Long-term pCO2 dynamics in rivers in the Chesapeake Bay watershed

Streams and rivers are major exporters of C and other dissolved materials from watersheds to coastal waters. In streams and rivers, substantial amounts of terrigenous organic C is metabolized and degassed as CO₂ to the atmosphere. A long-term evaluation of CO₂ dynamics in streams is essential for understanding factors controlling CO₂ dynamics in streams in response to changes in climate and land-use. Long-term changes in the partial pressure of CO₂ (pCO₂) were computed in the Anacostia River and the lower Potomac River in the Chesapeake Bay watershed. Long-term estimates were made using routine monitoring data of pH, total alkalinity, and dissolved nutrients from 1985 to 2006 at 14 stations. Longitudinal variability in pCO₂ dynamics was also investigated along these rivers downstream of the urban Washington D.C. metropolitan area. Both rivers were supersaturated with CO₂ with respect to atmospheric CO₂ levels (392 μatm) and the highly urbanized Anacostia waters (202–9694 μatm) were more supersaturated than the Potomac waters (557–3800 μatm). Long-term variability in pCO₂ values may be due to changes in river metabolism and organic matter and nutrient loadings. Both rivers exchange significant amounts of CO₂ with the atmosphere (i.e., Anacostia at 0.2–72 mmol m⁻² d⁻¹ and Potomac at 0.12–24 mmol m⁻² d⁻¹), implying that waterways receiving organic matter and nutrient subsidies from urbanized landscapes have the potential to increase river metabolism and atmospheric CO₂ fluxes along the freshwater–estuarine continuum.     

Time and temperature dependency of carbon dioxide triggered metal(loid) mobilization in soil

Assessing the influence of CO₂ on soil and aquifer geochemistry is a task of increasing interest when considering risk assessment for geologic carbon sequestration. Leakage and CO₂ ascent can lead to soil acidification and mobilization of potentially toxic metals and metalloids due to desorption or dissolution reactions. We studied the CO₂ influence on an Fe(III) (oxyhydr)oxide rich, gleyic Fluvisol sampled in close vicinity to a Czech mofette site and compared the short-term CO₂ influence in laboratory experiments with observations on long-term influence at the natural site. Six week batch experiments with/without CO₂ gas flow at 3 different temperatures and monitoring of liquid phase metal(loid) concentrations revealed two main short-term mobilization processes. Within 1 h to 1 d after CO₂ addition, mobilization of weakly adsorbed metal cations occurred due to surface protonation, most pronounced for Mn (2.5–3.3 fold concentration increase, mobilization rates up to 278 ± 18 μg Mn kg_soil⁻¹ d⁻¹) and strongest at low temperatures. However, total metal(loid) mobilization by abiotic desorption was low. After 1–3 d significant Fe mobilization due to microbially-triggered Fe(III) (oxyhydr)oxide dissolution began and continued throughout the experiment (up to 111 ± 24 fold increase or up to 1.9 ± 0.6 mg Fe kg_soil⁻¹ d⁻¹). Rates increased at higher temperature and with a higher content of organic matter. The Fe(III) mineral dissolution was coupled to co-release of incorporated metal(loid)s, shown for As (up to 16 ± 7 fold, 11 ± 8 μg As kg_soil⁻¹ d⁻¹). At high organic matter content, re-immobilization due to resorption reactions could be observed for Cu. The already low pH (4.5–5.0) did not change significantly during Fe(III) reduction due to buffering from sorption and dissolution reactions, but a drop in redox potential (from > +500 mV to minimum +340 ± 20 mV) occurred due to oxygen depletion. We conclude that microbial processes following CO₂ induction into a soil can contribute significantly to metal(loid) mobilization, especially at optimal microbial growth conditions (moderate temperature, high organic carbon content) and should be considered for carbon sequestration monitoring and risk assessment.     

Holocene development and permafrost history in sub‐arctic peatlands in Tavvavuoma,northern Sweden

Under changing climatic conditions permafrost peatlands can play an important role in the global carbon budget through permafrost carbon feedbacks and shifts in carbon assimilation. To better predict future dynamics in these ecosystems an increased understanding of their Holocene carbon and permafrost history is needed. In Tavvavuoma, northern Sweden, we have performed detailed analyses of vegetation succession and geochemical properties at six permafrost peatland sites. Peatland initiation took place around 10 000 to 9600 cal. a BP, soon after retreat of the Fennoscandian Ice Sheet, and the peatlands have remained permafrost‐free fens throughout most of the Holocene. At the four sites that showed a continuous accumulation record during the late Holocene radiocarbon dating of the shift from wet fen to dry bog vegetation, characteristic of the present permafrost peatland surface, suggests that permafrost developed at around 600–100 cal. a BP. At the other two sites peat accumulation was halted during the late Holocene, possibly due to abrasion, making it more difficult to imply the timing of permafrost aggradation. However also at these sites there are no indications of permafrost inception prior to the Little Ice Age. The mean long‐term Holocene carbon accumulation rate at all six sites was 12.3±2.4 gC m⁻² a⁻¹ (±SD), and the mean soil organic carbon storage was 114±27 kg m⁻².     

Multiproxy analysis of inception and development of the Lac‐à‐la‐Tortue peatland complex,St Lawrence Lowlands,eastern Canada

The initial conditions for the development of a large peatland complex in the St Lawrence Lowlands were reconstructed to increase the understanding of early development and expansion modes in this region. Peatland basin morphometry was identified by creating a model based on over 1500 existing peat depth measurements, and six cores were extracted along transects from a central (deepest) location towards the margins. C accumulation rates and ecohydrological conditions were reconstructed from plant macrofossils, testate amoeba assemblages and ¹⁴C chronologies. Luminescence dating was performed to better delineate the timing of dune stabilization in the area and potentially related climate changes. Shallow freshwater plant communities acted as nuclei for the development of a rich minerotrophic fen around 10 300 cal. a BP in the deepest part of a shallow depression at the surface of the St‐Maurice river delta. Peat inception was followed by the paludification of peripheral parabolic dune systems. Luminescence dating suggested dune stabilization between 11 500 and 10 900 years ago. The initial rich fen persisted until 9500 cal. a BP, and was replaced by a poor fen dominated by sedges as a result of a decrease in mineral nutrient influx from upland runoff. The shift to ombrotrophic conditions in the oldest section of Lac‐à‐la‐Tortue peatland started around 5150 cal. a BP. This major ecohydrological change coincides with those observed in several other peatlands in southern Québec. Variations in carbon and peat accumulation rates in both ombrotrophic and minerotrophic sectors appear to have been primarily controlled by hydroseral succession, peat‐forming vegetation, hydrological conditions, topography and fire activity. This study is the first to provide a quantification of the total carbon pool of a peatland complex in southern Québec at 6.39 Mt C, corresponding to a mean C mass per area of 96.9 kg C m⁻² (σ = 50.60 kg C m⁻²).     

The influence of climate,hydrology and permafrost on Holocene peat accumulation at 3500 m on the eastern Qinghai–Tibetan Plateau

Peatland of the eastern Qinghai–Tibetan Plateau lies at the convergence of the East Asian and Indian monsoon systems in eastern Asia. To understand the evolution of this peatland and its potential to provide new insights into the Holocene evolution of the East Asian monsoon a 6 m peat core was collected from the undisturbed central part of a peat deposit near Hongyuan. The age-depth profile was determined using 16 ¹⁴C-AMS age dates, the peat analysed for a range of environmental variables including carbon, nitrogen and hydrogen concentration, bulk density, δ¹³C and the associated spring water analysed for hydrogen and oxygen isotopes. The age-depth profile of the recovered peat sequence covers the period from 9.6 to 0.3 kyr BP and is linear indicating that the conditions governing productivity and decay varied little over the Holocene. Using changes in carbon density, organic carbon content and its δ¹³C, cold dry periods of permafrost characterised by low density and impeded surface drainage were identified. The low δ¹⁸O and δD values of the spring water emanating around the peat deposit, down to ?13.8 and ?102‰ (VSMOW), respectively, with an inverse relationship between electrical conductivity and isotopic composition indicate precipitation under colder and drier conditions relative to the present day. In view of the current annual mean air temperature of 1 °C this suggests conditions in the past have been conducive to permafrost. Inferred periods of permafrost correspond to independently recognised cold periods in other Holocene records from across China at 8.6, 8.2–7.8, 5.6–4.2, 3.1 and 1.8–1.5 kyr BP. The transition to a cold dry climate appears to be more rapid than the subsequent recovery and cold dry periods at Hongyuan are of longer duration than equivalent cold dry periods over central and eastern China. Light–dark banding peat on a scale of 15–30 years from 9.6 to 5.5 kyr BP may indicate a strong influence of decadal oscillations possibly the Pacific Decadal Oscillation and a potential link between near simultaneous climatic changes in the northwest Pacific, ENSO, movement of the Intertropical Convergence Zone and the East Asian Monsoon.     

Globally increased pelagic carbonate production during the Mid-Brunhes dissolution interval and the CO2 paradox of MIS 11

The Mid-Brunhes dissolution interval (MBDI) represents a period of global carbonate dissolution, lasting several hundred thousand years, centred around Marine Isotope Stage (MIS) 11. Here we report the effects of dissolution in ODP core 982, taken from 1134 m in the North Atlantic. Paradoxically, records of atmospheric CO₂ from Antarctic ice-cores reveal no long term trend over the last 400 kyr and suggest that CO₂ during MIS 11 was no higher than during the present interglacial. We suggest that a global increase in pelagic carbonate production during this period, possibly related to the proliferation of the Gephyrocapsa coccolithophore, could have altered marine carbonate chemistry in such a way as to drive increased dissolution under the constraints of steady state. An increase in the production of carbonate in surface waters would cause a drawdown of global carbonate saturation and increase dissolution at the seafloor. In order to reconcile the record of atmospheric CO₂ variability we suggest that an increase in the flux of organic matter from the surface to deep ocean, associated with either a net increase in primary production or the enhanced ballasting effect provided by an increased flux of CaCO₃, could have countered the effect of increased calcification on CO₂.     

Goethite, calcite, and organic matter from Permian and Triassic soils: carbon isotopes and CO2 concentrations

Pedogenic goethites in each of two Early Permian paleosols appear to record mixing of two isotopically distinct CO₂ components—atmospheric CO₂ and CO₂ from in situ oxidation of organic matter. The δ¹³C values measured for the Fe(CO₃)OH component in solid solution in these Permian goethites are −13.5‰ for the Lower Leonardian (∼283 Ma BP) paleosol (MCGoeth) and −13.9‰ for the Upper Leonardian (∼270 Ma BP) paleosol (SAP). These goethites contain the most ¹³C-rich Fe(CO₃)OH measured to date for pedogenic goethites crystallized in soils exhibiting mixing of the two aforementioned CO₂ components. δ¹³C measured for 43 organic matter samples in the Lower Leonardian (Waggoner Ranch Fm.) has an average value of −20.3 ± 1.1‰ (1s). The average value yields a calculated Early Permian atmospheric Pco₂ value of about 1 × PAL, but the scatter in the measured δ¹³C values of organic matter permits a calculated maximum Pco₂ of 11 × PAL (PAL = present atmospheric level). Measured values of the mole fraction of Fe(CO₃)OH in MCGoeth and SAP correspond to soil CO₂ concentrations in the Early Permian paleosol profiles of 54,000 and 50,000 ppmV, respectively. Such high soil CO₂ concentrations are similar to modern soils in warm, wet environments.The average δ¹³C values of pedogenic calcite from 9 paleosol profiles stratigraphically associated with MCGoeth (Waggoner Ranch Fm.) range from −6.5‰ to −4.4‰, with a mean δ¹³C value for all profiles of −5.4‰. Thus, the value of Δ¹³C between the pedogenic calcite data set and MCGoeth is 8.1 (±0.9)‰, which is in reasonable accord with the value of 7.7‰ expected if atmospheric Pco₂ and organic matter δ¹³C values were the same for both paleosol types. Furthermore, the atmospheric Pco₂ calculated for the Early Permian from the average measured carbon isotopic compositions of the paleosol calcite and organic matter is also analytically indistinguishable from 1 × PAL, with a maximum calculated atmospheric Pco₂ (permitted by one standard deviation of the organic matter δ¹³C value) of ∼5 × PAL.If, however, measured average δ¹³C values of the plant organic matter are more positive than the original soil organic matter as a result of diagenetic loss of ¹³C-depleted, labile organic compounds, calculated Permian atmospheric Pco₂ using these ¹³C-enriched organic values would underestimate the actual atmospheric Pco₂ using either goethite or calcite. This is the first stratigraphically constrained, intrabasinal study to compare ancient atmospheric CO₂ concentrations calculated from pedogenic goethite and calcite. These results demonstrate that the two different proxies record the same information about atmospheric CO₂.The Fe(CO₃)OH component in pedogenic goethite from a Triassic paleosol in Utah is significantly enriched in ¹³C relative to Fe(CO₃)OH in goethites from soils in which there are mixtures of two isotopic CO₂ components. Field-relationships and the δ¹³C value (−1.9‰) of the Triassic goethite indicate that this ancient paleosol profile experienced mixing of three isotopically distinct CO₂ components at the time of goethite crystallization. The three components were probably atmospheric CO₂, CO₂ from in situ oxidation of organic matter and CO₂ from in situ dissolution of preexisting calcite. Although mixing of three isotopically distinct CO₂ components, as recorded by Fe(CO₃)OH in goethite, has been described in modern soil, this is the first example from a documented paleosol. Its preservation affirms the need for careful, case-by-case assessment of ancient paleosols to establish that goethite in any particular soil is likely to be a valid proxy of atmospheric Pco₂.     

Mercury enrichment and Hg isotopes in Cretaceous–Paleogene boundary successions: Links to volcanism and palaeoenvironmental impacts

We investigate the use of Hg as a proxy for volcanism by studying four distal and two proximal sections in relation to the Deccan volcanic center, straddling the Cretaceous–Paleogene (KPg) boundary at (a) Højerup (Denmark), Bottaccione and Padriciano (Italy), (b) Meghalaya and Jhilmili (India), and (c) Bajada del Jagüel (Argentina). Hg sequestration by organic matter results in constant Hg/TOC ratio and linear correlation between Hg content of the sediments and total organic carbon (TOC).Elevated Hg concentrations that deviate from this linear relationship represent most likely true Hg anomalies and these notable Hg/TOC spikes (all TOC <1%) are found in the Meghalaya, Bottaccione and Højerup sections within the CF2 planktic foraminiferal biozone (spike I), at the KPg boundary (spike II), and within the P1a planktic foraminiferal subzone (spike III). Spike III occurs also in the Jhilmili section. No clear correlation between Hg/TOC and Al₂O₃ exists in any of the studied sections. The Hg anomalies probably result from strong volcanic episodes of the Deccan phase-2 (started 250 kyr before the KPg boundary and lasted for 750 kyr) that exhaled sulfuric aerosols, carbon dioxide and other toxic agents which reached a critical threshold, represented in true Hg enrichments in the paleoenvironments. The possibility that Hg enrichments resulted from anoxia scavenging on the seafloor and penetration downward into sediments is not supported in the stratigraphic record of Mo/Al ratios redox proxy.Hg isotopes were analyzed in samples from all KPg boundary sections in this study and from Bidart, France, the latter for comparison. Hg isotopes yielded δ²⁰²Hg values ranging from −1 to −2‰ and Δ²⁰¹Hg signatures from 0 to 0.05‰ (spike II in Højerup, Bottaccione and Meghalaya KPg boundary layers) consistent with volcanic emission of Hg (0 to −2‰). The δ²⁰²Hg in spike I in Meghalaya and Padriciano and spike III in Jhilmili is consistent with volcanic emission of Hg. Two samples from Bajada del Jagüel and four from Bidart, however, display isotope signals compatible with volcanic emission/chondrite Hg. The results of three other samples are characteristic for reworked sediment, soil and/or peat. Most of the data show small positive Δ²⁰¹Hg, in favor of long-term atmospheric transport prior to deposition, supporting a volcanic origin for the Hg. The present study broadens, therefore, the potential use of Hg as stratigraphic marker and, moreover, confirms that in the critical KPg transition, Hg was enriched in paleoenvironments at three distinct stages during the Deccan phase-2.     

Greenhouse gas emissions from soils—A review

Soils act as sources and sinks for greenhouse gases (GHG) such as carbon dioxide (CO₂), methane (CH₄), and nitrous oxide (N₂O). Since both storage and emission capacities may be large, precise quantifications are needed to obtain reliable global budgets that are necessary for land-use management (agriculture, forestry), global change and for climate research. This paper discusses exclusively the soil emission-related processes and their influencing parameters. It reviews soil emission studies involving the most important land-cover types and climate zones and introduces important measuring systems for soil emissions. It addresses current shortcomings and the obvious bias towards northern hemispheric data.When using a conservative average of 300 mg CO₂e m⁻² h⁻¹ (based on our literature review), this leads to global annual net soil emissions of ≥350 Pg CO₂e (CO₂e = CO₂ equivalents = total effect of all GHG normalized to CO₂). This corresponds to roughly 21% of the global soil C and N pools. For comparison, 33.4 Pg CO₂ are being emitted annually by fossil fuel combustion and the cement industry.     

Volatile organic acids and microbial processes in the Yegua formation,east-central Texas

Geochemical and microbiological evidence indicates that viable microorganisms produce and consume volatile organic acids (VOA) in the Yegua formation. Acetic and propionic acid concentrations in mudstones range from 200 to 1270 and 20 to 38 nmol·gdw⁻¹ respectively, whereas concentrations in sands are 50–200 and less than 20 nmol·gdw⁻¹. VOA concentrations in sediments and in laboratory incubations suggest net production of VOAs by microorganisms in mudstones, and net consumption of VOAs by SO₄ reducing bacteria (SRB) in sands. Notably, SRB activity is mostly confined to aquifer sands.Vertical diffusion and advection were modeled to estimate acetic acid transport from aquitard to aquifer. Assuming that SRB completely respire the acetic acid transported into the aquifer (3.2 μmol·l⁻¹·m·a⁻¹), the CO₂ production rate in the aquifer sands is 5.3 μmol·l⁻¹·a⁻¹. This slow mineralization rate of in situ organic matter is within the range for deep aquifers, and probably accounts for the long-term survival of microorganisms in oligotrophic environments. Finally, the microbial communities in Yegua sediments appear to exhibit a loose commensalism, with microorganisms in aquitards providing VOAs for respiratory processes (i.e., SO₄ reduction) in aquifers.     

Characteristics,genesis and classification of a basin peat soil under negative human impact in Turkey

The objective of this research was to investigate the morphology, genesis and classification of organic soils formed on depression and flat land around Lake Yenicaga, west-central Turkey. Formation of the area has been influenced by tectonic and karst processes. This peatland is important in this area due to its extensive use as a horticultural plant growth medium resulting from positive physical and chemical properties. Organic soils in the study area were formed in nutrient-rich conditions and it is classified as typical basin peat. Four representative pedons were excavated in the study area based on extensive observations performed with random grid method using an auger. Samples were taken from horizons in each profile for laboratory analyses. Organic matter contents ranged from 12.5 to 91.5% across all four pedons. Fiber contents were between 4.3 and 91.5%, and N ranged from 0.56 to 2.19%. Cation exchange capacity ranged from 37 to 222 cmol kg⁻¹, bulk density from 0.09 to 0.78 g cm⁻³, lime from 0.15 to 2.62%. The pH and EC_e values ranged from 5.38 to 7.92 and 0.50 to 3.80 dS m⁻¹, respectively. Sand, silt and clay contents of the organic soils ranged between 0.75–3.92, 40.70–74.77 and 24.15–57.30%, respectively. Differences in organic soils were found to depend on the environment, botanical origins, decomposition degrees, and groundwater composition. The organic soils of the research area were classified in the typic, hemic and hydric subgroups of Medifibrists (Soil Taxonomy 1999).     

Modern carbon burial in Lake Qinghai,China

The quantification of carbon burial in lake sediments, and carbon fluxes derived from different origins are crucial to understand modern lacustrine carbon budgets, and to assess the role of lakes in the global carbon cycle. In this study, we estimated carbon burial in the sediment of Lake Qinghai, the largest inland lake in China, and the carbon fluxes derived from different origins. We find that: (1) The organic carbon burial rate in lake sediment is approximately 7.23 g m⁻² a⁻¹, which is comparable to rates documented in many large lakes worldwide. We determined that the flux of riverine particulate organic carbon (POC) is approximately 10 times higher than that of dissolved organic carbon (DOC). Organic matter in lake sediments is primarily derived from POC in lake water, of which approximately 80% is of terrestrial origin. (2) The inorganic carbon burial rate in lake sediment is slightly higher than that of organic carbon. The flux of riverine dissolved inorganic carbon (DIC) is approximately 20 times that of DOC, and more than 70% of the riverine DIC is drawn directly and/or indirectly from atmospheric CO₂. (3) Both DIC and DOC are concentrated in lake water, suggesting that the lake serves as a sink for both organic and inorganic carbon over long term timescales. (4) Our analysis suggests that the carbon burial rates in Lake Qinghai would be much higher in warmer climatic periods than in cold ones, implying a growing role in the global carbon cycle under a continued global warming scenario.     

Calcite dissolution driven by benthic mineralization in the deep-sea: in situ measurements of Ca2+, pH,pCO2 and O2

In situ measured microprofiles of Ca²⁺, pCO₂, pH and O₂ were performed to quantify the CaCO₃ dissolution and organic matter mineralization in marine sediments in the eastern South Atlantic. A numerical model simulating the organic matter decay with oxygen was used to estimate the calcite dissolution rate. From the oxygen microprofiles measured at four stations along a 1300-m isobath of the eastern African margin and one in front of the river Niger at a water depth of 2200 m the diffusive oxygen uptake (DOU) and oxygen penetration depth (OPD) was calculated. DOU rates were in the range of 0.3 to 3 mmol m⁻² d⁻¹ and showed a decrease with increasing water depth, corresponding to an increase in OPD. The calculated amount of degradated organic matter is in the range of 1 to 8.5 gC m⁻² a⁻¹. The metabolic CO₂, released from mineralization of the organic matter drives calcite dissolution in these sediments overlain by calcite-supersaturated water. Fluxes across the sediment water interface calculated from the in situ Ca²⁺ microprofiles were 0.6 mmol m⁻² d⁻¹ for two stations at a water depth of 1300 m. The ratio of calcite dissolution flux and organic C degradation is 0.53 and 0.97, respectively. The microprofiles indicate that CO₂ produced within the upper oxic sediment layer dissolves up to 85% of the calcite rain to the seafloor. Modeling our O₂, pH and Ca²⁺ profiles from one station predicted a calcite dissolution rate constant for this calcite-poor site of 1000 mol kgw⁻¹ a⁻¹ (mol per kg water and year), which equals 95% d⁻¹. This rate constant is at the upper end of reported in situ values.     

Use of mineral/solution equilibrium calculations to assess the potential for carnotite precipitation from groundwater in the Texas Panhandle,USA

This study investigated the potential for the uranium mineral carnotite (K₂(UO₂)₂(VO₄)₂·3H₂O) to precipitate from evaporating groundwater in the Texas Panhandle region of the United States. The evolution of groundwater chemistry during evaporation was modeled with the USGS geochemical code PHREEQC using water-quality data from 100 groundwater wells downloaded from the USGS National Water Information System (NWIS) database. While most modeled groundwater compositions precipitated calcite upon evaporation, not all groundwater became saturated with respect to carnotite with the system open to CO₂. Thus, the formation of calcite is not a necessary condition for carnotite to form. Rather, the determining factor in achieving carnotite saturation was the evolution of groundwater chemistry during evaporation following calcite precipitation. Modeling in this study showed that if the initial major-ion groundwater composition was dominated by calcium-magnesium-sulfate (>70 precent Ca + Mg and >50 percent SO₄ + Cl) or calcium-magnesium-bicarbonate (>70 percent Ca + Mg and <70 percent HCO₃ + CO₃) and following the precipitation of calcite, the concentration of calcium was greater than the carbonate alkalinity (2mCa⁺² > mHCO₃⁻ + 2mCO₃⁻²) carnotite saturation was achieved. If, however, the initial major-ion groundwater composition is sodium-bicarbonate (varying amounts of Na, 40–100 percent Na), calcium-sodium-sulfate, or calcium-magnesium-bicarbonate composition (>70 percent HCO₃ + CO₃) and following the precipitation of calcite, the concentration of calcium was less than the carbonate alkalinity (2mCa⁺² < mHCO₃^- + 2mCO₃⁻²) carnotite saturation was not achieved. In systems open to CO_2, carnotite saturation occurred in most samples in evaporation amounts ranging from 95 percent to 99 percent with the partial pressure of CO₂ ranging from 10^−3.5 to 10^−2.5 atm. Carnotite saturation occurred in a few samples in evaporation amounts ranging from 98 percent to 99 percent with the partial pressure of CO₂ equal to 10^−2.0 atm. Carnotite saturation did not occur in any groundwater with the system closed to CO₂.     

Soil mercury distribution in adjacent coniferous and deciduous stands highly impacted by acid rain in the Ore Mountains,Czech Republic

Forests play a primary role in the cycling and storage of mercury (Hg) in terrestrial ecosystems. This study aimed to assess differences in Hg cycling and storage resulting from different vegetation at two adjacent forest stands - beech and spruce. The study site Načetín in the Czech Republic's Black Triangle received high atmospheric loadings of Hg from coal combustion in the second half of the 20th century as documented by peat accumulation rates reaching 100 μg m⁻² y⁻¹. In 2004, the annual litterfall Hg flux was 22.5 μg m⁻² y⁻¹ in the beech stand and 14.5 μg m⁻² y⁻¹ in the spruce stand. Soil concentrations and pools of Hg had a strong positive relation to soil organic matter and concentrations of soil sulfur (S) and nitrogen (N). O-horizon Hg concentrations ranged from 245 to 495 μg kg⁻¹ and were greater in the spruce stand soil, probably as a result of greater dry Hg deposition. Mineral soil Hg concentrations ranged from 51 to 163 μg kg⁻¹ and were greater in the beech stand soil due to its greater capacity to store organic carbon (C). The Hg/C ratio increased with depth from 0.3 in the O-horizon to 3.8 μg g⁻¹ in the C horizon of spruce soil and from 0.7 to 2.7 μg g⁻¹ in beech soil. The Hg/C ratio was greater at all mineral soil depths in the spruce stand. The organic soil Hg pools in beech and spruce stands (6.4 and 5.7 mg m⁻², respectively) were considerably lower than corresponding mineral soil Hg pools (39.1 and 25.8 mg m⁻²). Despite the important role of S in Hg cycling, differences in soil Hg distribution at both stands could not be attributed to differences in soil sulfur speciation.     

Factors affecting the dissolution kinetics of volcanic ash soils: dependencies on pH,CO2, and oxalate

Laboratory experiments were conducted with volcanic ash soils from Mammoth Mountain, California to examine the dependence of soil dissolution rates on pH and CO₂ (in batch experiments) and on oxalate (in flow-through experiments). In all experiments, an initial period of rapid dissolution was observed followed by steady-state dissolution. A decrease in the specific surface area of the soil samples, ranging from 50% to 80%, was observed; this decrease occurred during the period of rapid, initial dissolution. Steady-state dissolution rates, normalized to specific surface areas determined at the conclusion of the batch experiments, ranged from 0.03 μmol Si m⁻² h⁻¹ at pH 2.78 in the batch experiments to 0.009 μmol Si m⁻² h⁻¹ at pH 4 in the flow-through experiments. Over the pH range of 2.78–4.0, the dissolution rates exhibited a fractional order dependence on pH of 0.47 for rates determined from H⁺ consumption data and 0.27 for rates determined from Si release data. Experiments at ambient and 1 atm CO₂ demonstrated that dissolution rates were independent of CO₂ within experimental error at both pH 2.78 and 4.0. Dissolution at pH 4.0 was enhanced by addition of 1 mM oxalate. These observations provide insight into how the rates of soil weathering may be changing in areas on the flanks of Mammoth Mountain where concentrations of soil CO₂ have been elevated over the last decade. This release of magmatic CO₂ has depressed the soil pH and killed all vegetation (thus possibly changing the organic acid composition). These indirect effects of CO₂ may be enhancing the weathering of these volcanic ash soils but a strong direct effect of CO₂ can be excluded.     

Fe(CO3)OH in goethite from a mid-latitude North American Oxisol: estimate of atmospheric CO2 concentration in the Early Eocene “climatic optimum”

Measured mole fractions (X) and δ¹³C values of the Fe(CO₃)OH component in pedogenic goethite from a mid-latitude Oxisol of Early Eocene age (≈52 Ma B.P.) range from 0.0014 to 0.0064 and −20.1 to −15.4‰, respectively. These values of X imply that concentrations of CO₂ gas in the paleosol were ≈7400 to ≈34,000 ppm. δ¹³C and 1/X are correlated and define a linear, soil-CO₂ diffusive mixing line with a positive slope. Such positive slopes are characteristic of mixing of two isotopically distinct CO₂ endmembers (atmospheric CO₂ and CO₂ from oxidation of soil organic matter). From the intercept of the mixing line, it is calculated that the δ ¹³C value of organic matter in the ancient soil was ≈−28.0‰. The magnitude of the slope implies an Early Eocene atmospheric CO₂ concentration of ≈2700 ppm.A simple model for forest soils suggests that a “canopy effect” may cause atmospheric CO₂ concentrations deduced from pedogenic minerals to underestimate the actual concentrations of atmospheric CO₂. If a significant forest canopy were present at the time of formation of pedogenic goethite in the Ione Fm, the concentration of 2700 ppm calculated for atmospheric CO₂ could be slightly low, but the underestimate is expected to be < ≈300 ppm (i.e., less than the analytical uncertainty). The relatively high concentration of 2700 ppm inferred for atmospheric CO₂ at ≈52 Ma B.P. would have been coincident with the Early Eocene climatic optimum. This result seems to support the case for an important role for variations of atmospheric CO₂ in the modification of global paleoclimate.     

Geochemical comparison between gas in fluid inclusions and gas produced from the Upper Triassic Xujiahe Formation,Sichuan Basin,SW China

Natural gas in the Xujiahe Formation of the Sichuan Basin is dominated by hydrocarbon (HC) gas, with 78–79% methane and 2–19% C₂₊ HC. Its dryness coefficient (C₁/C_1–5) is mostly < 0.95. The gas in fluid inclusions, which has low contents of CH₄ and heavy hydrocarbons (C₂₊) and higher contents of non-hydrocarbons (e.g. CO₂), is a typical wet gas produced by thermal degradation of kerogen. Gas produced from the Upper Triassic Xujiahe Formation (here denoted field gas) has light carbon isotope values for methane (δ¹³C₁: −45‰ to −36‰) and heavier values for ethane (δ¹³C₂: −30‰ to −25‰). The case is similar for gas in fluid inclusions, but δ¹³C₁ = −36‰ to −45‰ and δ¹³C₂ = −24.8‰ to −28.1‰, suggesting that the gas experienced weak isotopic fractionation due to migration and water washing. The field gas has δ¹³C_CO2 values of −15.6‰ to −5.6‰, while the gas in fluid inclusions has δ¹³C_CO2 values of −16.6‰ to −9‰, indicating its organic origin. Geochemical comparison shows that CO₂ captured in fluid inclusions mainly originated from source rock organic matter, with little contribution from abiogenic CO₂. Fluid inclusions originate in a relatively closed system without fluid exchange with the outside following the gas capture process, so that there is no isotopic fractionation. They thus present the original state of gas generated from the source rocks. These research results can provide a theoretical basis for gas generation, evolution, migration and accumulation in the basin.     

Stable isotopes of pedogenic carbonates from the Somma–Vesuvius area,southern Italy,over the past 18 kyr: palaeoclimatic implications

Stable isotopes were measured in the carbonate and organic matter of palaeosols in the Somma–Vesuvius area, southern Italy in order to test whether they are suitable proxy records for climatic and ecological changes in this area during the past 18000 yr. The ages of the soils span from ca. 18 to ca. 3 kyr BP. Surprisingly, the Last Glacial to Holocene climate transition was not accompanied by significant change in δ¹⁸O of pedogenic carbonate. This could be explained by changes in evaporation rate and in isotope fractionation between water and precipitated carbonate with temperature, which counterbalanced the expected change in isotope composition of meteoric water. Because of the rise in temperature and humidity and the progressive increase in tree cover during the Holocene, the Holocene soil carbonates closely reflect the isotopic composition of meteoric water. A cooling of about 2°C after the Avellino eruption (3.8 ka) accounts for a sudden decrease of about 1‰ in δ¹⁸O of pedogenic carbonate recorded after this eruption. The δ¹³C values of organic matter and pedogenic carbonate covary, indicating an effective isotope equilibrium between the organic matter, as the source of CO₂, and the pedogenic carbonate. Carbon isotopes suggest prevailing C₃ vegetation and negligible mixing with volcanogenic or atmospheric CO₂. Copyright © 2000 John Wiley & Sons, Ltd.     

Contrasting the sorption of Zn by oxyhydroxides of Mn and Fe,and organic matter along a mineral-poor to mineral-rich fen gradient

The geochemistry of Mn and Fe in surface pools, pore-waters and surface peats and the sorption of Zn by the surface peats was contrasted among 15 peatlands sampled along a mineral-poor to mineral-rich fen gradient. Sorption of Zn by surficial peats was compared via distribution coefficients, both total (K_DT) and partial (K_DERMn, K_DRFe and K_DORG), where ER Mn, R Fe and ORG are amounts of Zn recovered from the easily reducible Mn oxides, reducible Fe oxides, and organic components of peat, respectively. Apparent stability constants (K_As) for Zn sorption onto oxides of Fe recovered from the surface peats were also calculated and compared along the same gradient. Peat geochemistry was peatland dependent; mineral-poor fens had less easily reducible Mn and greater amounts of organic matter (%Loss on Ignition; LOI) versus mineral-rich fens (range of 0.66–8.6 mm kg⁻¹ for ER Mn and 20–88% LOI for organic matter). Reducible Fe also varied among peatlands (range 51–315 mm kg⁻¹) but was independent of the mineral-poor to mineral-rich fen gradient. Comparison of partial K_Ds for amounts of Zn sorped onto the ER Mn, R Fe and ORG components of peat indicated that sorption was dominated by R Fe in all peatlands. K_DTs ranged from 0.54–2.00. In contrast to other aquatic systems, however, the range in K_DTs was not related to either surface or pore-water pH. K_As ranged from 0.36 to 3.06 and were also independent of surface or pore-water pH. However, average K_As (but not K_DTs), were greater for mineral-poor fens (P<0.02), suggesting greater Zn binding by surface peats of mineral-poor fens versus either the moderately poor or mineral-rich peatlands. Other water chemistry variables, such as pore-water base cation concentrations, weakly correlated to Zn partitioning onto R Fe (r=−0.35, P=0.05), but did not fully explain differences in Zn partitioning among peatlands. Greater average K_As for the mineral-poor peatlands may in part be due to the presence of strong metal-organic matter-Fe oxide complexes in the Sphagnum dominated peatlands as well as lower pore-water base cation concentrations that occur in the mineral-poor peatland as compared to the more mineral-rich fens.