Testing the palaeoclimatic significance of the Northern Irish bog oak record

We present an analysis of the Northern Irish bog oak record presented in Turney et al. (2005) for the last 4500 years. The record is compared with a compiled peatland water table record from the same region and palaeohydrological data from northern England and mid-latitude Europe. It is apparent that there is no consistent relationship between the population frequency of Irish bog oaks and the palaeohydrological reconstructions, illustrating that the record is not reflecting wetness changes in peatlands. We suggest that the bog oaks should be scrutinised on a within-site and a site-by-site basis to assess the spatial coherency of the shifts in tree populations and the synchronicity of phases of germination and dying off (GDO). Further work is needed to critically examine the controls on the establishment and demise of bog oaks on Irish peatlands before these data can be used as a palaeoclimate proxy. Only then can they be used to test solar forcing of Holocene climate change.

Confirming the Existence of Gaps and Depletions in the Irish Oak Tree-Ring Record

In the course of building the 7000 year Belfast long oak chronology a series of depletion problems were encountered. These problems were overcome by 1984 when the completion of the long chronology was announced. The solution to the bridging of the various ‘gaps’ in the Irish chronology lay in the use of long sections of oak chronology from Britain. Now that a quarter of a century has elapsed and large numbers of additional oak samples, and site assemblages, have been accumulated it seems reasonable to review the ‘gaps’ in order to see if the Irish chronology could now be constructed without the use of British material. That is, are the depletion periods in the Irish chronology still evident, and if so, what might they imply about past conditions and human populations? The perhaps surprising conclusion is that the original depletions are still evident after 25 years of quasi-random sampling by archaeologists and palaeoecologists throughout Ireland.

Field observation of sequestration of uranium in iron-rich sediments under sequential reduction-oxidation conditions at the DOE Oak Ridge IFRC

At the U.S. DOE Oak Ridge Integrated Field Research Challenge (ORIFRC) site, the iron content of shallow subsurface materials (i.e. weathered saprolite) is relatively high (up to 5-6% as w/w), and therefore, the forms of the iron species present plays a critical role in the long-term sequestration of uranium. A long term pilot-scale study of the bioreduction and reoxidation of uranium conducted at the ORIFRC area 3 site, adjacent to the former S-3 disposal ponds (source zone), has provided us with the opportunity to study the impact of iron species on the sequestration of U(VI). The aqueous U(VI) concentrations at the site were decreased to below the EPA MCL through the intermittent injection of ethanol as the electron donor. Previous field tests indicated that both oxygen and nitrate could oxidize the bioreduced U(IV) and cause a short-term rebound of aqueous phase uranium concentration after the oxidative agents were delivered directly to the bioreduced zone.

A field test has been conducted to examine the long-term effect of exposure of bioreduced sediments to nitrate in contaminated groundwater for more than 1,380 days at the Area 3 site. Contaminated groundwater was allowed to invade the previously bioreduced zone via the natural groundwater gradient after an extended period in which reducing conditions were maintained and the bioreduced zone was protected from the influx of upgradient contaminated groundwater. The geochemical response to the invasion of contaminated groundwater was dependent on whether the monitoring location is in the middle or the fringe of the previously bioreduced zone. In general, the nitrate concentrations in the previously bioreduced area, increased gradually from near zero to ~50-300 mM within 200 days and then stabilized. The pH declined from bioreduced levels of 6.2-6.7 to below 5.0. Uranium concentrations rebounded in all monitoring wells but at different rates. At most locations U concentrations rebounded, declined and then rebounded again. Methane gas disappeared while a significant level (20,000 to 44,000 ppmv) N2O was found in the groundwater of monitoring wells after three years of reoxidization.

The U(IV) in sediments was mainly reoxidized to U(VI) species. Based on XANES analysis, the predominate uranium in all samples after re-oxidation was similar to a uranyl nitrate form. But the U content in the sediment remained as high as that determined after bioreduction activates were completed, indicating that much of the U is still sequestrated in situ. SEM observations of surged fine sediments revealed that clusters of colloidal-sized (200-500nm) U-containing precipitates appeared to have formed in situ, regardless from sample of FW106 in non-bioactivity control area or of pre-bioreduced FW101-2 and FW102-3. Additionally, SEM-EDS and microprobe analysis, showed that the U-containing precipitates (~1% U) in FW106 are notably higher in Fe, compared to the precipitates (~1-2.5% U) from FW101-2 and FW102-3. However, XRF analysis indicated that the U content was remained as high as 2180 and 1810 mg/kg with U/Fe ratio at 0.077 and 0.055 vs 0.037 g/g, respectively in pre-bioreduced FW101-2 and FW102-3, suggesting more U sequestrated by Fe in pre-bioreduced sediments.