δC and δN variations in Weddell Sea particulate organic matter

The δ¹³C and δ¹⁵N of particulate organic matter (POM) sampled from the Weddell Sea in 1986 and 1988 ranged from −30.4 to − 16.7%o and from −5.4 to +41.3%o, respectively. These large variations in POM δ¹³C and δ¹⁵N may reflect spatial/temporal changes in the concentrations and isotope abundances of CO₂(aq.) and NH₄⁺, respectively. Elevated isotope values were found exclusively in POM in or closely associated with sea ice, which may be the source of the ¹³C- and ¹⁵N-enriched sediments observed in this region.     

Microsomal cytochrome P-450 function in fish evaluated with polyclonal and monoclonal antibodies to cytochrome P-450E from scup (Stenotomus chrysops)

Monooxygenase reactions catalyzed by cytochromes P-450 are paramount in the oxidative metabolism of many xenobiotics, determining both the persistence and effects of numerous types of compounds. Immunological probes are proving useful in evaluating the functions of P-450 isozymes in microsomal preparations from many species. The regulation of specific isozymes by endogenous and exogenous factors can also be evaluated with such probes. Here we describe studies on the activities apparently catalyzed by induced P-450 in fish, evaluated with both polyclonal and monoclonal antibodies to cytochrome P-450E, the apparent major β-naphthoflavone(BNF) or methylcholanthrene(MC)-inducible isozyme purified from scup (S. chrysops) liver.     

Early diagenesis in rapidly accumulating sediments on the Alboran slope, ODP site 976

 The oxidation and reduction that occur during early diagenesis of sediments has been studied in the interstitial waters of a rapidly accumulating sedimentary sequence from the Mediterranean margin of Spain. A series of reactions that are mediated by progressively lower free energy derived from oxidation of organic matter is evident in the sedimentary sequence. Iron and manganese are rapidly reduced. Phosphate and alkalinity maxima at a subbottom depth of 15 m indicate maximal organic matter degradation. Methane first appears at ∼20 m subbottom after sulfate is depleted, and its concentrations quickly climb. Received: 27 October 1997 / Revision received: 4 March 1998     

Modeling the effects of bond environment on equilibrium iron isotope fractionation in ferric aquo-chloro complexes

Four or five sets of ab initio models, including Unrestricted Hartree Fock (UHF) and hybrid Density Functional Theory (DFT) are calculated for each species in a series of aqueous ferric aquo-chloro complexes: , , , FeCl₃(H₂O)₃, FeCl₃(H₂O)₂, , FeCl₅H₂O²⁻, , ) in order to determine the relative isotopic fractionation among the complexes, to compare the results of different models for the same complexes, to examine factors that influence the magnitude of the isotopic fractionation, and to compare bond-partner-driven fractionation with redox-driven fractionation.Relative to , all models show a nearly linear decrease in ⁵⁶Fe/⁵⁴Fe as the number of Cl⁻ ions per Fe³⁺ ion increases, with slopes of −0.8‰ to −1.0‰ per Cl⁻ at 20 °C. At 20 °C, 1000 ln β (β = ⁵⁶Fe/⁵⁴Fe reduced partition function ratio relative to a dissociated Fe atom) values range from 8.93‰ to 9.73‰ for , 8.04-9.12‰ for , 7.61-8.73‰ for , 7.14-8.25‰ for , and 3.09-4.41‰ for . The fractionation between and ranges from 1.5‰ to 2.6‰, depending on the model; this is comparable in magnitude to fractionation effects due to Fe³⁺/Fe²⁺ redox reactions. β values from the UHF models are consistently higher than those from the hybrid DFT models.Isotopic fractionation is shown to be sensitive to differences in ligand bond stiffness (above), coordination number, bond length, and the frequency of the asymmetric Fe-X stretching vibrational mode, as predicted by previous theoretical studies. Complexes with smaller coordination numbers have higher 1000 ln β (7.46‰, 5.25‰, and 3.48‰ for , ,, respectively, from the B3LYP/6-31G(d) model). Species with the same number of chlorides but fewer waters also show the effect of coordination number on 1000 ln β: (7.46‰ vs. 7.05‰ for FeCl₃(H₂O)₂ vs. FeCl₃(H₂O)₃ and 5.25‰ vs. 4.94‰ for vs. FeCl₅H₂O²⁻ with the B3LYP/6-31G(d) model). As more Fe-Cl bonds substitute for Fe-OH₂ bonds (with a resulting decrease in β), the lengths of the Fe-Cl bonds and the Fe-O bonds increase.Preliminary modeling of shows an Fe³⁺/Fe²⁺ fractionation of 3.2‰ for the B3LYP/6-31G(d) model, in agreement with previous studies. The addition of an explicit outer hydration sphere of 12 H₂O molecules to models of improves agreement with measured vibrational frequencies and bond lengths; 1000 ln β increases by 0.8-1.0‰. An additional hydration sphere around increases 1000 ln β by only 0.1‰.Isotopic fractionations predicted for this simple system imply that ligands present in an aqueous iron environment are potentially important drivers of fractionation, and suggest that significant fractionation effects are likely in other aqueous systems containing sulfides or organic ligands. Fractionation effects due to both speciation and redox must be considered when interpreting iron isotope fractionations in the geological record.     

The statistical distribution of magnetotelluric apparent resistivity and phase

The marginal distributions for the magnetotelluric (MT) magnitude squared response function (and hence apparent resistivity) and phase are derived from the bivariate complex normal distribution that describes the distribution of response function estimates when the Gauss–Markov theorem is satisfied and the regression random errors are normally distributed. The distribution of the magnitude squared response function is shown to be non-central chi-squared with 2 degrees of freedom, with the non-centrality parameter given by the squared magnitude of the true MT response. The standard estimate for the magnitude squared response function is biased, with the bias proportional to the variance and hence important when the uncertainty is large. The distribution reduces to the exponential when the expected value of the MT response function is zero. The distribution for the phase is also obtained in closed form. It reduces to the uniform distribution when the squared magnitude of the true MT response function is zero or its variance is very large. The phase distribution is symmetric and becomes increasingly concentrated as the variance decreases, although it is shorter-tailed than the Gaussian. The standard estimate for phase is unbiased. Confidence limits are derived from the distributions for magnitude squared response function and phase. Using a data set taken from the 2003 Kaapvaal transect, it is shown that the bias in the apparent resistivity is small and that confidence intervals obtained using the non-parametric delta method are very close to the true values obtained from the distributions. Thus, it appears that the computationally simple delta approximation provides accurate estimates for the confidence intervals, provided that the MT response function is obtained using an estimator that bounds the influence of extreme data.     

A grid nesting method for large-eddy simulation of planetary boundary-layer flows

A method for performing nested grid calculations with a large-eddy simulation code is described. A common numerical method is used for all meshes, and the grid architecture consists of a single outer or coarse grid, and nested or fine grids, which overlap in some common region. Inter-grid communication matches the velocity, pressure and potential temperature fields in the overlap region. Resolved and sub-grid scale (SGS) turbulent fluxes and kinetic energy on the fine grid are averaged to the coarse grid using a conservation rule equivalent to Germano's identity used to develop dynamic SGS models.Simulations of a slightly convective, strong shear planetary boundary layer were carried out with varying surface-layer resolutions. Grid refinements in the (x, y, z) directions of up to (5, 5, 2) times were employed. Two-way interaction solutions on the coarse and fine meshes are successfully matched in the overlap region on an instantaneous basis, and the turbulent motions on the fine grid blend smoothly into the coarse grid across the grid interface. With surface-layer grid nesting, significant increases in resolved eddy fluxes and variances are found. The energy-scale content of the vertical velocity, and hence vertical turbulent fluxes, appear to be most influenced by increased grid resolution. Vertical velocity spectra show that the dominant scale shifts towards higher wavenumbers (smaller scales) and the magnitude of the peak energy is increased by more than a factor of 3 with finer resolution. Outside of the nested region the average heat and momentum fluxes and spectra are slightly influenced by the fine resolution in the surface layer. From these results we conclude that fine resolution is required to resolve the details of the turbulent motions in the surface layer. At the same time, however, increased resolution in the surface layer does not appreciably alter the ensemble statistics of the resolved and SGS motions outside of the nested region.     

Chromophoric Dissolved Organic Matter (CDOM) In Rainwater,Southeastern North Carolina,USA

The abundance and optical characteristics of dissolved organic matter (DOM) were determined in 120 rain samples collected in Wilmington, North Carolina, USA, between February 21, 2002 and August 11, 2003. All rainwater samples contained chromophoric dissolved organic matter (CDOM) as well as fluorescent compounds. The absorbance spectra of CDOM in the samples decreased exponentially with wavelength with little or no measurable absorbance past 550 nm. Fluorescence excitation emission spectra (EEMS) of the precipitation revealed the presence of four major peaks indicating both terrestrial and marine influences. There was a strong positive correlation between total integrated fluorescence and the absorbance coefficient at 300 nm in rainwater samples, suggesting that these optical properties are directly interrelated and that the compounds responsible for absorbance may be the same as those responsible for fluorescence. Air-mass back-trajectory analysis indicated elevated CDOM levels in continentally influenced rainwater relative to marine dominated events implying that anthropogenic and/or terrestrial sources are important contributors to CDOM levels in precipitation. The presence of highly absorbing and fluorescing CDOM in rainwater has significant ramifications in atmospheric chemistry and may play a previously unrecognized role in the wavelength dependent spectral attenuation of solar radiation by atmospheric waters.