Zanna Chase

Developing standards for dissolved iron in seawater

In nearly a dozen open- ocean fertilization experiments conducted by more than 100 researchers from nearly 20 countries, adding iron at the sea surface has led to distinct increases in photosynthesis rates and biomass. These experiments confirmed the hypothesis proposed by the late John Martin [Martin, 1990] that dissolved iron concentration is a key variable that controls phytoplankton processes in ocean surface waters. However, the measurement of dissolved iron concentration in seawater remains a difficult task [Bruland and Rue, 2001] with significant interlaboratory differences apparent at times. The availability of a seawater reference solution with well- known dissolved iron (Fe) concentrations similar to open- ocean values, which could be used for the calibration of equipment or other tasks, would greatly alleviate these problems [National Research Council (NRC), 2002]. The Sampling and Analysis of Fe (SAFe) cruise was staged from Honolulu, Hawaii, to San Diego, Calif., between 15 October and 8 November 2004 to collect data and samples that were later used to provide this reference material. Here we provide a brief report on the cruise results, which have produced a tenfold improvement in the variability of iron measurements, and announce the availability of the SAFe dissolved Fe in seawater standards.

The influence of particle composition and particle flux on scavenging of Th, Pa and Be in the ocean

We have examined the relative affinity of Th, Pa and Be for sorption from seawater onto particles of variable composition (opal, carbonate, lithogenic particles and organic carbon). Nuclide concentrations in particles collected from time-series sediment traps were normalized by the dissolved nuclide concentration in the overlying water column in order to compute partition coefficients under conditions spanning a wide range of particle flux and particle composition. Our results suggest that the affinity of particles for Pa and Be increases with their increasing opal content and decreasing carbonate content, while the affinity of particles for Th increases with increasing carbonate content, and decreases with increasing opal content. We find no correlation between the aluminosilicate content of particles and their affinity for scavenging of any of these elements. Extrapolating to a pure CaCO3 end member, the partition coefficient for Th (9.0×106 g g−1) is ∼40 times greater than for Pa, and roughly 100 times greater than for Be, whereas for a pure opal end member, the partition coefficient for Th (3.9×105 g g−1) is slightly less than that for Pa and Be. Partition coefficients decrease with increasing particle flux in open-ocean settings, but not in an ocean-margin region. This kinetic effect reflects the increasing contribution of unaltered surface material reaching the sediment traps as particle flux increases. The degree of fractionation between Pa and Th and between Be and Th depends on the opal:carbonate rain ratio. These results challenge the use of sedimentary 231Pa/230Th and 10Be/230Th ratios as simple proxies of particle flux. However, the strong dependence of nuclide scavenging on the opal:carbonate rain ratio may provide a needed tool for reconstructing past changes in planktonic community composition.

Accumulation of biogenic and lithogenic material in the Pacific sector of the Southern Ocean during the past 40,000 years

The 230Th-normalization technique was applied to surface sediments and down-core records from the Pacific sector of the Southern Ocean between 120°W and 170°W in order to reconstruct vertical rain rates, corrected for lateral redistribution of sediment. Preserved rain rates of opal, organic carbon and biogenic Ba all indicate that biological productivity south of the Antarctic Polar Front (APF) was much lower than today during the Last Glacial Maximum (LGM), probably in response to increased ice cover. However, by analogy with modern opal fluxes south of the ACC, we show that year-round ice cover is not a prerequisite for very low rates of opal accumulation. Available records from north of the APF indicate little to no change in opal export, in contrast to records from the Indian and Atlantic sectors, which show enhanced opal export north of the APF during the LGM. Glacial records from north of 66°S in the Pacific all show lithogenic fluxes that were greater than today, but significantly lower than lithogenic fluxes in the glacial Atlantic and Indian sectors. Together, these new records from the Pacific sector show that during the LGM the three basins of the Southern Ocean were significantly more differentiated than today. The observed inter-basin distribution of lithogenic fluxes and opal burial, and the presumed geographical distribution of increased dust input to the Southern Ocean during the LGM, are consistent with an Atlantic–Indian–Pacific gradient in the degree of iron-stimulated diatom productivity within the zone lying between the APF and the Subantarctic Front. Previous studies, which focused primarily on the Atlantic sector, may have overestimated the glacial increase in the strength of the biological pump in the Southern Ocean.

Evidence from authigenic uranium for increased productivity of the glacial subantarctic ocean

Authigenic uranium is precipitated in reducing sediments and therefore responds both to changes in particulate organic carbon flux to the sediment and to changes in the oxygen concentration of bottom waters. By examining a large number of cores over a wide latitudinal and depth range in the Atlantic sector of the Southern Ocean, we hope to distinguish between a predominantly productivity-driven authigenic U signal and a circulation or sediment-focusing signal. We find little to no authigenic U in Holocene sediments throughout the South Atlantic Ocean. Glacial sediments north of ∼40°S lack authigenic U, whereas sediments from the Subantarctic Zone show substantial enrichments in authigenic U relative to the Holocene (up to ∼5.3 ppm). The widespread distribution of glacial U enrichment, even in cores with no glacial-interglacial change in mass accumulation rate, implies that U deposition was not caused by an increased supply of organic carbon via sediment focusing. Authigenic U and organic carbon in a shallow core (∼1000 m) from the Subantarctic region show the same glacial increase found in the deep cores. Because this site was well ventilated during the Last Glacial Maximum, its record provides further evidence that increased glacial productivity of the Subantarctic region contributed to the high concentrations of authigenic U found in the glacial sections of deep cores.

Iron links river runoff and shelf width to phytoplankton biomass along the U.S. West Coast

A poleward increase in phytoplankton biomass along the West Coast of North America has been attributed to increasing river runoff towards the north. We combine streamflow and shelf width data with satellite-derived estimates of phytoplankton biomass to quantify the relationship between these variables. We find that a combination of winter streamflow and shelf width can account for over 80% of the spatial variance in summer chlorophyll within 50 km of the coast. At a given location, interannual variability in streamflow is not associated with interannual variability in chlorophyll. We attribute these relationships to the role of rivers as suppliers of the micronutrient iron, and the role of the shelf as a ‘capacitor’ for riverine iron, charging during the high-flow winter season and discharging during the upwelling season. Data from the Oregon shelf confirm that, during winter, a significant fraction of riverine iron escapes the estuary and reaches the coastal ocean.

Distribution and variability of iron input to Oregon coastal waters during the upwelling season

generally higher in spring (mean of 2.1 and 33.9 nmol L 1 , respectively) than in summer (means of 1.4 and 15.4 nmol L 1 ). In spring and summer, high iron concentrations in surface waters were associated with both cold and saline, recently upwelled waters, and with fresh, relatively warm water influenced by the Columbia River. Comparison of total dissolvable iron in 0.45 mm filtered and in unfiltered samples indicated a substantial contribution from particulate iron. Iron concentrations in summer were generally lower than in spring throughout the water column, with the exception of the near-bottom, where concentrations were generally higher in summer than spring. Optical backscatter data from moored sensors were used to infer the vertical and cross-shelf transport of iron-bearing particles during the upwelling season over a steep shelf. Cross-correlation analysis showed downslope movement of particles from the deep inner shelf to the deep midshelf. There was also evidence for sinking of biogenic particles at the midshelf and inner shelf, but we found no evidence of upslope transport of benthic particles. Sufficient iron is available in this system to meet the demands of the phytoplankton, which are able to make full use of available nitrate. Citation: Chase, Z., B. Hales, T. J. Cowles, R. Schwartz, and A. van Green (2005), Distribution and variability of iron input to Oregon coastal waters during the upwelling season, J. Geophys. Res., 110, C10S12, doi:10.1029/2004JC002590.

Comment on ''Do geochemical estimates of sediment focusing pass the sediment test in the equatorial Pacific?'' by M. Lyle et al

Accurately estimating the vertical flux of material reaching the seafloor from the overlying surface waters is essential for the paleoceanographic reconstruction of a wide variety of oceanic processes. Two approaches are currently being used. One consists of estimating mass accumulation rates (MAR) between dated horizons as the product of linear sedimentation rates, sediment dry bulk densities, and concentrations. One pitfall with this approach is that sediments can be redistributed on the seafloor by bottom currents, and their accumulation may not necessarily reflect the true vertical rain rate originating from the overlying water column. To address this problem, the method of 230Th normalization was developed [Bacon, 1984]. This method is based on the assumption that the rapid scavenging of 230Th produced in the water column by decay of dissolved uranium results in its flux to the seafloor always being close to its known rate of production. To the extent that this assumption is correct, scavenged 230Th can be used as a reference to estimate the settling flux of other sedimentary constituents and to correct for sediment redistribution on the seafloor [Henderson and Anderson, 2003; Francois et al., 2004].

Dissolution of fluoride complexes following microwave-assisted hydrofluoric acid digestion of marine sediments

Microwave-assisted, hydrofluoric acid digestion is an increasingly common tool for the preparation of marine sediment samples for analysis by a variety of spectrometric techniques. Here we report that analysis of terrigenous-dominated sediment samples occasionally results in anomalously low values for several elements, including Al, Ba, Ca, Mg, and Sr. Measured concentrations of these elements increased with time between sample preparation and sample analysis, reaching stable values after 8-29 days. This lag is explained by the formation and subsequent dissolution of poorly soluble fluoride phases during digestion. Other elements, such as Fe, Mn, and Ti, showed little or no lag and were quickly measurable at a stable value. Full re-dissolution of the least soluble fluorides, which incorporate Al and Mg, requires up to four weeks at room temperature, and this duration can vary among sedimentary matrices. This waiting time can be reduced to 6 days (or shorter) if the samples are heated to ≈ 60°C for 24h.

Controls on biogenic silica burial in the Southern Ocean

Understanding the controls on opal export in the Southern Ocean can inform both the prediction of how the leakage of silicic acid from the Southern Ocean responds to climate and the interpretation of paleo-proxies. We have compiled a database of 185 230Thorium-normalized opal burial rates and 493 opal concentration measurements in Southern Ocean sediments and matched these with environmental climatologies. By subdividing the Southern Ocean on the basis of oceanographic regions and interpolating the opal burial rates, we estimate a total biogenic Si burial south of 40°S of 2.3 ± 1.0 Tmol Si yr−1. In both the seasonally ice-covered and permanently ice-free regions we can explain 73% of opal burial variability from surface ocean properties. Where sea ice is present for at least part of the year, the length of the ice-free season determines the upper limit of opal burial in the underlying sediments. In the ice-free regions of the Southern Ocean, the supply of silicic acid through winter mixing is the most important factor. Our results do not support a strong role of iron in controlling opal burial. We do however find that satellite-derived net primary production increases with increasing (modeled) dust delivery. These findings support the decoupling between carbon and opal fluxes in the Southern Ocean. When corrected for opal dissolution, the observed opal fluxes are in reasonable agreement with fluxes simulated using an ocean biogeochemical model. However, the results suggest current preservation algorithms for opal could be improved by incorporating the composition of particle flux, not only its magnitude.

Recent mine spill adds to contamination of southern Spain

The retaining wall of a tailings reservoir collapsed at a zinc mine in Spain last spring, releasing into the watershed possibly nearly as much zinc as the mine produces annually. The accident happened April 25,1998, at the Los Frailes mine near Aznalcollar in southern Spain, sending ∼5 x 106m3 of acid sludge into the Guadiamar River. Based on a suite of water and river bank sediment samples collected downstream of the spill on May 1–3, 1998, an estimated 40,000 to 120,000 tons of Zn was added to the watershed. This is comparable to the annual production capacity of the mine of 125,000 tons. While the scale of the accident was certainly very large, an equivalent amount of Zn has been reaching the adjacent Tinto-Odiel estuary every 1–2 years as a result of mining since the middle of the 19th century. Emergency dikes were built shortly after the accident to prevent contamination of Donana National Park, an important wildlife reserve 40 km to the south of the mine. The composition of samples collected north of the park suggest this diversion was effective.