Major ion concentrations and chlorine isotope composition of water-soluble chloride and structurally bound chloride in DSDP/ODP serpentinized ultramafic rocks

Eight DSDP/ODP cores were analyzed for major ion concentrations and d37Cl values of water-soluble chloride (d37Clwsc) and structurally bound chloride (d37Clsbc) in serpentinized ultramafic rocks. This diverse set of cores spans a wide range in age, temperature of serpentinization, tectonic setting, and geographic location of drilled serpentinized oceanic crust. Three of the cores were sampled at closely spaced intervals to investigate downhole variation in Cl concentration and chlorine isotope composition. The average total Cl content of all 86 samples is 0.26±0.16 wt.% (0.19±0.10 wt.% as water-soluble Cl (Xwsc) and 0.09±0.09 wt.% as structurally bound Cl (Xsbc)). Structurally bound Cl concentration nearly doubles with depth in all cores; there is no consistent trend in water-soluble Cl content among the cores. Chlorine isotope fractionation between the structurally bound Cl**- site and the water-soluble Cl**- site varies from -1.08? to +1.16?, averaging to +0.21?. Samples with negative fractionations may be related to reequilibration of the water-soluble chloride with seawater post-serpentinite formation. Six of the cores have positive bulk d37Cl values (+0.05? to +0.36?); the other two cores (173-1068A (Leg-Hole) and 84-570) have negative bulk d37Cl values (-1.26? and -0.54?). The cores with negative d37Cl values also have variable Cl**-/SO4**2- ratios, in contrast to all other cores. The isotopically positive cores (153-920D and 147-895E) show no isotopic variation with depth; the isotopically negative core (173-1068A) decreases by ~1? with depth for both the water-soluble and structurally bound Cl fractions. Non-zero bulk d37Cl values indicate Cl in serpentinites was incorporated during original hydration and is not an artifact of seawater infiltration during drilling. Cores with positive d37Cl values are most likely explained by open system fractionation during hydrothermal alteration, with preferential incorporation of 37Cl from seawater into the serpentinite and loss of residual light Cl back to the ocean. Fluid / rock ratios were probably low as evidenced by the presence of water-soluble salts. The two isotopically negative cores are characterized by a thick overlying sedimentary package that was in place prior to serpentinization. We believe the low d37Cl values of these cores are a result of hydration of ultramafic rock by infiltrating aqueous pore fluids from the overlying sediments. The resulting serpentinites inherit the characteristic negative d37Cl values of the pore waters. Chlorine stable isotopes can be used to identify the source of the serpentinizing fluid and ultimately discern chemical and tectonic processes involved in serpentinization.

Influence of sugar cane burning on aerosol soluble ion composition in Southeastern Brazil

Seasonal variability in the major soluble ion composition of atmospheric particulate matter in the principal sugar cane growing region of central São Paulo State indicates that pre-harvest burning of sugar cane plants is an important influence on the regional scale aerosol chemistry. Samples of particulate matter were collected between April 1999 and February 2001 in coarse (> 3.5 mum) and fine (< 3.5 mum) fractions, and analysed for HCOO-, CH3COO-, C2C42-, SO42- . Results indicated that the principal sources of the aerosols investigated NO3-, Cl-, Na+, K+, NH4+, Mg2+ and Ca2+ were local or regional in nature (scale of tens to a few hundreds of km), and that differences between air masses of varying origins were small. Fine particles were typically acidic, containing secondary nitrates, sulphates and organic species. Coarse fraction concentrations were mainly influenced by physical parameters (wind speed, movement of vehicles and surface condition) affecting rates of re-suspension, although secondary nitrate and sulphate were also present in the larger particles.Concentrations of all measured species except sodium and chloride were higher during the burning season. Although concentrations were lower than often found in polluted urban environments, the massive increases during much of the year, due to a single anthropogenic activity (sugar cane burning) are indicative of a very large perturbation of the lower troposphere in the region relative to the natural condition. These aerosols are suspected of promoting respiratory disease. They also represent an important mechanism for the tropospheric transport of species relevant to surface acidification (sulphates, nitrates, ammonium and organic acids) and soil nutrient status (potassium, nitrogen, ammonium, calcium), so their impact on fragile natural ecosystems (following deposition) needs to be considered. (C) 2004 Elsevier Ltd. All rights reserved.

Haemolymph inorganic ion composition of crustaceans from the Southern Ocean

Brachyuran and anomuran decapod crabs do not occur in the extremely cold waters of the Antarctic continental shelf whereas caridean and other shrimp-like decapods, amphipods and isopods are highly abundant. Differing capacities for extracellular ion regulation, especially concerning magnesium, have been hypothesised to determine cold tolerance and by that the biogeography of Antarctic crustaceans. Magnesium is known to have a paralysing effect, which is even more distinct in the cold. As only few or no data exist on haemolymph ionic composition of Sub-Antarctic and Antarctic crustaceans, haemolymph samples of 12 species from these regions were analysed for the concentrations of major inorganic ions (Na+, K+, Ca2+, Mg2+, Cl-, SO4 2-) by ion chromatography. Cation relationships guaranteed neuromuscular excitability in all species. Sulphate and potassium correlated positively with magnesium concentration. The Antarctic caridean decapod as well as the amphipods maintained low (6-20% of ambient sea water magnesium concentration), Sub-Antarctic brachyuran and anomuran crabs as well as the Antarctic isopods high (54-96% of ambient sea water magnesium concentration) haemolymph magnesium levels. In conclusion, magnesium regulation may explain the biogeography of decapods, but not that of the peracarids.

(Table 2) Salinity, pH, alkalinity and major ion concentrations in ANDRILL core AND-2A pore water

The compositional record of the AND-2A drillcore is examined using petrological, sedimentological, volcanological and geochemical analysis of clasts, sediments and pore waters. Preliminary investigations of basement clasts (granitoids and metasediments) indicate both local and distal sources corresponding to variable ice-volume and ice-flow directions. Low abundance of sedimentary clasts (e.g., arkose, litharenite) suggests reduced contributions from sedimentary covers while intraclasts (e.g., diamictite, conglomerate) attest to intrabasinal reworking. Volcanic material includes pyroclasts (e.g., pumice, scoria), sediments and lava. Primary and reworked tephra layers occur within the Early Miocene interval (1093 to 640 metres below sea floor mbsf). The compositions of volcanic clasts reveal a diversity of alkaline types derived from the McMurdo Volcanic Group. Finer-grained sediments (e.g., sandstone, siltstone) show increases in biogenic silica and volcanic glass from 230 to 780 mbsf and higher proportions of terrigenous material c. 350 to 750 mbsf and below 970 mbsf. Basement clast assemblages suggest a dominant provenance from the Skelton Glacier - Darwin Glacier area and from the Ferrar Glacier - Koettlitz Glacier area. Provenance of sand grains is consistent with clast sources. Thirteen Geochemical Units are established based on compositional trends derived from continuous XRF scanning. High values of Fe and Ti indicate terrigenous and volcanic sources, whereas high Ca values signify either biogenic or diagenic sources. Highly alkaline and saline pore waters were produced by chemical exchange with glass at moderately elevated temperatures.

EISCAT observations of ion composition and temperature anisotropy in the high-latitude F-region

The papers by Winser et al. [(1990) J. atmos. terr. Phys.52, 501] and Häggström and Collis [(1990) J. atmos. terr. Phys.52, 519] used plasma flows and ion temperatures, as measured by the EISCAT tristatic incoherent scatter radar, to investigate changes in the ion composition of the ionospheric F-layer at high latitudes, in response to increases in the speed of plasma convection. These studies reported that the ion composition rapidly changed from mainly O+ to almost completely (>90%) molecular ions, following rapid increases in ion drift speed by >1 km s−1. These changes appeared inconsisent with theoretical considerations of the ion chemistry, which could not account for the large fractions of molecular ions inferred from the obsevations. In this paper, we discuss two causes of this discrepancy. First, we reevaluate the theoretical calculations for chemical equilibrium and show that, if we correct the derived temperatures for the effect of the molecular ions, and if we employ more realistic dependences of the reaction rates on the ion temperature, the composition changes derived for the faster convection speeds can be explained. For the Winser et al. observations with the radar beam at an aspect angle of ϕ = 54.7° to the geomagnetic field, we now compute a change to 89% molecular ions in < 2 min, in response to the 3 km s−1 drift. This is broadly consistent with the observations. But for the two cases considered by Häggström and Collis, looking along the field line (ϕ = 0°), we compute the proportion of molecular ions to be only 4 and 16% for the observed plasma drifts of 1.2 and 1.6 km s−1, respectively. These computed proportions are much smaller than those derived experimentally (70 and 90%). We attribute the differences to the effects of non-Maxwellian, anisotropic ion velocity distribution functions. We also discuss the effect of ion composition changes on the various radar observations that report anisotropies of ion temperature.

Major carotenoid composition of Brazilian Valencia orange juice: Identification and quantification by HPLC

The carotenoid composition of Brazilian Valencia orange juice was determined by open column chromatography (OCC) and high-performance liquid chromatography. Carotenoid pigments were extracted using acetone and saponified using 10% methanolic potassium hydroxide. Sixteen pigments were isolated by OCC and identified as alpha-carotene, zeta-carotene, beta-carotene, alpha-cryptoxanthin, beta-cryptoxanthin, lutein-5,6-epoxide, violaxanthin, lutein, antheraxanthin, zeaxanthin, luteoxanthin A, luteoxanthin B, mutatoxanthin A, mutatoxanthin B, auroxanthin B and trollichrome B. Thirteen carotenoid pigments were separated using a ternary gradient (acetonitrile-methanol-ethyl acetate) elution on a C-18 reversed-phase column. Among these, violaxanthin, lutein, zeaxanthin, beta-cryptoxanthin, zeta-carotene, alpha-carotene, and beta-carotene were quantified. The total carotenoid content was 12 +/- 6.7 mg/1, and the major carotenoids were lutein (23%), beta-cryptoxanthin (21%), and zeaxanthin (20%). 2005 Elsevier Ltd. All rights reserved.

Representativeness and seasonality of major ion records derived from NEEM firn cores

The seasonal and annual representativeness of ionic aerosol proxies (among others, calcium, sodium, ammonium and nitrate) in various firn cores in the vicinity of the NEEM drill site in northwest Greenland have been assessed. Seasonal representativeness is very high as one core explains more than 60 % of the variability within the area. The inter-annual representativeness, however, can be substantially lower (depending on the species) making replicate coring indispensable to derive the atmospheric variability of aerosol species. A single core at the NEEM site records only 30 % of the inter-annual atmospheric variability in some species, while five replicate cores are already needed to cover approximately 70 % of the inter-annual atmospheric variability in all species. The spatial representativeness is very high within 60 cm, rapidly decorrelates within 10 m but does not diminish further within 3 km. We attribute this to wind reworking of the snow pack leading to sastrugi formation. Due to the high resolution and seasonal representativeness of the records we can derive accurate seasonalities of the measured species for modern (AD 1990–2010) times as well as for pre-industrial (AD 1623–1750) times. Sodium and calcium show similar seasonality (peaking in February and March respectively) for modern and pre-industrial times, whereas ammonium and nitrate are influenced by anthro pogenic activities. Nitrate and ammonium both peak in May during modern times, whereas during pre-industrial times ammonium peaked during July–August and nitrate during June–July.

Major element composition of phenocrysts from the volcanic basement of ODP Hole 125-786B, Izu forearc region, Philippine Sea

Early arc volcanism during Eocene to Oligocene in the Izu forearc region was investigated during ODP Legs 125 and 126 in 1989, and effusive and intrusive volcanics were recovered from Leg 125 Site 786. These rocks were all classified into boninites and associated rocks by Leg 125 Shipboard Scientific Party, and they concluded that boninitic volcanism had occurred before 40 Ma, and arc tholeiitic volcanism began after 40 Ma. In this study, lava flows and breccias that classified into boninite series are divided into two groups, tholeiite and boninite, based on petrographical and petrological properties. Both series are also distinguished by bulk rock composition. It is considered that the sources of both rock types have similar depleted compositions because of their similar, very low bulk HFSE concentrations. We suggest that boninitic and tholeiitic volcanism occurred closely in time and space, and reflected different temperature and water condition.