Results of Closed-Flow Column Experiments (zip-archive 2.3 MB)

The identification of transport parameters by inverse modeling often suffers from equifinality or parameter correlation when models are fitted to observations of the solute breakthrough in column outflow experiments. This parameters uncertainty can be approached by the application of multiple experimental designs such as column experiments in open-flow mode and the recently proposed closed-flow mode. Latter are characterized by the recirculation of the column effluent into the solution supply vessel that feeds the inflow. Depending on the experimental conditions, the solute concentration in the solution supply vessel and the effluent follows a damped sinusoidal oscillation. As a result, the closed-flow experiment provides additional observables in the breakthrough curve. The evaluation of these emergent features allows intrinsic control over boundary conditions and impacts the uncertainty of parameters in inverse modeling. We present a comprehensive sensitivity analysis to illustrate the potential application of closed-flow experiments. We show that the sensitivity with respect to the apparent dispersion can be controlled by the experimenter leading to a decrease in parameter uncertainty as compared to classical experiments by an order of magnitude for optimal settings. With these finding we are also able to reduce the equifinality found for situations, where rate-limited interactions impede a proper determination of the apparent dispersion and rate coefficients. Furthermore, we show the expected breakthrough curve for equilibrium and kinetic sorption, the latter showing strong similarities to the behavior found for completely mixed batch reactor experiments. This renders the closed-flow mode a useful complementary approach to classical column experiments.

Observations on the propagation of internal tidal waves on the continental slope off Sierra Leone

During R/V Meteor-cruise no. 30 4 moorings with 17 current meters were placed on the continental slope of Sierra Leone at depths between 81 and 1058 meters. The observation period started on March 8, 1973, 16.55 hours GMT and lasted 19 days for moorings M30_068MOOR, M30_069MOOR, M30_070MOOR on the slope and 9 days for M30_067MOOR on the shelf. One current meter recorded at location M30_067MOOR for 22 days. Hydrographic data were collected at 32 stations by means of the "Kieler Multi-Meeressonde". Harmonic analysis is applied to the first 15 days of the time series to determine the M2 and S2 tides. By vertically averaging of the Fourier coefficients the field of motion is separated into its barotropic and its baroclinic component. The expected error generated by white Gaussian noise is estimated. To estimate the influence of the particular vertical distribution of the current meters, the barotropic M2 tide is calculated by ommitting and interchanging time series of different moorings. It is shown that only the data of moorings M30_069MOOR, M30_070MOOR and M30_067MOOR can be used. The results for the barotropic M2 tide agree well with the previous publications of other authors. On the slope at a depth of 1000 m there is a free barotropic wave under the influence of the Coriolis-force propagating along the slope with an amplitude of 3.4 cm S**-1. On the shelf, the maximum current is substantially greater (5.8 cm s**-1) and the direction of propagation is perpendicular to the slope. As for the continental slope a separation into different baroclinic modes using vertical eigenmodes is not reasonable, an interpretation of the total baroclinic wave field is tried by means of the method of characteristis. Assuming the continental slope to generate several linear waves, which superpose, baroclinic tidal ellipses are calculated. The scattering of the direction of the major axes M30_069MOOR is in contrast to M30_070MOOR, where they are bundled within an angle of 60°. This is presumably caused by the different character of the bottom topography in the vicinity of the two moorings. A detailed discussion of M30_069MOOR is renounced since the accuracy of the bathymetric chart is not sufficient to prove any relation between waves and topography. The bundeling of the major axes at M30_070MOOR can be explained by the longslope changes of the slope, which cause an energy transfer from the longslope barotropic component to the downslope baroclinic component. The maximum amplitude is found at a depth of 245 m where it is expected from the characteristics originating at the shelf edge. Because of the dominating barotropic tide high coherence is found between most of the current meters. To show the influence of the baroclinic tidal waves, the effect of the mean current is considered. There are two periods nearly opposite longshore mean current. For 128 hours during each of these periods, starting on March 11, 05.00, and March 21, 08.30, the coherences and energy spectra are calculated. The changes in the slope of the characteristics are found in agreement with the changes of energy and coherence. Because of the short periods of nearly constant mean current, some of the calculated differences of energy and coherence are not statistically significant. For the M2 tide a calculation of the ratios of vertically integrated total baroclinic energy and vertically integrated barotropic kinetic energy is carried out. Taking into account both components (along and perpendicular to the slope) the obtained values are 0.75 and 0.98 at the slope and 0.38 at the shelf. If each component is considered separately, the ratios are 0.39 and 1.16 parallel to the slope and 5.1 and 15.85 for the component perpendicular to it. Taking the energy transfer from the longslope component to the doenslope component into account, a simple model yields an energy-ratio of 2.6. Considering the limited application of the theory to the real conditions, the obtained are in agreement with the values calculated by Sandstroem.

Photosynthetic parameters, chlorophyll concentration, and diffuse attenuation coefficients in the Rhode River, Maryland (USA), 1990-2009

Parameters in the photosynthesis-irradiance (P-E) relationship of phytoplankton were measured at weekly to bi-weekly intervals for 20 yr at 6 stations on the Rhode River, Maryland (USA). Variability in the light-saturated photosynthetic rate, PBmax, was partitioned into interannual, seasonal, and spatial components. The seasonal component of the variance was greatest, followed by interannual and then spatial. Physiological models of PBmax based on balanced growth or photoacclimation predicted the overall mean and most of the range, but not individual observations, and failed to capture important features of the seasonal and interannual variability. PBmax correlated most strongly with temperature and the concentration of dissolved inorganic carbon (IC), with lesser correlations with chlorophyll a, diffuse attenuation coefficient, and a principal component of the species composition. In statistical models, temperature and IC correlated best with the seasonal pattern, but temperature peaked in late July, out of phase with PBmax, which peaked in September, coincident with the maximum in monthly averaged IC concentration. In contrast with the seasonal pattern, temperature did not contribute to interannual variation, which instead was governed by IC and the additional lesser correlates. Spatial variation was relatively weak and uncorrelated with ancillary measurements. The results demonstrate that both the overall distribution of PBmax and its relationship with environmental correlates may vary from year to year. Coefficients in empirical statistical models became stable after including 7 to 10 yr of data. The main correlates of PBmax are amenable to automated monitoring, so that future estimates of primary production might be made without labor-intensive incubations.

Mg/Ca and Sr/Ca in calcites and estimated distribution coefficients in marine sediments (Table 2)

Recrystallization processes in marine sediments can alter the extent to which biogenic calcite composition serves as a proxy of oceanic chemical and isotopic history. Models of calcite recrystallization developed to date have resulted in significant insights into these processes, but are not completely adequate to describe the conditions of recrystallization. Marine sediments frequently have concentration gradients in interstitial dissolved calcium, magnesium, and strontium which have probably evolved during sediment accumulation. Realistic, albeit simplified, models of the temporal evolution of interstitial water profiles of Ca, Mg, and Sr were used with several patterns of recrystallization rate variation to predict the composition of recrystallized inorganic calcite. Comparison of predictions with measured Mg/Ca and Sr/Ca ratios in severely altered calcite samples from several Deep Sea Drilling Project sites demonstrates that models incorporating temporal variation in interstitial water composition more successfully predict observed calcite compositions than do models which rely solely on present-day interstitial water chemistry. Temporal changes in interstitial composition are particularly important in interpreting Mg/Ca ratios in conjunction with Sr/Ca ratios. Estimates of Mg distribution coefficients from previous observations in marine sediments, much lower than those in laboratory studies of inorganic calcite, are confirmed by these results. Evaluation of the effects of diagenetic alteration of biogenic calcium carbonate sediment must be a site-specific process, taking into account accumulation history, present interstitial chemistry and its variation in the past, and sample depths and ages.