Calibration and application of B/Ca, Cd/Ca, and d11B in Neogloboquadrina pachyderma (sinistral)

The North Atlantic and Norwegian Sea are prominent sinks of atmospheric CO2 today, but their roles in the past remain poorly constrained. In this study, we attempt to use B/Ca and d11B ratios in the planktonic foraminifera Neogloboquadrina pachyderma (sinistral variety) to reconstruct subsurface water pH and pCO2 changes in the polar North Atlantic during the last deglaciation. Comparison of core-top results with nearby hydrographic data shows that B/Ca in N. pachyderma (s) is mainly controlled by seawater [B(OH)4]?/[HCO3]? with a roughly constant partition coefficient (KD =([B/Ca]of CaCO3)/([B(OH)4]-/[HCO3]-)of seawater) of 1.48 ± 0.15 * 10**-3 (2sigma), and d11B in this species is offset below d11B of the borate in seawater by 3.38 ± 0.71 per mil (2sigma). These values represent our best estimates with the sparse available hydrographic data close to our core-tops. More culturing and sediment trap work is needed to improve our understanding of boron incorporation into N. pachyderma (s). Application of a constant KD of 1.48 * 10**-3 to high resolution N. pachyderma (s) B/Ca records from two adjacent cores off Iceland shows that subsurface pCO2 at the habitat depth of N. pachyderma (s) (~50 m) generally followed the atmospheric CO2 trend but with negative offsets of ~10-50 ppmv during 19-10 ka. These B/Ca-based reconstructions are supported by independent estimates from low-resolution d11B measurements in the same cores. We also calibrate and apply Cd/Ca in N. pachyderma (s) to reconstruct nutrient levels for the same down cores. Like today's North Atlantic, past subsurface pCO2 variability off Iceland was significantly correlated with nutrient changes that might be linked to surface nutrient utilization and mixing within the upper water column. Because surface pCO2 (at 0 m water depth) is always lower than at deeper depths and if the application of a constant KD is valid, our results suggest that the polar North Atlantic has remained a CO2 sink during the calcification seasons of N. pachyderma (s) over the last deglaciation.

(Table 2) Weight percent organic carbon from ODP Site 138-847

As the length of marine cores increases and sampling intervals decrease, the need for rapid and inexpensive means of determining sediment composition has become apparent. In this study we examine one potentially useful technique for assessing compositional changes in marine cores, diffuse reflectance spectrophotometry. We examined near-ultraviolet, visible, and near-infrared reflectance spectra from five data sets. Each data set consists of calibration samples and test samples. The calibration samples' spectra were related to a sediment component using multiple linear regression. The resulting regression or calibration equations were then evaluated using the test samples. Calibration equations were written relating spectra to several sediment components incduding carbonate (Atlantic and east Pacific Rise ODP Site 847), organic carbon content (Atlantic and east Pacific Rise), and opal content (east Pacific Rise). The correlation coefficients for the regression equations ranged from a high of 0.99 for carbonate and opal at ODP Site 847 to a low of 0.97 for Atlantic carbonate indicating that spectral variations are highly correlated to sediment composition. All of the equations include a substantial number of variables from shorter visible and longer near ultraviolet wavelengths suggesting that these wavelengths are especially important for devices designed specifically to scan marine cores. Although equations for estimating organic and carbonate content appear independent of other sediment components, the opal equation is strongly dependent on carbonate content indicating that opal concentration is correlated to carbonate content. Tests of the calibration equations indicated that all our equations reasonably estimate the pattern of changes, either down core or in surface sediments. Where our spectral estimates have difficulty is with absolute values, frequently over or underestimating observed values by a substantial amount. Within these limitations diffuse reflectance spectrophotometry can be a useful tool for characterizing marine cores and as our understanding of the relationship between spectra and mineralogy improves so will estimates of absolute values.

Absorption coefficients of particulate matter and chlorophyll a concentrations at time series station OLIPAC

Spectral absorption coefficients of total particulate matter ap (lambda) were determined using the in vitro filter technique. The present analysis deals with a set of 1166 spectra, determined in various oceanic (case 1) waters, with field chl a concentrations ([chl]) spanning 3 orders of magnitude (0.02-25 mg/m**3). As previously shown [Bricaud et al., 1995, doi:10.1029/95JC00463] for the absorption coefficients of living phytoplankton a phi (lamda), the ap (labda) coefficients also increase nonlinearly with [chl]. The relationships (power laws) that link ap (lambda) and a phi (lambda) to [chl] show striking similarities. Despite large fluctuations, the relative contribution of nonalgal particles to total absorption oscillates around an average value of 25-30% throughout the [chl] range. The spectral dependence of absorption by these nonalgal particles follows an exponential increase toward short wavelengths, with a weakly variable slope (0.011 ± 0.0025/nm). The empirical relationships linking ap (lambda) to ([chl]) can be used in bio-optical models. This parameterization based on in vitro measurements leads to a good agreement with a former modeling of the diffuse attenuation coefficient based on in situ measurements. This agreement is worth noting as independent methods and data sets are compared. It is stressed that for a given ([chl]), the ap (lambda) coefficients show large residual variability around the regression lines (for instance, by a factor of 3 at 440 nm). The consequences of such a variability, when predicting or interpreting the diffuse reflectance of the ocean, are examined, according to whether or not these variations in ap are associated with concomitant variations in particle scattering. In most situations the deviations in ap actually are not compensated by those in particle scattering, so that the amplitude of reflectance is affected by these variations.

Contiunous surface water uncorrected and quench-corrected active fluorescence and derived chlorophyll a concentration using calibration by HPLC pigments during POLARSTERN cruise ANT-XXV/1

The relationship between phytoplankton assemblages and the associated optical properties of the water body is important for the further development of algorithms for large-scale remote sensing of phytoplankton biomass and the identification of phytoplankton functional types (PFTs), which are often representative for different biogeochemical export scenarios. Optical in-situ measurements aid in the identification of phytoplankton groups with differing pigment compositions and are widely used to validate remote sensing data. In this study we present results from an interdisciplinary cruise aboard the RV Polarstern along a north-to-south transect in the eastern Atlantic Ocean in November 2008. Phytoplankton community composition was identified using a broad set of in-situ measurements. Water samples from the surface and the depth of maximum chlorophyll concentration were analyzed by high performance liquid chromatography (HPLC), flow cytometry, spectrophotometry and microscopy. Simultaneously, the above- and underwater light field was measured by a set of high spectral resolution (hyperspectral) radiometers. An unsupervised cluster algorithm applied to the measured parameters allowed us to define bio-optical provinces, which we compared to ecological provinces proposed elsewhere in the literature. As could be expected, picophytoplankton was responsible for most of the variability of PFTs in the eastern Atlantic Ocean. Our bio-optical clusters agreed well with established provinces and thus can be used to classify areas of similar biogeography. This method has the potential to become an automated approach where satellite data could be used to identify shifting boundaries of established ecological provinces or to track exceptions from the rule to improve our understanding of the biogeochemical cycles in the ocean.

(Table 1) Viscosity coefficients at various temperatures of samples from ODP Hole 176-735B

Ocean Drilling Program (ODP) Hole 735B was drilled to a depth of 1.5 km in a tectonic window of gabbroic lower oceanic crust created at the Southwest Indian Ridge. The gabbros have a very stable natural remanent magnetization (NRM) of reversed polarity with most unblocking temperatures slightly below the Curie temperature of magnetite. The NRM includes a drilling-induced overprint but its intensity decays strongly towards the interior of the drill core. The demagnetization data yield no or only a very small secondary magnetization component acquired during the present Brunhes chron or an earlier normal chron, suggesting cooling through most of the blocking temperature range during chron C5r and a strong resistance against the acquisition of thermoviscous magnetization. A novel furnace has been designed to measure magnetizations and their time dependences at high temperatures (up to 580 deg C) inside a commercial SQUID magnetometer. Magnetic viscosity experiments have been conducted on the gabbros at temperatures up to 550 deg C to determine the time and temperature stability of remanent magnetization. Viscosities are generally small and increase little with temperature below the main blocking temperature, where the increase becomes almost an order of magnitude. Extrapolations to geological times infer viscous acquisitions that would be 5-25% of a thermoremanence in 100 kyr and at temperatures of 200-500 deg C. At ocean bottom temperature the predicted magnetization of one sample acquired in the present Brunhes chron should be 10% of the NRM. However, this is not recognized during NRM demagnetization and partial thermoremanent magnetization (pTRM) acquisitions at 250 deg C are also much smaller than predicted. It thus appears that the NRMs are generally magnetically harder than magnetizations acquired after heating to 570 deg C in the laboratory. Susceptibility changes during heating are small (<5%) indicating a seemingly stable magneto-mineralogy, but conspicuous minima occur after heating to 520 deg C. Also, quasi paleointensity experiments reveal characteristic patterns in the NRM/pTRM ratios and also large increases in pTRM capacity after heating to 570 deg C. Moreover, anhysteretic remanent magnetization acquisition in the low field range (<=10 mT) is strongly enhanced after heating by factors up to three. The alteration of the magneto-mineralogy is interpreted to result from the annealing of defects in magnetite that originate from tectonically induced strain. The oceanic gabbros of Hole 735B are thus ideal source layer material for marine magnetic anomalies, and secondary thermoviscous acquisition, as a possible cause for anomalous skewness, is essentially absent.

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.