Biogas from MSW landfill: Composition and determination of chlorine content with the AOX (adsorbable organically bound halogens) technique

An exhaustive characterization of the biogas from some waste disposal facilities has been carried out. The analysis includes the main components (methane, carbon dioxide, nitrogen and oxygen) as well as trace components such as hydrogen sulphide, ammonia and VOCs (volatile organic compounds) including siloxanes and halogenated compounds. VOCs were measured by GC/MS (Gas Chromatography/Mass Spectrometry) using two different procedures: thermal desorption of the Tenax TA and Carbotrap 349 tubes and SPME (Solid Phase Micro-Extraction). A method has been established to measure the total halogen content of the biogas with the AOX (adsorbable organically bound halogens) technique. The equipment used to analyze the samples was a Total Organic Halogen Analyzer (TOX-100). Similar results were obtained when comparing the TOX (Total Organic Halogen) values with those obtained by GC/MS. The halogen content in all the samples was under 22 mg Cl/Nm3 which is below the limit of 150 mg/Nm3 proposed in the Spanish Regulations for any use of the biogas. The low chlorine content in the biogas studied, as well as the low content of other trace compounds, makes it suitable for use as a fuel for electricity generating engines.

Non-spectral interferences due to the presence of sulfuric acid in inductively coupled plasma mass spectrometry

Results of a systematic study concerning non-spectral interferences from sulfuric acid containing matrices on a large number of elements in inductively coupled plasma–mass spectrometry (ICP-MS) are presented in this work. The signals obtained with sulfuric acid solutions of different concentrations (up to 5% w w− 1) have been compared with the corresponding signals for a 1% w w− 1− nitric acid solution at different experimental conditions (i.e., sample uptake rates, nebulizer gas flows and r.f. powers). The signals observed for 128Te+, 78Se+ and 75As+ were significantly higher when using sulfuric acid matrices (up to 2.2-fold for 128Te+ and 78Se+ and 1.8-fold for 75As+ in the presence of 5 w w-1 sulfuric acid) for the whole range of experimental conditions tested. This is in agreement with previously reported observations. The signal for 31P+ is also higher (1.1-fold) in the presence of sulfuric acid. The signal enhancements for 128Te+, 78Se+, 75As+ and 31P+ are explained in relation to an increase in the analyte ion population as a result of charge transfer reactions involving S+ species in the plasma. Theoretical data suggest that Os, Sb, Pt, Ir, Zn and Hg could also be involved in sulfur-based charge transfer reactions, but no experimental evidence has been found. The presence of sulfuric acid gives rise to lower ion signals (about 10–20% lower) for the other nuclides tested, thus indicating the negative matrix effect caused by changes in the amount of analyte loading of the plasma. The elemental composition of a certified low-density polyethylene sample (ERM-EC681K) was determined by ICP-MS after two different sample digestion procedures, one of them including sulfuric acid. Element concentrations were in agreement with the certified values, irrespective of the acids used for the digestion. These results demonstrate that the use of matrix-matched standards allows the accurate determination of the tested elements in a sulfuric acid matrix.

(Table 1) Age determination of sediment core MD02-2589

Sortable silt mean grain sizes together with oxygen and carbon isotopic data produced on the benthic foraminiferal species Fontbotia wuellerstorfi are used to construct high-resolution records of near-bottom flow vigour and deep water ventilation at a core site MD02-2589 located at 2660 m water depth on the southern Agulhas Plateau. The results suggest that during glacial periods (marine oxygen isotope stages 2 and 6, MIS 2 and MIS 6, respectively), there was a persistent contribution of a well-ventilated water mass within the Atlantic to Indian oceanic gateway with a d13C signature similar to present-day Northern Component Water (NCW), e.g., North Atlantic Deep Water (NADW). The records of chemical ventilation and near-bottom flow vigor reflect changes in the advection of northern source waters and meridional variability in the location of the Antarctic Circumpolar Current and its associated fronts. We suggest that during Termination II (TII), changes in chemical ventilation are largely decoupled from near-bottom physical flow speeds. A mid-TII climate optimum is associated with a low-flow speed plateau concurrent with a period of increased ventilation shown in the benthic d13C of other Southern Ocean records but not in our benthic d13C of MD02-2589. The climate optimum is followed by a period of southern cooling around 128 ka coincident with a stronger influence of NCW to interglacial levels at around 124 ka. All proxy records show a near synchronous and rapid shift during the transition from MIS 5a-4 (73 ka). This large event is attributed to a rapid decrease in NADW influence and replacement over the Agulhas Plateau by southern source waters.

Age determination of sediment cores of the southeastern Weddell Sea, Antarctica

On the continental margin of the southeastern Weddell Sea, Antarctica, several channel-ridge systems can be traced on the eastern side of the Crary Fan. Swath mapping of the bathymetry reveals three southwest-northeast trending ridges up to 300 m high with channels on their southeastern side. The structures occur on a terrace of the continental slope in water depths of 2000 - 3300 m. We carried out sedimentological studies on cores from three sites. Two of the studied cores are from ridges, one is from the northwestern part of the terrace. The stratigraphy of the recovered sediments is based on accelerator mass spectrometer 14C determinations, stable oxygen and carbon isotopes analyses and paleomagnetic measurements. The sediments represent a period from the last glacial maximum (LGM) to recent time. They are composed predominantly of terrigenous components. We distinguish four different sedimentary facies and assign them to processes controlling sedimentation. Microlaminated muds and cross-stratified coarse-silty sediments originated from contour currents. Bioturbated sediments reflect the increasing influence of hemipelagic sedimentation. Structureless sediments with high contents of ice-rafted debris characterize slumps. The inferred contour currents shaping the continental slope during the LGM were canalized within the channels and supplied microlaminated mud to the western sedimentary ridges due to deflection to the left induced by the Coriolis force. The lamination of the sediments is attributed to seasonal variations of current velocities. The thermohaline bottom currents were directed to the northeast and hence opposite to the Weddell Gyre. Cross-stratified coarse-silty contourites on the ridges are intercalated with the muds and indicate spillover of faster thermohaline flows. Average sedimentation rates on the terrace of the continental slope were unusually high (250 cm/ka) during the LGM, indicating active growth phases of the Crary Fan during glacial intervals. A substantial environmental change at 19.5 - 20 ka is documented in the sediments by a gradual change from lamination to bioturbation. During the recent interglacial, bioturbated sediments were deposited in all parts of the terrace. Because of a reduction of the contour current velocities (4-7 cm/s), the water masses of the Weddell Gyre, supplying fine-grained sediments from northeast, gain a greater influence on sedimentation on the continental slope. Higher percentages of microfossils indicate enhanced biogenic productivity. Increased iceberg activity is documented by greater amounts of ice-rafted debris. The interglacial sedimentation rates decrease to a few cm/ka and indicate that the Crary Fan became relatively sediment-starved during interglacial intervals.

Age determination and paleotemperatures of sediment cores TTR17-1_384B and TTR17-1_436B in the Alboran Sea

Climate conditions in the westernmost Mediterranean (Alboran Sea basin) over the last two millennia have been reconstructed through integration of molecular proxies applied for the first time in this region at such high resolution. Two temperature proxies, one based on isoprenoid membrane lipids of marine Thaumarchaeota (TEXH86-tetraether index of compounds consisting of 86 carbons) and the other on alkenones produced by haptophytes (UK'37 ratio) were applied to reconstruct sea surface temperature (SST). Both records reveal a progressive long term decline in SST over the last two millennia and an increased rate of warming during the second half of the twentieth century. This is in accord with previous temperature reconstructions for the Northern Hemisphere. TEXH86 temperature values are higher than those inferred from UK'37, probably due to differences in the bloom season of haptophytes and Thaumarchaeota, and reflect summer SST. The branched vs. isoprenoid tetraether index (BIT index) suggests a low contribution of soil organic matter (OM) to the sedimentary OM. The stable carbon isotopic composition of long chain n-alkanes indicates a predominant C3 plant contribution, with no major change in vegetation over the last 2000 yr. The distribution of long chain 1,14-diols (most likely sourced by Proboscia species in this setting) provided insight into variation in upwelling conditions during the last 2000 yr and depicts a correlation with the North Atlantic Oscillation (NAO) index, providing evidence of enhanced wind induced upwelling during periods of a persistent positive mode of the NAO.

Age determination and stable isotope record of sediment core MR06-04_PC23A

Millennial-scale variability in the behavior of North Pacific Intermediate Water during the last glacial and deglacial period, and its association with Dansgaard-Oeschger (D-O) cycles and Heinrich events, are examined based on benthic foraminiferal oxygen and carbon isotopes (d18Obf and d13Cbf) and %CaCO3 using a sediment core recovered from the northeastern slope of the Bering Sea. A suite of positive d18Obf excursions at intermediate depths of the Bering Sea, which seem at least in part associated with increases in the d18Obf gradients between the Bering and Okhotsk Seas, suggest the Bering Sea as a proximate source of intermediate water during several severe stadial episodes in the last glacial and deglacial period. Absence of such d18Obf gradients during periods of high surface productivity in the Bering and Okhotsk Seas, which we correlate to D-O interstadials, suggests a reduction in intermediate water production in the Bering Sea and subsequent introduction of nutrient-rich deep waters from the North Pacific into intermediate depths of the Bering Sea. We argue that a reorganization of atmospheric circulation in the high-latitude North Pacific during severe cold episodes in the last glacial and deglacial period created favorable conditions for brine rejection in the northeastern Bering Sea. The resulting salinity increase in the cold surface waters could have initiated intermediate (and deep) water formation that spread out to the North Pacific.

(Table A1) Uranium and Thorium determination from IODP Site 310-M0007B

The Integrated Ocean Drilling Program (IODP) Expedition 310 recovered drill cores from the drowned reefs around the island of Tahiti (17°40'S, 149°30'W), many of which contained samples of massive corals from the genus Porites. Herein we report on one well-preserved fossil coral sample: a 13.6 cm long Porites sp. dated by uranium series techniques at 9523 ± 33 years. Monthly delta18O and Sr/Ca determinations reveal nine clear and robust annual cycles. Coral delta18O and Sr/Ca determinations estimate a mean temperature of ca. 24.3°C (ca. 3.2°C colder than modern) for Tahiti at 9.5 ka; however, this estimate is viewed with caution since potential sources of cold bias in coral geochemistry remain to be resolved. The interannual variability in coral delta18O is similar between the 9.5 ka coral record and a modern record from nearby Moorea. The seasonal cycle in coral Sr/Ca is approximately the same or greater in the 9.5 ka coral record than in modern coral records from Tahiti. Paired analysis of coral delta18O and Sr/Ca indicates cold/wet (warm/dry) interannual anomalies, opposite from those observed in the modern instrumental record.