Probing molecular-level transformations of dissolved organic matter: insights on photochemical degradation and protozoan modification of DOM from electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry

Molecular-level characterization of natural organic matter (NOM) has been elusive due to the inherent complexity of natural organic mixtures and to the fact that individual components are often polar and macromolecular. Electrospray ionization (ESI) is a “soft” ionization technique that ionizes polar compounds from aqueous solution prior to injection into a mass spectrometer. The highest resolution and mass accuracy of compounds within NOM have been achieved when ESI is combined with an ultrahigh-resolution mass spectrometer such as the Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS). With this technique, individual molecules within a variety of natural organic mixtures can be detected and their elemental composition can be determined. At low mass-to-charge (m/z) ratio, the resolution is high enough to assign exact molecular formulas allowing specific components of these mixtures to be identified. In addition to molecular identification, we can now use ESI FT-ICR MS to examine molecular-level changes in different organic mixtures as a function of relevant geo-processes, such as microbial alterations and photochemistry. Here we present the results from the application of ESI FT-ICR MS to two geochemical questions: (1) the effect of photoirradiation on the molecular composition of fulvic acids and (2) the role of protozoan grazers in the modification of DOM in aquatic systems.     

Reconstruction of sea surface dimethylsulfide in the North Pacific during 1970s to 2000s

We proposed an empirical equation of sea surface dimethylsulfide (DMS, nM) using sea surface temperature (SST, K), sea surface nitrate (SSN, μM) and latitude (L, °N) to reconstruct the sea surface flux of DMS over the North Pacific between 25°N and 55°N: ln DMS = 0.06346 · SST − 0.1210 · SSN − 14.11 · cos(L) − 6.278 (R² = 0.63, p < 0.0001). Applying our algorithm to climatological hydrographic data in the North Pacific, we reconstructed the climatological distributions of DMS and its flux between 25 °N and 55 °N. DMS generally increased eastward and northward, and DMS in the northeastern region became to 2–5 times as large as that in the southwestern region. DMS in the later half of the year was 2–4 times as large as that in the first half of the year. Moreover, applying our algorithm to hydrographic time series datasets in the western North Pacific from 1971 to 2000, we found that DMS in the last three decades has shown linear increasing trends of 0.03 ± 0.01 nM year^− 1 in the subpolar region, and 0.01 ± 0.001 nM year^− 1 in the subtropical region, indicating that the annual flux of DMS from sea to air has increased by 1.9–4.8 μmol m^− 2 year^− 1. The linear increase was consistent with the annual rate of increase of 1% of the climatological averaged flux in the western North Pacific in the last three decades.     

Temperature fluctuations in the atmospheric surface layer over the thermally inhomogeneous underlying surface

The influence of both spatial and temporal temperature inhomogeneities of the underlying surface on the temperature field in an unstably stratified atmospheric surface layer is considered. The methods of correlation and spectral analyses are proposed to estimate statistical characteristics of surface-air temperature fluctuations caused by both turbulent mixing and inhomogeneities in the temperature of the underlying surface. Analysis of experimental data obtained from measurements in the atmospheric surface layer yields estimates for the contribution made by the time-dependent thermal properties of the underlying surface to the total variance of air-temperature fluctuations. It is shown that the additional air-temperature fluctuations generated by surface-temperature inhomogeneities and unrelated to shear flow may reach 70% and 30% of the total variance of measured fluctuations under variable cloudiness and clear skies, respectively. For the height z = 2 m within the wave-number range 2 × 10^?3 rad m^?1 < k < 0.1 rad m^?1, the contribution made by a spatial surface-temperature inhomogeneity to the variance of air-temperature fluctuations does not exceed 10% of the total variance. Correlation and spectral analyses of experimental data make it possible to isolate the spectra of properly turbulent fluctuations from the measured fluctuations and thus to obtain more accurate values of the universal function of similarity theory for temperature in the range of small wave numbers beyond the inertial range.     

Assessment of cytochrome P450 1A in harbour seals (Phoca vitulina) using a minimally-invasive biopsy approach

Biomarkers of organochlorine exposure, such as the induction of cytochrome P450 1A (CYP1A), can be used to assess the impact of environmental contaminants on the health of free-ranging marine mammal populations. The objective of the present study was to measure CYP1A in skin and liver biopsies obtained from live harbour seals (Phoca vitulina). Twelve harbour seal pups, aged three to five weeks, were captured from the Fraser River estuary, British Columbia, Canada, and temporarily held in captivity. Skin ( approximately 60 mg) and liver ( approximately 40 mg) biopsies, obtained while seals were under general anaesthesia, yielded sufficient tissue for the measurement of CYP1A by immunoblot analysis and ethoxyresorufin O-deethylase activity. A short-term exposure experiment, in which harbour seals (n=3) were treated orally with beta-naphthoflavone (BNF), resulted in increased hepatic and cutaneous CYP1A protein levels, consistent with observations in other mammals. This study is the first to measure CYP1A in skin and liver biopsies from live harbour seals and to report in vivo BNF-associated CYP1A induction in a marine mammal. The results demonstrate that microsamples collected using minimally-invasive techniques can provide toxicologically-relevant information form marine mammals.     

Design of a 3D Chirp Sub-bottom Imaging System

Chirp sub-bottom profilers are marine acoustic devices that use a known and repeatable source signature (1–24 kHz) to produce decimetre vertical resolution cross-sections of the sub-seabed. Here the design and development of the first true 3D Chirp system is described. When developing the design, critical factors that had to be considered included spatial aliasing, and precise positioning of sources and receivers. Full 3D numerical modelling of the combined source and receiver directivity was completed to determine optimal source and receiver geometries. The design incorporates four source transducers (1.5–13 kHz) that can be arranged into different configurations, including Maltese Cross, a square and two separated pairs. The receive array comprises 240 hydrophones in 60 groups whose group-centres are separated by 25 cm in both horizontal directions, with each hydrophone group containing four individual elements and a pre-amplifier. After careful consideration, it was concluded that the only way to determine with sufficient accuracy the source–receiver geometry, was to fix the sources and receivers within a rigid array. Positional information for the array is given by a Real Time Kinematic GPS and attitude system incorporating four antennas to give position, heading, pitch and roll. It is shown that this system offers vertical positioning accuracy with a root-mean-square (rms) error less than 2.6 cm, while the horizontal positioning rms error was less than 2.0 cm. The system is configured so that the Chirp source signature can be chosen by software aboard the acquisition vessel. The complete system is described and initial navigational and seismic data results are presented. These data demonstrate that the approach of using fixed source-receiver geometry combined with RTK navigation can provide complete 3D imaging of the sub-surface.     

Composition and distribution of meiobenthos in amursky bay (peter the great bay, the east sea)

Qualitative and quantitative composition of meiobenthos was studied in Amursky Bay (Peter the Great Bay, the East Sea). Ten taxonomic groups were found, where nematodes were dominant. Density of meiobenthos in ground sediments of the Bay were not uniform, and the average density was measured at 126.4±62.3 ind. m^-2. 56 species of nematodes were detected, and dominant species wereSabatieria palmaris, Paracanthonchus macrodon, Sphaerolaimus limosus, S. gracilis andOncholaimium ramosum. Five taxocenes of nematodes were allocated based on the results of cluster analysis and species domination according to density. Low diversity in species composition of nematodes was noted in the northwestern part of the Bay, which is a zone of desalination, and in the eastern part, which is exposed to household drains.     

Shoreline variability via empirical orthogonal function analysis: Part I temporal and spatial characteristics

Empirical orthogonal functions (EOFs) or principal components were used to extract the significant modes of shoreline variability from several data sets collected at three very different locations. Although EOFs have proven to be a valuable tool in the analysis of nearshore data, most applications have focused on the ability of the technique to describe cross-shore or profile variability. Here however, EOFs were used to help identify the dominant modes of longshore shoreline variability at Duck, North Carolina, the Gold Coast, Australia, and at several locations within the Columbia River Littoral Cell in the U.S. Pacific Northwest. In part one of this analysis, characteristic patterns of shoreline variability identified by the EOF analysis are described in detail. At each site, the dominant modes consisting of the first four eigenfunctions were found to describe nearly 95% of the total shoreline variability. At both Duck and the Gold Coast, several interesting longshore periodic features suggestive of sand waves were identified, while boundary effects related to natural headlands and navigational structures/entrances dominated the Pacific Northwest data sets.