Simulation of salinity effects on past, present, and future soil organic carbon stocks

Soil organic carbon (SOC) models are used to predict changes in SOC stocks and carbon dioxide (CO(2)) emissions from soils, and have been successfully validated for non-saline soils. However, SOC models have not been developed to simulate SOC turnover in saline soils. Due to the large extent of salt-affected areas in the world, it is important to correctly predict SOC dynamics in salt-affected soils. To close this knowledge gap, we modified the Rothamsted Carbon Model (RothC) to simulate SOC turnover in salt-affected soils, using data from non-salt-affected and salt-affected soils in two agricultural regions in India (120 soils) and in Australia (160 soils). Recently we developed a decomposition rate modifier based on an incubation study of a subset of these soils. In the present study, we introduce a new method to estimate the past losses of SOC due to salinity and show how salinity affects future SOC stocks on a regional scale. Because salinity decreases decomposition rates, simulations using the decomposition rate modifier for salinity suggest an accumulation of SOC. However, if the plant inputs are also adjusted to reflect reduced plant growth under saline conditions, the simulations show a significant loss of soil carbon in the past due to salinization, with a higher average loss of SOC in Australian soils (55 t C ha(-1)) than in Indian soils (31 t C ha(-1)). There was a significant negative correlation (p < 0.05) between SOC loss and osmotic potential. Simulations of future SOC stocks with the decomposition rate modifier and the plant input modifier indicate a greater decrease in SOC in saline than in non-saline soils under future climate. The simulations of past losses of SOC due to salinity were repeated using either measured charcoal-C or the inert organic matter predicted by the Falloon et al. equation to determine how much deviation from the Falloon et al. equation affects the amount of plant inputs generated by the model for the soils used in this study. Both sets of results suggest that saline soils have lost carbon and will continue to lose carbon under future climate. This demonstrates the importance of both reduced decomposition and reduced plant input in simulations of future changes in SOC stocks in saline soils.     

Role of soil health in maintaining environmental sustainability of surface coal mining

Mountaintop coal mining (MCM) in the Southern Appalachian forest region greatly impacts both soil and aquatic ecosystems. Policy and practice currently in place emphasize water quality and soil stability but do not consider upland soil health. Here we report soil organic carbon (SOC) measurements and other soil quality indicators for reclaimed soils in the Southern Appalachian forest region to quantify the health of the soil ecosystem. The SOC sequestration rate of the MCM soils was 1.3 MgC ha(-1) yr(-1) and stocks ranged from 1.3 ± 0.9 to 20.9 ± 5.9 Mg ha(-1) and contained only 11% of the SOC of surrounding forest soils. Comparable reclaimed mining soils reported in the literature that are supportive of soil ecosystem health had SOC stocks 2.5-5 times greater than the MCM soils and sequestration rates were also 1.6-3 times greater. The high compaction associated with reclamation in this region greatly reduces both the vegetative rooting depth and infiltration of the soil and increases surface runoff, thus bypassing the ability of soil to naturally filter groundwater. In the context of environmental sustainability of MCM, it is proposed that the entire watershed ecosystem be assessed and that a revision of current policy be conducted to reflect the health of both water and soil.     

Release of trace organic compounds during the decomposition of municipal solid waste components

Landfill gas contains numerous speciated organic compounds (SOCs) including alkanes, aromatics, chlorinated aliphatic hydrocarbons, alcohols, ketones, terpenes, chlorofluoro compounds, and siloxanes. The source, rate and extent of release of these compounds are poorly understood. The objective of this study was to characterize the release of SOCs and the regulated parameter, non-methane organic compounds (NMOCs) during the decomposition of residential refuse and its major biodegradable components [paper (P), yard waste (YW), food waste (FW)]. Work was conducted under anaerobic conditions in 8-L reactors operated to maximize decomposition. Refuse and YW were also tested under aerobic conditions. NMOC release during anaerobic decomposition of refuse, P, YW, and FW was 0.151, 0.016, 0.038, and 0.221 mg-C dry g(-1), respectively, while release during aerobic decomposition of refuse and YW was 0.282 and 0.236 mg-C dry g(-1), respectively. The highest NMOC release was measured under abiotic conditions (3.01 mg-C dry g(-1)), suggesting the importance of gas stripping. NMOC release was faster than CH4 production in all treatments. Terpenes and ketones accounted for 32-96% of SOC release in each treatment, while volatile fatty acids were not a significant contributor. Release in aerobic systems points to the potential importance of composting plants as an emissions source.     

Carbon sequestration in soil by in situ catalyzed photo-oxidative polymerization of soil organic matter

Here we describe an innovative mechanism for carbon sequestration in soil by in situ photopolymerization of soil organic matter under biomimetic catalysis. Three different Mediterranean soils were added with a synthetic water-soluble iron-porphyrin, irradiated by solar light, and subjected first to 5 days incubation and, then, 15, and 30 wetting and drying (w/d) cycles. The in situ catalyst-assisted photopolymerization of soil organic carbon (SOC) increased water stability of soil aggregates both after 5 days incubation and 15 w/d cycles, but not after 30 w/d cycles. Particle-size distribution of all treated soils confirmed the induced soil physical improvement, by showing a concomitant lower yield of the clay-sized fraction and larger yields of either coarse sand- or fine sand-size fractions, depending on soil texture, though only after 5 days incubation. The gain in soil physical quality was reflected by the shift of OC content from small to large soil aggregates, thereby suggesting that photopolymerization stabilized OC by both chemical and physical processes. A further evidence of the carbon sequestration capacity of the photocatalytic treatment was provided by the significant reduction of CO(2) respired by all soils after both incubation and w/d cycles. Our findings suggest that "green" catalytic technologies may potentially be the bases for future practices to increase soil carbon stabilization and mitigate CO(2) emissions from arable soils.     

Efficient decomposition of perfluorocarboxylic acids and alternative fluorochemical surfactants in hot water

Decomposition of C5-C9 perfluorocarboxylic acids (PFCAs) and perfluoroether carboxylic acids (alternatives to PFCA-based surfactants) in hot water in a sealed reactor was investigated. Although PFCAs showed almost no decomposition in hot water at 80 degrees C in the absence of persulfate (S2O8(2-)), the addition of S2O8(2-) to the reaction system led to efficient decomposition, even at this relatively low temperature. The major products in the aqueous and gas phases were F- ions and CO2, respectively, and short-chain PFCAs were also detected in the aqueous phase. For example, when an aqueous solution containing perfluorooctanoic acid (PFOA, 374 microM) and S2O8(2-) (50.0 mM) was heated at 80 degrees C for 6 h, PFOA concentration in the aqueous phase fell below 1.52 microM (detection limit of HPLC with conductometric detection), and the yields of F- ions [i.e., (moles of F- formed) /(moles of fluorine content in initial PFOA)] and CO2 [i.e, (moles of CO2 formed) /(moles of carbon content in initial PFOA)] were 77.5% and 70.2%, respectively. This method was also effective in decomposing perfluoroether carboxylic acids, such as CF3OC2F4OCF2COOH, CF3OC2F4OC2F4OCF2COOH, and C2F5OC2F4OCF2COOH, which are alternatives to PFCA-based surfactants, producing F- and CO2 with yields of 82.9-88.9% and 87.7-100%, respectively, after reactions at 80 degrees C for 6 h. In addition, the method was successfully used to decompose perfluorononanoic acid in a floor wax solution. When PFOAwastreated at a higher temperature (150 degrees C), other decomposition reactions occurred: the formation of F- and CO2 was dramatically decreased, and 1H-perfluoroalkanes (C(n)F(2n+1)H, n = 4-7) formed in large amounts. This result clearly indicates that treatment with high-temperature water was not suitable for the decomposition of PFCAs to F-: surprisingly, the relatively low temperature of 80 degrees C was preferable.     

Total cations in the size-fractions of some british and malayan soils and their release to H+-resins

Total K, Na, Ca and Mg in the sand, silt and clay of six British and four Malayan soils and the proportions released to H⁺-resins in 1 h, 3, 10, 23 and 43 days were measured. The clays contained and released to the resins more K and Mg than coarser fractions. The release was continuous except from the acid Malayan soils which stopped releasing K after 3 days. More Mg was released to the resins than K, although no non-exchangeable Mg but much non-exchangeable K was released to ryegrass grown in the soils (after liming). This suggests that H⁺-resins caused structural decomposition of the clay minerals which, together with the anomolous K release from acid soils, would limit their usefulness for measuring soil cations available to crops.     

Efficient decomposition of environmentally persistent perfluorocarboxylic acids by use of persulfate as a photochemical oxidant

Photochemical decomposition of persistent perfluorocarboxylic acids (PFCAs) in water by use of persulfate ion (S2O8(2-)) was examined to develop a technique to neutralize stationary sources of PFCAs. Photolysis of S2O8(2-) produced highly oxidative sulfate radical anions (SO4-), which efficiently decomposed perfluorooctanoic acid (PFOA) and other PFCAs bearing C4-C8 perfluoroalkyl groups. The major products were F- and CO2; also, small amounts of PFCAs with shorter than initial chain lengths were detected in the reaction solution. PFOA at a concentration of 1.35 mM (typical of that in untreated wastewater after an emulsifying process in fluoropolymer manufacture) was completely decomposed by a photochemical system with 50 mM S2O8(2-) and 4 h of irradiation from a 200-W xenon-mercury lamp. The initial PFOA decomposition rate was 11 times higherthan with photolysis alone. All sulfur-containing species in the reaction solution were eventually transformed to sulfate ions by this method. This method was successfully applied to the decomposition of perfluorononanoic acid contained in a floor wax solution.     

Variation in peak growing season net ecosystem production across the canadian arctic

Tundra ecosystems store vast amounts of soil organic carbon, which may be sensitive to climatic change. Net ecosystem production, NEP, is the net exchange of carbon dioxide (CO(2)) between landscapes and the atmosphere, and represents the balance between CO(2) uptake by photosynthesis and release by decomposition and autotrophic respiration. Here we examine CO(2) exchange across seven sites in the Canadian low and high Arctic during the peak growing season (July) in summer 2008. All sites were net sinks for atmospheric CO(2) (NEP ranged from 5 to 67 g C m(-2)), with low Arctic sites being substantially larger CO(2) sinks. The spatial difference in NEP between low and high Arctic sites was determined more by CO(2) uptake via gross ecosystem production than by CO(2) release via ecosystem respiration. Maximum gross ecosystem production at the low Arctic sites (average 8.6 μmol m(-2) s(-1)) was about 4 times larger than for high Arctic sites (average 2.4 μmol m(-2) s(-1)). NEP decreased with increasing temperature at all low Arctic sites, driven largely by the ecosystem respiration response. No consistent temperature response was found for the high Arctic sites. The results of this study clearly indicate there are large differences in tundra CO(2) exchange between high and low Arctic environments and this difference should be a central consideration in studies of Arctic carbon balance and climate change.     

Evaluation of holistic approaches to predicting the concentrations of metals in field-cultivated rice

Measurements of metals in soils by diffusive gradients in thin films (DGT) have previously been shown to be linearly related to metals measured in shoots of plants grown in pots. We examine the relationships between metals measured by DGT and other techniques with metals in the roots and unpolished grains of rice cultivated under field conditions at 18 sites in Jiangsu province, China. Rhizosphere soils of rice were collected and the concentrations of Cd, Cu, Pb, and Zn were determined on soil solution, acetic acid, and calcium chloride (CaCl2) extractions and by DGT. Simple linear regression analyses between concentrations of metals in plants and those measured using DGT and chemical extractions showed a very good fit for DGT measurements of the concentrations of all four metals in both rice roots and unpolished grains. Good fits were also found using soil solution and acetic acid extractions, but the correlation coefficients were lower than those obtained by DGT. CaCl2 extractions provided the poorest fits for all four metals. Multivariate analyses were used to assess the impact of pH, dissolved organic carbon (DOC), soil organic carbon (SOC), cation exchange capacity (CEC), and texture. Two principal components were extracted. The first was well correlated with SOC, DOC, and clay proportion and is therefore representative of "organic matter". The second primarily correlated positively with pH and negatively with CEC and is representative of "inorganic ions". When these principle components were included in multiple linear regression, correlation coefficients for plots involving metals in soil solution and in extractions using acetic acid and CaCl2 were improved, but there was little change in the correlation coefficients for comparable plots using metals measured by DGT. These results show for the first time that the DGT measurement quantitatively incorporates the main factors affecting bioavailability.     

Factors affecting the efficiency of carbon monoxide photoproduction in the St. Lawrence estuarine system (Canada)

This study examined the effects of water temperature and the origin (terrestrial vs marine) and light history of chromophoric dissolved organic matter (CDOM) on the apparent quantum yields of carbon monoxide (CO) photoproduction for water samples collected along a salinity gradient (salinity range: 0-33) in the St. Lawrence estuarine system (Canada). The solar insolation-weighted mean apparent quantum yield of CO (phico) decreased as much as fourfold with increasing salinity and showed a strong positive correlation with the dissolved organic carbon-specific absorption coefficient at 254 nm. This suggests that terrestrial CDOM is more efficient at photochemically producing CO than is marine algae-derived CDOM and that aromatic moieties are likely involved in this photoprocess. CDOM photobleaching, mainly at the very early stage, dramatically decreased phico (by up to 6.4 times) for low-salinity samples, but photobleaching had little effect on the most marine sample. For a 20 degree C increase in temperature, phico increased by approximately 70% for low-salinity samples and 30-40% for saline samples. This study demonstrates that water temperature, as well as the CDOM's origin and light history, strongly affect the efficiency of CO photoproduction. These factors should be taken into account in modeling the photochemical fluxes of CO and other related CDOM photoproducts on varying spatiotemporal scales.     

Improved Characterization of Soil Organic Matter by Thermal Analysis Using CO(2)/H(2)O Evolved Gas Analysis

Simultaneous thermal analysis [i.e., thermogravimetry (TG) and differential scanning calorimetry (DSC)] is frequently used in materials science applications and is increasingly being used to study soil organic matter (SOM) stability. Yet, important questions remain, especially with respect to how the soil mineral matrix affects TG-DSC results, which could confound the interpretation of relationships between thermal and biogeochemical SOM stability. The objective of this study was to explore the viability of using infrared gas analyzer (IRGA) based CO(2)/H(2)O evolved gas analysis (EGA) as a supplement or alternative to TG-DSC to improve the characterization of SOM. Here, we subjected reference samples and a set of 28 diverse soil samples from across the U.S. to TG-DSC coupled with IRGA-based EGA. The results showed the technical validity of coupling TG-DSC and CO(2)-EGA, with more than 80% of the theoretically evolved CO(2)-C recovered during pure cellulose and CaCO(3) analysis. CO(2)-EGA and DSC thermal profiles were highly similar, with correlation coefficients generally >0.90. Additionally, CO(2)/H(2)O-EGA proved useful to improve the accuracy of baseline correction, detect the presence of CaCO(3) in soils, and identify SOM oxidative reactions normally hidden in DSC analysis by simultaneous endothermic reactions of soil minerals. Overall, this study demonstrated that IRGA-based CO(2)/H(2)O-EGA constitutes a valuable complement to conventional TG-DSC analysis for SOM characterization.     

Particle-phase chemistry of secondary organic material: modeled compared to measured O:C and H:C elemental ratios provide constraints

Chemical mechanisms for the production of secondary organic material (SOM) are developed in focused laboratory studies but widely used in the complex modeling context of the atmosphere. Given this extrapolation, a stringent testing of the mechanisms is important. In addition to particle mass yield as a typical standard for model-measurement comparison, particle composition expressed as O:C and H:C elemental ratios can serve as a higher dimensional constraint. A paradigm for doing so is developed herein for SOM production from a C(5)-C(10)-C(15) terpene sequence, namely isoprene, α-pinene, and β-caryopyhllene. The model MCM-SIMPOL is introduced based on the Master Chemical Mechanism (MCM v3.2) and a group contribution method for vapor pressures (SIMPOL). The O:C and H:C ratios of the SOM are measured using an Aerosol Mass Spectrometer (AMS). Detailed SOM-specific AMS calibrations for the organic contribution to the H(2)O(+) and CO(+) ions indicate that published O:C and H:C ratios for SOM are systematically too low. Overall, the measurement-model gap was small for particle mass yield but significant for particle-average elemental composition. The implication is that a key chemical pathway is missing from the chemical mechanism. The data can be explained by the particle-phase homolytic decomposition of organic hydroperoxides and subsequent alkyl-radical-promoted oligomerization.     

基于盆栽试验分析3种品牌稻草秸秆腐熟剂对植烟土壤有机碳组分的影响

为了解秸秆腐熟剂在植烟土壤中的施用效果,通过盆钵模拟培养试验,分析了稻草秸秆分别配施化肥和含不同微生物优势菌种的腐熟剂后土壤速效养分、有机碳及其组分和有机碳稳定性评价指标的变化,研究了稻草秸秆配施腐熟剂对植烟土壤有机碳组分的影响。结果表明,相比单施化肥,稻草秸秆配施化肥的土壤颗粒有机碳(POC)、易氧化有机碳(EOC)及溶解有机碳(DOC)含量(质量分数)分别显著升高36.89%、30.77%和75.73%,稻草秸秆配施腐熟剂的土壤碱解氮(AN)、有效磷(AP)、总有机碳(TOC)、POC、EOC及DOC含量(质量分数)分别显著升高了17.42%~28.33%、49.94%~55.68%、10.46%~15.20%、39.32%~74.27%、54.36%~64.62%和84.58%~124.27%;稻草秸秆分别配施化肥和腐熟剂均可显著提高土壤活性有机碳组分的有效率,且可降低有机碳的抗氧化能力,但后者更显著;主成分分析显示,稻草秸秆配施腐熟剂在提高土壤TOC含量的同时,提高了土壤活性有机碳组分的有效率且降低了有机碳抗氧化性能;稻草秸秆分别配施细菌+真菌(XZ)和细菌+真菌+放线菌(XZF)为优势菌种的腐熟剂对植烟土壤有效养分和有机碳组分的影响无明显差异。      

Efficient photochemical decomposition of long-chain perfluorocarboxylic acids by means of an aqueous/liquid CO2 biphasic system

Photochemical decomposition of persistent and bioaccumulative long-chain (C9-C11) perfluorocarboxylic acids (PFCAs) with persulfate ion (S2O8(2-)) in an aqueous/liquid CO2 biphasic system was examined to develop a technique to neutralize stationary sources of the long-chain PFCAs. The long-chain PFCAs, namely, perfluorononanoic acid (PFNA), perfluorodecanoic acid (PFDA), and perfluoroundecanoic acid (PFUA), which are used as emulsifying agents and as surface treatment agents in industry, are relatively insoluble in water but are soluble in liquid CO2; therefore, introduction of liquid CO2 to the aqueous photoreaction system reduces the interference of colloidal PFCA particles. When the biphasic system was used to decompose these PFCAs, the extent of reaction was 6.4-51 times as high as that achieved in the absence of CO2. In the biphasic system, PFNA, PFDA, and PFUA (33.5-33.6 micromol) in 25.0 mL of water were 100%, 100%, and 77.1% decomposed, respectively, after 12 h of irradiation with a 200-W xenon-mercury lamp; F- ions were produced as a major product, and short-chain PFCAs, which are less bioaccumulative than the original PFCAs, were minor products. All of the initial S2O8(2-) was transformed to SO42-. The system also efficiently decomposed PFCAs at lower concentrations (e.g., 4.28-16.7 micromol of PFDA in 25.0 mL) and was successfully applied to decompose PFNA in floor wax.     

Current and historical deposition of PBDEs, pesticides, PCBs, and PAHs to Rocky Mountain National Park

An analytical method was developed for the trace analysis of 98 semivolatile organic compounds (SOCs) in remote, high-elevation lake sediment. Sediment cores from Lone Pine Lake (west of the Continental Divide) and Mills Lake (east of the Continental Divide) in Rocky Mountain National Park, CO, were dated using 210Pb and 137Cs and analyzed for polybrominated diphenyl ethers (PBDEs), organochlorine pesticides, phosphorothioate pesticides, thiocarbamate pesticides, amide herbicides, triazine herbicides, polychlorinated biphenyls (PCBs), and polycyclic aromatic hydrocarbons (PAHs) using this method. SOC deposition profiles were reconstructed, and deposition half-lives and doubling times were calculated, for U.S. historic-use pesticides (HUPs) and current-use pesticides (CUPs) as well as PBDEs, PCBs, and PAHs. Sediment records indicate that the deposition of CUPs has increased in recent years, while the deposition of HUPs has decreased since U.S. restriction, but has not been eliminated. This is likely due to the revolatilization of HUPs from regional soils, atmospheric transport, and deposition. Differences in the magnitude of SOC sediment fluxes, flux profiles, time trends within those profiles, and isomeric ratios suggest that SOC deposition in high-elevation ecosystems is dependent on regional upslope wind directions and site location with respect to regional sources and topographic barriers.     

Soil CO2 emissions from Northern Andean páramo ecosystems: effects of fallow agriculture

The effects of fallow agriculture on soil organic matter (SOM) dynamics and CO2 emissions were assessed in the tropical Andean páramo ecosystem. Possible changes during the cultivation-fallow cycle were monitored in four areas of the Quebrada Pi?uelas valley (Venezuela). Uncultivated soils and plots at different stages of a complete cultivation--fallow cycle were incubated, and SOM mineralization kinetics was determined. Soils exhibited a low SOM mineralization activity, total CO2 evolved never reaching 3% of soil carbon, pointing to a stabilized SOM. Potential soil CO2 effluxes differed significantly according to their plot aspect: northeast (NE)-aspect soils presented higher CO2 effluxes than southwest (SW)-aspect soils. Soil CO2 emissions decreased after ploughing as compared to virgin páramo; low CO2 effluxes were still observed during cropping periods, increasing progressively to reach the highest values after 4-5 y of fallow. In all cases, experimental C mineralization data was fitted to a double exponential kinetic model. High soil labile C pool variability was observed, and two different trends were identified: NE-oriented soils showed more labile C and a wider range of values than SW-facing soils. Labile C positively correlated with CO2 effluxes and negatively with its instantaneous mineralization rate. The instantaneous mineralization rate of the recalcitrant C pool positively correlated with %C evolved as CO2 and negatively with soil C and Al2O3 contents, suggesting the importance of aluminum on SOM stability. The CO2 effluxes from these ecosystems, as well as the proportion of soil C released to the atmosphere, seem to depend not only on the size of the labile C pool but also on the accessibility of the more stabilized SOM. Therefore, fallow agriculture produces moderate changes in SOM quality and temporarily alters the CO2 emission capacity of these soils.     

Mechanisms of hydrogen peroxide decomposition in soils

The rates and mechanisms of hydrogen peroxide (H2O2) decomposition were examined in a series of soil suspensions at H2O2 concentrations comparable to those found in rainwaters. The formation of hydroxyl radical (OH) as a possible decomposition intermediate was investigated using a new, highly sensitive method. In surface soils with higher organic matter or manganese content, H2O2 usually decayed rapidly, with disproportionation to water and dioxygen dominating the decomposition, whereas the formation of the hydroxyl radical (OH) represented <10% of the total H2O2 decomposed. In contrast, for soils with lower organic matter content, H2O2 usually decayed much more slowly, but OH was a major product of the H2O2 decomposed. The decomposition was principally associated with soil particles, not the soil supernatant. Different sterilization techniques indicated that decomposition of H2O2 was at least partly due to biological activity. Because the loss of H2O2 can largely be accommodated by the production of O2 and OH within these soils, our results suggest that disproportionation through a catalase-type mechanism and the production of OH through a Haber-Weiss mechanism represent the principal routes through which H2O2 is lost.     

湖北恩施烤烟平顶期烟田碳通量日变化研究

为了深入了解烟田碳排放对环境的影响,利用静态箱．红外二氧化碳分析仪法对湖北恩施不同有机肥烟田碳通量的日变化特征进行了调查。结果表明,在烟草平顶期,烟田生态系统碳通量具有明显的日变化规律,最高值出现在17：30-19：30,最低值出现在11：30--3：30,其变化趋势与土壤湿度呈极显著负相关,菜枯、烟秆生物肥替代处理均显著促进了烟田生态系统碳排放。而烟田土壤碳通量的日变化整体波动较小,最大值出现在9：30,最小值在7：30,且其变化趋势与气温、地表温度、5cm地温、10cm地温均呈显著或极显著正相关。研究发现,烟田生态系统碳通量的主要贡献者是烟草的净光合作用,而不是土壤呼吸,且烟田生态系统碳通量的日变化幅度大于土壤。     

Isotopic disequilibrium during uptake of atmospheric CO2 into mine process waters: implications for CO2 sequestration

Dypingite, a hydrated Mg-carbonate mineral, was precipitated from high-pH, high salinity solutions to investigate controls on carbon fixation and to identify the isotopic characteristics of mineral sequestration in mine tailings. δ(13)C values of dissolved inorganic carbon content and synthetic dypingite are significantly more negative than those predicted for equilibrium exchange of CO(2) gas between the atmosphere and solution. The measured δ(13)C of aqueous carbonate species is consistent with a kinetic fractionation that results from a slow diffusion of atmospheric CO(2) into solution. During dypingite precipitation, dissolved inorganic carbon concentrations decrease and δ(13)C values become more negative, indicating that the rate of CO(2) uptake into solution was outpaced by the rate of carbon fixation within the precipitate. This implies that CO(2) gas uptake is rate-limiting to CO(2) fixation. δ(13)C of carbonate mineral precipitates in mine tailings and of DIC in mine process waters display similar (13)C-depletions that are inconsistent with equilibrium fractionation. Thus, the rate of carbon fixation in mine tailings may also be limited by supply of CO(2). Carbon sequestration could be accelerated by increasing the partial pressure of CO(2) in tailings ponds or by using chemicals that enhance the uptake of gaseous CO(2) into aqueous solution.