Climate control on terrestrial biospheric carbon turnover.

Terrestrial vegetation and soils hold three times more carbon than the atmosphere. Much debate concerns how anthropogenic activity will perturb these surface reservoirs, potentially exacerbating ongoing changes to the climate system. Uncertainties specifically persist in extrapolating point-source observations to ecosystem-scale budgets and fluxes, which require consideration of vertical and lateral processes on multiple temporal and spatial scales. To explore controls on organic carbon (OC) turnover at the river basin scale, we present radiocarbon (14C) ages on two groups of molecular tracers of plant-derived carbon-leaf-wax lipids and lignin phenols-from a globally distributed suite of rivers. We find significant negative relationships between the 14C age of these biomarkers and mean annual temperature and precipitation. Moreover, riverine biospheric-carbon ages scale proportionally with basin-wide soil carbon turnover times and soil 14C ages, implicating OC cycling within soils as a primary control on exported biomarker ages and revealing a broad distribution of soil OC reactivities. The ubiquitous occurrence of a long-lived soil OC pool suggests soil OC is globally vulnerable to perturbations by future temperature and precipitation increase. Scaling of riverine biospheric-carbon ages with soil OC turnover shows the former can constrain the sensitivity of carbon dynamics to environmental controls on broad spatial scales. Extracting this information from fluvially dominated sedimentary sequences may inform past variations in soil OC turnover in response to anthropogenic and/or climate perturbations. In turn, monitoring riverine OC composition may help detect future climate-change-induced perturbations of soil OC turnover and stocks.

Groundwater discharge impacts marine isotope budgets of Li, Mg, Ca, Sr, and Ba.

Groundwater-derived solute fluxes to the ocean have long been assumed static and subordinate to riverine fluxes, if not neglected entirely, in marine isotope budgets. Here we present concentration and isotope data for Li, Mg, Ca, Sr, and Ba in coastal groundwaters to constrain the importance of groundwater discharge in mediating the magnitude and isotopic composition of terrestrially derived solute fluxes to the ocean. Data were extrapolated globally using three independent volumetric estimates of groundwater discharge to coastal waters, from which we estimate that groundwater-derived solute fluxes represent, at a minimum, 5% of riverine fluxes for Li, Mg, Ca, Sr, and Ba. The isotopic compositions of the groundwater-derived Mg, Ca, and Sr fluxes are distinct from global riverine averages, while Li and Ba fluxes are isotopically indistinguishable from rivers. These differences reflect a strong dependence on coastal lithology that should be considered a priority for parameterization in Earth-system models.

An extraterrestrial trigger for the mid-Ordovician ice age: Dust from the breakup of the L-chondrite parent body.

The breakup of the L-chondrite parent body in the asteroid belt 466 million years (Ma) ago still delivers almost a third of all meteorites falling on Earth. Our new extraterrestrial chromite and 3He data for Ordovician sediments show that the breakup took place just at the onset of a major, eustatic sea level fall previously attributed to an Ordovician ice age. Shortly after the breakup, the flux to Earth of the most fine-grained, extraterrestrial material increased by three to four orders of magnitude. In the present stratosphere, extraterrestrial dust represents 1% of all the dust and has no climatic significance. Extraordinary amounts of dust in the entire inner solar system during >2 Ma following the L-chondrite breakup cooled Earth and triggered Ordovician icehouse conditions, sea level fall, and major faunal turnovers related to the Great Ordovician Biodiversification Event.

Global carbon export from the terrestrial biosphere controlled by erosion.

Riverine export of particulate organic carbon (POC) to the ocean affects the atmospheric carbon inventory over a broad range of timescales. On geological timescales, the balance between sequestration of POC from the terrestrial biosphere and oxidation of rock-derived (petrogenic) organic carbon sets the magnitude of the atmospheric carbon and oxygen reservoirs. Over shorter timescales, variations in the rate of exchange between carbon reservoirs, such as soils and marine sediments, also modulate atmospheric carbon dioxide levels. The respective fluxes of biospheric and petrogenic organic carbon are poorly constrained, however, and mechanisms controlling POC export have remained elusive, limiting our ability to predict POC fluxes quantitatively as a result of climatic or tectonic changes. Here we estimate biospheric and petrogenic POC fluxes for a suite of river systems representative of the natural variability in catchment properties. We show that export yields of both biospheric and petrogenic POC are positively related to the yield of suspended sediment, revealing that POC export is mostly controlled by physical erosion. Using a global compilation of gauged suspended sediment flux, we derive separate estimates of global biospheric and petrogenic POC fluxes of 157(+74)(-50) and 43(+61)(-25) megatonnes of carbon per year, respectively. We find that biospheric POC export is primarily controlled by the capacity of rivers to mobilize and transport POC, and is largely insensitive to the magnitude of terrestrial primary production. Globally, physical erosion rates affect the rate of biospheric POC burial in marine sediments more strongly than carbon sequestration through silicate weathering. We conclude that burial of biospheric POC in marine sediments becomes the dominant long-term atmospheric carbon dioxide sink under enhanced physical erosion.

Determination of osmium concentrations and (187)Os/(188)Os of crude oils and source rocks by coupling high-pressure, high-temperature digestion with sparging OsO(4) into a multicollector inductively coupled plasma mass spectrometer.

The (187)Os/(188)Os ratio that is based on the ß(-)-decay of (187)Re to (187)Os (t1/2 = 41.6 billion years) is widely used to investigate petroleum system processes. Despite its broad applicability to studies of hydrocarbon deposits worldwide, a suitable matrix-matched reference material for Os analysis does not exist. In this study, a method that enables Os isotope measurement of crude oil with in-line Os separation and purification from the sample matrix is proposed. The method to analyze Os concentration and (187)Os/(187)Os involves sample digestion under high pressure and high temperature using a high pressure asher (HPA-S, Anton Paar), sparging of volatile osmium tetroxide from the sample solution, and measurements using multicollector inductively coupled plasma mass spectrometry (MC-ICPMS). This methods significantly reduced the total procedural time compared to conventional Carius tube digestion followed by Os separation and purification using solvent extraction, microdistillation and N-TIMS analysis. The method yields Os concentration (28 ± 4 pg g(-1)) and (187)Os/(188)Os (1.62 ± 0.15) of commercially available crude oil reference material NIST 8505 (1 S.D., n = 6). The reference material NIST 8505 is homogeneous with respect to Os concentration at a test portion size of 0.2 g. Therefore, (187)Os/(188)Os composition and Os concentration of NIST 8505 can serve as a matrix-matched reference material for Os analysis. Data quality was assessed by repeated measurements of the USGS shale reference material SCo-1 (sample matrix similar to petroleum source rock) and the widely used Liquid Os Standard solution (LOsSt). The within-laboratory reproducibility of (187)Os/(188)Os for a 5 pg of LOsSt solution, analyzed with this method over a period of 12 months was ∼1.4% (1 S.D., n = 26), respectively.

Complex anthropogenic sources of platinum group elements in aerosols on Cape Cod, USA.

Platinum group elements (PGE) of anthropogenic origin have been reported in rainwater, snow, roadside soil and vegetation, industrial waste, and urban airborne particles around the world. As recent studies have shown that PGE are bioavailable in the environment and pose health risks at chronic levels, the extent of PGE pollution is of global concern. In this study, we report PGE concentrations and osmium isotope ((187)Os/(188)Os) ratios of airborne particles (particulate matter, PM10) collected in Woods Hole, a small coastal village on Cape Cod, Massachusetts, U.S.A. The sampling site is more than 100 km away from the nearest urban centers (Boston, Providence) and has no large industrial emission center within a 30 km radius. The study reveals that, although PGE concentrations in rural airborne particulate matter are orders of magnitude lower than in urban aerosols, 69% of the total osmium is of anthropogenic origin. Anthropogenic PGE signatures in airborne particles are thus not restricted to large cities with high traffic flows and substantial industries; they can also be found in rural environments. We further conclude that the combination of Pt/Rh concentration ratios and (187)Os/(188)Os composition can be used to trace PGE sources. The Pt/Rh and (187)Os/(188)Os composition of Woods Hole aerosols indicate that the anthropogenic PGE fraction is primarily sourced from ore smelting processes, with possible minor contributions from fossil fuel burning and automobile catalyst-derived materials. Our results further substantiate the use of (187)Os/(188)Os in source apportionment studies on continental scales.

Anthropogenic disturbance of element cycles at the Earth's surface.

The extent to which humans are modifying Earth's surface chemistry can be quantified by comparing total anthropogenic element fluxes with their natural counterparts (Klee and Graedel, 2004). We quantify anthropogenic mass transfer of 77 elements from mining, fossil fuel burning, biomass burning, construction activities, and human apportionment of terrestrial net primary productivity, and compare it to natural mass transfer from terrestrial and marine net primary productivity, riverine dissolved and suspended matter fluxes to the ocean, soil erosion, eolian dust, sea-salt spray, cosmic dust, volcanic emissions, and for helium, hydrodynamic escape from the Earth's atmosphere. We introduce an approach to correct for losses during industrial processing of elements belonging to geochemically coherent groups, and explicitly incorporate uncertainties of element mass fluxes through Monte Carlo simulations. We find that at the Earth's surface anthropogenic fluxes of iridium, osmium, helium, gold, ruthenium, antimony, platinum, palladium, rhenium, rhodium and chromium currently exceed natural fluxes. For these elements mining is the major factor of anthropogenic influence, whereas petroleum burning strongly influences the surficial cycle of rhenium. Our assessment indicates that if anthropogenic contributions to soil erosion and eolian dust are considered, anthropogenic fluxes of up to 62 elements surpass their corresponding natural fluxes.

Anthropogenic forcings on the surficial osmium cycle.

Osmium is among the least abundant elements in the Earth's continental crust. Recent anthropogenic Os contamination of the environment from mining and smelting activities, automotive catalytic converter use, and hospital discharges has been documented. Here we present evidence for anthropogenic overprinting of the natural Os cycle using a ca. 7000-year record of atmospheric Os deposition and isotopic composition from an ombrotrophic peat bog in NW Spain. Preanthropogenic Os accumulation in this area is 0.10 +/- 0.04 ng m(-2) y(-1). The oldest strata showing human influence correspond to early metal mining and processing on the Iberian Peninsula (ca. 4700-2500 cal. BP). Elevated Os accumulation rates are found thereafter with a local maximum of 1.1 ng m(-2) y(-1) during the Roman occupation of the Iberian Peninsula (ca. 1930 cal. BP) and a further increase starting in 1750 AD with Os accumulation reaching 30 ng m(-2) y(-1) in the most recent samples. Osmium isotopic composition ((187)Os/(188)Os) indicates that recent elevated Os accumulation results from increased input of unradiogenic Os from industrial and automotive sources as well as from enhanced deposition of radiogenic Os through increased fossil fuel combustion and soil erosion. We posit that the rapid increase in catalyst-equipped vehicles, increased fossil fuel combustion, and changes in land-use make the changes observed in NW Spain globally relevant.

Determining chondritic impactor size from the marine osmium isotope record.

Decreases in the seawater 187Os/188Os ratio caused by the impact of a chondritic meteorite are indicative of projectile size, if the soluble fraction of osmium carried by the impacting body is known. Resulting diameter estimates of the Late Eocene and Cretaceous/Paleogene projectiles are within 50% of independent estimates derived from iridium data, assuming total vaporization and dissolution of osmium in seawater. The variations of 187Os/188Os and Os/Ir across the Late Eocene impact-event horizon support the main assumptions required to estimate the projectile diameter. Chondritic impacts as small as 2 kilometers in diameter should produce observable excursions in the marine osmium isotope record, suggesting that previously unrecognized impact events can be identified by this method.

Platinum group elements in airborne particles in Mexico City.

Automobile exhaust catalysts using platinum group elements (PGE) have been mandatory on new cars in the Mexico City Metropolitan Area (MCMA) since 1991. Platinum, Pd, Rh, Ir, and Os concentrations and the isotopic composition of Os were determined in PM10 samples from the MCMA. Samples were prepared by isotope dilution NiS fire assay, and analysis was performed by magnetic sector ICP-MS using a single collector instrument for Pt, Pd, Rh, and Ir analysis and a multicollector instrument for Os analysis. Pt, Pd, and Rh concentrations at a downtown location (Merced) increased from < or =1.7 pg of Pt m(-3), 2.7 (4.0) pg of Pd m(-3), and 1.2+/-0.9 pg of Rh m(-3) in 1991 to 9.6 +/- 1.8 pg of Pt m(-3), 10.2+/-1.8 pg of Pd m(-3), and 2.8 +/-0.6 pg of Rh m(-3) in 2003. Concentrations at five sites in MCMA in 2003 averaged 9.3+/-1.9 pg of Pt m(-3), 11+/-4 pg of Pd m(-3), and 3.2+/- 1.0 pg of Rh m(-3). In contrast, Ir and Os concentrations and Os isotopic composition remained relatively constant and were 0.08+/-0.04 pg of Ir m(-3), 0.030 +/-0.007 pg of Os m(-3), and 0.60+/-0.04, respectively, in the MCMA in 2003. Elevated Pt, Pd, and Rh concentrations in the MCMA are attributed to automobile catalysts. A Pt-Pd-Rh concentration peak in 1993 suggests that early catalysts emitted a larger amount of PGE, possibly due to factors inherent in the technology or the use of inappropriate gasoline. Therefore, this study suggests that the current introduction of automobile catalysts in developing countries may result in elevated PGE concentrations if it is not accompanied by infrastructures and policy measures supporting their efficient use.

Importance of automobile exhaust catalyst emissions for the deposition of platinum, palladium, and rhodium in the northern hemisphere.

An estimated 500 million vehicles worldwide are equipped with an exhaust catalyst that uses platinum group elements (PGE) as the main active components and thus contribute to global PGE emissions. Although PGE emitted from automobile exhaust catalysts were first believed to remain in the roadside environment, we propose here that fine PGE-containing particles in automobile exhaust have resulted in a widespread distribution of emitted PGE. Regional and long-range transport of PGE from automobile exhaust catalysts is supported by elevated PGE deposition in both a peat bog located 250 m from traffic and in central Greenland, respectively. Russian smelters were also found to contribute to PGE contamination in central Greenland. Deposition rates estimated for the roadside environment, the peat bog, and central Greenland were used to provide a first estimate of PGE deposition in the northern hemisphere. The results show that deposition of regionally or long-range transported PGE accounts for a large fraction of total PGE deposition, and PGE deposition in the roadside environment represents less than 5% of the total deposition. Transport at the regional and global scales represents an important component in the environmental cycle of emitted PGE and needs to be further studied to fully assess the environmental fate of PGE from automobile exhaust catalysts.

Platinum group element concentrations and osmium isotopic composition in urban airborne particles from Boston, Massachusetts.

Platinum, Pd, Rh, and Os were found to occur at elevated concentrations in airborne particles (PM10) collected at urban sites in Boston, MA. Average Pt, Pd, Rh, and Os concentrations were 6.9 +/- 1.9, 8.1 +/- 1.8, 1.50 +/- 0.50, and 0.068 (-0.068 + 0.070) pg m(-3), respectively. Elevated Pt, Pd, and Rh concentrations are attributed to automobile catalysts, which use Pt, Pd, and Rh for the removal of pollutants from engine exhaust gas. An automobile catalyst source is supported by significant correlations between these elements and by a Pt/Rh similar to that in catalysts. Elevated Os concentrations are also believed to be the result of emission from automobile catalysts in which Os occurs as an impurity. The isotopic composition of Os (187Os/ 188Os) ranged from 0.30 to 2.90, indicating large variations in Os sources. Osmium has a predominantly anthropogenic origin at concentrations > 0.1 pg m(-3), whereas natural sources are more important at lower Os concentrations. Osmium isotopic composition also indicates that Pt, Pd, and Rh in Boston air are of almost exclusive anthropogenic origin, with a relatively small natural contribution. Our results indicate that scavenging by rain plays a major role in the atmospheric residence time and environmental fate of PGE.

Source characterisation of atmospheric platinum group element deposition into an ombrotrophic peat bog.

Platinum, palladium, rhodium, iridium and osmium were found to be enriched relative to their expected natural concentrations in peat samples from Thoreau's Bog, an ombrotrophic peat bog in Concord, Massachusetts. The source of osmium into the bog was determined from its isotopic composition (187Os/188Os). Osmium is composed of 4% lithogenic osmium from atmospheric soil dust, 41% of anthropogenic osmium and 55% of osmium from a non-lithogenic, non anthropogenic source, with rain being a likely candidate for the latter. Significant anthropogenic and rain contributions are also expected for iridium. In contrast, platinum, palladium and rhodium are almost exclusively anthropogenic. The larger enrichments of platinum, palladium and rhodium indicate that automobile catalysts are the source of platinum group elements to Thoreau's bog. The bog is located approximately 300 m from a major road and, therefore, the occurrence of platinum elements is evidence for regional dispersion of these metals. The absence of a clear trend following the introduction of catalysts indicates that platinum group elements are not quantitatively conserved in peat with downward leaching and plants playing an important role in the accumulation of platinum group elements.

Recent changes in platinum group element concentrations and osmium isotopic composition in sediments from an urban lake.

Automobile catalyst emissions have resulted in the occurrence of elevated Pt, Pd, and Rh concentration in the urban and roadside environment. We investigate the chronology of platinum group elements (PGE) accumulation in dated sediments from an urban lake near Boston, MA. Chronological profiles demonstrate that Pt, Pd, and Rh concentrations increased following the introduction in catalysts with accumulation rates 6-16 times larger in 1992-2002 than prior to the introduction of catalysts. Ratios of these elements closely match their ratios in catalysts, providing further evidence of an automobile source. Iridium and Ru accumulation in sediments also increased following the introduction of catalysts, and while past Os contamination is associated with leather tanning, recent changes in the isotopic composition of Os indicate another anthropogenic source for this element. The PGE have similar geochemical properties and are difficult to separate from one another, and therefore, we suggest that automobile catalyst emissions also result in increasing environmental concentrations of Ir, Ru, and Os, which occur as impurities in catalysts. An automobile catalyst source of Ir and Os is supported by elevated concentrations of these elements in a tunnel dust sample.