Annual variation of atmospheric carbonyl sulfide in the marine atmosphere in the Southern Indian Ocean

Measurements of the concentrations of carbonyl sulfide (COS) in the marine atmosphere were made over a period of two years in the southern Indian Ocean (Amsterdam Island, 37°50 S–77°31 E; March 1987–February 1988 and April 1989–February 1990). The mean atmospheric COS concentration for the whole period was 475±48 pptv (n=544). Atmospheric COS concentrations show no significant seasonal variation with a summer to winter ratio of 1.05. Taking into account the observed variability of the atmospheric COS concentration (10%), a value of 1.4 yr is estimated as a lower limit for the atmospheric COS lifetime. A comparison of the COS data at Amsterdam Island with those obtained in the Southern Hemisphere in the past 12 yr does not reveal any significant trend in the tropospheric background COS mixing ratio.     

Flow directions in ash-flow tuffs: a comparison of geological and magnetic susceptibility measurements, Tshirege member (upper Bandelier Tuff), Valles caldera, New Mexico, USA

This study concludes that the elongation axis (K ₁) of the ellipsoid of anisotropic magnetic susceptibility (AMS) is a suitable proxy for flow axis in ashflow tuffs. 153 oriented samples (176 specimens) were studied from 18 sites in the 1.1 Ma Tshirege member of the Bandelier Tuff. These sites are distributed around the Valles caldera at distances of 5–25 km outside of the rim.K ₁ axes correlate well with postulated radial flow axes at 13 sites.K ₁ also agrees with measured geological flow indicators, mainly imbricated larger clasts, at 7 sites. At 2 of the 5 sites where significant disagreement is seen between theoretical radial flow directions and measuredK ₁ axes, theK ₁ axes correspond well with geological flow indicators, indicating that the divergence of flow from the predicted radial flow pattern is real. Two major topographic buttresses are suggested as the cause of flow divergence for the Tshirege ash flows: the San Pedro buttress northwest of the caldera, and the San Miguel buttress in the southeast. In situK ₁ axes plunge about 7° toward the source at two-thirds of the sites; therefore the plunge ofK ₁ is a plausible in situ indicator for thedirection of flow. Multiple flow zones in sections of several meters thickness indicate changes of flow direction that are both rapid and large during ash-flow emplacement. These observations raisre the question of how best to represent mean flow directions in ash-flow sheets: by eigenvector methods, by vector-sum methods, or by modes. A method for measuring imbrication of larger clasts using apparent dips in vertical joints is outlined. Imbrication, determined in this way at one-third of the sites, dips toward the source, i.e., up-flow. The minimum (K ₃) axis of the AMS ellipsoid correlates with the flow foliation rather than with the larger clast imbrication. The flow axes of ash flows correspond with theK ₁ axes, not with the declination ofK ₃ axes as suggested by some authors. Initial dip of the sampled ash flows is not large and does not affect the paleomagnetic remanence direction, which is reversed with a mean ofD=173.5°,I=-38.4°, ₉₅=3.4°N=18. This mean is not different at the 95% confidence level from that of earlier workers. The mean pole, at 098.0°E, 74.8°N,A ₉₅=3.3°,N=18, is about 15° far-sided relative to the expected time-averaged geomagnetic pole, suggesting a history of emplacement too short to adequately average secular variation.     

Distribution and fluxes of metals in the St. Lawrence River from the outflow of Lake Ontario to Québec City

Six anchor stations in the St. Lawrence River from the outflow of Lake Ontario to Quebec City, were occupied for ca. 24 hours in June 1987 during low flow conditions. Samples of water and suspended particulate matter were separated by continuous-flow centrifugation, and were collected every two hours.During this sampling period, fluxes of dissolved forms of zinc, copper and nickel increased in Lac St. François and downstream relative to the sum of the fluxes for the two upstream stations at the outflow of Lake Ontario. Increases in the flux of dissolved zinc and copper were pronounced below Montreal and above Lac St. Pierre. For particulate forms of metals, all five metals show that there are significant inputs in the section of the St. Lawrence River between Lac St. François and the station just above the entrance to Lac St. Pierre.The average concentrations of dissolved cadmium, lead, zinc, copper and nickel ranged from 7–23 ng/l; 9–35 ng/l; 0.434–0.939 g/l; 0.15–0.89 g/l and 0.58–1.12 g/l respectively.Regression analysis of the dissolved and particulate metal concentrations suggests that the concentration of dissolved cadmium, lead, zinc and nickel can be predicted from the regression equation and the determination of particulate metal concentration. This prediction appears to be independent of the suspended particulate matter concentration which varies from ca. 1 to 10 mg/l from the outflow of Lake Ontario to Québec City.     

Natural recolonization of a productive tropical pond: Day to day variations in the photosynthetic parameters

Chlorophyll pigments (CHL), primary productivity (PP) and particulate nitrogen (N_p) in relation to several environmental factors were monitored during planktonic colonization of an aquaculture pond (Layo, Côte d'Ivoire). How interactions between the organisms are established in an initially azoic environment were investigated. From March, 15 (D1) to March, 31 (D16), the system transformation went through three stages. First, a precolonization by heterotrophic microbial community from D1 to D2 (N_p < 1 m maximum at D2: 243 mg m^–2; CHL around 0). Then, a pioneer microalgal community developped from D3 to D7 (maximum CHL on D6: 19 mg m^–2; PP: 1.0 g C m^–2 d^–1) with a significant contribution of picoplankton (CHL and PP < 3 m: 33 and 23% of the total, respectively). Finally, a second microalgal colonization was noticed from D9 to D12 (maximum CHL: 55 mg m^–2, PP: 2.8 g C m^–2 d^–1), largely dominated by nanoplankton (CHL and PP > 3 m: 95 and 99% of the total, respectively). Overall, photosynthetic activity appeared to be closely linked to algal biomass. The study of autotrophic biomass and activity in different size classes in relation to the other parameters allowed us to precise the origin of the biomass fluctuations. The first bloom appeared to be controlled by selective grazing on small algae. The second algal development ended when N requirement represented at least 69% of N supply (in the N — NH₄ form). This control was enhanced by the appearance of rotifers, leading to a more complex equilibrium.     

Magma sources for Mesozoic anorogenic granites of the White Mountain magma series,New England,USA

The magma sources for granitic intrusions related to the Mesozoic White Mountain magma series in northern New England, USA, are addressed relying principally upon Nd isotopes. Many of these anorogenic complexes lack significant volumes of exposed mafic lithologies and have been suspected of representing crustal melts. Sm–Nd and Rb–Sr isotope systematics are used to evaluate magma sources for 18 felsic plutons with ages ranging from about 120 to 230 Ma. The possibility of crustal sources is further examined with analyses of representative older crust including Paleozoic granitoids which serve as probes of the lower crust in the region. Multiple samples from two representative intrusions are used to address intrapluton initial isotopic heterogeneities and document significant yet restricted variations (<1 in _Nd). Overall, Mesozoic granite plutons range in _Nd [T] from +4.2 to -2.3, with most +2 to 0, and in initial ⁸⁷Sr/⁸⁶Sr from 0.7031 to 0.709. The isotopic variations are roughly inversely correlated but are not obviously related to geologic, geographic, or age differences. Older igneous and metamorphic crust of the region has much lower Nd isotope ratios with the most radiogenic Paleozoic granitoid at _Nd [180 Ma] of -2.8. These data suggest mid-Proterozoic separation of the crust in central northern New England. Moreover, the bulk of the Mesozoic granites cannot be explained as crustal melts but must have large mantle components. The ranges of Nd and Sr isotopes are attributed to incorporation of crust by magmas derived from midly depleted mantle sources. Crustal input may reflect either magma mixing of crustal and mantle melts or crustal assimilation which is the favored interpretation. The results indicate production of anorogenic granites from mantle-derived mafic magmas.     

Na-rich carbonate inclusions in perovskite and calzirtite from the Guli intrusive Ca-carbonatite,polar Siberia

Carbonate phases, some rich in Na₂O and comparatively rich in SrO and BaO, occur as inclusions in perovskite and calzirtite (Ca₂Zr₅Ti₂O₁₆) in the carbonatite of the Guli complex, Siberia. This is the first record of alkali carbonates, akin to nyerereite [Na₂Ca(CO₃)₂], in plutonic igneous rocks. The inclusion populations suggest that the parental magma of the complex was Ca-rich but developed Na-rich differentiates during the latest stages. This points to the dominant calcic carbonatites of the complex not being derivatives of alkali-rich parental carbonatites. These alkali-rich carbonate inclusions (and rare inclusions of djerfisherite) have been preserved due to the resistance of perovskite and calzirtite to processes of leaching, hydrothermal alteration and weathering.     

High pressure experimental calibration of the olivine-orthopyroxene-spinel oxygen geobarometer: implications for the oxidation state of the upper mantle

Synthetic spinel harzburgite and lherzolite assemblages were equilibrated between 1040 and 1300° C and 0.3 to 2.7 GPa, under controlled oxygen fugacity (f _{O 2}). f _{O 2} was buffered with conventional and open double-capsule techniques, using the Fe−FeO, WC-WO₂-C, Ni−NiO, and Fe₃O₄−Fe₂O₃ buffers, and graphite, olivine, and PdAg alloys as sample containers. Experiments were carried out in a piston-cylinder apparatus under fluid-excess conditions. Within the P-T-X range of the experiments, the redox ratio Fe³⁺/ΣFe in spinel is a linear function of f _{O 2} (0.02 at IW, 0.1 at WCO, 0.25 at NNO, and 0.75 at MH). It is independent of temperature at given Δlog(f _{O 2}), but decreases slightly with increasing Cr content in spinel. The Fe³⁺/ΣFe ratio falls with increasing pressure at given Δlog(f _{O 2}), consistent with a pressure correction based on partial molar volume data. At a specific temperature, degree of melting and bulk composition, the Cr/(Cr+Al) ratio of a spinel rises with increasing f _{O 2}. A linear least-squares fit to the experimental data gives the semi-empirical oxygen barometer in terms of divergence from the fayalite-magnetite-quartz (FMQ) buffer:

An Example of Island-Arc Petrogenesis: Geochemistry and Petrology of the Southern Luzon Arc, Philippines

Volcanism throughout the Luzon arc is associated with eastwardsubduction of the South China Sea floor along the Manila Trench.The southern section of the arc, the focus of this study, extendsfrom the Lingayen-Dingalan fault to the small islands just southof Luzon. Two segments appear to exist along this section ofthe arc the northern Bataan and southern Mindoro segments whichare separated by the Macolod Corridor. The volcanic rocks have typical arc phenocryst mineralogies:olivine, clinopyroxene, plagioclase, and titanomagnetite inthe most mafic rocks and clinopyroxene, plagioclase, orthopyroxene,titanomagnetite, ? amphibole in the more felsic samples. Complexzoning, sieve textures, and decoupling of incompatible traceelements suggest that processes such as assimilation have takenplace. The rocks from the study area range from basalts to rhyolitesand show typical calc-alkaline features. The rocks of the MacolodCorridor and Mindoro segment are particularly enriched in largeion lithophile elements (LILE), light rare earth elements (LREE),and radiogenic Sr compared with the Bataan segment. The datafall within the mantle array on Sr-Nd isotopic diagrams andgrade toward higher Sr and lower Nd isotopic values from northto south. A likely source for the volcanics of this study is either amid-ocean ridge basalt (MORB)-type mantle that undergoes higherdegrees of partial melting than regions involved in MORB generationor a previously depleted source. We suggest that the high fieldstrength element (HFSE) anomalies have been derived throughdifferential element partitioning during fluid transport fromthe subducted lithosphere to the mantle wedge. Continental crustal material seems to play a significant roleparticularly in the Macolod Corridor and the Mindoro segment,based on the high LILE, La/Sm ratios, radiogenic Sr isotopes,and ¹⁸O values. The Macolod Corridor and the Mindoro segmenthave undergone source contamination by crustal material fromthe North Palawan-Mindoro crustal block either during the collisionof this block with the Manila Trench or by subduction of sedimentsrich in this crustal material. A similar component has alsobeen detected in the Bataan segment but in minor amounts. Thetrace element and isotopic differences between the northernand southern sections of the arc are interpreted in terms ofvariable composition (i. e., variable amounts of a crustal componentintroduced from the Palawan-Mindoro crustal terrain) of themetasomatic fluids released into the source.     

Littoral '92

Reports

Littoral '92     

New compositional and optical data for antimonian and bismuthian varieties of hemusite from Japan

Summary New compositional and optical data are reported for antimonian and antimonianbismuthian varieties of hemusite from epithermal Au-Ag-Cu deposits in Japan. The empirical formula for the antimonian variety, from the Iriki mine is: (Cu_5.83Fe_0.14Ag_0.01)_5.98Mo_1.03(Sn_0.54Sb_0.41Te_0.03Bi_0.02)_1.00(S_7.85Se_0.15)_8.00, and that of the Sb-Bi variety from the Kawazu mine is: (Cu_5.84Fe_0.14Ag_0.01)_5.99Mo_1.03(Sn_0.82Sb_0.11Bi_0.l0Te_0.04)_1.07(S_7.80Se_0.12)_7.92. The theoretical formula of hemusite is Cu⁺ ₄Cu²⁺ ₂MO⁴⁺Sn⁴⁺S₈, whilst the most probable formula of the Iriki hemusite is Cu⁺ _4.5CU²⁺ _1.5Mo⁴⁺Sn⁴⁺ _0.5Sb⁵⁺ _0.5S₈, with Sb⁵⁺ substituting for Sn⁴⁺ and forming (SbS₄)^3– tetrahedra as might be expected, given that the metal to sulphur ratio is 1, and given the sphalerite-like structure of the mineral. However Bi³⁺ cannot be so accommodated, resulting in a deficiency in (S + Se) for Kawazu hemusite. Reflectance spectra for both are compared with those of the tungsten analogue (compositional) of hemusite, kiddcreekite. The relationship between hemusitesensu stricto and these newly reported varieties is discussed in terms of simple and coupled chemical substitutions, and inferences are drawn on the valency of Sb, Bi, Mo and Cu in the hemusite structure.

---

Neue chemische und optische Daten für antimon- und bismuthführende Varietäten von Hemusit aus Japan

Zusammenfassung Neue chemische und optische Daten für antimon- und bismuthführende Hemusite auf epithermalen Au-Ag-Cu Lagerstätten in Japan werden vorgelegt. Die empirische Formel für die antimon-führende Varietät aus der Iriki-Mine ist: (Cu_5.83Fe_0.14Ag_0.01)_5.98Mo_1.03(Sn_0.54Sb_0.41Te_0.03Bi_0.02)_1.00 (S_7.85Se_0.15)_8.00, und die der Sb-Bi Varietät aus der Kawazu Mine ist: (Cu_5.84Fe_0.14Ag_0.01)_5.99M0_1.03(Sn_0.82Sb_0.11Bi_0.l0Te_0.04)_1.07 (S_7.80Se_0.12)_7.92. Die theoretische Formel von Hemusit ist Cu⁺ ₄Cu²⁺ ₂Mo⁴⁺Sn⁴⁺S₈, während die wahrscheinlichere Formel für den Hemusit von Iriki Cu⁺ ₄Cu²⁺ _1.5Mo⁴⁺Sn⁴⁺ _0.5Sb⁵⁺ _0.5S₈, mit Sb⁵⁺ an der Stelle von Sn⁴⁺, das(SbS₄)^3– Tetraeder bildet, wie zu erwarten ist, unter der Voraussetzung, da das Metall zu Schwefelverhältnis 1 und die Struktur sphaleritähnlich ist. Bi³⁺ kann jedoch nicht in dieser Weise untergebracht werden, und das führt zu einem Mangel an (S + Se) für den Hemusit von Kawazu. Die Reflektions-Spektren beider Minerale werden mit denen des Wolfram-Equivalents von Hemusit (Kiddcreekit) verglichen. Die Beziehung zwischen Hemusitsensu stricto und diesen jetzt beschriebenen Varietäten wird auf der Basis einfacher und gekoppelter chemischer Substitution diskutiert. Auf dieser Basis werden Schlüsse auf die Valenz von Sb, Bi Mo und Cu in der Hemusit-Struktur gezogen.