The composition and crystallinity of the near-surface regions of weathered alkali feldspars

Our ability to identify thin non-stoichiometric and amorphous layers beneath mineral surfaces has been tested by undertaking X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) work on alkali feldspars from pH 1 dissolution experiments. The outcomes of this work were used to help interpret XPS and TEM results from alkali feldspars weathered for <10,000 years in soils overlying the Shap Granite (north-west England). The chemistry of effluent solutions indicates that silica-rich layers a few nanometers in thickness formed during the pH 1 experiments. These layers can be successfully identified by XPS and have lower Al/Si, Na/Si, K/Si and Ca/Si values than the outermost ∼9 nm of unweathered controls. Development of Al-Si non-stoichiometry is coupled with loss of crystal structure to produce amorphous layers that are identifiable by TEM where >∼2.5 nm thick, whereas the crystallinity of albite is retained despite leaching of Na to depths of tens to hundreds on nanometers. Integration of XPS data over the outermost 6-9 nm of naturally weathered Shap feldspars shows that they have stoichiometric Al/Si and K/Si ratios, which is consistent with findings of previous TEM work on the same material that they lack amorphous layers. There is some XPS evidence for loss of K from the outermost couple of nanometers of Shap orthoclase, and the possibility of leaching of Na from albite to greater depths cannot be excluded using the XPS or TEM results. This study demonstrates that the leached layer model, as formulated from laboratory experiments, is inapplicable to the weathering of alkali feldspars within acidic soils, which is an essentially stoichiometric reaction.     

Geochemistry and mineralogy of arsenic in (natural) anaerobic groundwaters

Here new data from field bioremediation experiments and geochemical modeling are reported to illustrate the principal geochemical behavior of As in anaerobic groundwaters. In the field bioremediation experiments, groundwater in Holocene alluvial aquifers in Bangladesh was amended with labile water-soluble organic C (molasses) and MgSO₄ to stimulate metabolism of indigenous SO₄-reducing bacteria (SRB). In the USA, the groundwater was contaminated by Zn, Cd and SO₄, and contained <10 μg/L As under oxidized conditions, and a mixture of sucrose and methanol were injected to stimulate SRB metabolism. In Bangladesh, groundwater was under moderately reducing conditions and contained ∼10 mg/L Fe and ∼100 μg/L As. In the USA experiment, groundwater rapidly became anaerobic, and dissolved Fe and As increased dramatically (As > 1000 μg/L) under geochemical conditions consistent with bacterial Fe-reducing conditions. With time, groundwater became more reducing and biogenic SO₄ reduction began, and Cd and Zn were virtually completely removed due to precipitation of sphalerite (ZnS) and other metal sulfide mineral(s). Following precipitation of chalcophile elements Zn and Cd, the concentrations of Fe and As both began to decrease in groundwater, presumably due to formation of As-bearing FeS/FeS₂. By the end of the six-month experiment, dissolved As had returned to below background levels. In the initial Bangladesh experiment, As decreased to virtually zero once biogenic SO₄ reduction commenced but increased to pre-experiment level once SO₄ reduction ended. In the ongoing experiment, both SO₄ and Fe(II) were amended to groundwater to evaluate if FeS/FeS₂ formation causes longer-lived As removal. Because As-bearing pyrite is the common product of SRB metabolism in Holocene alluvial aquifers in both the USA and Southeast Asia, it was endeavored to derive thermodynamic data for arsenian pyrite to better predict geochemical processes in naturally reducing groundwaters. Including the new data for arsenian pyrite into Geochemist’s Workbench, its stability field completely dominates in reducing Eh–pH space and “displaces” other As-sulfides (orpiment, realgar) that have been implied to be important in previous modeling exercises and reported in rare field conditions.     

Diel Patterns in Chlorophyll <Emphasis Type="Italic">a</Emphasis> Specific Absorption Coefficient and Absorption Efficiency Factor of Picoplankton

Diel patterns in the chlorophyll a specific absorption coefficient of surface picoplankton, a*_pico (γ) (m²·[mg chlorophyll a]⁻¹), were studied at 7 stations under daily cycle of in situ light condition in the western subarctic Pacific and Japan Sea. All the data were normalized by dividing the anomaly with daily averaged a*_pico (γ). Opposite diel patterns were observed for the normalized a*_pico (443) and a*_pico (675) with maximum toward dawn or dusk and minimum toward midday at 4 stations under low-irradiance (LI) conditions and vice versa at 3 stations under high-irradiance (HI) conditions. The absorption efficiency factors at red absorption peak, Q _a (675), were determined by reconstruction with intracellular chlorophyll a concentration and cell diameter. The normalized Q _a (675) also showed diel pattern with maximum toward midday and minimum toward dawn or dusk under LI. The diel pattern in a*_pico (675) and Q _a (675) were primarily caused by changes in intracellular chlorophyll a concentration due to photoadaptation under LI. The diel pattern in a*_pico (443) was influenced by pigmentation, as recognized by blue to red ratio [a*_pico (443)/a*_pico (675)] under HI. This study proposed that the opposite diel pattern in a*_pico (γ) might occur for a wide range of algal species. The results presented here have important consequences for the interpretation of diel variations in optical properties observed in the open ocean.     

Fate and effects of a heavy fuel oil spill on a Georgia salt marsh

Addition of a heavy oil to a Spartina salt marsh in the autumn resulted in high concentrations of polycyclic aromatic hydrocarbons in sediment and benthic animals. The highest concentrations of phenanthrene, chrysene and fluoranthene in the sediment were 112, 105 and 75 ng/g sediment, respectively. These concentrations rapidly decreased during the 20 week period following the spill. The times for these hydrocarbons to decrease to 50% of their highest values, i.e. half-life, were approximately 100, 70 and 30 days in sediment, mussels and oysters, respectively. Benthic macrofauna species showed three responses to oil addition which included no change, an increase, or a decrease in the population. No changes were noted in populations of fiddler crabs (Uca pugnax), oysters (Crassostrea virginica), and mussels (Modiolus demissus). Mud snails (Nassarius obsoleta) increased in density after the spill due to immigration of adult snails from untreated areas to scavenge on animals killed by the oil. Many of the adult periwinkles (Littorina irrorata) were killed by the oil. In the spring, juvenile periwinkles recolonised to oiled areas as a result of larvae settling.     

An alkaline unwinding assay for the detection of DNA damage in aquatic organisms

This paper reports a rapid and facile procedure for obtaining of DNA from small, whole aquatic organisms (fathead minnow, Pimephales promelas) as well as from the liver of another species (bluegill sunfish, Lepomis macrochirus) and the subsequent estimation of its double strandedness. DNA was isolated from various tissues by homogenization in a basic pH solution containing detergent followed by differential extraction using organic solvents. Additional purification was accomplished by molecular sieve chromatography. Under defined alkaline unwinding conditions, the amount of double-stranded and single-stranded DNA was determined using the bisbenzimidazole dye Hoechst 33258. The technique was used to detect the occurrence of strand breaks in DNA of fathead minnows chemically exposed to benzo[a]pyrene.     

Internal generation of waves: Delta source function method and source term addition method

In this study, we investigate two internal wave generation methods in numerical modeling of time-dependent equations for water wave propagation, i.e., delta source function method and source term addition method, the latter of which has been called the line source method in literatures. We derive delta source functions for the Boussinesq-type equations and extended mild-slope equations. By applying the fractional step splitting method, we show that the delta source function method is equivalent to the source term addition method employing the energy velocity. This suggests that the energy velocity should be used rather than the phase velocity for the transport of incident wave energy in the source term addition method. Finally, the performance of the delta source function method is verified by accurately generating nonlinear cnoidal waves as well as linear waves for horizontally one-dimensional cases.     

Generation of random waves in time-dependent extended mild-slope equations using a source function method

We develop techniques of numerical wave generation in the time-dependent extended mild-slope equations of Suh et al. [1997. Time-dependent equations for wave propagation on rapidly varying topography. Coastal Engineering 32, 91–117] and Lee et al. [2003. Extended mild-slope equation for random waves. Coastal Engineering 48, 277–287] for random waves using a source function method. Numerical results for both regular and irregular waves in one and two horizontal dimensions show that the wave heights and the frequency spectra are properly reproduced. The waves that pass through the wave generation region do not cause any numerical disturbances, showing usefulness of the source function method in avoiding re-reflection problems at the offshore boundary.     

Effects of salinity, temperature and food type on the uptake and elimination rates of cd, cr, and zn in the asiatic clamcorbicula fluminea

Laboratory radiotracer experiments were conducted to determine assimilation efficiencies (AE) from ingested algal food and oxic sediment particles, uptake rates from the dissolved phase, and the efflux rates of Cd, Cr and Zn in the Asiatic clamCorbicula fluminea. Among three elements, AE from both algal and sediment food was greatest for Cd, followed by Zn and Cr. The AEs of tested elements from algal food(Phaeodactylum tricornutum) were consistently higher than those from sediments at a given salinity and temperature. The influence of salinity (0, 4 and 8 psu) and temperature (5, 13 and 21¼) on the metal AEs was not evident for most tested elements, except Cd AEs from sediment. The rate constant of metal uptake from the dissolved phase (k _u was greatest for Cd, followed by Zn and Cr in freshwater media. However, in saline water, thek _u of Zn were greater than those of Cd. The influx rate of all tested metals increased with temperature. The efflux rate constant was greatest for Cr (0.02 d^-1), followed by Zn (0.010~0.017 d^-1) and Cd (0.006 d^-1). The efflux rate constant for Zn in clam tissues depurated in 0 psu (0.017 d^-1) was faster than that in 8 psu (0.010 d^-1). Overall results showed that the variation of salinity and temperature in estuarine systems can considerably influence the metal bioaccumulation potential in the estuarine clamC. fluminea. The relatively high Cd accumulation capacity ofC. fluminea characterized by the high AE, high dissolved influx rate and low efflux rate, suggested that this clam species can be used as an efficient biomonitor for the Cd contamination in freshwater and estuarine environments.     

CO<Subscript>2</Subscript> Flux Measurements over the Sea Surface by Eddy Correlation and Aerodynamic Techniques

The measurements of the vertical transport of CO₂ were carried out over the Sea of Japan using the specially designed pier of Kyoto University on September 20 to 22, 2000. CO₂ fluxes were measured by the eddy correlation and aerodynamic techniques. Both techniques showed comparable CO₂ fluxes during sea breeze conditions: −0.001 to −0.08 mg m⁻²s⁻¹ with the mean of −0.05 mg m⁻²s⁻¹. This means that the measuring site satisfies the fetch requirement for meteorological observations under sea breeze conditions. Moreover, the eddy diffusivity coefficient used in the aerodynamic technique is found to be consistent with the coefficient used in the eddy correlation technique. The present result leads us to conclude that the aerodynamic technique may be applicable to underway CO₂ flux measurements over the ocean and may be used in place of the bulk technique. The important point is the need to maintain a measuring accuracy of CO₂ concentration difference of the order of 0.1 ppmv on the research vessels or the buoys.     

Roles of Biogeochemical Processes in the Oceanic Carbon Cycle Described with a Simple Coupled Physical-Biogeochemical Model

To evaluate the contribution of biogeochemical processes to the oceanic carbon cycle and to calculate the ratio of calcium carbonate to organic carbon downward export, we have incorporated biological and alkalinity pumps in the yoked high-latitude exchange/interior diffusion-advection (YOLDA) model. The biogeochemical processes are represented by four parameters. The values of the parameters are tuned so that the model can reproduce the observed phosphate and alkalinity distributions in each oceanic region. The sensitivity of the model to the biogeochemical parameters shows that biological production rates in the euphotic zone and decomposition depths of particulate matters significantly influence horizontal and vertical distributions of biogeochemical substances. The modeled vertical fluxes of particulate organic phosphorus and calcium carbonate are converted to vertical carbon fluxes by the biological pump and the alkalinity pump, respectively. The downward carbon flux from the surface layer to the deep layer in the entire region is estimated to be 3.36 PgC/yr, which consists of 2.93 PgC/yr from the biological pump and 0.43 PgC/yr from the alkalinity pump, which is consistent with previous studies. The modeled rain ratio is higher with depth and higher in the Pacific and Indian Oceans than in the Atlantic Ocean. The global rain ratio at the surface layer is calculated to be 0.14 to 0.15. This value lies between the lower and higher ends of the previous estimates, which range widely from 0.05 to 0.25. This study indicates that the rain ratio is unlikely to be higher than 0.15, at least in the surface waters.