Surface in situ measurements of atmospheric CO, CH4, and CO2 combined with selected meteorological measurements at the University of Wollongong, Australia

Wollongong, Australia is an urban site at the intersection of anthropogenic, biomass burning, biogenic and marine sources of atmospheric trace gases. The location offers a valuable opportunity to study drivers of atmospheric composition in the Southern Hemisphere. Here, a record of surface carbon monoxide (CO), methane (CH4) and carbon dioxide (CO2) was measured with an in situ Fourier transform infrared trace gas analyser between April 2011 and August 2014. Clean air was found to arrive at Wollongong in approximately 10% of air masses. Biomass burning influence was evident in the average annual cycle of clean air CO during austral spring. A significant negative short-term trend was found in clean air CO (-1.5 nmol/mol/a), driven by a reduction in northern Australian biomass burning. Significant short-term positive trends in clean air CH4 (5.4 nmol/mol/a) and CO2 (1.9 ?mol/mol/a) were consistent with the long-term global average trends. Polluted Wollongong air was investigated using wind-direction/wind-speed clustering, which revealed major influence from local urban and industrial sources from the south. High values of CH4, with anthropogenic DCH4/DCO2 enhancement ratio signatures, originated from the northwest, in the direction of local coal mining. A pollution climatology was developed for the region using back trajectory analysis and DO3/DCO enhancement ratios. Ozone production environments in austral spring and summer were associated with anticyclonic meteorology on the east coast of Australia, while ozone depletion environments in autumn and winter were associated with continental transport, or fast moving trajectories from southern latitudes. This implies the need to consider meteorological conditions when developing policies for controlling air quality.

Geochemistry of reduction haloes in ODP Holes 135-834A and 135-837A

The sediment column overlying basement in the Lau Basin consists of a sequence of volcaniclastic turbidites interbedded with hemipelagic clayey nannofossil mixed sediments, overlain in turn by a sequence of hemipelagic clayey nannofossil oozes containing sporadic calcareous turbidites. The clayey nannofossil oozes and mixed sediments are pervasively stained by hydrothermally derived iron and manganese oxyhydroxides. Sharply defined, lighter colored bands occur in the hemipelagic sediments, immediately beneath some (but by no means all) volcaniclastic and calcareous turbidites. These are identified as reduction haloes, of a type previously identified in quite different turbidite/pelagic sequences. The haloes are attributed to the burial of labile surficial Corg by turbidites, followed by the remineralization of this Corg with Mn and Fe oxyhydroxides as electron acceptors. The resultant characteristic Mn and Fe concentration/depth profiles are described, and a model is proposed for their development. The color alteration of the halo is ascribed to the removal of Mn oxyhydroxides, because, although the Fe content fluctuates through the haloes, this does not appear to affect their color. Other elements (Co, Cu, and Ni) are also at low concentration levels in the haloes like Mn, consistent with remobilization and migration out of the halo section, although the profile shapes are not identical with those of Mn. The behavior of V is distinctive in that it appears to have migrated into the haloes to be enriched there. Haloes are unlikely to form if turbidite emplacement is erosive and removes the near-surface layer, which generally is the most fluid part of the sediment and contains the highest levels of reactive Corg to drive the reduction process. Conversely, the presence of a halo implies that emplacement of the overlying turbidite did not significantly erode the pre-existing sediment/water interface.

Geochemistry and mineralogy of sediments from the Atlantis II Fracture Zone

Thirteen sediment samples, including calcareous ooze, sandy clay, volcanic sand, gravel, and volcanic breccia, from Ocean Drilling Program (ODP) Sites 732B, 734B, 734G and Conrad Cruise 27-9, Station 17, were examined. Contents of major and trace elements were determined using XRF or ICP (on samples <0.5 g). Determinations of rare earth elements (REE) were performed using ICP-MS. Mineralogy was determined using XRD. On the basis of the samples studied, the sediments accumulating in the Atlantis II Fracture Zone are characterized by generally high MgO, Cr, and Ni contents compared with other deep-sea sediments. A variety of sources are reflected in the mineralogy and geochemistry of these sediments. Serpentine, brucite, magnetite, and high MgO, Cr, and Ni contents indicate derivation from ultramafic basement. The occurrence of albite, analcime, primary mafic minerals, and smectite/chlorite in some samples, coupled with high SiO2, Al2O3, TiO2, Fe2O3, V, and Y indicate contribution from basaltic basement. A third major sediment source is characterized as biogenic material and is reflected primarily in the presence of carbonate minerals, and high CaO, Sr, Pb, and Zn in certain samples. Kaolinite, illite, quartz, and some chlorite are most likely derived from continental areas or other parts of the ocean by long-distance sediment transport in surface or other ocean currents. Proportions of source materials in the sediments reflect the thickness of the sediment cover, slope of the seafloor, and the nature of and proximity to basement lithologies. REE values are low compared to other deep-sea sediments and indicate no evidence of hydrothermal activity in the Atlantis II Fracture Zone sediments. This is supported by major- and trace-element data.

Chemical and isotope compositions of main phases of metalliferous sediments from holes of DSDP Leg 92

The carbonate-free metalliferous fraction of thirty-nine sediment samples from four DSDP Leg 92 sites has been analyzed for 12 elements, and a subset of 16 samples analyzed for Pb isotopic composition. The main geochemical features of this component are as follows: i) very high concentrations of Fe and Mn, typically 25-39% and 5-14%, respectively; ii) Al and Ca contents generally less than 2% and 5%, respectively; iii) high Cu (1000-2000 ppm), and Zn and Ni (500-1000 ppm) values; and iv) Co and Pb concentrations of 100-250 ppm. In terms of element partitioning within the metalliferous fraction, amorphous to poorly crystallized oxide-oxyhydroxides removed by the second leach carry virtually all of the Mn, and about 90% of the Ca, Sr and Ni. The well-crystallized goethite-rich material removed by the third leach carries the majority of Fe, Cu, and Pb. These relations hold for sediments as young as ~1-2 Ma, indicating early partitioning of hydrothermal Fe and Mn into separate phases. Calculated mass accumulation rates (MAR) for Fe, Mn, Cu, Pb, Zn and Ni in the bulk sediment show the same overall trends at three of the sites, with greatest MAR values near the basement, and a general decrease in MAR values towards the tops of the holes (for sediments deposited above the lysocline). These relations strongly support the concept of a declining hydrothermal contribution of these elements away from a ridge axis. Nevertheless, MAR values for these metals up to ~200 km from the ridge axis are orders of magnitude higher than on abyssal seafloor plains where there is no hydrothermal influence. Mn/Fe ratios throughout the sediment column at two sites indicate that the composition of the hydrothermal precipitates changed during transport through seawater, becoming significantly depleted in Mn beyond ~200-300 km from the axis, but maintaining roughly the same proportion of Fe. Most of the Pb isotope data for the Leg 92 metalliferous sediments form approximately linear arrays in the conventional isotopic plots, extending from the middle of the field for mid-ocean ridge basalts toward the field for Mn nodules. The array of data lying between these two end-members is most readily interpreted in terms of simple linear mixing of Pb derived from basaltic and seawater end-member sources. The least radiogenic sediments reflect the average Pb isotope composition of discharging hydrothermal solutions and ocean-ridge basalt at the EPR over the ~4-8 Ma B.P. interval. Pb in sediments deposited up to 250 km from the axis can be almost entirely of basaltic-hydrothermal origin. Lateral transport of some basaltic Pb by ocean currents appears to extend to distances of at least 1000 km west of the East Pacific Rise.

(Table 4+5, Page 290) Distribution of Mn, Fe, Cu. Pb, Zn, Ni and Co in single manganese nodules

Chemical analyses of manganese nodules from the Central Pacific Basin show that their chemical composition varies regionally, although that of the associated sediments is markedly uniform throughout the basin. Mn content varies from 16 to 32% in average. Its higher value is generally found in nodules from siliceous clay and a few from deep-sea clay. Fe content tends to enrich in nodules from deep-sea clay area. Most manganese nodules, except those from deep-sea clay, are remarkably depleted in Fe compared with ones from the other Pacific regions. Mostly, Cu and Ni contents exceed 1% in nodules from siliceous clay, and decrease towards the northwest of the basin where deep-sea clay is distributed. The inter-element relationship between manganese nodules and associated sediments suggests that the mechanism of incorporation of major and minor elements in nodules is apparently different from that of the associated sediments. This finding seems to provide a new interpretation on the problem why manganese nodules having low accumulation rate are not buried by the associated sediments with greater sedimentation rate and then occur on sediment-seawater interface.

Sediment properties, contents and accumulation rates of Hg in cores of Upper Quaternary sediments from the Deryugin Basin, Okhotsk Sea

The Hg distribution and some mineralogical-geochemical features of bottom sediments up to a depth of 10 m in the Deryugin Basin showed that the high and anomalous Hg contents in the Holocene deposits are confined to a spreading riftogenic structure and separate fluid vents within it. The accumulations of Hg in the the sediments were caused by its fluxes from gas and low-temperature hydrothermal vents under favorable oceanological conditions in the Holocene. The two mainly responsible for the high and anomalous Hg contents are infiltration (fluxes of hydrothermal or gas fluids from the sedimentary cover) and plume (Hg precipitation from water plumes with certain hydrochemical conditions forming above endogenous sources). The infiltration anomalies of Hg were revealed in the following environments: (1) near gas vents on the northeastern Sakhalin slope, where high Hg contents are associated only with Se and were caused by the accumulation of gases ascending from beneath the gas hydrate layer; (2) in the area of inferred occasionally operating low-temperature hydrothermal seeps in the central part of the Deryugin Basin, in which massive barite chimneys, hydrothermal Fe-Mn crusts, and anomalous contents of Mn, Ba, Zn, and Ni in sediments develop.

Chemical, isotope and mineral composition of hydrothermally altered upper oceanic crust drilled at ODP Site 129-801C

ODP Hole 801C penetrates >400 m into 170-Ma oceanic basement formed at a fast-spreading ridge. Most basalts are slightly (10-20%) recrystallized to saponite, calcite, minor celadonite and iron oxyhydroxides, and trace pyrite. Temperatures estimated from oxygen isotope data for secondary minerals are 5-100°C, increasing downward. At the earliest stage, dark celadonitic alteration halos formed along fractures and celadonite, and quartz and chalcedony formed in veins from low-temperature (<100°C) hydrothermal fluids. Iron oxyhydroxides subsequently formed in alteration halos along fractures where seawater circulated, and saponite and pyrite developed in the host rock and in zones of restricted seawater flow under more reducing conditions. Chemical changes include variably elevated K, Rb, Cs, and H2O; local increases in FeT, Ba, Th, and U; and local losses of Mg and Ni. Secondary carbonate veins have 87Sr/86Sr = 0.706337 - 0.707046, and a negative correlation with d18O results from seawater-basalt interaction. Carbonates could have formed at any time since the formation of Site 801 crust. Variable d13C values (-11.2? to 2.9?) reflect the incorporation of oxidized organic carbon from intercalated sediments and changes in the d13C of seawater over time. Compared to other oceanic basements, a major difference at Site 801 is the presence of two hydrothermal silica-iron deposits that formed from low-temperature hydrothermal fluids at the spreading axis. Basalts associated with these horizons are intensely altered (60-100%) to phyllosilicates, calcite, K-feldspar, and titanite; and exhibit large increases in K, Rb, Cs, Ba, H2O, and CO2, and losses of FeT, Mn, Mg, Ca, Na, and Sr. These effects may be common in crust formed at fast-spreading rates, but are not ubiquitous. A second important difference is that the abundance of brown oxidation halos along fractures at Site 801 is an order of magnitude less than at some other sites (2% vs. 20-30%). Relatively smooth basement topography (<100 m) and high sedimentation rate (8 m/Ma) probably restricted the access of oxygenated seawater. Basement lithostratigraphy and early low-temperature hydrothermal alteration and mineral precipitation in fractures at the spreading axis controlled permeability and limited later flow of oxygenated seawater to restricted depth intervals.

Chemical composition of ferromanganese micronodules and bulk sediments from ODP Hole 199-1216A

Distribution, size, mineral, and chemical compositions of ferromanganese micronodules (FMMNs) and chemical composition of host sediments were examined in a series of red clay samples with ages from Eocene to the present at Ocean Drilling Program Leg 199, Site 1216, south of the Molokai Fracture Zone in the Central Pacific Basin. The number of FMMNs changed drastically throughout the 40-m-long red clay intervals. FMMNs are abundant in the upper 9 m of core, decrease between 9 and 25 meters below seafloor (mbsf) with depth, and are very rare from 30 to 40 mbsf. Chemical composition of FMMNs showed high Mn/Fe ratios and Ni and Cu contents and a distinct positive Ce anomaly because of the existence of buserite. This suggests that FMMNs in the red clay from 25 mbsf to the top of the cored interval were deposited continuously in an oxic diagenetic bottom environment. The red clay below 30 mbsf with higher Mn contents contains few FMMNs but abundant tiny Mn particles within brown silicates coated by Fe (oxy-hydro)oxides. This indicates that the mode of manganese deposition changed between 25 and 30 mbsf.

Concentrations of suspended matter and heavy metals in melted ice- and snow water from the Barents Sea

In September-October 1998, during Cruise 14 of R/V Akademik Fedorov to the Barents Sea, in the region of 82° N between the Spitsbergen and Novaya Zemlya archipelagos samples of snow and ice were collected within four polygons. By means of atomic absorption with an electothermal atomizer (onboard the ship) in filtered (dissolved form) and unfiltered (sum of dissolved and particulate forms) samples of snow melt and ice melt concentrations of Fe, Mn, Cu, Cr, Ni, Co, Pb, and Cd were determined in order to estimate level of potential contamination of snow and ice with these metals. Excluding data on Ni, Cd (and probably Cu) in ice that were regarded to be unsatisfactory because of probable contamination of the ice samples during drilling concentrations of all the elements in snow and ice of the northern part of the Barents Sea appeared to be close to their background values or below. An attempt to identify the main sources of metal supply to snow from the atmosphere by comparison of ratios of metal particulate form to total content in snow of the Barents Sea and the same ratios in snow samples from clean regions of Finland and from contaminated areas of the Kola Peninsula showed that aerosols in the area of the expedition were supplied into the Barents Sea atmosphere from different sources, both natural and anthropogenic.

Chemical composition of hydrothermal sulfide minerals from the Rainbow, Logachev-1, and Logachev-2 hydrothermal fields

Composition of ore minerals in MAR sulflde occurrences related to ultramaflc rocks was studied using methods of mineragraphy, electron microscopy, microprobe analysis, and X-ray analysis. Objects are located at various levels of maturity of sulflde mounds owing to differences in age, duration and degree of activity of the following hydrothermal systems: generally inactive Logatchev-1 field (up to 66.5 ka old), inactive Logatchev-2 field (3.9 ka), and generally active Rainbow field (up to 23 ka). Relative to MAR submarine ore occurrences in the basalt substrate, mineralization in the hydrothermal fields mentioned above is characterized by high contents of Au, Cd, Co, and Ni, along with presence of accessory minerals of Co and Ni. The studied mounds differ in quantitative ratios of major minerals and structural-textural features of ores that suggest their transformation. Ores in the Logatchev-1 field are characterized by the highest Cu content and development of a wide range of multistage contrast exsolution structures of isocubanite and bornite. In the Logatchev-2 field, sphalerite-chalcopyrite and gold-arsenic exsolution structures are present, but isocubanite exsolution structures are less diverse and contrast. The Rainbow field is marked by presence of homogenous isocubanite and the subordinate development of exsolution structures. The authors have identified four new phases in the Cu-Fe-S system. Phases X and Y (close to chalcopyrite and isocubanite, respectively) make up lamellae among isocubanite exsolution products in the Logatchev-1 and Logatchev-2 fields. Phase Y includes homogenous zones in zonal chimneys of the Rainbow field. Phases A and B formed in the orange bornite domain at low-temperature alteration of chalcopyrite in the Logatchev-1 field. Mineral assemblages of the Cu-S system are most abundant and diverse in the Logatchev-1 field, but their development is minimal in the Logatchev-2 field where mainly Cu-poor sulfides of the geerite-covellite series have been identified. Specific features of mineral assemblages mentioned above reflect the maturity grade of sulfide mounds and can serve as indicators of maturity.

Sediments and tephra layers from the southern Tyrrhenian abyssal plain near Marsili Seamount

From the south-eastern Tyrrhenian deep-sea floor, four sediment cores of "Meteor" cruise 22 (1971) are described. These cores were taken in the basin between the Aeolian Islands and the Marsili Seamount, an elevation of more tha 3000 m above the sea floor. The sedimentation of the deep-sea basin is distinguished by a sequence of turbidites with a high sedimentation rate. The composition of the clastic material and the position of the cores in the mouth area of the morphologically very pronounced Stromboli Canyon suggest an interpretation of the turbidite sequence as fan of this canyon onto the deep-sea floor. A white rhyolitic pumice-tephra at the base of the 4 m thick sequence of turbidites in core M22-102 has been correlated with the Pelato eruption of the island of Liparo in the 6th century A.D. At the foot of the Marsili Seamount - apparently in morphologically elevated positions - the influence of the turbidite sedimentation increases, the rate of sedimentation is lower and stratigraphic omissions are probable. Here, rather compacted globigerina marls have been found in only 15 -25 cm depth. In addition, volcanic material in the form of lapilli layers, palagonitized ashes and detrital volcanic sands of the Marsili Seamount have been encountered in this area. An up to 3 cm thick layer of completely palagonitized basaltic ash intercalates with the marls at the base of two cores. Layers of very fresh olivine basaltic lapilli in core 103 and palagonitized lapilli of latitic composition in core 104 testify to an explosive submarine volcanism of the Marsili Seamount. According to the stratigraphy of core 103, the latest manifestations of this basaltic volcanism belong to the late Pleistocene (Emiliana huxleyi-zone of Nannoplankton stratigraphy) The basaltic lapilli are glassy to perhyaline with phenocrysts or microphenocrysts predominantely of olivine. The petrological character of the basaltic volcanites with high MgO, Ni, Cr and high MgO/FeO- and Ni/Co-ratios exhibits primitive basaltic features. These basalts clearly differ from basalts of the ocean floors, mid-ocean ridges and marginal basins. Prominent features are a missing iron-enrichment trend and low TiO2. Al2O3 tends to be high, as well as K2O and related trace elements (Ba, Sr). In spite of silica undrsaturation and high color index, the Marsili basalt exhibit some analogies with the calcalkaline basalts of the Aeolian arc, as well as the undersaturated basalts of some other circumoceanic areas.

Geochemistry and isotopes at DSDP Leg 80 Holes

Thirty-eight samples from DSDP Sites 549 to 551 were analyzed for major and minor components and trace element abundances. Multivariate statistical analysis of geochemical data groups the samples into two major classes: an organic-carbon- rich group (> 1% TOC) containing high levels of marine organic matter and certain trace elements (Cu, Zn, V, Ni, Co, Ba, and Cr) and an organic-carbon-lean group depleted in these components. The greatest organic and trace metal enrichments occur in the uppermost Albian to Turanian sections of Sites 549 to 551. Carbon-isotopic values of bulk carbonate for the middle Cenomanian section of Site 550 (2.35 to 2.70 per mil) and the upper Cenomanian-Turonian sections of Sites 549 (3.35 to 4.47 per mil) and 551 (3.13 to 3.72 per mil) are similar to coeval values reported elsewhere in the region. The relatively heavy d13C values from Sites 549 and 551 indicate that this interval was deposited during the global "oceanic anoxic event" that occurred at the Cenomanian/Turonian boundary. Variation in the d18O of bulk carbonate for Section 550B-18-1 of middle Cenomanian age suggests that paleosalinity and/or paleotemperature variations may have occurred concurrently with periodic anoxia at this site. Climatically controlled increases in surface-water runoff may have caused surface waters to periodically freshen, resulting in stable salinity stratification

Iridium and other element concentrations and magnetostratigraphy across the Cretaceous/Tertiarty boundary in ODP Hole 122-761C

Samples from Ocean Drilling Program Hole 761C, collected on both sides of the Cretaceous/Tertiary boundary have been analyzed for their chemical and mineralogical content. The sediment consists of nannofossil ooze with variable amounts of clay. The boundary is marked by a color change associated with a nearly step-like decrease of the carbonate fraction. Paleomagnetic data and the drop of the carbonate content indicate that a strong reduction of the sedimentation rate occurred at the boundary and persisted for million of years. An iridium anomaly of 80 ng/cm**2, together with overabundances of Cr and Fe, are found in close coincidence with the planktonic crisis. These enrichments can be explained by the infall of =0.16 g/cm2 of Cl-like chondritic material. Co and Ni enrichments and a great quantity of Ni-rich magnetites are also observed in the basal Danian. These elements and minerals excepted, the composition of the insoluble fraction appears to be nearly unchanged across the boundary. Chemical and mineralogical observations support a cosmic origin for the Cretaceous/Tertiary event but do not reveal the presence of any significant impact ejecta.

Geochemistry and mineralogy of variably altered dacite volcanic rocks from ODP Leg 193 sites, PACMANUS field

A geochemical, mineralogical, and isotopic database comprising 75 analyses of Ocean Drilling Program (ODP) Leg 193 samples has been prepared, representing the variable dacitic volcanic facies and alteration types observed in drill core from the subsurface of the PACMANUS hydrothermal system (Table T1. The data set comprises major elements, trace and rare earth elements (REE), various volatiles (S, F, Cl, S, SO4, CO2, and H2O), and analyses of 18O and 86Sr/87Sr for bulk rock and mineral separates (anhydrite). Furthermore, normative mineral proportions have been calculated based on the results of X-ray diffraction (XRD) analysis (Table T2) using the SOLVER function of the Microsoft Excel program. Several of the samples analyzed consist of mesoscopically distinctive domains, and separate powders were generated to investigate these hand specimen-scale heterogeneities. Images of all the samples are collated in Figure F1, illustrating the location of each powder analyzed and documenting which measurements were performed.