A Two-Stage Aerobic/Anaerobic Denitrifying Horizontal Bioreactor Designed for Treating Ammonium and H2S Simultaneously

A two-stage bioreactor was operated for a period of 140 days in order to develop a post-treatment process based on anaerobic bioxidation of sulfite. This process was designed for simultaneously treating the effluent and biogas of a full-scale UASB reactor, containing significant concentrations of NH4 and H2S, respectively. The system comprised of two horizontal-flow bed-packed reactors operated with different oxygen concentrations. Ammonium present in the effluent was transformed into nitrates in the first aerobic stage. The second anaerobic stage combined the treatment of nitrates in the liquor with the hydrogen sulfide present in the UASB-reactor biogas. Nitrates were consumed with a significant production of sulfate, resulting in a nitrate removal rate of 0.43 kg N m(3) day(-1) and a parts per thousand yen92 % efficiency. Such a removal rate is comparable to those achieved by heterotrophic denitrifying systems. Polymeric forms of sulfur were not detected (elementary sulfur); sulfate was the main product of the sulfide-based denitrifying process. S-sulfate was produced at a rate of about 0.35 kg m(3) day(-1). Sulfur inputs as S-H2S were estimated at about 0.75 kg m(3) day(-1) and Chemical Oxygen Demand (COD) removal rates did not vary significantly during the process. DGGE profiling and 16S rRNA identified Halothiobacillus-like species as the key microorganism supporting this process; such a strain has not yet been previously associated with such bioengineered systems.

Hydrogen and Methane Production, Energy Recovery, and Organic Matter Removal from Effluents in a Two-Stage Fermentative Process

This study evaluates the potential for using different effluents for simultaneous H-2 and CH4 production in a two-stage batch fermentation process with mixed microflora. An appreciable amount of H-2 was produced from parboiled rice wastewater (23.9 mL g(-1) chemical oxygen demand [COD]) and vinasse (20.8 mL g(-1) COD), while other effluents supported CH4 generation. The amount of CH4 produced was minimum for sewage (46.3 mL g(-1) COD), followed by parboiled rice wastewater (115.5 mL g(-1) COD) and glycerol (180.1 mL g(-1) COD). The maximum amount of CH4 was observed for vinasse (255.4 mL g(-1) COD). The total energy recovery from vinasse (10.4 kJ g(-1) COD) corresponded to the maximum COD reduction (74.7 %), followed by glycerol (70.38 %, 7.20 kJ g(-1) COD), parboiled rice wastewater (63.91 %, 4.92 kJ g(-1) COD), and sewage (51.11 %, 1.85 kJ g(-1) COD). The relatively high performance of vinasse in such comparisons could be attributed to the elevated concentrations of macronutrients contained in raw vinasse. The observations are based on kinetic parameters of H-2 and CH4 production and global energy recovery of the process. These observations collectively suggest that organic-rich effluents can be deployed for energy recovery with sequential generation of H-2 and CH4.

The reconstruction of paleoclimate variability in Northern Germany, during marine isotope stage 5

In order to obtain a better understanding about the influence of post-depositional diagenesis on speleothem 230Th/U-ages and paleoclimate variability during Marine Isotope Stage (MIS) 5 in northern Germany, four stalagmites from the Riesenberghöhle (RBH) were investigated by thin section analysis, 230Th/U-dating as well as stable oxygen and carbon isotope and laser ablation inductively coupled mass spectrometry (LA-ICPMS) trace element analysis. The RBH is located in the Weser Hills and is one of the northernmost limestone caves in Germany.rnMulti collector (MC) ICPMS 230Th/U-ages and thin section analysis of the RBH stalagmites shows that some growth phases of the stalagmites were diagenetically altered after their deposition. The impact of post-depositional diagenesis (PDD) on the 230Th/U-ages is modeled, and potential processes leading to PDD are discussed. In this context, it is suggested that PDD may be induced by rapid climate change at the inception of the GIS.rnDespite of the dating uncertainties resulting from PDD, 230Th/U-dating shows that the RBH stalagmites grew during the Eemian and most of the Greenland Interstadials (GIS) during MIS 5. Thus, the growth phases of the RBH stalagmites might be related to a reorganization of the Atlantic Meridional Overturning Circulation (AMOC). The stable isotope (δ13C and δ18O) and the trace element variability of the stalagmites reflects rapid changes of past temperature and precipitation on millennial and sub-millennial timescales. These past climate changes can be amplified by orbitally forced variations of the July solar insolation at 65°N.

Dinoflagellate cyst assemblages, oxygen isotope records of foraminifera, and alkenone and Mg/Ca-based SST estimates for the time interval 3.40-3.18 Ma (Late Pliocene) from five North Atlantic and Caribbean sediment cores

The early Late Pliocene (3.6 to ~3.0 million years ago) is the last extended interval in Earth's history when atmospheric CO2 concentrations were comparable to today's and global climate was warmer. Yet a severe global glaciation during marine isotope stage (MIS) M2 interrupted this phase of global warmth ~3.30 million years ago, and is seen as a premature attempt of the climate system to establish an ice-age world. Our geochemical and palynological records from five marine sediment cores along a Caribbean to eastern North Atlantic transect show that increased Pacific-to-Atlantic flow via the Central American Seaway weakened the North Atlantic Current (NAC) and attendant northward heat transport prior to MIS M2. The consequent cooling of the northern high latitude oceans permitted expansion of the Greenland ice sheet during MIS M2, despite near-modern atmospheric CO2 concentrations. Before and after MIS M2, heat transport via the NAC was crucial in maintaining warm climates comparable to those predicted for the end of this century.

Oxygen isotopes, IRD and SST reconstruction for the interval MIS31-19 of IODP Site 306-U1314

Early and Mid-Pleistocene climate, ocean hydrography and ice sheet dynamics have been reconstructed using a high-resolution data set (planktonic and benthic d18O time series, faunal-based sea surface temperature (SST) reconstructions and ice-rafted debris (IRD)) record from a high-deposition-rate sedimentary succession recovered at the Gardar Drift formation in the subpolar North Atlantic (Integrated Ocean Drilling Program Leg 306, Site U1314). Our sedimentary record spans from late in Marine Isotope Stage (MIS) 31 to MIS 19 (1069-779 ka). Different trends of the benthic and planktonic oxygen isotopes, SST and IRD records before and after MIS 25 (~940 ka) evidence the large increase in Northern Hemisphere ice-volume, linked to the cyclicity change from the 41-kyr to the 100-kyr that occurred during the Mid-Pleistocene Transition (MPT). Beside longer glacial-interglacial (G-IG) variability, millennial-scale fluctuations were a pervasive feature across our study. Negative excursions in the benthic d18O time series observed at the times of IRD events may be related to glacio-eustatic changes due to ice sheets retreats and/or to changes in deep hydrography. Time series analysis on surface water proxies (IRD, SST and planktonic d18O) of the interval between MIS 31 to MIS 26 shows that the timing of these millennial-scale climate changes are related to half-precessional (10 kyr) components of the insolation forcing, which are interpreted as cross-equatorial heat transport toward high latitudes during both equinox insolation maxima at the equator.

A low-latitude Upper Pleistocene oxygen isotope stack

Below oxygen isotope stage 16, the orbitally derived time-scale developed by Shackleton et al. (1990) from ODP site 677 in the equatorial Pacific differs significantly from previous ones (e.g. Kominz and Pisias, 1979 doi:10.1126/science.204.4389.171; Morley and Hays, 1981 doi:10.1016/0012-821X(81)90034-0, Imbrie et al. 1984), yielding estimated ages for the last Earth magnetic reversals that are 5-7% older than the K/Ar values (Mankinen and Dalrymple, 1979 doi:10.1029/JB084iB02p00615; Berggren et al., 1985; Harland and Armstrong, 1989) but are in good agreement with recent Ar/Ar dating (Baksi et al., 1991; 1992 doi:10.1126/science.256.5055.356; Spell and McDougall, 1992 doi:10.1029/92GL01125). These results suggest that in the lower Brunhes and upper Matuyama chronozones most deep-sea climatic records retrieved so far apparently missed or misinterpreted several oscillations predicted by the astronomical theory of climate. To test this hypothesis, we studied a high-resolution oxygen isotope record from giant piston core MD900963 (Maldives area, tropical Indian Ocean) in which precession-related oscillations in delta18O are particularly well expressed, owing to the superimposition of a local salinity signal on the global ice volume signal (Rostek et al., 1993 doi:10.1038/364319a0). Three additional precession-related cycles are observed in oxygen isotope stages 17 and 18 of core MD900963, compared to the SPECMAP composite curves (Imbrie et al., 1984; Prell et al., 1986 doi:10.1029/PA001i002p00137), and stage 21 clearly presents three precession oscillations, as predicted by Shackleton et al. (1990). The precession peaks found in the delta18O record from core MD900963 are in excellent agreement with climatic oscillations predicted by the astronomical theory of climate. Our delta18O record therefore permits the development of an accurate astronomical time-scale. Based on our age model, the Brunhes-Matuyama reversal is dated at 775 +/- 10 ka, in good agreement with the age estimate of 780 ka obtained by Shackleton et al. (1990) and recent radiochronological Ar/Ar datings on lavas (Baksi et al., 1991; 1992; Spell and McDougall, 1992). We developed a new low-latitude, Upper Pleistocene delta18O reference record by stacking and tuning the delta18O records from core MD900963 and site 677 to orbital forcing functions.

Sedimentology and stable oxygen isotope ratios of foraminifera from cores of the Porcupine Seabight, Northeast Atlantic

Large carbonate mound structures have been discovered in the northern Porcupine Seabight (Northeast Atlantic) at depths between 600 and 1000 m. These mounds are associated with the growth of deep-sea corals Lophelia pertusa and Madrepra oculata. In this study, three sediment cores have been analysed. They are from locations close to Propeller Mound, a 150 m high ridge-like feature covered with a cold-water coral ecosystem at its upper flanks. The investigations are concentrated on grain-size analyses, carbon measurements and on the visual description of the cores and computer tomographic images, to evaluate sediment content and structure. The cores portray the depositional history of the past ~31 kyr BP, mainly controlled by sea-level fluctuations and the climate regime with the advance and retreat of the Irish Ice Sheet onto the Irish Mainland Shelf. A first advance of glaciers is indicated by a turbiditic release slightly older than 31 kyr BP, coherent with Heinrich event 3 deposition. During Late Marine Isotope Stage 3 (MIS 3) and MIS 2 shelf erosion prevailed with abundant gravity flows and turbidity currents. A change from glaciomarine to hemipelagic contourite sedimentation during the onset of the Holocene indicates the establishment of the strong, present-day hydrodynamic regime at intermediate depths. The general decrease in accumulation of sediments with decreasing distance towards Propeller Mound suggests that currents (turbidity currents, gravity flows, bottom currents) had a generally stronger impact on the sediment accumulation at the mound base for the past ~31 kyr BP, respectively.

Quaternary oxygen isotope record of planktonic foraminifera from ODP Site 805 on the Ontong Java Plateau

The oxygen isotope records of G. sacculifer and Pulleniatina in the uppermost three cores at Ocean Drilling Program Hole 805C span the last 1.6 m.y., an estimate based on Fourier stratigraphy. The last 700,000 yr are dominated by both eccentricity and obliquity-related orbital fluctuations. The range of variation of delta18O values is about 1.5?, of which ca. 75% may be assigned to global ice-volume effect. The remainder of the range is shared by the effects of surface temperature variation, thermocline depth change (in the case of Pulleniatina, especially), and differential dissolution. Before 1 Ma, obliquity-related fluctuations dominate. The transition between obliquity- and eccentricity-dominated time occurs between ca. 1 and 0.7 Ma. It is marked by irregularities in phase relationships, the source of which is not clear. The age of the Brunhes/Matuyama boundary is determined as 794,000 yr by obliquity counting. However, an age of 830,000 yr also is compatible with the counts of both eccentricity and obliquity cycles. In the first case, Stage 19 (which contains the boundary) is coincident with the crest of the 19th obliquity cycle, setting the first crest downcore equal to zero, and counting backward (o19). In the second, Stage 19 coincides with o20. No evidence was found for fluctuations related to precession (23 and 19 k.y.) rising above the noise level, using plain Fourier expansion on the age model of the entire series. Detailed stratigraphic comparison with the Quaternary record of Hole 806B allows the recognition of major dissolution events (which increase the difference in delta18O values of G. sacculifer at the two sites). These occur at Stages 11-13, 16-17, and near 1.5 Ma (below o33).

Oxygen isotope composition of benthic and planktonic foraminifera from ODP Holes 146-893A and 167-1017B

The detailed structure and timing of the penultimate deglaciation are insufficiently defined yet critical for understanding mechanisms responsible for abrupt climate change. Here we present oxygen isotope records (from planktonic and benthic foraminifera) at unprecedented resolution encompassing late marine oxygen isotope stage (MIS) 6 and Termination II (ca. 150-120 ka) from the Santa Barbara Basin, supported by additional southern California margin records, a region highly sensitive to millennial-scale climate oscillations during the last deglaciation. These records reveal millennial- and centennial-scale climate variability throughout the interval, including an interstadial immediately preceding the deglaciation, a brief warm event near the beginning of Termination II, and a Bølling-Allerød-Younger Dryas-like climate oscillation midway through the deglaciation. Recognition of these events in an oxygen isotope record from a 230Th-dated stalagmite allows the adoption of this radiometric chronology for the California margin records. This chronology supports the Milankovitch theory of deglaciation. The suborbital history of climate variability during Termination II may account for records of early deglaciation.

Sea surface temperatures during Marine Isotope Stage (MIS) 11

The Marine Isotope Stage (MIS) 11 (424-374 ka) was characterized by a protracted deglaciation and an unusually long climatic optimum. It remains unclear to what degree the climate development during this interglacial reflects the unusually weak orbital forcing or greenhouse gas trends. Previously, arguments about the duration and timing of the MIS11 climatic optimum and about the pace of the deglacial warming were based on a small number of key records, which appear to show regional differences. In order to obtain a global signal of climate evolution during MIS11, we compiled a database of 78 sea surface temperature (SST) records from 57 sites spanning MIS11, aligned these individually on the basis of benthic (N = 28) or planktonic (N = 31) stable oxygen isotope curves to a common time frame and subjected 48 of them to an empirical orthogonal function (EOF) analysis. The analysis revealed a high commonality among all records, with the principal SST trend explaining almost 49% of the variability. This trend indicates that on the global scale, the surface ocean underwent rapid deglacial warming during Termination V, in pace with carbon dioxide rise, followed by a broad SST optimum centered at ~410 kyr. The second EOF, which explained ~18% of the variability, revealed the existence of a different SST trend, characterized by a delayed onset of the temperature optimum during MIS11 at ~398 kyr, followed by a prolonged warm period lasting beyond 380 kyr. This trend is most consistently manifested in the mid-latitude North Atlantic and Mediterranean Sea and is here attributed to the strength of the Atlantic meridional overturning circulation. A sensitivity analysis indicates that these results are robust to record selection and to age-model uncertainties of up to 3-6 kyr, but more sensitive to SST seasonal attribution and SST uncertainties >1 °C. In order to validate the CCSM3 (Community Climate System Model, version 3) predictive potential, the annual and seasonal SST anomalies recorded in a total of 74 proxy records were compared with runs for three time slices representing orbital configuration extremes during the peak interglacial of MIS11. The modeled SST anomalies are characterized by a significantly lower variance compared to the reconstructions. Nevertheless, significant correlations between proxy and model data are found in comparisons on the seasonal basis, indicating that the model captures part of the long-term variability induced by astronomical forcing, which appears to have left a detectable signature in SST trends.