Greenland records of aerosol source and atmospheric lifetime changes from the Eemian to the Holocene.

The Northern Hemisphere experienced dramatic changes during the last glacial, featuring vast ice sheets and abrupt climate events, while high northern latitudes during the last interglacial (Eemian) were warmer than today. Here we use high-resolution aerosol records from the Greenland NEEM ice core to reconstruct the environmental alterations in aerosol source regions accompanying these changes. Separating source and transport effects, we find strongly reduced terrestrial biogenic emissions during glacial times reflecting net loss of vegetated area in North America. Rapid climate changes during the glacial have little effect on terrestrial biogenic aerosol emissions. A strong increase in terrestrial dust emissions during the coldest intervals indicates higher aridity and dust storm activity in East Asian deserts. Glacial sea salt aerosol emissions in the North Atlantic region increase only moderately (50%), likely due to sea ice expansion. Lower aerosol concentrations in Eemian ice compared to the Holocene are mainly due to shortened atmospheric residence time, while emissions changed little.

A Method for Continuous (239)Pu Determinations in Arctic and Antarctic Ice Cores.

Atmospheric nuclear weapons testing (NWT) resulted in the injection of plutonium (Pu) into the atmosphere and subsequent global deposition. We present a new method for continuous semiquantitative measurement of (239)Pu in ice cores, which was used to develop annual records of fallout from NWT in ten ice cores from Greenland and Antarctica. The (239)Pu was measured directly using an inductively coupled plasma-sector field mass spectrometer, thereby reducing analysis time and increasing depth-resolution with respect to previous methods. To validate this method, we compared our one year averaged results to published (239)Pu records and other records of NWT. The (239)Pu profiles from the Arctic ice cores reflected global trends in NWT and were in agreement with discrete Pu profiles from lower latitude ice cores. The (239)Pu measurements in the Antarctic ice cores tracked low latitude NWT, consistent with previously published discrete records from Antarctica. Advantages of the continuous (239)Pu measurement method are (1) reduced sample preparation and analysis time; (2) no requirement for additional ice samples for NWT fallout determinations; (3) measurements are exactly coregistered with all other chemical, elemental, isotopic, and gas measurements from the continuous analytical system; and (4) the long half-life means the (239)Pu record is stable through time.

Constraints on soluble aerosol iron flux to the Southern Ocean at the Last Glacial Maximum.

Relief of iron (Fe) limitation in the Southern Ocean during ice ages, with potentially increased carbon storage in the ocean, has been invoked as one driver of glacial-interglacial atmospheric CO2 cycles. Ice and marine sediment records demonstrate that atmospheric dust supply to the oceans increased by up to an order of magnitude during glacial intervals. However, poor constraints on soluble atmospheric Fe fluxes to the oceans limit assessment of the role of Fe in glacial-interglacial change. Here, using novel techniques, we present estimates of water- and seawater-soluble Fe solubility in Last Glacial Maximum (LGM) atmospheric dust from the European Project for Ice Coring in Antarctica (EPICA) Dome C and Berkner Island ice cores. Fe solubility was very variable (1-42%) during the interval, and frequently higher than typically assumed by models. Soluble aerosol Fe fluxes to Dome C at the LGM (0.01-0.84 mg m(-2) per year) suggest that soluble Fe deposition to the Southern Ocean would have been ≥10 × modern deposition, rivalling upwelling supply.

Timing and climate forcing of volcanic eruptions for the past 2,500 years.

Volcanic eruptions contribute to climate variability, but quantifying these contributions has been limited by inconsistencies in the timing of atmospheric volcanic aerosol loading determined from ice cores and subsequent cooling from climate proxies such as tree rings. Here we resolve these inconsistencies and show that large eruptions in the tropics and high latitudes were primary drivers of interannual-to-decadal temperature variability in the Northern Hemisphere during the past 2,500 years. Our results are based on new records of atmospheric aerosol loading developed from high-resolution, multi-parameter measurements from an array of Greenland and Antarctic ice cores as well as distinctive age markers to constrain chronologies. Overall, cooling was proportional to the magnitude of volcanic forcing and persisted for up to ten years after some of the largest eruptive episodes. Our revised timescale more firmly implicates volcanic eruptions as catalysts in the major sixth-century pandemics, famines, and socioeconomic disruptions in Eurasia and Mesoamerica while allowing multi-millennium quantification of climate response to volcanic forcing.

Synthetic nitrogen fertilizers deplete soil nitrogen: a global dilemma for sustainable cereal production.

Cereal production that now sustains a world population of more than 6.5 billion has tripled during the past 40 yr, concurrent with an increase from 12 to 104 Tg yr(-1) of synthetic N applied largely in ammoniacal fertilizers. These fertilizers have been managed as a cost-effective form of insurance against low yields, without regard to the inherent effect of mineral N in promoting microbial C utilization. Such an effect is consistent with a net loss of soil organic C recently observed for the Morrow Plots, America's oldest experiment field, after 40 to 50 yr of synthetic N fertilization that substantially exceeded grain N removal. A similar decline in total soil N is reported herein for the same site and would be expected from the predominantly organic occurrence of soil N. This decline is in agreement with numerous long-term baseline data sets from chemical-based cropping systems involving a wide variety of soils, geographic regions, and tillage practices. The loss of organic N decreases soil productivity and the agronomic efficiency (kg grain kg(-1) N) of fertilizer N and has been implicated in widespread reports of yield stagnation or even decline for grain production in Asia. A major global evaluation of current cereal production systems should be undertaken, with a view toward using scientific and technological advances to increase input efficiencies. As one aspect of this strategy, the input of ammoniacal N should be more accurately matched to crop N requirement. Long-term sustainability may require agricultural diversification involving a gradual transition from intensive synthetic N inputs to legume-based crop rotations.

The myth of nitrogen fertilization for soil carbon sequestration.

Intensive use of N fertilizers in modern agriculture is motivated by the economic value of high grain yields and is generally perceived to sequester soil organic C by increasing the input of crop residues. This perception is at odds with a century of soil organic C data reported herein for the Morrow Plots, the world's oldest experimental site under continuous corn (Zea mays L.). After 40 to 50 yr of synthetic fertilization that exceeded grain N removal by 60 to 190%, a net decline occurred in soil C despite increasingly massive residue C incorporation, the decline being more extensive for a corn-soybean (Glycine max L. Merr.) or corn-oats (Avena sativa L.)-hay rotation than for continuous corn and of greater intensity for the profile (0-46 cm) than the surface soil. These findings implicate fertilizer N in promoting the decomposition of crop residues and soil organic matter and are consistent with data from numerous cropping experiments involving synthetic N fertilization in the USA Corn Belt and elsewhere, although not with the interpretation usually provided. There are important implications for soil C sequestration because the yield-based input of fertilizer N has commonly exceeded grain N removal for corn production on fertile soils since the 1960s. To mitigate the ongoing consequences of soil deterioration, atmospheric CO(2) enrichment, and NO(3)(-) pollution of ground and surface waters, N fertilization should be managed by site-specific assessment of soil N availability. Current fertilizer N management practices, if combined with corn stover removal for bioenergy production, exacerbate soil C loss.

Southern Ocean sea-ice extent, productivity and iron flux over the past eight glacial cycles.

Sea ice and dust flux increased greatly in the Southern Ocean during the last glacial period. Palaeorecords provide contradictory evidence about marine productivity in this region, but beyond one glacial cycle, data were sparse. Here we present continuous chemical proxy data spanning the last eight glacial cycles (740,000 years) from the Dome C Antarctic ice core. These data constrain winter sea-ice extent in the Indian Ocean, Southern Ocean biogenic productivity and Patagonian climatic conditions. We found that maximum sea-ice extent is closely tied to Antarctic temperature on multi-millennial timescales, but less so on shorter timescales. Biological dimethylsulphide emissions south of the polar front seem to have changed little with climate, suggesting that sulphur compounds were not active in climate regulation. We observe large glacial-interglacial contrasts in iron deposition, which we infer reflects strongly changing Patagonian conditions. During glacial terminations, changes in Patagonia apparently preceded sea-ice reduction, indicating that multiple mechanisms may be responsible for different phases of CO2 increase during glacial terminations. We observe no changes in internal climatic feedbacks that could have caused the change in amplitude of Antarctic temperature variations observed 440,000 years ago.

A technique for the examination of polar ice using the scanning electron microscope.

The microstructure and location of impurities in polar ice are of great relevance to ice core studies. We describe a reliable method to examine ice in the scanning electron microscope (SEM). Specimens were cut in a cold room and could have their surfaces altered by sublimation either before (pre-etching) or after (etching) introduction to the cryo-chamber of the SEM. Pre-etching was used to smooth surfaces, whilst etching stripped away layers from the specimen surface, aiding the location of particles in situ, and allowing embedded structures to be revealed. X-ray analysis was used to determine the composition of localized impurities, which in some cases had been concentrated on the surface by etching. Examining uncoated surfaces was found to be advantageous and did not detract from qualitative X-ray analysis. Imaging uncoated was performed at low accelerating voltages and probe currents to avoid problems of surface charging.

Improved diffusion methods for nitrogen and 15nitrogen analysis of Kjeldahl digests.

Simple methods are described that permit the use of either H3BO3 indicator solution or acidified filter disks to collect NH3 liberated by treatment of Kjeldahl digests with NaOH. These methods incorporate modifications to improve reliability, analytical capacity, and convenience. A semimicro digest was diluted to 25 mL with deionized water, and a 10 mL aliquot, containing up to 4 mg N (150 microg N for diffusions into acidified disks), was transferred to a shell vial, which was placed inside a 473 mL (1 pint) Mason jar containing 10 mL 10N NaOH. The NH3 liberated by overturning the vial was collected after 12 to 48 h at ambient temperature, or after 4 h at 45 to 50 degrees C on a hotplate, for quantitative and/or isotope-ratio analyses. With either H3BO3 indicator solution or acidified filter disks, recovery of diffused N was quantitative. Isotope-ratio analyses of diffused N from 15N-labeled chemical, plant, and soil samples were within 3% of analyses using steam distillation.

A potent greenhouse gas identified in the atmosphere: SF(5)CF(3)

We detected a compound previously unreported in the atmosphere, trifluoromethyl sulfur pentafluoride (SF(5)CF(3)). Measurements of its infrared absorption cross section show SF(5)CF(3) to have a radiative forcing of 0.57 watt per square meter per parts per billion. This is the largest radiative forcing, on a per molecule basis, of any gas found in the atmosphere to date. Antarctic firn measurements show it to have grown from near zero in the late 1960s to about 0.12 part per trillion in 1999. It is presently growing by about 0.008 part per trillion per year, or 6% per year. Stratospheric profiles of SF(5)CF(3) suggest that it is long-lived in the atmosphere (on the order of 1000 years).

Biodegradation of atrazine under denitrifying conditions.

Anaerobic biodegradation of atrazine by the bacterial isolate M91-3 was characterized with respect to mineralization, metabolite formation, and denitrification. The ability of the isolate to enhance atrazine biodegradation in anaerobic sediment slurries was also investigated. The organism utilized atrazine as its sole source of carbon and nitrogen under anoxic conditions in fixed-film (glass beads) batch column systems. Results of HPLC and TLC radiochromatography suggest that anaerobic biotransformation of atrazine by microbial isolate M91-3 involved hydroxyatrazine formation. Ring cleavage was demonstrated by 14CO2 evolution. Denitrification was confirmed by detection of 15N2 in headspace samples of K15NO3-amended anaerobic liquid cultures. In aquatic sediments, mineralization of uniformly ring-labeled [14C]atrazine occurred in both M91-3-inoculated and uninoculated sediment. Inoculation of sediments with M91-3 did not significantly enhance anaerobic mineralization of atrazine as compared to uninoculated sediment, which suggests the presence of indigenous organisms capable of anaerobic atrazine biodegradation. Results of this study suggest that the use of M91-3 in a fixed-film bioreactor may have applications in the anaerobic removal of atrazine and nitrate from aqueous media.

Use of nitrous oxide as a purge gas for automated nitrogen isotope analysis by the Rittenberg technique.

An apparatus that operates with an isotope-ratio mass spectrometer to automatically perform nitrogen isotope analyses by the Rittenberg technique was modified to permit the use of nitrous oxide (N(2)O) instead of Freon (CCl(2)F(2) or CHClF(2)) for the purging of air prior to hypobromite oxidation of ammonium-N to N(2) in a plastic microplate. Analytical performance was unaffected by the modifications. Up to 768 samples can be processed in a single loading, at a rate of 6 to 12 samples/h. Within the range of 0.2 to 20 atom % (15)N, isotope-ratio analyses of 50 to 200 mug of N using the automated Rittenberg apparatus (ARA) with a double-collector mass spectrometer were accurate to within 0.7%, as compared to manual Rittenberg analyses of 1 mg of N using the same mass spectrometer with a dual-inlet system. Automated analyses of 20mug of N were accurate to within 2%, and automated analyses of 10 mug of N were accurate to within 7%. The relative standard deviation for measurements at the natural abundance level (10 analyses, 20-200 mug of N) was < 0.04 %.

Preparation of aqueous standards for low temperature X-ray microanalysis.

A technique, using Nuclepore polycarbonate membrane filters as a containing medium for very small volumes of ionic standard solutions, to produce homogeneous ice standards is described. The standards are suitable for use in a scanning electron microscope. The relationship between elemental X-ray counts and ionic concentration is found to be linear. The method is rapid and simple. Minimum detectable concentrations are given.

Refinement and evaluation of an automated mass spectrometer for nitrogen isotope analysis by the Rittenberg technique.

An apparatus designed to automatically perform hypobromite oxidations of ammonium salt samples for nitrogen isotope analyses with a mass spectrometer was modified to improve performance and reduce analysis time. As modified, reference N(2) is admitted to the mass spectrometer between samples from a dedicated inlet manifold, for calibration at the same pressure as that of the preceding sample. Analyses can be performed on samples containing 10 mug to 1 mg of N (or more), at a rate of up to 350 samples/day. When operated with a double-collector mass spectrometer, the standard deviation at the natural abundance level (10 analyses, 50-150 mug N) was <0.0001 atom % (15)N. Very little memory was observed when natural abundance samples (0.366 atom % (15)N) were analysed. following samples containing 40 atom % (15)N. Analyses in the range, 0.2 to 1 atom % (15)N (50-150 mug N), were in good agreement with manual Rittenberg analyses (1 mg N) using a dual-inlet system, and precision was comparable. For enrichments of 2 to 20 atom % (15)N, automated analyses were slightly lower than manual analyses, which was attributed to outgassing of N(2) from the plastic microplate used to contain samples.

Ruminal nitrogen metabolism in steers as affected by feed intake and dietary urea concentration.

Four multiple-cannulated steers (340 kg) were used in a 4 X 4 Latin square design with a 2 X 2 factorial arrangement of treatments. Steers were fed a diet of 50% ground hay and 50% concentrate at two intakes (1.4 and 2.1% of BW), with urea and 15N-enriched ammonium sulfate infused continuously into the rumen at .4 or 1.2% of diet DM. Ratios of purines and diaminopimelic acid-N to N in fluid-associated and particulate-associated bacteria and in protozoa were similar among treatments but were lower for protozoa than for bacteria. Diaminopimelic acid-N:N was higher for fluid-associated vs. particulate-associated bacteria. Enrichment of 15N was similar between bacteria among treatments and was 30% lower for protozoa. Turnover rates of 15N in bacteria, NH3N, and non-NH3N pools were faster for steers infused with 1.2 than those infused with .4% urea, indicating less efficient usage of ammonia with higher urea. A method is described to estimate the proportion of duodenal nitrogen comprising bacterial and protozoal nitrogen.