Detlef E. Schulz-Bull

Global temperature calibration of the alkenone unsaturation index (UK′37) in surface waters and comparison with surface sediments

In this paper, we compile the current surface seawater C37 alkenone unsaturation (UK′37) measurements (n = 629, −1 to 30°C temperature range) to derive a global, field-based calibration of UK′37 with alkenone production temperature. A single nonlinear “global” surface water calibration of UK′37 accurately predicts alkenone production temperatures over the diversity of modern-day oceanic environments and alkenone-synthesizing populations (T = −0.957 + 54.293(UK′37) − 52.894(UK′37)2 + 28.321(UK′37)3, r2 = 0.97, n = 567). The mean standard error of estimation is 1.2°C with insignificant bias in estimated production temperature among the different ocean regions sampled. An exception to these trends is regions characterized by strong lateral advection and extreme productivity and temperature gradients (e.g., the Brazil-Malvinas Confluence). In contrast to the surface water data, the calibration of UK′37 in surface sediments with overlying annual mean sea surface temperature (AnnO) is best fit by a linear model (AnnO = 29.876(UK′37) − 1.334, r2 = 0.97, n = 592). The standard error of estimation (1.1°C) is similar to that of the surface water production calibration, but a higher degree of bias is observed among the regional data sets. The sediment calibration differs significantly from the surface water calibration. UK′37 in surface sediments is consistently higher than that predicted from AnnO and the surface water production temperature calibration, and the magnitude of the offset increases as the surface water AnnO decreases. We apply the global production temperature calibration to the coretop UK′37 data to estimate the coretop alkenone integrated production temperature (coretop IPT) and compare this with the overlying annual mean sea surface temperature (AnnO). We use simple models to explore the possible causes of the deviation observed between the coretop temperature signal, as estimated by UK′37, and AnnO. Our results indicate that the deviation can best be explained if seasonality in production and/or thermocline production as well as differential degradation of 37:3 and 37:2 alkenones both affect the sedimentary alkenone signal.

Basin‐wide particulate carbon flux in the Atlantic Ocean: Regional export patterns and potential for atmospheric CO2 sequestration

Particle flux data from 27 sites in the Atlantic Ocean have been compiled in order to determine regional variations in the strength and efficiency of the biological pump and to quantify carbon fluxes over the ocean basin, thus estimating the potential oceanic sequestration of atmospheric CO2. An algorithm is derived relating annual particulate organic carbon (POC) flux to primary production and depth that yields variations in the export ratio (ER = POC flux/primary production) at 125 m of between 0.08 and 0.38 over the range of production from 50 to 400 g C m−2 yr−1. Significant regional differences in changes of the export ratio with depth are related to the temporal stability of flux. Sites with more pulsed export have higher export ratios at 125 m but show more rapid decreases of POC flux with depth, resulting in little geographic variation in fluxes below ∼3000 m. The opposing effects of organic carbon production and calcification on ΔpCO2 of surface seawater are considered to calculate an “effective carbon flux” at the depth of the euphotic zone and at the base of the winter mixed layer. POC flux at the base of the euphotic zone integrated over the Atlantic Ocean between 65°N and 65°S amounts to 3.14 Gt C yr−1. Of this, 5.7% is remineralized above the winter mixed layer and thus does not contribute to CO2 sequestration on climatically relevant timescales. The effective carbon flux, termed Jeff, amounts to 2.47 Gt C yr−1 and is a measure of the potential sequestration of atmospheric CO2 for the area considered. A shift in the composition of sedimenting particles (seen in a decrease of the opal:carbonate ratio) is seen across the entire North Atlantic, indicating a basin-wide phenomenon that may be related to large-scale changes in climatic forcing.

Chlorobiphenyls: model compounds for metabolism in food chain organisms and their potential use as ecotoxicological stress indicators by application of the metabolic slope concept.

A model is described to explain the compositional similarities and differences in chlorobiphenyls (CBs) in members of marine food chains, including water. Four groups of CBs are distinguished based on the presence/absence of vicinal H-atoms in o,m and/or m,p vicinal H-atoms, according to structure-activity relations for their biotransformation by cytochrome P-450 1A and 2B isozymes. Contents of CBs (X) in water, diatom, mussel, copepod, worm, shrimp, flounder, herring, and harbor porpoise were transformed into molar X/153 ratios (CB-153 is persistent) and plotted against X/153 ratios in diatom, lacking metabolic efficiency. For each metabolic group, a linear plot results. Their slopes indicate relative metabolic efficiencies of cytochrome P-450 isozymes. Indication of PB-type enzyme activity in harbor porpoise, flounder, and herring that was not observed before biochemically is new. Metabolic slopes of CBs can also be used as environmental stress indicators by comparison of slopes in a selected organism in areas with different degrees of contamination.

Chlorobiphenyls (PCB) and PAHs in water masses of the northern North Atlantic

Concentrations of 23 individual chlorobiphenyls (CBs) and 6 polyaromatic hydrocarbons (PAHs) were determined in different water masses of the North Atlantic Ocean around Iceland. The study was carried out in the framework of the second Intergovernmental Oceanographic Commission (IOC) baseline studies of contaminants in the North Atlantic Ocean, involving trace organics and trace elements. Concentrations of individual CBs were extremely low. In solution, they varied between <2 and 126 fg dm−3 and in suspension between <2 and 1400 fg dm−3. The values for their sum (∑CB) were between 10 and 1048 in solution, and 286–11 241 fg dm−3 in suspension. ∑PAHs were present in the <5–65 pg dm−3 range, p,p′-DDE and hexachlorobenzene were <2 fg dm−3. The concentrations of CBs and PAHs decreased from the surface towards the bottom at each station. The lowest concentrations were found in Norwegian Sea Deep Water (∑CB 10 fg dm−3), concurrent with the lowest halocarbon concentrations found during the cruise. Values in near-surface waters were considerably lower than those determined at mid-latitudes of the North Atlantic. These findings reflect the mixing of water bodies with higher CB concentrations from the central North Atlantic with less contaminated waters from the Arctic Ocean. Concentrations in suspension exceeded those in solution in most samples, as a result of the relatively high suspended matter concentrations in the waters around Iceland. Particulate CB and PAH concentrations were positively correlated with particulate organic carbon concentrations. This suggests that suspended organic material is a carrier for these relatively apolar organic compounds in the water column. The data do not support the co-distillation concept suggested in the literature.

Distribution of individual chlorobiphenyls (PCB) in solution and suspension in the Baltic Sea

Single and multidimensional GC-ECD techniques were applied to determine individual chlorobiphenyls (CBs) in solution and in suspended particles in the Baltic Sea (some data were also obtained for the adjacent German Bight in the North Sea). Large volumes (up to 1100 dm3) were analysed in transects in November 1988 and 1989 and in spring 1991. Salinity and temperature were measured continuously along the sampling tracks in all three cruises; nutrients and pH only in the latter two cruises. Concentrations of individual CBs in solution were in the sub- and low pg dm−3 range (detection limit being 0.05 pg dm−3), and of their sum between 2 and 237 pg dm−3. These concentrations are considerably lower than previously reported data. This is mainly the result of the elimination of contamination and interference problems in the sampling, clean-up and GC-ECD procedures. It may also partly reflect the reduction in the production and use of PCBs in the last decade. The highest concentrations in solution originated from local sources in the Belt Sea and the Gulf of Finland. Regional differences were found for the compositions of the CB mixtures in solution. The lowest concentrations of CBs in solution were found in areas and periods of plankton production (spring 1991), with ΣCB concentrations between 2 and 14 pg dm−3. The compositions of the CB mixtures showed regional differences in each cruise. These could be interpreted in terms of mixing between different water bodies. The classification of transects on the basis of these CB patterns agreed well with the distinction of water bodies on the basis of T-S diagrams and hydrochemical data. Concentrations of individual CBs in suspension were generally 0.1–0.5 pg dm−3, those of their sum (ΣCB) between 4 and 6 pg dm−3 during the autumn cruises. Extremely high values were found in the Belt Sea-Kattegat area in spring 1991 (up to 589 pg dm−3 for individual CBs and up to 2859 pg dm−3 for ΣCB). This probably reflects the uptake of CBs into particulates during a plankton bloom. Primary production may effectively remove CBs from the water column into the sediments. The amounts of chlorobiphenyls presently stored in the sediments of the Baltic Sea exceed the amounts in the water column by several orders of magnitude. The compositions of the CB mixtures differed considerably between solution and suspension. The relations between log K′d (apparent particle/water partition coefficient) and log Kow (octanol-water distribution coefficient) suggest the existence of (quasi-)equilibrium conditions in autumn. Deviations from this behaviour arise from biological activity in spring. The contribution of toxic congeners to the CB mixtures was dominated by the mono- and di-ortho-Cl substituted derivatives of the most toxic non-ortho-Cl CBs. The toxicity of the CB mixtures in solution was between 0.01 and 12fg dm−3 TEQs (TCDD toxic equivalents). CBs-77, -118, -105 and -156 had the largest contributions to TEQs.

An in-situ filtration/extraction system for the recovery of trace organics in solution and on particles tested in deep ocean water

A system for in-situ filtration and extraction of organics in natural waters has been developed and tested down to 4000 m in the Atlantic Ocean. Up to 2000 dm3 water can be filtered and extracted at low suspended matter concentrations. The sampling equipment has new features for the analysis of trace organic compounds: contamination is extremely low, this can be checked and cured, if necessary, and water flow can be selected and maintained at a constant rate. Various resins can be applied, with different optimum flow rates for the efficient extraction of the compounds of interest. The properties of the resin (here XAD-2) do not change with depth. The operation of the unit is controlled by menu-driven software. All relevant data are stored for later evaluation. Tests in the deep Atlantic resulted in total procedural blanks, including sampling, as low as 0/003 pg dm−3 for individual chlorobiphenyls (CBs), HCB and DDE and 0.5 pg dm−3 for individual PAHs. Actual dissolved concentrations were in the range 0.005–0.1 pg dm−3 for CBs, HCB and DDE and 0.5–140 pg dm−3 for PAHs.

Polychlorinated biphenyls in air and water of the North Atlantic and Arctic Ocean

Air and seawater samples were collected on board the R/V Polarstern during a scientific expedition from Germany to the Arctic Ocean during June–August 2004. The air data show a strong decline with latitude with the highest polychlorinated biphenyl (PCB) concentrations in Europe and the lowest in the Arctic. ΣICES PCBs in air range from 100 pg m−3 near Norway to 0.8 pg m−3 in the Arctic. A comparison with other data from previous and ongoing land-based air measurements in the Arctic region suggests no clear temporal decline of PCBs in the European Arctic since the mid-1990s. Dissolved concentrations of Σ6PCBs (28/31, 52, 101, 118, 138, 153) in surface seawater were <1 pg L−1. Dominant PCBs in seawater were 28/31 and 52 (0.1–0.44 pg L−1), with PCBs 101, 118, and 138 < 0.1 pg L−1. In seawater, PCB 52 displayed the highest concentrations in the northernmost samples, while PCBs 101, 118, and 138 showed slightly decreasing trends with increasing latitude. Fractionation was observed for PCBs in seawater with the relative abundance of PCBs 28 and 52 increasing and that of the heavier congeners decreasing with latitude. However, in air only 15–20% of the variability of atmospheric PCBs can be explained by temperature. Owing to large uncertainties in the Henrys Law constant (HLC) values, fugacity quotients for PCBs were estimated using different HLCs reported in the literature. These indicate that on average, deposition dominates over volatilization for PCBs in the Arctic region with a strong increase in the middle of the transect near the marginal ice zone (78–79°N). The increase in fugacity ratio is mainly caused by an increase in air concentration in this region (possibly indirectly caused by ice melting being a source of PCBs to the atmosphere).

Seasonal variability of the long-chain alkenone flux and the effect on the U37k′-index in the Norwegian Sea

A seasonally-varying sedimentation pattern was observed for the alkenone flux measured with sediment traps in the northern North Atlantic. In the Norwegian Sea (traps were set at 500, 1000 and 3000 m) the alkenone flux varied between 0.1 and 7.1 μg m−2 d−1 and followed the seasonal pattern of the bulk parameters. Maximum fluxes occurred from mid-October until mid-November and were also high in May. A surprising result was that considerably higher particle fluxes were observed at 3000 m. For the alkenone flux, the highest additional input of 250% was observed during the period when sediment resuspension was greatest in summer. At the Barents Sea continental margin (traps at 1840 and 1950 m) the alkenone fluxes follow the sedimentation pattern of the bulk parameters, with a less visible signal of distinct seasonality observed in the 1950 m trap. The sedimentation of total alkenones varied between 0.8 and 144 μg m−2 d−1 at 1840 m and between 0.5 and 31.0 μg m−2 d−1 at 1950 m. Resuspension and lateral advection contributed significantly to measured fluxes in the two near-bottom traps. Alkenone concentrations were determined in faecal pellets of Appendicularia, ostracods and euphausids from selected samples at the Barents Sea site. The alkenone flux in pellets (4% to 24% of total) was 5 to 6 times higher at 1950 m depth than at 1840 m and the major part (77–78%) of the total flux of C37:3 reaching the near-bottom trap at 1950 m was associated with faecal pellets of the meso-zooplankton. Spatial and temporal variations of the U37k′ signals were observed, indicating that the imprint in the alkenone signal depends on the origin and transport pathway of the organic material. Strong deviations occur in areas where nepheloid layers contribute particles of long residence times to the primary flux.

Polychlorinated biphenyls in North Sea water

Thirty-one individual chlorobiphenyl congeners (CBs) were analysed in water from the North Sea. Single column gas chromatographic and multidimensional gas chromatographic techniques were used to separate the constituents of the complex mixtures. Characteristic concentrations of individual CBs in off-shore water were between <0.05 and 2 pg dm−3, and up to 40 pg dm−3 in near-coastal waters. ΣCB values in off-shore waters were two to three times higher than values measured in the open Atlantic. Most concentrations in suspended matter were below the limit of detection (0.05 pg dm−3 in 100 dm3 samples). The most toxic (non-ortho-Cl substituted) CBs and their ortho-chlorine substituted derivatives were also determined. The sum of their concentrations was two to four times smaller than that of the non- or less toxic CBs. High concentrations and different compositions of the CB mixtures were found in the region where oil platforms are located. The much lower concentration levels reported here compared with older data reflect the improved measures to avoid contamination during sampling and laboratory procedures, as well as the analysis of a large volume of sea water (at least 100 dm3 for off-shore waters).

High resolution PCB analysis of kanechlor, phenoclor and sovol mixtures using multidimensional gas chromatography

Abstract Kanechlor-300, -400, -500 and -600, Phenoclor DP-3, -4, -5 and -6 and Sovol mixtures were analyzed for their chlorobiphenyl (CB) composition using high-resolution one-dimensional and multidimensional gas chromatography-electron capture detection (MDGC-ECD) techniques. The congener patterns of tested Kanechlor and Phenoclor mixtures resembled Aroclor 1016, 1242, 1254 and 1260. However, differences in the percentage contribution of minor constituents were noticed among these mixtures, which could be due to variations in the boiling-point fractionation of these commercial products. CB pattern of Sovol was different from the rest of the mixtures tested. It showed a composition in between ca. 30%, 40%, 50% and 60% overall chlorine levels. MDGC-ECD study showed the presence of hitherto unnoticed non-CB compounds coeluting with CBs in some commercial PCBs. The use of these mixtures as quantitation standards should be considered with caution. CB patterns of Sovol and a water extract of the Gulf of Finlan...