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Bicarbonate content of groundwater in carbonate rock in eastern North America

In carbonate-rock terrane the most effective solution occurs where soil and vegetative cover facilitate biogenic production and storage of CO 2 in the soil until part of it is carried downward in percolating water. Bicarbonate data for groundwater in eastern North America are examined in the light of these conditions, of the CO 2 content of soil gas, and of the timing of groundwater recharge relative to seasonal changes in soil temperature. There appears to be no well-marked relation between latitude and bicarbonate content of groundwater in this region. Interplay of all the factors listed above, and of lithology and soil types, is evidently such that under optimum conditions the amount of solution of carbonate rock is roughly comparable, per unit of groundwater recharge, over the region from Ohio to Florida (and, perhaps, to Puerto Rico and Yucatan). Relatively low HCO 3 concentrations observed in much of the southern United States are attributed to low production and storage of CO 2 in sandy soil that is poor in organic matter. On the other hand, concentrations observed in Ontario, New York and Michigan are markedly higher than is to be expected from interrelations of the factors considered. These high values, apparently anomalous, are attributed in part to solution of granular glacial drift derived largely from carbonate rock.

Journal of Hydrology↗

Tertiary carbonate-dissolution cycles on the Sierra Leone Rise, eastern equatorial Atlantic Ocean

Most of the Tertiary section on Sierra Leone Rise off northwest Africa consists of chalk, marl, and limestone that show cyclic alterations of clay-rich and clay-poor beds about 20–60 cm thick. On the basis of biostratigraphic accumulation rates, the cycles in Oligocene and Miocene chalk have periods which average about 44,000 years, and those in Eocene siliceous limestone have periods of 4000–27,000 years. Several sections were sampled in detail to further define the cycles in terms of content of CaCO 3 , clay minerals, and relative abundances of calcareous nannofossils. Extending information gained by analyses of Pleistocene cores from the continental margin of northwest Africa to the Tertiary cycles on Sierra Leone Rise, both dilution by noncarbonate material and dissolution of CaCO 3 could have contributed to the observed relative variations in clay and CaCO 3 . However, dissolution of CaCO 3 as the main cause of the carbonate-clay cycles on the Sierra Leone Rise, rather than dilution by clay, is suggested by the large amount of change (several thousand percent) in terrigenous influx required to produce the observed variations in amount of clay and by the marked increase in abundance of dissolution-resistant discoasters relative to more easily dissolved coccoliths in low-carbonate parts of cycles. The main cause of dissolution of CaCO 3 was shoaling of the carbonate compensation depth (CCD) during the early Neogene and climatically induced fluctuations in the thickness of Antarctic Bottom Water.

Marine Geology↗

Simulated dynamics of carbon stocks driven by changes in land use, management and climate in a tropical moist ecosystem of Ghana

Sub-Saharan Africa is large and diverse with regions of food insecurity and high vulnerability to climate change. This project quantifies carbon stocks and fluxes in the humid forest zone of Ghana, as a part of an assessment in West Africa. The General Ensemble biogeochemical Modeling System (GEMS) was used to simulate the responses of natural and managed systems to projected scenarios of changes in climate, land use and cover, and nitrogen fertilization in the Assin district of Ghana. Model inputs included historical land use and cover data, historical climate records and projected climate changes, and national management inventories. Our results show that deforestation for crop production led to a loss of soil organic carbon (SOC) by 33% from 1900 to 2000. The results also show that the trend of carbon emissions from cropland in the 20th century will continue through the 21st century and will be increased under the projected warming and drying scenarios. Nitrogen (N) fertilization in agricultural systems could offset SOC loss by 6% with 30 kg N ha −1 year −1 and by 11% with 60 kg N ha −1 year −1 . To increase N fertilizer input would be one of the vital adaptive measures to ensure food security and maintain agricultural sustainability through the 21st century.

Agriculture, Ecosystems and Environment↗

Tracing groundwater with low-level detections of halogenated VOCs in a fractured carbonate-rock aquifer, Leetown Science Center, West Virginia, USA

Measurements of low-level concentrations of halogenated volatile organic compounds (VOCs) and estimates of groundwater age interpreted from 3 H/ 3 He and SF 6 data have led to an improved understanding of groundwater flow, water sources, and transit times in a karstic, fractured, carbonate-rock aquifer at the Leetown Science Center (LSC), West Virginia. The sum of the concentrations of a set of 16 predominant halogenated VOCs (TDVOC) determined by gas chromatography with electron-capture detector (GC–ECD) exceeded that possible for air–water equilibrium in 34 of the 47 samples (median TDVOC of 24,800 pg kg −1 ), indicating that nearly all the water sampled in the vicinity of the LSC has been affected by addition of halogenated VOCs from non-atmospheric source(s). Leakage from a landfill that was closed and sealed nearly 20 a prior to sampling was recognized and traced to areas east of the LSC using low-level detection of tetrachloroethene (PCE), methyl chloride (MeCl), methyl chloroform (MC), dichlorodifluoromethane (CFC-12), and cis-1,2-dichloroethene (cis-1,2-DCE). Chloroform (CHLF) was the predominant VOC in water from domestic wells surrounding the LSC, and was elevated in groundwater in and near the Fish Health Laboratory at the LSC, where a leak of chlorinated water occurred prior to 2006. The low-level concentrations of halogenated VOCs did not exceed human or aquatic-life health criteria, and were useful in providing an awareness of the intrinsic susceptibility of the fractured karstic groundwater system at the LSC to non-atmospheric anthropogenic inputs. The 3 H/ 3 He groundwater ages of spring discharge from the carbonate rocks showed transient behavior, with ages averaging about 2 a in 2004 following a wet climatic period (2003–2004), and ages in the range of 4–7 a in periods of more average precipitation (2008–2009). The SF 6 and CFC-12 data indicate older water (model ages of 10s of years or more) in the low-permeability shale of the Martinsburg Formation located to the west of the LSC. A two-a record of specific conductance, water temperature, and discharge recorded at 30-min intervals demonstrated an approximately 3-month lag in discharge at Gray Spring. The low groundwater ages of waters from the carbonate rocks support rapid advective transport of contaminants from the LSC vicinity, yet the nearly ubiquitous occurrence of low-level concentrations of halogenated VOCs at the LSC suggests the presence of long-term persistent sources, such as seepage from the closed and sealed landfill, infiltration of VOCs that may persist locally in the epikarst, exchange with low-permeability zones in fractured rock, and upward leakage of older water that may contain elevated concentrations of halogenated VOCs from earlier land use activities.

West Virginia↗

A land-use and land-cover modeling strategy to support a national assessment of carbon stocks and fluxes

Changes in land use, land cover, disturbance regimes, and land management have considerable influence on carbon and greenhouse gas (GHG) fluxes within ecosystems. Through targeted land-use and land-management activities, ecosystems can be managed to enhance carbon sequestration and mitigate fluxes of other GHGs. National-scale, comprehensive analyses of carbon sequestration potential by ecosystem are needed, with a consistent, nationally applicable land-use and land-cover (LULC) modeling framework a key component of such analyses. The U.S. Geological Survey has initiated a project to analyze current and projected future GHG fluxes by ecosystem and quantify potential mitigation strategies. We have developed a unique LULC modeling framework to support this work. Downscaled scenarios consistent with IPCC Special Report on Emissions Scenarios (SRES) were constructed for U.S. ecoregions, and the FORE-SCE model was used to spatially map the scenarios. Results for a prototype demonstrate our ability to model LULC change and inform a biogeochemical modeling framework for analysis of subsequent GHG fluxes. The methodology was then successfully used to model LULC change for four IPCC SRES scenarios for an ecoregion in the Great Plains. The scenario-based LULC projections are now being used to analyze potential GHG impacts of LULC change across the U.S.

Applied Geography↗

Feasibility of measuring dissolved carbon dioxide based on head space partial pressures

We describe an instrument prototype that measures dissolved carbon dioxide (DC) without need for standard wetted probe membranes or titration. DC is calculated using Henry's Law, water temperature, and the steady-state partial pressure of carbon dioxide that develops within the instrument's vertical gas-liquid contacting chamber. Gas-phase partial pressures were determined with either an infrared detector (ID) or by measuring voltage developed by a pH electrode immersed in an isolated sodium carbonate solution (SC) sparged with recirculated head space gas. Calculated DC concentrations were compared with those obtained by titration over a range of DC (2, 4, 8, 12, 16, 20, 24, and 28mg/l), total alkalinity (35, 120, and 250mg/l as CaCO3), total dissolved gas pressure (-178 to 120 mmHg), and dissolved oxygen concentrations (7, 14, and 18 mg/l). Statistically significant (P < 0.001) correlations were established between head space (ID) and titrimetrically determined DC concentrations (R2 = 0.987-0.999, N = 96). Millivolt and titrimetric values from the SC solution tests were also correlated (P < 0.001, R 2 = 0.997, N = 16). The absolute and relative error associated with the use of the ID and SC solution averaged 0.9mg/l DC and 7.0% and 0.6 mg/l DC and 9.6%, respectively. The precision of DC estimates established in a second test series was good; coefficients of variation (100(SD/mean)) for the head space (ID) and titration analyses were 0.99% and 1.7%. Precision of the SC solution method was 1.3%. In a third test series, a single ID was coupled with four replicate head space units so as to permit sequential monitoring (15 min intervals) of a common water source. Here, appropriate gas samples were secured using a series of solenoid valves (1.6 mm bore) activated by a time-based controller. This system configuration reduced the capital cost per sample site from US$ 2695 to 876. Absolute error averaged 2.9, 3.1, 3.7, and 2.7 mg/ l for replicates 1-4 (N = 36) during a 21-day test period (DC range, 36-40 mg/l). The ID meter was then modified so as to provide for DO as well as DC measurements across components of an intensive fish production system. ?? 2003 Elsevier B.V. All rights reserved.

Aquacultural Engineering↗

Microbial methane from in situ biodegradation of coal and shale: A review and reevaluation of hydrogen and carbon isotope signatures

Stable carbon and hydrogen isotope signatures of methane, water, and inorganic carbon are widely utilized in natural gas systems for distinguishing microbial and thermogenic methane and for delineating methanogenic pathways (acetoclastic, hydrogenotrophic, and/or methylotrophic methanogenesis). Recent studies of coal and shale gas systems have characterized in situ microbial communities and provided stable isotope data (δD-CH 4 , δD-H 2 O, δ 13 C-CH 4 , and δ 13 C-CO 2 ) from a wider range of environments than available previously. Here we review the principal biogenic methane-yielding pathways in coal beds and shales and the isotope effects imparted on methane, document the uncertainties and inconsistencies in established isotopic fingerprinting techniques, and identify the knowledge gaps in understanding the subsurface processes that govern H and C isotope signatures of biogenic methane. We also compare established isotopic interpretations with recent microbial community characterization techniques, which reveal additional inconsistencies in the interpretation of microbial metabolic pathways in coal beds and shales. Collectively, the re-assessed data show that widely-utilized isotopic fingerprinting techniques neglect important complications in coal beds and shales. Isotopic fingerprinting techniques that combine δ 13 C-CH 4 with δD-CH 4 and/or δ 13 C-CO 2 have significant limitations: (1) The consistent ~ 160‰ offset between δD-H 2 O and δD-CH 4 could imply that hydrogenotrophic methanogenesis is the dominant metabolic pathway in microbial gas systems. However, hydrogen isotopes can equilibrate between methane precursors and coexisting water, yielding a similar apparent H isotope signal as hydrogenotrophic methanogenesis, regardless of the actual methane formation pathway. (2) Non-methanogenic processes such as sulfate reduction, Fe oxide reduction, inputs of thermogenic methane, anaerobic methane oxidation, and/or formation water interaction can cause the apparent carbon isotope fractionation between δ 13 C-CH 4 and δ 13 C-CO 2 (α 13 C CO2-CH4 ) to differ from the true methanogenic fractionation, complicating interpretation of methanogenic pathways. (3) Where little-fractionating non-methanogenic bacterial processes compete with highly-fractionating methanogenesis, the mass balance between CH 4 and CO 2 is affected. This has implications for δ 13 C values and provides an alternative interpretation for net C isotope signatures than solely the pathways used by active methanogens. (4) While most of the reviewed values of δD-H 2 O - δD-CH 4 and α 13 C CO2-CH4 are apparently consistent with hydrogenotrophic methanogenesis as the dominant pathway in coal beds and shales, recent microbial community characterization techniques suggest a possible role for acetoclastic or methylotrophic methanogenesis in some basins.

Chemical Geology↗

The carbon budget of the northern cryosphere region

The northern cryosphere is undergoing substantial warming of permafrost and loss of sea ice. Release of stored carbon to the atmosphere in response to this change has the potential to affect the global climate system. Studies indicate that the northern cryosphere has been not only a substantial sink for atmospheric CO 2 in recent decades, but also an important source of CH 4 because of emissions from wetlands and lakes. Analyses suggest that the sensitivity of the carbon cycle of the region over the 21st Century is potentially large, but highly uncertain because numerous pathways of response will be affected by warming. Further research should focus on sensitive elements of the carbon cycle such as the consequences of increased fire disturbance, permafrost degradation, and sea ice loss in the northern cryosphere region.

Current Opinion in Environmental Sustainability↗

A review of single-sample-based models and other approaches for radiocarbon dating of dissolved inorganic carbon in groundwater

Numerous methods have been proposed to estimate the pre-nuclear-detonation 14 C content of dissolved inorganic carbon (DIC) recharged to groundwater that has been corrected/adjusted for geochemical processes in the absence of radioactive decay ( 14 C 0 ) - a quantity that is essential for estimation of radiocarbon age of DIC in groundwater. The models/approaches most commonly used are grouped as follows: (1) single-sample-based models, (2) a statistical approach based on the observed (curved) relationship between 14 C and δ 13 C data for the aquifer, and (3) the geochemical mass-balance approach that constructs adjustment models accounting for all the geochemical reactions known to occur along a groundwater flow path. This review discusses first the geochemical processes behind each of the single-sample-based models, followed by discussions of the statistical approach and the geochemical mass-balance approach. Finally, the applications, advantages and limitations of the three groups of models/approaches are discussed. The single-sample-based models constitute the prevailing use of 14 C data in hydrogeology and hydrological studies. This is in part because the models are applied to an individual water sample to estimate the 14 C age, therefore the measurement data are easily available. These models have been shown to provide realistic radiocarbon ages in many studies. However, they usually are limited to simple carbonate aquifers and selection of model may have significant effects on 14 C 0 often resulting in a wide range of estimates of 14 C ages. Of the single-sample-based models, four are recommended for the estimation of 14 C 0 of DIC in groundwater: Pearson's model, (Ingerson and Pearson, 1964; Pearson and White, 1967), Han & Plummer's model (Han and Plummer, 2013), the IAEA model (Gonfiantini, 1972; Salem et al., 1980), and Oeschger's model (Geyh, 2000). These four models include all processes considered in single-sample-based models, and can be used in different ranges of 13 C values. In contrast to the single-sample-based models, the extended Gonfiantini & Zuppi model (Gonfiantini and Zuppi, 2003; Han et al., 2014) is a statistical approach. This approach can be used to estimate 14 C ages when a curved relationship between the 14 C and 13 C values of the DIC data is observed. In addition to estimation of groundwater ages, the relationship between 14 C and δ 13 C data can be used to interpret hydrogeological characteristics of the aquifer, e.g. estimating apparent rates of geochemical reactions and revealing the complexity of the geochemical environment, and identify samples that are not affected by the same set of reactions/processes as the rest of the dataset. The investigated water samples may have a wide range of ages, and for waters with very low values of 14 C, the model based on statistics may give more reliable age estimates than those obtained from single-sample-based models. In the extended Gonfiantini & Zuppi model, a representative system-wide value of the initial 14 C content is derived from the 14 C and δ 13 C data of DIC and can differ from that used in single-sample-based models. Therefore, the extended Gonfiantini & Zuppi model usually avoids the effect of modern water components which might retain ‘bomb’ pulse signatures. The geochemical mass-balance approach constructs an adjustment model that accounts for all the geochemical reactions known to occur along an aquifer flow path (Plummer et al., 1983; Wigley et al., 1978; Plummer et al., 1994; Plummer and Glynn, 2013), and includes, in addition to DIC, dissolved organic carbon (DOC) and methane (CH 4 ). If sufficient chemical, mineralogical and isotopic data are available, the geochemical mass-balance method can yield the most accurate estimates of the adjusted radiocarbon age. The main limitation of this approach is that complete information is necessary on chemical, mineralogical and isotopic data and these data are often limited. Failure to recognize the limitations and underlying assumptions on which the various models and approaches are based can result in a wide range of estimates of 14 C 0 and limit the usefulness of radiocarbon as a dating tool for groundwater. In each of the three generalized approaches (single-sample-based models, statistical approach, and geochemical mass-balance approach), successful application depends on scrutiny of the isotopic ( 14 C and 13 C) and chemical data to conceptualize the reactions and processes that affect the 14 C content of DIC in aquifers. The recently developed graphical analysis method is shown to aid in determining which approach is most appropriate for the isotopic and chemical data from a groundwater system.

Earth-Science Reviews↗

Salt marsh ecosystem restructuring enhances elevation resilience and carbon storage during accelerating relative sea-level rise

Salt marshes respond to sea-level rise through a series of complex and dynamic bio-physical feedbacks. In this study, we found that sea-level rise triggered salt marsh habitat restructuring, with the associated vegetation changes enhancing salt marsh elevation resilience. A continuous record of marsh elevation relative to sea level that includes reconstruction of high-resolution, sub-decadal, marsh elevation over the past century, coupled with a lower-resolution 1500-year record, revealed that relative sea-level rose 1.5 ± 0.4 m, following local glacial isostatic adjustment (1.2 mm/yr). As sea-level rise has rapidly accelerated, the high marsh zone dropped 11 cm within the tidal frame since 1932, leading to greater inundation and a shift to flood- and salt-tolerant low marsh species. Once the marsh platform fell to the elevation favored by low-marsh Spartina alterniflora , the elevation stabilized relative to sea level. Currently low marsh accretion keeps pace with sea-level rise, while present day high marsh zones that have not transitioned to low marsh have a vertical accretion deficit. Greater biomass productivity, and an expanding subsurface accommodation space favorable for salt marsh organic matter preservation, provide a positive feed-back between sea-level rise and marsh platform elevation. Carbon storage was 46 ± 28 g C/m 2 /yr from 550 to 1800 CE, increasing to 129 ± 50 g C/m 2 /yr in the last decade. Enhanced carbon storage is controlled by vertical accretion rates, rather than soil carbon density, and is a direct response to anthropogenic eustatic sea-level rise, ultimately providing a negative feedback on climate warming.

Massachusetts↗

Road-testing the outreach best practices manual: Applicability for implementation of the development phase projects by the regional carbon sequestration partnerships

Geologic carbon dioxide (CO 2 ) storage verification tests by the U.S. Department of Energy’s (DOE’s) seven Regional Carbon Sequestration Partnerships (RCSPs) provided the experience base for the Public Outreach and Education for Carbon Storage Projects, a best practices manual, published in December 2009. This paper summarizes these outreach best practices; discusses their application in Aquistore, a greenfield CO 2 storage project under way in western Canada; and reviews the implications for applying the best practices to new projects during the Development Phase of the DOE’s RCSP Program.

Energy Procedia↗

Reactive-transport modeling of iron diagenesis and associated organic carbon remineralization in a Florida (USA) subterranean estuary

Iron oxides are important terminal electron acceptors for organic carbon (OC) remineralization in subterranean estuaries, particularly where oxygen and nitrate concentrations are low. In Indian River Lagoon, Florida, USA, terrestrial Fe-oxides dissolve at the seaward edge of the seepage face and flow upward into overlying marine sediments where they precipitate as Fe-sulfides. The dissolved Fe concentrations vary by over three orders of magnitude, but Fe-oxide dissolution rates are similar across the 25-m wide seepage face, averaging around 0.21 mg/cm 2 /yr. The constant dissolution rate, but differing concentrations, indicate Fe dissolution is controlled by a combination of increasing lability of dissolved organic carbon (DOC) and slower porewater flow velocities with distance offshore. In contrast, the average rate constants of Fe-sulfide precipitation decrease from 21.9 × 10 − 8 s − 1 to 0.64 × 10 − 8 s − 1 from the shoreline to the seaward edge of the seepage face as more oxygenated surface water circulates through the sediment. The amount of OC remineralized by Fe-oxides varies little across the seepage face, averaging 5.34 × 10 − 2 mg/cm 2 /yr. These rates suggest about 3.4 kg of marine DOC was remineralized in a 1-m wide, shore-perpendicular strip of the seepage face as the terrestrial sediments were transgressed over the past 280 years. During this time, about 10 times more marine solid organic carbon (SOC) accumulated in marine sediments than were removed from the underlying terrestrial sediments. Indian River Lagoon thus appears to be a net sink for marine OC.

Florida↗

Deep root activity overprints weathering of petrogenic organic carbon in shale

The oxidation of organic carbon in sedimentary bedrock (petrogenic OC, OC p e t r o "> petro ) is increasingly recognized as a potential source of CO 2 to the atmosphere. Recent studies provide evidence for the mobilization and oxidation of OC p e t r o "> petro in sedimentary bedrock during rock weathering. However, the mechanisms and rates remain uncertain, particularly where overlying soils and vegetation drive contemporaneous oxidation of recently fixed organic carbon. Here, we quantify OC p e t r o "> petro weathering across a 16 m shale depth profile in a steep, rapidly eroding forested hillslope in the Northern California Coast Ranges. We report solid and gas phase radiocarbon and stable isotope analyses of samples extracted from specialized in-situ samplers, and a supporting laboratory incubation experiment of the shale regolith. OC p e t r o "> petro is removed from the weathered bedrock at a rate of approximately 0.12 gC/m 3 yr, which is orders of magnitude lower than the rate of OC p e t r o "> petro oxidation we achieved in the laboratory with crushed samples (557.1 gC/m 3 /yr). This disparity occurs despite high O 2 ( g ) "> 2(g) content across the depth profile, indicating that physical accessibility of OC p e t r o "> petro can regulate oxidative weathering. There is no direct radiocarbon evidence of OC p e t r o "> petro oxidation in CO 2 ( g ) "> 2(g) across the upper 13 m of the weathering profile during both wet and dry seasons. Instead, vadose zone CO 2 ( g ) "> 2(g) production at the site is dominated by respiration of recently fixed carbon associated with deep rooting. OC p e t r o "> petro is clearly mobilized across the vadose zone during weathering in this rapidly eroding, oxygen-rich, biologically dynamic hillslope, but at rates far below what can be measured given the contribution of root-derived CO 2 ( g ) "> 2(g) .

California↗

Ion microprobe measurement of strontium isotopes in calcium carbonate with application to salmon otoliths

The ion microprobe has the capability to generate high resolution, high precision isotopic measurements, but analysis of the isotopic composition of strontium, as measured by the 87 Sr/ 86 Sr ratio, has been hindered by isobaric interferences. Here we report the first high precision measurements of 87 Sr/ 86 Sr by ion microprobe in calcium carbonate samples with moderate Sr concentrations. We use the high mass resolving power (7000 to 9000 M.R.P.) of the SHRIMP-RG ion microprobe in combination with its high transmission to reduce the number of interfering species while maintaining sufficiently high count rates for precise isotopic measurements. The isobaric interferences are characterized by peak modeling and repeated analyses of standards. We demonstrate that by sample-standard bracketing, 87 Sr/ 86 Sr ratios can be measured in inorganic and biogenic carbonates with Sr concentrations between 400 and 1500 ppm with ∼2‰ external precision (2σ) for a single analysis, and subpermil external precision with repeated analyses. Explicit correction for isobaric interferences (peak-stripping) is found to be less accurate and precise than sample-standard bracketing. Spatial resolution is ∼25 μm laterally and 2 μm deep for a single analysis, consuming on the order of 2 ng of material. The method is tested on otoliths from salmon to demonstrate its accuracy and utility. In these growth-banded aragonitic structures, one-week temporal resolution can be achieved. The analytical method should be applicable to other calcium carbonate samples with similar Sr concentrations.

Geochimica et Cosmochimica Acta↗

Landscape scale controls on the vascular plant component of dissolved organic carbon across a freshwater delta

Lignin phenol concentrations and compositions were determined on dissolved organic carbon (DOC) extracts (XAD resins) within the Sacramento-San Joaquin River Delta (the Delta), the tidal freshwater portion of the San Francisco Bay Estuary, located in central California, USA. Fourteen stations were sampled, including the following habitats and land-use types: wetland, riverine, channelized waterway, open water, and island drains. Stations were sampled approximately seasonally from December, 1999 through May, 2001. DOC concentrations ranged from 1.3 mg L -1 within the Sacramento River to 39.9 mg L -1 at the outfall from an island drain (median 3.0 mg L -1 ), while lignin concentrations ranged from 3.0 &mu;L -1 within the Sacramento River to 111 &mu;L -1 at the outfall from an island drain (median 11.6 &mu;L -1 ). Both DOC and lignin concentrations varied significantly among habitat/land-use types and among sampling stations. Carbon-normalized lignin yields ranged from 0.07 mg (100 mg OC) -1 at an island drain to 0.84 mg (100 mg OC) -1 for a wetland (median 0.36 mg (100 mg OC) -1 ), and also varied significantly among habitat/land-use types. A simple mass balance model indicated that the Delta acted as a source of lignin during late autumn through spring (10-83% increase) and a sink for lignin during summer and autumn (13-39% decrease). Endmember mixing models using S:V and C:V signatures of landscape scale features indicated strong temporal variation in sources of DOC export from the Delta, with riverine source signatures responsible for 50% of DOC in summer and winter, wetland signatures responsible for 40% of DOC in summer, winter, and late autumn, and island drains responsible for 40% of exported DOC in late autumn. A significant negative correlation was observed between carbon-normalized lignin yields and DOC bioavailability in two of the 14 sampling stations. This study is, to our knowledge, the first to describe organic vascular plant DOC sources at the level of localized landscape features, and is also the first to indicate a significant negative correlation between lignin and DOC bioavailability within environmental samples. Based upon observed trends: (1) Delta features exhibit significant spatial variability in organic chemical composition, and (2) localized Delta features appear to exert strong controls on terrigenous DOC as it passes through the Delta and is exported into the Pacific Ocean.

California↗

A sequential selective dissolution method to quantify storage and stability of organic carbon associated with Al and Fe hydroxide phases

Stabilization of SOM (soil organic matter) is regulated in part by sorption and desorption reactions happening at mineral surfaces, as well as precipitation and dissolution of organo-metal complexes. Fe and Al hydroxides play a particularly significant role in SOM stabilization in soils due to their ubiquitous distribution and their highly reactive surface properties. Iron and Al hydroxides exist in soils across a wide spectrum of crystallinity, ranging from dissolved Fe and Al cations which combine with organics to form organo-metal precipitates to the more crystalline end members, goethite and gibbsite, which sorb SOM through a variety of molecular interactions. Though the importance of these sorption and precipitation reactions has long been recognized, the distribution of SOM among Fe and Al hydroxides of differing crystallinity has not been well quantified, nor has the timescale over which these stabilization mechanisms operate. In an attempt to measure the distribution of organic C among (i) Al- and Fe-humus complexes (ii) short-range-order (SRO) Al and Fe hydroxide surfaces and (iii) crystalline Fe oxyhydroxide surfaces, a single method combining several selective mineral dissolutions was applied to soils of four different geneses (a tropical forest Andisol, a temperate forest basaltic Mollisol, a Mediterranean coastal prairie Mollisol, and a northern mixed hardwood forest Spodosol). The traditional reactants used in selective dissolutions were replaced with carbon-free analogues so that the carbon released along with the Fe and Al at each stage of the selective dissolution process could be measured. Selective dissolutions were performed sequentially: Na-pyrophosphate (organo-Al and Fe complexes) followed by hydroxylamine (SRO Al and Fe hydroxides) followed by dithionite-HCl (crystalline Fe hydroxides). Carbon, Al, and Fe concentrations, as well as radiocarbon abundance were measured in the solutions yielded by each stage of the selective dissolution process. Results suggest that precipitation of organo-metal complexes (Na-pyrophosphate extractable C) often accounts for the largest pool of stabilized C among the three selectively dissolved pools, but these complexes were 14 C enriched in comparison to C from the other selectively dissolved pools and the residual C left on crystalline mineral surfaces after all three stages of selective dissolution. Hydroxylamine and dithionite-HCl extractable C pools were, on average, small and often below detection level in temperate soils. However, radiocarbon values for these C pools were generally depleted in comparison to other pools. These results suggest variation in organo-mineral complex stability is associated with degree of crystallinity of the mineral phase. Overall, this work suggests that sequential selective dissolution methods are a promising tool for characterizing the content and isotopic composition of soil C associated with distinct organo-mineral and organo-metal associations.

Geoderma↗

Impacts of land use and climate change on carbon dynamics in south-central Senegal

Total carbon stock in vegetation and soils was reduced 37% in south-central Senegal from 1900 to 2000. The decreasing trend will continue during the 21st century unless forest clearing is stopped, selective logging dramatically reduced, and climate change, if any, relatively small. Developing a sustainable fuelwood and charcoal production system could be the most feasible and significant carbon sequestration project in the region. If future climate changes dramatically as some models have predicted, cropland productivity will drop more than 65% around 2100, posing a serious threat to food security and the efficiency of carbon sequestration projects.

Journal of Arid Environments↗

Refining PAH and PCB bioavailability predictions in industrial sediments using source-fingerprinting, particle size, and bulk carbon, Puget Sound, Washington

Nearshore marine sediments in a Puget Sound, Washington industrial embayment had elevated levels of PAHs, PCBs and DDTs. Chemical fingerprints implicated nearshore sources including creosote, industrial oil and tar waste, and a landfill. Elevated concentrations were confined to an approximate 300-m shoreline buffer in the industrial waterfront, suggesting high site fidelity and limited along-shore or off-shore transport. Total PAH concentrations approximately doubled when including alkylated compounds. The industrial sediments often exceeded toxicity criteria; however, chemicals were likely less bioavailable than predicted, in part, due to assumed strong sorption to anthropogenic carbon like coal tar. Analyses of separated particle-size fractions showed that approximately half of PAHs were associated with particles greater than 500 μm, suggesting that a wide range of particle sizes are relevant to occurrence and transport. Predicted freely dissolved chemical concentrations in sediment pore water were unrealistically high using a bulk organic carbon sorption coefficient. When reduced to environmentally reasonable levels by applying a high-sorption partition coefficient applicable to contaminated sediments, predicted freely dissolved concentrations in some industrial sediments exceeded sublethal effect levels or surface water quality standards. Chemical assemblages predicted in the freely dissolved aqueous fraction, which is relevant for biotic uptake from water, shifted to predominantly low molecular weight as compared to sediment, highlighting the role of exposure pathways in bioavailability. Insights from chemical fingerprinting coupled with co-analysis of bulk carbon and grain size allowed refinement of bioavailability assessments of complex chemical mixtures in contaminated nearshore environments that are relevant for ecosystem health and restoration.

Washington↗