusion rates through time suggests a loss of ~70% erupted lava by flow front crumbling and accumulation as debris flows below sea level. Derived relationships between effusion rate, flow length, and number of active vents showed systematic and correlated variations with time where spreading of volume between numerous flows caused an otherwise good correlation between effusion rate, flow length to break down. Observations collected during this eruption are useful in helping to understand lava flow processes on steep slopes, as well as in interpreting old lava–debris sequences found in other steep-sided volcanoes subject to effusive activity.

Description: Published

Description: JCR Journal

Description: reserved

Description: Bulk atmospheric deposition of major cations (Na, K, Ca, Mg) and anions (Cl, F, SO4) were measured at 15 sites around an active volcano, Mount Etna, from 2001 to 2003. Their composition indicates several natural sources, among which deposition of plume-derived volcanogenic gas compounds is prevalent for F, Cl and S. Plume-derived acidic compounds are also responsible for the prevailing acidic composition of the samples collected on the summit of the volcano (pH in the 2.45–5.57 range). Cation species have complex origin, including deposition of plume volcanogenic ash and aerosols and soil-dust wind re-suspension of either volcanic or carbonate sedimentary rocks. Variation of the deposition rates during the March 2001– March 2003 period, coupled with previous measurements from 1997 to 2000 (Appl Geochem 16:985–1000, 2001), were compared with the variation of SO2 flux, volcanic activity and rainfall. The deposition rate was mainly controlled by rainfall. Commonly, about 0.1–0.9% of HF, HCl and SO2 emitted by the summit crater’s plume were deposited around the volcano. We estimate that ∼2 Gg of volcanogenic sulphur were deposited over the Etnean area during the 2002–2003 flank eruption, at an average rate of ∼24 Mg day−1 which is two orders of magnitude higher than that typical of quiescent degassing phases.

Description: Published

Description: 255-265

Description: JCR Journal

Description: open

Description: Forward Looking Infrared Radiometer (FLIR) cameras offer a unique view of explosive volcanism by providing an image of calibrated temperatures. In this study, 344 eruptive events at Stromboli volcano, Italy, were imaged in 2001–2004 with a FLIR camera operating at up to 30 Hz. The FLIR was effective at revealing both ash plumes and coarse ballistic scoria, and a wide range of eruption styles was recorded. Eruptions at Stromboli can generally be classified into two groups: Type 1 eruptions, which are dominated by coarse ballistic particles, and Type 2 eruptions, which consist of an optically-thick, ash-rich plume, with (Type 2a) or without (Type 2b) large numbers of ballistic particles. Furthermore, Type 2a plumes exhibited gas thrust velocities (〉15 m s−1) while Type 2b plumes were limited to buoyant velocities (〈15 m s−1) above the crater rim. A given vent would normally maintain a particular gross eruption style (Type 1 vs. 2) for days to weeks, indicating stability of the uppermost conduit on these timescales. Velocities at the crater rim had a range of 3–101 m s−1, with an overall mean value of 24 m s−1. Mean crater rim velocities by eruption style were: Type 1= 34 m s−1, Type 2a=31 m s−1, Type 2b=7 m s−1. Eruption durations had a range of 6–41 s, with a mean of 15 s, similar among eruption styles. The ash in Type 2 eruptions originates from either backfilled material (crater wall slumping or ejecta rollback) or rheological changes in the uppermost magma column. Type 2a and 2b behaviors are shown to be a function of the overpressure of the bursting slug. In general, our imaging data support a broadening of the current paradigm for strombolian behavior, incorporating an uppermost conduit that can be more variable than is commonly considered.

Description: NSF grant no. EAR-0207734, NERC grant no. NER/B/S/2001/00707, the USGS Volcano Hazards Program and the Geophysical Institute at the University of Alaska Fairbanks

Description: Published

Description: 769-784

Description: 1.5. TTC - Sorveglianza dell'attività eruttiva dei vulcani

Description: JCR Journal

Description: reserved

Description: Submitted in partial fulfillment of the requirements for the degree of Master of Science at the Massachusetts Institute of Technology and the Woods Hole Oceanographic Institution November, 1978

Description: The distribution of dissolved silica in the deep western North Atlantic Ocean is presented. The potential temperature-dissolved silica relationship is compared with the potential temperature salinity relationship in the North Atlantic Deep Water. Geographical variations in the potential temperature- dissolved silica relationship are discussed with particular emphasis on the low silica signal of the Western Boundary Undercurrent (WBUC). The WBUC is shown to have a significant influence on the potential temperature-dissolved silica relationship from the tail of the Grand Banks of Newfoundland to Cape Hatteras. It is suggested that a region of enhanced mixing is present west of 65°W that is responsible for the observed changes in the dissolved silica distribution.

Description: Submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy at the Massachusetts Institute of Technology and the Woods Hole Oceanographic Institution February 2007

Description: Oceanic spreading centers are sites of magmatic, tectonic, and hydrothermal processes. In this thesis I present experimental and seismological constraints on the evolution of these complex regions of focused crustal accretion and extension. Experimental results from drained, triaxial deformation experiments on partially molten olivine reveal that melt extraction rates are linearly dependent on effective mean stress when the effective mean stress is low and non-linearly dependent on effective mean stress when it is high. Microearthquakes recorded above an inferred magma reservoir along the TAG segment of the Mid-Atlantic Ridge delineate for the first time the arcuate, subsurface structure of a long-lived, active detachment fault. This fault penetrates the entire oceanic crust and forms the high-permeability pathway necessary to sustain long-lived, high-temperature hydrothermal venting in this region. Long-lived detachment faulting exhumes lower crustal and mantle rocks. Residual stresses generated by thermal expansion anisotropy and mismatch in the uplifting, cooling rock trigger grain boundary microfractures if stress intensities at the tips of naturally occurring flaws exceed a critical stress intensity factor. Experimental results coupled with geomechanical models indicate that pervasive grain boundary cracking occurs in mantle peridotite when it is uplifted to within 4 km of the seafloor. Whereas faults provide the high-permeability pathways necessary to sustain high-temperature fluid circulation, grain boundary cracks form the interconnected network required for pervasive alteration of the oceanic lithosphere. This thesis provides fundamental constraints on the rheology, evolution, and alteration of the lithosphere at oceanic spreading centers.

Description: Research was funded by a MIT Presidential Fellowship and NSF grants OCE-0095936, OCE-9907224, OCE-0137329, OCE-6892222, and OCE-6897400.

Description: Submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy at the Massachusetts Institute of Technology and the Woods Hole Oceanographic Institution December 1997

Description: A new tomographic technique is employed to investigate the structure and dynamics of the Pacific upper mantle. We invert band-center travel times of ScS reverberations and frequency-dependent travel times of direct S phases, upper-mantle guided waves such as SS and SSS, and the R1 and G1 surface waves for the 2D composite structure in the plane of two Pacific corridors. The frequency-dependent travel times of the turning and surface waves are measured from all three components of ground motion as phase delays relative to a radially-anisotropic, spherically-symmetric oceanic mantle model, and their 2D Fréchet kernels are constructed by a coupled-mode algorithm. The travel times of the primary ScSn and sScSn phases and their first-order reverberations from the 410 and 660 discontinuities are measured as individual phases and the 2D Fréchet kernels for these band-limited signals are calculated using the paraxial ray approximation. The model parameters include shear-speed variations throughout the mantle, perturbations to radial shear-wave anisotropy in the uppermost mantle, and the topography of the 410 and 660 discontinuities. We construct vertical tomograms through two mantle corridors: one between the Tonga subduction zone and Oahu, Hawaii, which traverses the central Pacific Ocean; and the other between the Ryukyu subduction zone and Oahu, which samples the northern Philippine Sea, the western Pacific, and the entire Hawaiian swell. Tests demonstrate that the data sets for the two corridors resolve the lateral structure in the upper mantle with a scale length of a few hundreds kilometers and greater but that the resolving power decreases rapidly in the lower mantle. The model for the Tonga-Hawaii corridor reveals several interesting features, the most significant being a regular pattern of high and low shear velocities in the upper mantle between Tonga and Hawaii. These variations, which are well resolved by the data set, have a horizontal wavelength of 1500 km, a vertical dimension of 700 km, and an amplitude of about 3%, and they show a strong positive correlation with seafloor topography and geoid-height variations along this corridor. The geoid highs correspond to a series of northwest-trending swells associated with the major hotspots of the Society, Marquesas, and Hawaiian Islands. Where these swells cross the corridor, they are underlain by high shear velocities throughout the uppermost mantle, so it is unlikely that their topography is supported by thermal buoyancy. This result is substantiated by the model from the Ryukyu-Hawaii corridor, which exhibits a prominent, fast region that extends beneath the entire Hawaiian swell. This anomaly, which resides in the uppermost 200-300 km of the mantle, is also positively correlated with the undulations of the Hawaiian-swell height. The other dominant features in the Ryukyu-Hawaii model include the high-velocity subducting slabs beneath the Ryukyu and Izu-Bonin seismic zones, which extend throughout the entire upper mantle; a very low-velocity in the uppermost 160 km of the mantle beneath the northern Philippine Sea, which is ascribed to the presence of extra water in this region; and a pronounced minimum in the amount of radial anisotropy near Hawaii, which is also seen along the Tonga-Hawaii corridor. A joint inversion of the data from the two corridors reveals the same anomaly pattern and clearly demonstrates that the swells in the Central Pacific are underlain by fast velocities. It is therefore implied that the topography of the swells in the central Pacific is supported by a chemical buoyancy mechanism which is generated by basaltic volcanism and the formation of its low-density peridotitic residuum. While the basaltic depletion mechanism can produce high shear velocities in the uppermost 200 km, it cannot explain the depth extent of the fast anomalies beneath the swells which, along Tonga-Hawaii corridor, extend well into the transition zone. It is therefore hypothesized that the central Pacific is underlain by a system of convective rolls that are confined above the 660-km discontinuity. It is likely that these rolls are predominantly oriented in the direction of plate motion (like "Richter rolls ") but the limited depth of the fast anomaly beneath the Hawaiian swell (200-300 km) suggests that their pattern is probably more complicated. Nevertheless, this convection pattern appears to be strongly correlated with the locations of the Tahitian, Marquesan, and Hawaiian hotspots, which raises interesting questions for Morgan's hypothesis that these hotspots are the surface manifestations of deep-mantle plumes.

Description: This research was supported by the National Science Foundation under grant EAR- 9628351 and by the Defense Special Weapons Agency under grant DSW A-F49620-95-1- 0051.

Description: Submitted in partial fulfillment of the requirements of the degree of Master of Science at the Massachusetts Institute of Technology and the Woods Hole Oceanographic Institution June 2004

Description: Laterally extensive, well-developed clinoforms have been mapped in Early Cretaceous deposits located in the northeastern 27,000 km2 of the Colvile Basin, North Slope of Alaska. Using public domain 2-D seismic data, well logs, core photographs, and grain size data, depositional geometries within the Nanushuk and Torok formations were interpreted in order to constrain the transport conditions associated with progradation of the shoreline and construction of the continental margin out of detritus shed from the ancestral Brooks Range. Using STRATA, a synthetic stratigraphic modeling package, constructional clinoform geometries similar to those preserved in the North Slope clinoform volume (32,400 km3) were simulated. Sediment flux, marine and nonmarine diffusivities, and basin subsidence were systematically varied until a match was found for the foreset and topset slopes, as well as progradation rates over a 6 milion year period. The ability of STRATA to match the seismically interpreted geometries allows us to constrain measures of possible water and sediment discharges consistent with the observed development of the Early Cretaceous c1inoform suite. Simulations indicate that, in order to reproduce observed geometries and trends using constant input parameters, the subsidence rate must be very small, only a fraction of the most likely rate calculated from the seismic data. Constant sediment transport parameters can successfully describe the evolution of the prograding margin only in the absence of tectonic subsidence. However, further work is needed to constrain the absolute magnitude of these values and determine a unique solution for the NPR-A clinoforms.

Description: Submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy at the Massachusetts Institute of Technology and the Woods Hole Oceanographic Institution October, 1976

Description: Considerable geological and geophysical evidence now exists to support the hypothesis that seawater circulates through freshly intruded basalt at the mid-ocean ridges. As a consequence of this process, reactions between basalt and seawater take place at elevated temperatures. The mineralogy and chemistry of hydrothermally altered pillow basalts dredged from the Mid-Atlantic Ridge, and belonging to the greenschist facies, have been studied in order to determine the mineralogical changes that result from hyrdrothennal alteration, and to assess the chemical fluxes that result from these reactions in terms of their possible significance in elemental geochemical budgets as potential sources and sinks for elements in seawater. Where possible, pillow basalts were studied that showed varíous degrees of a1teration within a single rock. Such samples provide the best evidence that they have been affected by hydrothermal alteration, rather than regional burial metamorphism, and provide the most useful information for elemental flux calculatìons. During hydrothermal alteration, plagioclase is generally albitised, sometimes with the formation of epidote, and albite may be subsequently a1tered to chlorite. Plagioclase, in association with skeletal clinopyroxene, alters to chlorite and epidote. Olivine is pseudomorphed by chlorite, and clinopyroxene alters to actinolite. The glassy matrix alters to an intergrowth of actinolite and chlorite. Vein minerals irclude chlorite, actinolite, epidote, quartz, and sulphides. On the basis of their minaralogy, the samples may be subdivided into chlorite-rich (〉15% chlorite and 〈15% epidote) and epidote-rich (〉15% epidote and 〈15% chlorite) assemblages. The chlorite-rich assemblages lose CaO and gain MgO, while the epidote-rich samples show very little change in composition compared with their basalt precursor. The epidote-rich samples are more oxidised than their precursors, while the chlorite-rich rocks can be further suhdivided into those that maintain the same proportions of fetrous and ferric iron, and those that show an increase in ferrous iron due to the precipitation of pyrite. The major chemical changes that occur during hydrothermal alteration of pillow basalts are uptake of MgO and H2O, and loss of SiO2 and CaO. The concentrations of Na2O and K2O are apparently not greatly changed, although. they do show some variations in the core-to rim analyses. Consideration of the elemental fluxes in terms of steady-state geochemical mass balances indicates that hydrothermal alteration provides a sink for Mg, which is extremely important in solving the problem of apparent excess magnesium input to the oceans. The amount of calcium that is leached from the rock may be of significance in the geochemical budget of calcium. The concentration of silica in the circulating fluid is probably controlled by the solubility of quartz, and considerable redistribution of silica takes place within the basaltic pile. The changes in the redox conditions during hydrothermal alteration do not affect the present-day oxidation states of the atmosphere and hydrosphere. Trace element analyses indicate that copper and strontium are leached out of the rock and migrate in the circulating fluid, with local precipitation of Cu as sulphides in veins. Li, B, Mn, Ba, Ni and Co show sufficient variation in concentration and location within the altered basalts to indicate that some leaching does take place, and hence hydrothermal alteration of basalts could produce a metal-enriched solution, which may be important in the formation of metalliferous sediments at active mid-ocean ridges.

Description: Most of this work was supported by the National Science Foundation Grants OCE-74-2297l and DES-75-l6596.

Description: Submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy at the Massachusetts Institute of Technology and the Woods Hole Oceanographic Institution April, 1976

Description: The marine geochemical cycles of iron, copper, nickel, and cadmium were studied in order to provide a basis for oceanographic models for trace metals. Copper, nickel, and cadmium can be determined in a 100 ml seawater sample using cobalt pyrrolidine dithioacarbamate chelate coprecipitation and graphite atomizer atomic absorption spectrometry. Concentration ranges likely to be encountered and estimated (1δ) analytical precisions are copper, 1 to 6 nanomole/kg (±0.1); nickel, 3 to 12 nanomole/kg (±0.3); and cadmium, 0. 0 to 1.1 nanomole/kg (±0.1). The technique may be applied to freshwater samples with slight modification. A survey of several east coast U. S. estuaries established that an iron removal process occurs commonly when rivers mix with seawater. Laboratory mixing experiments using water from the Merrimack River (Mass.) and the Mullica River (New Jersey) demonstrated that rapid iron precipitation occurs as negatively-charged iron-organic colloids react with seawater cations and coagulate. This phenomenom was modeled using a synthetic, organic-stabilized colloidal suspension of goethite. The generality of the mechanism suggests that the world-average net river input of iron to the oceans is less than 1 μmole/kg of river water, an order of magnitude below previous estimates. Profiles of cadmium were obtained for 3 GEOSECS stations in the Pacific Ocean. Cadmium shows a consistent linear correlation with phosphate which demonstrates that cadmium is regenerated in a shallow cycle within the water column. The water column correlation is consistent with data on cadmium in marine organisms. Cadmium is enriched in upwelling regions which explains reports of cadmium enrichment in plankton from the Baja California upwelling region. Copper and nickel measurements have been made for three profiles from the Pacific Ocean. Observed copper concentrations range from 1 to 6 nanomole/kg; nickel varies from 3 to 12 nanomole/kg. Copper and nickel are removed from surface waters by uptake into organisms. As noted previously, nickel is regenerated partially in a shallow cycle (like P) and also in a deep cycle (like Ba). Copper is regenerated from biological debris at the bottom but is also scavenged from the mid and deep water column by an undetermined mechanism. The scavenging residence time is 1400 years. An estimate for the continental input of Ni, 7 nanomole/kg of river water, and Cu, 18 nanomole/kg of river water, was derived from measurements in the Amazon estuary. The oceanic residence times for nickel and copper are about 10,000 years. Evidence available on the uptake laws for trace metals by plankton suggests that a consistent relationship between the uptake law and the depth of regeneration may apply.

Description: Money in support of this research came at various times from the ONR, MIT UROP office, and a grant from the Doherty Foundation.

Description: The great oceans of the world all contain at intermediate depths less oxygen and more nitrate and phosphate than is found at either lesser or greater depths. This is one of the most marked physical features of the sea which must be attributed to the action of biological agencies. Those who have discussed this condition recently are agreed that it originates through the oxidation of organic matter derived primarily from the surface layers of the ocean, where alone the original synthesis of organic matter can occur. The condition obtaining at any depth is considered to depend upon the balance between the rate at which oxygen is removed from the water by respiratory and other metabolic processes and the renewal of oxygen in the layers in question by movements of the water. One group of investigators has emphasized the latter factor as the dominant one in determining the observed distribution of oxygen (Jacobsen, 1916; Dietrich, 1937; Wüst, 1935; Wattenberg, 1929, 1938). Oxygen content is reduced to the greatest extent at those depths in which the water is in minimal motion and hence the renewal of oxygen is least. Seiwell (1937) and Sverdrup (1938) have pointed out that this condition is not a necessity and is indeed in certain situations contrary to the apparent facts. They have shown that the observed distribution of oxygen may be accounted for by assuming various suitable relations between the rates at which oxidation occurs as a function of the depth and the rates of renewal by the circulation of water. These discussions appear to consider the state of the water to depend upon factors operative more or less locally and in situ. Specifically, oxidation is assumed to follow the sinking of organic matter from the surface to the depth in question in the discussions of Wattenberg (1937) and Seiwell (1937). The renewal of oxygen is assumed to depend on the horizontal circulation. Several considerations appear to have been given insuffcient weight in discussions of this subject. It is not at all clear why the depth of the oxygen minimum layer varies so greatly from place to place or what its relation is to the particular nutritive conditions in the sea's surface. Observations made in the relatively shallow water of the Gulf of Maine indicate that organic decomposition and oxidation take place for the most part not far from the sea surface. It seems not unreasonable to assume that the properties of the water which depend upon organic decomposition may have been determined primarily at a time when the water was relatively near the sea surface and that the water has subsequently moved into its observed position. The recent evidence, reviewed by Montgomery (1940), that mixing processes along surfaces of constant potential density may occur with great ease, even in the absence of directional flow, provides a convenient mechanism for establishing a distribution of oxygen and the products of organic activity at great depths which is dependent in large part on processes taking place much nearer the sea surface in remote regions. These considerations have suggested that the wellmarked evidence of decomposition which is observed at great depths in the central Atlantic Ocean may be due to the flow of water along surfaces of equal potential density from regions near the sea surface in high northern and southern latitudes rather than to the decay of organic matter derived directly from the overlying surface waters. This view requires that the characteristics of the water show a marked continuity in their distribution along layers of constant potential density, and that these layers emerge at or near to the sea surface in places suitable to produce the peculiar character of the layers in question. To test this possibility, data secured by the "Meteor," the "Discovery," and the "Atlantis" have been examined. The most illuminating information was secured from two north-south sections which together extend from Greenland to Antarctica. The South Atlantic was traversed by a section, made by the "Discovery" in April-May, 1931, extending along the thirtieth meridian from 57°36'S to 14°27'N ("Discovery" Reports, 1932). This is Section 2 of Clowes (1938). A section of the North Atlantic was constructed from the data secured by the "Atlantis" extending from 1°N to 34°N west of the fortieth meridian in March, 1932 (Stations 1158-1179), and from 39°N to 49°N near the fortieth meridian in September, 1935 (Stations 2485-2491), and by the "Meteor" (Stations 120-125) extending from 50°N to 58°N near the forty-fourth meridian, occupied in March, 1935 (Bull. Hydrographique, 1933, 1936). The data have been converted into suitable common units. Phosphate has been expressed as milligram-a toms phosphorus per cubic meter (γ-atoms P per liter) uncorrected for salt error. The function of the oxygen content which is of importance is the quantity which has disappeared from the water owing to metabolic processes. This has been approximated by assuming the water to have been saturated with air at the time it acquired its temperature and salinity at the sea surface and subtracting the recorded oxygen content from the value calculated on this assumption. The "apparent oxygen utilization" so obtained has been expressed as cubic centimeters per liter. In plotting the data for the sections, a rectangular grid on which latitude is represented horizon tally and sigma-τ is represented vertically has been chosen. Mon tgomery (1938) has shown that surfaces of equal sigma-τ are approximately of constant potential density. Consequently, on such a diagram the path of free movement by lateral mixing or flow is along horizontal lines. Any correlation of the distribution of a component of the sea water with potential density becomes at once apparent, if present. The surface of the sea and surfaces of any particular depth are represented by curved lines on the diagram. A grid of this type has been used by Spilhaus (1941) to distinguish different water types in the complex situation which exists at the margin of the Gulf Stream.

Description: Submitted in partial fulfillment of the requirements of the degree of Doctor of Philosophy at the Massachusetts Institute of Technology and the Woods Hole Oceanographic Institution June, 1973

Description: An experimental study of the interaction of metal ions with the surface of hydrous manganese dioxide has been completed. The results of these experiments have greatly improved our qualitative understanding of the adsorption mechanism and have also provided a means of testing quantitatively the proposal that the concentration of cobalt in manganese rich marine samples is due to adsorption of cobalt from sea water by hydrous manganese dioxide. This study has shown that there are two reasons why manganese dioxide is an efficient scavenger of metal ions from sea water. These are coulombic attraction and specific adsorption. The coulombic attraction is in response to the surface charge that originates because of acid-base reactions at the surface. The surface charge is pH dependent, and the pH of zero point of charge for the hydrous manganese dioxide used in this study was 2.25. The surface charge increases rapidly for pH values greater than the pH of zero point of charge and reaches values of -100 μcoul/cm2 by pH 8.0. However, the high surface charge cannot explain all the adsorption. This is because some metal ions exhibìt a strong specific adsorption on the surface. This specific adsorption is a direct reaction of the metal ions with the surface, releasing one proton from the surface for each metal ion adsorbed. The energy of this specific interaction is frequently greater than the energy of electrostatic attraction. Adsorption on hydrous manganese dioxide and the magnitude of the specific adsorption both increased in the order: Na = K 〈 Mn 〈 Ca 〈 Sr 〈 Ba 〈 Ni 〈 Zn 〈 Mn ≤ Co This suggests that the specific adsorption potential controls the adsorption selectivity of δMn02. An adsorption isotherm was constructed for cobalt, and these data were used to test the hypothesis that the enrichment of cobalt in the suspended matter of the Black Sea and in ferromanganoan sediments from the East Pacific Rise is due to adsorption of cobalt from sea water by manganese dioxide. The calculations indicate that adsorption is a feasible explanation for these examples.

Description: This research has been supported for various periods by funds granted by the National Science Foundation (GA-l3574) and U. S. Atomic Energy Commission Contract AT-(30-1)3566 and Graduate Fellowships provided by the Pan American Petroleum Foundation and by the Woods Hole Oceanographic Institution.

Description: Ground deformation occurring on the southern flank of Mt Etna volcano during the JulyAugust 2001 eruption was monitored by GPS measurements along an EW profile crossing the fissure system. This profile was measured eight times during the eruption, using the 'stop and go' semi-kinematic technique. Horizontal and vertical displacements between GPS surveys are reported for each station. The most significant event is a deformation episode occurring during the first week of the eruption, between 2527 July. Displacements were measured on benchmarks close to the eruptive fissure and the tensile 1989 fracture. Data inversions for measured displacements were performed using the Okada model. The model shows the narrowing of the 2001 dyke accompanied by a dextral dislocation along an east-dipping fault, parallel to the 1989 fracture.

Description: Published

Description: 336-341

Description: partially_open

Description: The 200203 Mt Etna flank eruption began on 26 October 2002 and finished on 28 January 2003, after three months of continuous explosive activity and discontinuous lava flow output. The eruption involved the opening of eruptive fissures on the NE and S flanks of the volcano, with lava flow output and fire fountaining until 5 November. After this date, the eruption continued exclusively on the S flank, with continuous explosive activity and lava flows active between 13 November and 28 January 2003. Multi-disciplinary data collected during the eruption (petrology, analyses of ash components, gas geochemistry, field surveys, thermal mapping and structural surveys) allowed us to analyse the dynamics of the eruption. The eruption was triggered either by (i) accumulation and eventual ascent of magma from depth or (ii) depressurisation of the edifice due to spreading of the eastern flank of the volcano. The extraordinary explosivity makes the 200203 eruption a unique event in the last 300 years, comparable only with La Montagnola 1763 and the 2001 Lower Vents eruptions. A notable feature of the eruption was also the simultaneous effusion of lavas with different composition and emplacement features. Magma erupted from the NE fissure represented the partially degassed magma fraction normally residing within the central conduits and the shallow plumbing system. The magma that erupted from the S fissure was the relatively undegassed, volatile-rich, buoyant fraction which drained the deep feeding system, bypassing the central conduits. This is typical of most Etnean eccentric eruptions. We believe that there is a high probability that Mount Etna has entered a new eruptive phase, with magma being supplied to a deep reservoir independent from the central conduit, that could periodically produce sufficient overpressure to propagate a dyke to the surface and generate further flank eruptions.

Description: Published

Description: 314-330

Description: partially_open

Description: Flank instability and collapse are observed at many volcanoes. Among these, Mt. Etna is characterized by the spreading of its eastern and southern flanks. The eastern spreading area is bordered to the north by the EW-trending Pernicana Fault System (PFS). During the 20022003 Etna eruption, ground fracturing along the PFS migrated eastward from the NE Rift, to as far as the 18 km distant coastline. The deformation consisted of dextral en-echelon segments, with sinistral and normal kinematics. Both of these components of displacement were one order of magnitude larger (~1 m) in the western, previously known, portion of the PFS with respect to the newly surveyed (~9 km long) eastern section (~0.1 m). This eastern section is located along a pre-existing, but previously unknown, fault, where displaced man-made structures give overall slip rates (11.9 cm/year), only slightly lower than those calculated for the western portion (1.42.3 cm/year). After an initial rapid motion during the first days of the 20022003 eruption, movement of the western portion of the PFS decreased dramatically, while parts of the eastern portion continued to move. These data suggest a model of spreading of the eastern flank of Etna along the PFS, characterized by eruptions along the NE Rift, instantaneous, short-lived, meter-scale displacements along the western PFS and more long-lived centimeter-scale displacements along the eastern PFS. The surface deformation then migrated southwards, reactivating, one after the other, the NNWSSE-trending Timpe and Trecastagni faults, with displacements of ~0.1 and ~0.04 m, respectively. These structures, along with the PFS, mark the boundaries of two adjacent blocks, moving at different times and rates. The new extent of the PFS and previous activity over its full length indicate that the sliding eastern flank extends well below the Ionian Sea. The clustering of seismic activity above 4 km b.s.l. during the eruption suggests a deep décollement for the moving mass. The collected data thus suggests a significant movement (volume 〉1,100 km3) of the eastern flank of Etna, both on-shore and off-shore.

Description: Published

Description: 417-430

Description: partially_open