Sulfur dioxide and dimethyl sulfide in the central Pacific troposphere

Boundary-layer and free-troposphere measurements of sulfur dioxide, dimethyl sulfide, and carbon disulfide were made during transits of the central and southern Pacific Ocean between Hawaii and Australia. Sulfur dioxide was generally less than 100 pptv and highly variable with no correlation with respect to geographic location or altitude. Dimethyl sulfide in the boundary layer had a concentration range of <10 to 200 pptv. Highest concentrations of DMS were in the equatorial region of the southern hemisphere although the concentrations were dependent on location and meteorological regime. In the region of the Fiji Islands several boundary layer samples had SO₂, DMS, and CS₂. In 1989, additional SO₂ measurements were made between Hawaii and the equator and to the west of Hawaii downwind of the Kilauea volcano plumes.Paper submitted to the 7th International Symposium of the Commission for Atmospheric Chemistry and Global Pollution on the Chemistry of the Global Atmosphere held in Chamrousse, France, from 5 to 11 September 1990.     

Distributions of pesticides and organic contaminants between water and suspended sediment,San Francisco Bay,California

Suspended-sediment and water samples were collected from San Francisco Bay in 1991 during low river discharge and after spring rains. All samples were analyzed for organophosphate, carbamate, and organochlorine pesticides; petroleum hydrocarbons; biomarkers; and polynuclear aromatic hydrocarbons. The objectives were to determine the concentrations of these contaminants in water and suspended sediment during two different hydrologic conditions and to determine partition coefficients of the contaminants between water and sediment. Concentrations of hydrophobic contaminants, such as polynuclear aromatic hydrocarbons, varied with location of sample collection, riverine discharge, and tidal cycle. Concentrations of hydrophobic contaminants in suspended sediments were highest during low river discharge but became diluted as agricultural soils entered the bay after spring rains. Polynuclear aromatic hydrocarbons defined as dissolved in the water column were not detected. The concentrations sorbed on suspended sediments were variable and were dependent on sediment transport patterns in the bay. In contrast, the relatively hydrophilic organophosphate pesticides, such as chlorpyrifos and diazinon, has a more uniform concentration in suspended sediment. These pesticides were detected only after spring rains. Most of the measured diazinon, at least 98% for all samples, was in the dissolved phase. Measured partition coefficients for diazinon generally were uniform, which suggests that suspended-sediment concentrations were close to equilibrium with dissolved concentrations. The concentration of diazinon sorbed to suspended sediments, at any given sampling site, was driven primarily by the more abundant solution concentration. The concentrations of diazinon sorbed to suspended sediments, therefore, were independent of the patterns of sediment movement.     

Metabasalts from the Mid-Atlantic Ridge: new insights into hydrothermal systems in slow-spreading crust

An extensive suite of hydrothermally altered rocks were recovered byAlvin and dredging along the MARK [Mid-Atlantic Ridge, south of the Kane Fracture Zone (23–24°N)] where detachment faulting has provided a window into the crustal component of hydrothermal systems. Rocks of basaltic composition are altered to two assemblages with these characteristics: (i) type I: albitic plagioclase (An_02–10)+mixed-layer smectite/chlorite or chlorite±actinolite±quartz±sphene, <10% of the clinopyroxene is altered, and there is no trace metal mobility; (ii) type II: plagioclase (An_10–30)+amphibole (actinolite-magnesio-hornblende) +chlorite+sphene, >20% of the clinopyroxene is altered, and Cu and Zn are leached. The geochemical signature of these alteration types reflects the relative proportion and composition of secondary minerals, and the degree of alteration of primary phases, and does not show simple predictive relationships. Element mobilities indicate that both alteration types formed at low water/rock ratios. The MARK assemblages are typical of the greenschist and transition to the amphibolite facies, and represent two distinct, albeit overlapping, temperature regimes: type I-180 to 300°C and type II-250 to 450°C. By analogy with DSDP/ODP Hole 504B and many ophiolites, the MARK metabasalts were altered within the downwelling limb of a hydrothermal cell and type I and II samples formed in the upper and lower portions of the sheeted like complex, respectively. Episodic magmatic and hydrothermal events at slow-spreading ridges suggest that these observed mineral assemblages represent the cumulative effects of more than one hydrothermal event. Groundmass and vein assemblages in the MARK metabasalts indicate either that alteration conditions did not change during successive hydrothermal events or that these assemblages record only the highest temperature event. Lack of retrograde reactions or overprinting of lower temperature assemblages (e.g., zeolites) suggests that there is a continuum in alteration conditions while crustal segments remain in the ridge axis environment. The type II samples may be representative of thereaction zone where compositions of hydrothermal fluids actively venting at the seafloor today become fixed. This prediction necessitates interaction between hydrothermal fluids and intersertal glass and/or mafic phases, in addition to plagioclase, in order to produce the observed range in vented fluid pH.     

Vertical distribution of infauna in sediments of a subestuary of central Chesapeake Bay

The vertical distribution of infauna was quantified in eight strata from 0–35 cm in sand and mud sediments of a lower mesohaline subestuary of Chesapeake Bay. Large numbers of small polychaetes, amphipods, and clams occurred in the upper 5 cm of both sediment types, whereas large clams (Macoma balthica in mud andMya arenaria in sand) extended down to 30 cm and comprised most of the biomass in their respective sediment types. There was extensive overlap of the species inhabiting both sediment types. Vertical stratification within and among species apparently reflected constraints on burrowing depth related to body size rather than resource partitioning among competitors. The maximal sediment penetration of 35 cm, which was exhibited byHeteromastus filiformis, was considerably less than the maximal penetration for deep burrowing species in some marine infaunal communities. Several species which burrowed deeper than 5 cm exhibited significant temporal shifts in their vertical distribution.     

Biogeochemical processes affecting the distribution and vertical transport of hydrocarbon residues in the coastal Mediterranean

Sediments, sediment trap material, dominant surface plankton and collected fecal material were sampled concurrently with surface seawater in a coastal Mediterranean ecosystem and analyzed for non-volatile hydrocarbons and chlorinated hydrocarbons. Results showed consistent partitioning of hydrocarbon classes between dissolved and particulate phases of surface waters which appeared to be related to component solubility and particle availability. Analysis of biological materials showed the biota were important not only in packaging residues into large, fast sinking particles, but also in modifying the composition of components through metabolism and selective incorporation into body tissues and feces. Apparent sedimentation rate was calculated by analysis of ²¹⁰Pb in sediment core samples and used to estimate average deposition rates of organics to the sea/sediment interface. The flux of particles through 100 m, as measured in the trap material in this sampling interval, was sufficient to balance most of the petroleum input to the sediments but accounted for only 17% of the average flux of PCBs to the sediments, and virtually none of the more soluble chlorinated hydrocarbon flux. Vertical transport via large fecal material compared to average background particles was seasonally low corresponding to a seasonal minimum in plankton biomass in late summer. Results show that hydrocarbon residues transported long distances away from input sources are highly modified, pointing to the geochemical significance of physical-chemical partitioning between seawater phases, incorporation into organisms and fecal material and biological/chemical degradation.     

The effect of Al(OH)4 on the dissolution rate of quartz

The influence of Al(OH)₄⁻ on the dissolution rate of quartz at pH 10-13 and 59-89 °C was determined using batch experiments. Al(OH)₄⁻ at concentrations below gibbsite solubility depressed the dissolution rate by as much as 85%, and this effect was greater at lower pH and higher Al(OH)₄⁻ concentration. Dissolution rates increased with increasing temperature; however, the percent decrease in rate due to the presence of Al(OH)₄⁻ was invariant with temperature for a given H⁺ activity and Al(OH)₄⁻ concentration. These data, along with what is known about Al-Si interactions at high pH, are consistent with Al(OH)₄⁻ and Na⁺ co-adsorbing on silanol sites and passivating the surrounding quartz surface. The observed pH dependence, and lack of temperature dependence, of inferred Al(OH)₄⁻ sorption also supports the assumption that the acid-base behavior of the surface silanol groups has only a small temperature dependence in this range. A Langmuir-type adsorption model was used to express the degree of rate depression for a given in situ pH and Al(OH)₄⁻ concentration. Incorporation of the rate data in the absence of aluminate into models that assume a first-order dependence of the rate on the fraction of deprotonated silanol sites was unsuccessful. However, the data are consistent with the hypothesis proposed in the literature that two dissolution mechanisms may be operative in alkaline solutions: nucleophilic attack of water on siloxane bonds catalyzed by the presence of a deprotonated silanol group and OH⁻ attack catalyzed by the presence of a neutral silanol group. The data support the dominance of the second mechanism at higher pH and temperature.     

Geomagnetism in the satellite era

Kathryn A Whaler considers the opportunities and challenges arising from the greatly enhanced geomagnetism data sets now available, in her 2006 Presidential Address.