Characterization of chromophoric dissolved organic matter (CDOM) in the Baltic Sea by excitation emission matrix fluorescence spectroscopy

Chromophoric dissolved organic matter (CDOM) is the major light absorber in the Baltic Sea. In this study, excitation emission matrix (EEM) fluorescence spectra and UV–visible absorption spectra of CDOM are reported as a function of salinity. Samples from different locations and over different seasons were collected during four cruises in 2002 and 2003 in the Baltic Sea in both Pomeranian Bay and the Gulf of Gdansk. Absorption by CDOM decreased with increased distance from the riverine source and reached a relatively stable absorption background in the open sea. Regression analysis showed that fluorescence intensity was linearly related to absorption by CDOM at 375 nm and a_CDOM(375) absorption coefficients were inversely related to salinity. Analysis of CDOM-EEM spectra indicated that a change in composition of CDOM occurred along the salinity gradient in the Baltic Sea. Analysis of percent contribution of respective fluorophore groups to the total intensity of EEM spectra indicated that the fluorescence peaks associated with terrestrial humic components of the CDOM and total integrated fluorescence decreased with decreasing CDOM absorption. In contrast, the protein-like fraction of CDOM decreased to a lesser degree than the others. Analysis of the percent contribution of fluorescence peak intensities to the total fluorescence along the salinity gradient showed that the contribution of protein-like fluorophores increased from 2.6% to 5.1% in the high-salinity region of the transect. Fluorescence and absorption changes observed in the Baltic Sea were similar to those observed in similar transects that have been sampled elsewhere, e.g. in European estuaries, Gulf of Mexico, Mid-Atlantic Bight and the Cape Fear River plume in the South Atlantic Bight, although the changes in the Baltic Sea occurred over a much smaller salinity gradient.     

Fast kimberlite ascent rates estimated from hydrogen diffusion profiles in xenolithic mantle olivines from southern Africa

Fourier transform infrared spectrometry (FTIR) analyses of olivines from peridotite xenoliths found in southern African kimberlites indicate 0 to 80 ppm H₂O concentrations. OH absorbance profiles across olivine grains show homogeneous H contents from core to edge for most samples. In one sample the olivines are H-free, while another has olivines characterized by lower H contents at the grain edges compared to the cores, indicating H loss during transport of the xenolith to the surface. Flat or near-flat H profiles place severe constraints on the duration of H loss from olivine grains, with implications for kimberlite magma ascent rates. Diffusion equations were used to estimate times of H loss of about 4 h for the sample with heterogeneous olivine H contents. Resulting kimberlite ascent rates are calculated to be 5-37 m s⁻¹ minimum, although these estimates are highly dependent on volatile contents and degassing behavior of the host kimberlite magma. Xenolithic olivines from alkali basalts generally have lower H contents and more pronounced H diffusion profiles than do those from kimberlites. This difference is likely caused by higher magma temperatures and lower ascent rates of alkali basalts compared to kimberlites.     

Direct determination of organic carbon in modern reef sediments and calcareous organisms after dissolution of carbonate

An improved method for the direct determination of organic carbon in calcareous marine sediments, organisms and particulate matter is described. Samples are dissolved in phosphoric acid to remove carbonates, purged with oxygen to remove CO₂, and the resulting acidic solution is analysed for total (dissolved and particulate) organic carbon. The method is rapid, involves minimal sample manipulation, and is both accurate (better than ± 2%) and precise (better than ± 0.2 mg organic carbon/g sediment). The method is especially suitable for modern carbonate sediments which have low levels of predominantly acid-soluble organic carbon.     

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.     

Economic benefit of the protection program for the Steller sea lion

This paper examines willingness to pay (WTP) for an endangered species across geographically nested samples using the Contingent Valuation Method (CVM). The three samples range from (1) the boroughs that contain critical habitat for the Steller sea lion to (2) the state that contains these boroughs to and (3) the entire United States. Depending on the assumptions of the model, WTP varies tremendously from sample to sample. WTP for the United States is the highest and it is the lowest for the boroughs. The null hypotheses that mean WTP estimates are greater then zero were rejected for the boroughs and the state but were not rejected for the United States based on the 95% confidence intervals.     

Effects of variable winds on biological productivity on continental shelves in coastal upwelling systems

The production and distribution of biological material in wind-driven coastal upwelling systems are of global importance, yet they remain poorly understood. Production is frequently presumed to be proportional to upwelling rate, yet high winds can lead to advective losses from continental shelves, where many species at higher trophic levels reside. An idealized mixed-layer conveyor (MLC) model of biological production from constant upwelling winds demonstrated previously that the amount of new production available to shelf species increased with upwelling at low winds, but declined at high winds [Botsford, L.W., Lawrence, C.A., Dever, E.P., Hastings, A., Largier, J., 2003. Wind strength and biological productivity in upwelling systems: an idealized study. Fisheries Oceanography 12, 245–259]. Here we analyze the response of this model to time-varying winds for parameter values and observed winds from the Wind Events and Shelf Transport (WEST) study region. We compare this response to the conventional view that the results of upwelling are proportional to upwelled volume. Most new production per volume upwelled available to shelf species occurs following rapid increases in shelf transit time due to decreases in wind (i.e. relaxations). However, on synoptic, event time-scales shelf production is positively correlated with upwelling rate. This is primarily due to the effect of synchronous periods of low values in these time series, paradoxically due to wind relaxations. On inter-annual time-scales, computing model production from wind forcing from 20 previous years shows that these synchronous periods of low values have little effect on correlations between upwelling and production. Comparison of model production from 20 years of wind data over a range of shelf widths shows that upwelling rate will predict biological production well only in locations where cross-shelf transit times are greater than the time required for phytoplankton or zooplankton production. For stronger mean winds (narrower shelves), annual production falls below the peak of constant wind prediction [Botsford et al., 2003. Wind strength and biological productivity in upwelling systems: an idealized study. Fisheries Oceanography 12, 245–259], then as winds increase further (shelves become narrower) production does not decline as steeply as the constant wind prediction.     

Characterization of dissolved organic matter across the Subtropical Convergence off the South Island,New Zealand

Dissolved organic matter (DOM) was investigated along a gradient across the Subtropical Convergence (STC) off the South Island, New Zealand. Ultrahigh resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS), excitation emission matrix fluorescence (EEM) spectroscopy, and molecular lignin analysis techniques were used to study this DOM. The analysis revealed a group of compounds found only in the coastal DOM samples, which were also characterized by an elevated terrestrial DOM fluorescence pattern and elevated lignin content if compared to the offshore samples. This group exhibited a high degree of carbon unsaturation, as evident from high double bond equivalence minus oxygen values (DBE-O > 9) and maximum fluorescence intensity. Sulfur-containing molecular formulae for summer DOM samples were much more abundant across the entire transect of the STC compared to winter and exhibited distinctly different hydrogen:carbon and oxygen:carbon elemental ratios, suggesting a possible correlation between biological activity and sulfur compounds. The molecular formulae common to all STC samples were compared with those calculated for DOM extracted from freshwater collected from a stream discharging into Doubtful Sound (West Coast, New Zealand). ESI-FT-ICR-MS measurements undertaken in negative electrospray ionization (ESI?) mode indicated that 30% of the molecular formulae were present in both types of DOM, while in positive ESI mode (ESI+) over 90% of the formulae were present in all samples. Hence, a significant portion of the molecular formulae assigned to the solid-phase extractable DOM pool (SPE-DOM) appear to be identical in oceanic and freshwater samples.     

Proglacial groundwater storage dynamics under climate change and glacier retreat

Proglacial aquifers are an important water store in glacierised mountain catchments that supplement meltwater-fed river flows and support freshwater ecosystems. Climate change and glacier retreat will perturb water storage in these aquifers, yet the climate-glacier-groundwater response cascade has rarely been studied and remains poorly understood. This study implements an integrated modelling approach that combines distributed glacio-hydrological and groundwater models with climate change projections to evaluate the evolution of groundwater storage dynamics and surface-groundwater exchanges in a temperate, glacierised catchment in Iceland. Focused infiltration along the meltwater-fed Virkisá River channel is found to be an important source of groundwater recharge and is projected to provide 14%–20% of total groundwater recharge by the 2080s. The simulations highlight a mechanism by which glacier retreat could inhibit river recharge in the future due to the loss of diurnal melt cycling in the runoff hydrograph. However, the evolution of proglacial groundwater level dynamics show considerable resilience to changes in river recharge and, instead, are driven by changes in the magnitude and seasonal timing of diffuse recharge from year-round rainfall. The majority of scenarios simulate an overall reduction in groundwater levels with a maximum 30-day average groundwater level reduction of 1 m. The simulations replicate observational studies of baseflow to the river, where up to 15% of the 30-day average river flow comes from groundwater outside of the melt season. This is forecast to reduce to 3%–8% by the 2080s due to increased contributions from rainfall and meltwater runoff. During the melt season, groundwater will continue to contribute 1%–3% of river flow despite significant reductions in meltwater runoff inputs. Therefore it is concluded that, in the proglacial region, groundwater will continue to provide only limited buffering of river flows as the glacier retreats.     

The problem of current channelling: A critical review

The notion that currents induced ‘elsewhere’, by external source fields, could wend their way in a frequency-independent ohmic-like manner through a region of interest has been the cause of many recent disputes within the geomagnetic induction community. In particular, two-dimensional (2D) models of the Rhinegraben, and of the region known as the ‘Eskdalemuir anomaly’ in southern Scotland, have been dismissed as erroneous by those who believe that the observations are more correctly interpreted as due to the effects of ‘channelled’ currents rather than ‘induced’ currents. In this review, attention is paid primarily to consider under what circumstances any perturbation of current flow, which may manifest itself as a ‘DC-like’ channelled current, could cause a ‘problem’ for those wishing to interpret their observations. Various concepts are introduced, particularly the ratio of 3D/2D current channelling numbers for the induction problem, which is shown to be the ratio of the length of the 3D body to the skin depth in the host medium. It is stressed that the worker must analyse his data by adequate statistical techniques, and that the simplest physical models possible, that describes the observations, must be sought. Finally, suggestions are made for further work to be undertaken.