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Estimates of sedimentary organic carbon burial fluxes based on inventory and isotope mass balance methods have been divergent. A new calculation of the isotope mass balance using a revised assessment of the inputs to the ocean-atmosphere system resolves the apparent discrepancy. Inputs include weathering of carbonate and old kerogen, geogenic methane oxidation, and volcanic and metamorphic degassing. Volcanic and metamorphic degassing comprise ≈23% of the total C input. Inputs from isotopically light OCpetro and CH 4-geo drive the mean δ 13 C of the input to =-8.0 ± 1.9‰, notably lower than the commonly assumed volcanic degassing value. The isotope mass balance model yields a modern burial flux =15.9 ± 6.6 Tmol y -1 . The impact of the mid-Miocene Climatic Optimum isotope anomaly is an integrated excess deposition ≈ 4.3 × 10 6 Tmol between 18 and 11 Ma, which is both longer and larger than estimates for the total degassing by the Columbia River Basalt eruptions, implying a complex carbon system response to large eruptive events. Monte Carlo evaluation finds that late Cenozoic net growth of the carbonate reservoir is very likely while net growth of the C org reservoir is less certain but more likely than not. At present, subduction does not appear to keep up with net sedimentation and the overall masses of sedimentary carbonate and organic carbon are likely increasing. Growth in the sedimentary C org reservoir implies oxidation of the surface environment and likely increases in atmospheric pO 2 ., Competing Interests: Competing interests statement:The author declares no competing interest.

The balance between photosynthetic organic carbon production and respiration controls atmospheric composition and climate 1,2 . The majority of organic carbon is respired back to carbon dioxide in the biosphere, but a small fraction escapes remineralization and is preserved over geological timescales 3 . By removing reduced carbon from Earth's surface, this sequestration process promotes atmospheric oxygen accumulation 2 and carbon dioxide removal 1 . Two major mechanisms have been proposed to explain organic carbon preservation: selective preservation of biochemically unreactive compounds 4,5 and protection resulting from interactions with a mineral matrix 6,7 . Although both mechanisms can operate across a range of environments and timescales, their global relative importance on 1,000-year to 100,000-year timescales remains uncertain 4 . Here we present a global dataset of the distributions of organic carbon activation energy and corresponding radiocarbon ages in soils, sediments and dissolved organic carbon. We find that activation energy distributions broaden over time in all mineral-containing samples. This result requires increasing bond-strength diversity, consistent with the formation of organo-mineral bonds 8 but inconsistent with selective preservation. Radiocarbon ages further reveal that high-energy, mineral-bound organic carbon persists for millennia relative to low-energy, unbound organic carbon. Our results provide globally coherent evidence for the proposed 7 importance of mineral protection in promoting organic carbon preservation. We suggest that similar studies of bond-strength diversity in ancient sediments may reveal how and why organic carbon preservation-and thus atmospheric composition and climate-has varied over geological time.

Colloids can be important vectors for the transport of contaminants in the environment, but little is known about colloid mobilization at the watershed scale. We present colloid concentration, composition, and flux data over a large range of hydrologic conditions from a small watershed (Gordon Gulch) in the foothills of the Colorado Front Range. Colloids, consisting predominantly of Si, Fe, and Al, were present in most stream samples but were not detected in groundwater samples. Mineralogical and morphological analysis indicated that the colloids were composed of kaolinite and illite clays with lesser amounts of amorphous Fe-hydroxides. Although colloid composition remained relatively constant over the sampled flow conditions, colloid concentrations varied considerably and increased as ionic strength of stream water decreased. The highest concentrations occurred during precipitation events after extended dry periods. These observations are consistent with laboratory studies that have shown colloids can be mobilized by decreases in pore-water ionic strength, which likely occurs during precipitation events. Colloidal particles constituted 30 to 35% of the Si mass flux and 93 to 97% of the Fe and Al mass fluxes in the <0.45-µm fraction in the stream. Colloids are therefore a significant and often overlooked component of mass fluxes whose temporal variations may yield insight into hydrologic flowpaths in this semiarid catchment., (Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.)

Trace elemental speciation in complex, real-world matrixes is a daunting task because of the low concentration of metals/metalloids and the correspondingly high molecular chemical noise. We constructed a liquid chromatography parallel elemental and molecular mass spectrometry (PEMMS) system and evaluated the use of peak elution profiles to identify trace molecular species containing specific heteroatoms, using the case of Se in yeast. We demonstrate that it is possible to use the HPLC-inductively coupled plasma (ICP)MS peak profile (retention time, width) to identify candidate ions with matching peak profiles in the molecular MS data. Proof of principle was demonstrated by C18 separation of three Se-amino acid standards (0.005-15 ppm as Se). The molecular MS (atmospheric pressure chemical ionization time-of-flight, APCI-TOF-MS) data set was converted into selected ion chromatograms of 0.05 Th width. ICPMS and APCI-TOF-MS ion chromatograms were fit by the Haarhoff-VanderLinde function using the following parameters: area, retention time, width, and skew. The ICPMS fit parameters were more reproducible than the APCI-TOF-MS fit parameters from run to run, and the APCI-TOF-MS signal was expected to limit correlation in most circumstances. Retention time and width were found to correlate well between the two MS systems for APCI-TOF-MS peaks with signal-to-fit-error (S/FE) of >25. Correction factors for differences in flow path length and peak broadening were required. The normalized correction factors were species and concentration independent and were stable from run to run. The skew parameter was found to be highly susceptible to noise and was not generally useful in matching ICPMS and APCI-TOF-MS peaks. An artificially noisy sample was generated by spiking 30 ppb Se-methionine (SeMet) and 5 ppb Se-methylselenocysteine (SeMSC) with unselenized yeast extract and run by PEMMS. The PEMMS software was able to detect four molecular MS peaks associated with SeMet and two for SeMSC, while filtering out >40 coeluting spectral peaks associated with chemical noise in each sample. In summary, we have demonstrated that correlated information in peak shape between parallel detectors can facilitate detection of trace elemental species in complex matrixes.

Silicon has a crucial role in many biogeochemical processes--for example, as a nutrient for marine and terrestrial biota, in buffering soil acidification and in the regulation of atmospheric carbon dioxide. Traditionally, silica fluxes to soil solutions and stream waters are thought to be controlled by the weathering and subsequent dissolution of silicate minerals. Rates of mineral dissolution can be enhanced by biological processes. But plants also take up considerable quantities of silica from soil solution, which is recycled into the soil from falling litter in a separate soil-plant silica cycle that can be significant in comparison with weathering input and hydrologic output. Here we analyse soil water in basaltic soils across the Hawaiian islands to assess the relative contributions of weathering and biogenic silica cycling by using the distinct signatures of the two processes in germanium/silicon ratios. Our data imply that most of the silica released to Hawaiian stream water has passed through the biogenic silica pool, whereas direct mineral-water reactions account for a smaller fraction of the stream silica flux. We expect that other systems exhibiting strong Si depletion of the mineral soils and/or high Si uptake rates by biomass will also have strong biological control on silica cycling and export.

Selective extraction techniques were used to assay the importance of specific solid phases in Pb binding by heterogeneous surface coating materials (biofilms) in Cayuga Lake, NY. Hydroxylamine hydrochloride (NH(2)OH.HC1) was used to extract easily reducible Mn oxides, and sodium dithionite (Na(2)S(2)O(4)) was used to extract Mn and Fe oxides in two sets of biofilm samples retrieved from the lake. Pb remaining after extraction was removed by extraction with 10% HNO(3), determined by analysis of Pb(208) using a sector field mass spectrometer with an inductively coupled plasma ion source (ICP-MS), and compared to the total extractable Pb. The results indicate that the greatest contribution to total Pb binding to the heterogeneous surface coating materials was from Mn oxides. Pb adsorption capacity of Mn oxides exceeded that of Fe oxides on a molar basis by approximately an order of magnitude. The high reactivity observed for natural Mn oxides indicates that they are biogenic in origin, consistent with expectations based on the relative biotic and abiotic rates of Mn(II) oxidation under circumneutral conditions. Collectively, these results confirm expectations based on prior observations of adsorption of added Pb by Cayuga Lake biofilms before and after selective extraction, and also confirm predictions for Pb phase association in the lake based on the behavior of laboratory surrogates for adsorptive surfaces., (Copyright 2003 Elsevier Science Ltd.)

An experimental tracer addition of (84)Sr to an unpolluted temperate forest site in southern Chile, as well as the natural variation of (87)Sr/(86)Sr within plants and soils, indicates that mechanisms in shallow soil organic horizons are of key importance for retaining and recycling atmospheric cation inputs at scales of decades or less. The dominant tree species Nothofagus nitida feeds nearly exclusively (>90%) on cations of atmospheric origin, despite strong variations in tree size and location in the forest landscape. Our results illustrate that (i) unpolluted temperate forests can become nutritionally decoupled from deeper weathering processes, virtually functioning as atmospherically fed ecosystems, and (ii) base cation turnover times are considerably more rapid than previously recognized in the plant available pool of soil. These results challenge the prevalent paradigm that plants largely feed on rock-derived cations and have important implications for understanding sensitivity of forests to air pollution.

We used isotopes of Sr to quantify weathering versus atmospheric sources of foliar Sr in 34 Hawaiian forests on young volcanic soils. The forests varied widely in climate, and in lava flow age and texture. Weathering supplied most of the Sr in most of the sites, but atmospheric deposition contributed 30-50% of foliar Sr in the wettest rainforests. A stepwise multiple regression using annual precipitation, distance from the ocean, and texture of the underlying lava explained 76% of the variation in Sr isotope ratios across the sites. Substrate age did not contribute significantly to variation in Sr isotope ratios in the range of ages evaluated here (11-3000 years), although atmospheric sources eventually dominate pools of biologically available Sr in Hawaiian rainforests in older substrates (≥150,000 years).

We report initial 87Sr/86Sr values from an Upper Proterozoic carbonate succession from Svalbard and East Greenland. This succession, now tectonically separated into three sequences, is thick, relatively continuous, and well preserved. The relative ages of the samples from within the basin are well constrained by litho-, bio-, and chemostratigraphic techniques. The data from this study and related data from the literature are used to construct a curve of 87Sr/86Sr for Upper Proterozoic seawater. The new data reported in this study substantially improve the isotopic record of Sr in seawater for the period between 650 and 800 Ma. The data indicate that delta 87Sr values of seawater were variable but low (delta 87Sr approximately -500 to -250) between 900 and 650 Ma, and rose rapidly to approximately +30 by 600 Ma. The range of variation of delta 87Sr in seawater during the Riphean-Vendian exceeds the entire range of delta 87Sr in seawater during the Phanerozoic. While variation in the average isotopic composition of Sr delivered to the oceans by rivers can account for some of the observed range, changes in the ratio of submarine hydrothermal flux to river water (continental) flux are responsible for the large variation in seawater Sr isotopic composition. Changes in the continental flux of Sr to the oceans can be related to tectonic factors. Large changes in the hydrothermal flux to river water flux ratio indicated by the data could have significant consequences for the chemistry of the ocean-atmosphere system.