Black carbon in soils from different land use areas of Shanghai,China: Level,sources and relationship with polycyclic aromatic hydrocarbons

Black carbon (BC) in soils plays a key role of carrying hydrophobic pollutants like polycyclic aromatic hydrocarbons (PAHs). However, little is known about the spatial distribution, sources of BC and its relationship with PAHs in urban soils. We studied BC, total organic carbon (TOC) and PAHs concurrently in 77 soils collected from downtown area, suburban and rural area and industrial area of Shanghai, China. BC was determined by both chemical oxidation (dichromate oxidation, BC_Cr) and chemo-thermal oxidation (CTO-375, BC_CTO). BC sources were identified qualitatively by BC/TOC concentration ratios and BC-cogenerated high molecular weight (HMW) PAH isomer ratios and quantitatively by principal component analysis followed by multiple linear regression (PCA-MLR). Results showed that BC_Cr concentration (4.65 g/kg on average) was significantly higher than BC_CTO (1.91 g/kg on average) in Shanghai soils. BC_Cr concentrations in industrial area were significantly higher than those in other two. Stronger correlation was found between PAHs and TOC, BC_Cr than that between PAHs and BC_CTO, which indicates the possibility of PAHs being carried by charcoal and other organic matters thus negating its exclusive dependence on soot. Charcoal was therefore suggested to be taken into account in studies of BC and its sorption of PAHs. BC/TOC ratios showed a mixed source of biomass burning and fossil fuel combustion. PCA scores of BC-cogenerated HMW PAHs isomer ratios in potential sources and soil samples clearly demonstrated that sources of BC in urban soils may fall into two categories: coal and biomass combustion, and traffic (oil combustion and tire wear). PCA-MLR of HMW PAHs concentrations in soil samples indicated that coal and oil combustion had the largest contribution to BC in urban soils while tire wear and biomass combustion were important in downtown and rural area, respectively, which indicated they were main sources of HMW PAHs and presumably of BC.     

Stable isotopic signatures of the modern land snail Eremina desertorum from a low-latitude (hot) dry desert—A study from the Petrified Forest,New Cairo,Egypt

This study was conducted on recent desert samples—including (1) soils, (2) plants, (3) the shell, and (4) organic matter from modern specimens of the land snail Eremina desertorum—which were collected at several altitudes (316–360 m above sea level) from a site in the New Cairo Petrified Forest. The soils and shell_{E. desertorum} were analyzed for carbonate composition and isotopic composition (δ¹⁸O, δ¹³C). The plants and organic matter_{E. desertorum} were analyzed for organic carbon content and δ¹³C. The soil carbonate, consisting of calcite plus minor dolomite, has δ¹⁸O values from −3.19 to −1.78‰ and δ¹³C values −1.79 to −0.27‰; covariance between the two values accords with arid climatic conditions. The local plants include C3 and C4 types, with the latter being dominant. Each type has distinctive bulk organic carbon δ¹³C values: −26.51 to −25.36‰ for C3-type, and −13.74 to −12.43‰ for C4-type plants.The carbonate of the shell_{E. desertorum} is composed of aragonite plus minor calcite, with relatively homogenous isotopic compositions (δ¹⁸O_mean = −0.28 ± 0.22‰; δ¹³C_mean = −4.46 ± 0.58‰). Most of the δ¹⁸O values (based on a model for oxygen isotope fractionation in an aragonite-water system) are consistent with evaporated water signatures. The organic matter_{E. desertorum} varies only slightly in bulk organic carbon δ¹³C values (−21.78 ± 1.20‰) and these values suggest that the snail consumed more of C3-type than C4-type plants. The overall offset in δ¹³C values (−17.32‰) observed between shell_{E. desertorum} carbonate and organic matter_{E. desertorum} exceeds the value expected for vegetation input, and implies that 30% of carbon in the shell_{E. desertorum} carbonate comes from the consumption of limestone material.     

Sr and Nd isotopes as tracers in pedogenic studies: Evidence for Saharan dust contribution to the soils of Muravera (Sardinia,Italy)

Sr and Nd isotopes were applied to 5 soil profiles from the Muravera area, in south-eastern Sardinia.All the soils, which have developed during the Quaternary on the Lower Paleozoic metamorphic basement except for one on Eocene carbonates, are located far from major sources of pollution. Therefore, they are suitable for testing pedogenic processes and geochemical evolution to benefit for environmental studies.The Sr isotopic ratios range largely (δ⁸⁷Sr = 1.7–65.9‰), even in each soil profile. In particular, the observed increase of δ⁸⁷Sr with depth in the most of the metamorphic rock-based soils can be accounted for by the downward decrease of Sr contributions from organic matter and Saharan dust, both displaying lower isotopic ratios than the soil bedrocks. The carbonate rock-based soil exhibits δ⁸⁷Sr higher (1.7–18.1‰) than the bedrock, indicating a significant contribution of radiogenic Sr from the siliciclastic fraction of the soil, and probably from dust input. The Nd isotopic ratios are slightly variable through the profiles (ɛ_Nd from −7.8 to −14.5), confirming little mobility of Nd and Sm during the pedogenesis. Among the minerals present in the soils, phosphates, albite, and calcite are those important in providing low radiogenic Sr and Nd to organic matter of the soils.Lastly, this isotopic study has in particular allowed for evaluating the potential proportion of contribution of Saharan dust to south-eastern Sardinia, thus corroborating the findings of other studies related to soils from the central-western Mediterranean.     

Stable carbon isotope geochemistry of adsorbed alkane gases in near-surface soils of the Saurashtra Basin,India

The stable carbon isotopic compositions of light hydrocarbon gases adsorbed in near-surface soil and sediments from the Saurashtra basin were characterized for their origin and maturity. Saurashtra is considered geologically prospective for oil and gas reserves; however, a major part of the basin is covered by the Deccan Traps, hindering the exploration of Mesozoic hydrocarbon targets. Surface geochemical prospecting, based on micro-seepage of hydrocarbons from subsurface accumulations, could be advantageous in such areas. In light of this, 150 soil samples were collected from the northwestern part of Saurashtra, around the Jamnagar area, where a thick sedimentary sequence of about 2–3 km exists under 1–1.5 km of Deccan basalt. The concentration of acid desorbed alkane gases from soil samples was found to vary (in ppb) as: methane (C₁) = 3–518; ethane (C₂) = 0–430; propane (C₃) = 0–331; i-butane (iC₄) = 0–297; n-butane (nC₄) = 2–116; i-pentane (iC₅) = 0–31 and n-pentane (nC₅) = 0–23, respectively.Fifteen samples with high concentrations of alkane gases were measured for their δ¹³C₁; δ¹³C₂ and δ¹³C₃ compositions using gas chromatography–combustion-isotope ratio mass spectrometry (GC–C-IRMS). The values for methane varied from ? 27 to ? 45.4‰, ethane from ? 20.9 to ? 27.6‰, and propane from ? 20.4 to ? 29.1‰ versus the Vienna PeeDee Belemnite (VPDB). The carbon isotope ratio distribution pattern represents isotopic characteristics pertaining to hydrocarbon gases derived from thermogenic sources. Comparisons of carbon isotopic signatures and compositional variations with the standard carbon isotopic models suggest that hydrocarbon gases found in the shallow depths of the study area are not of bacterial origin but are formed thermally from deeply buried organic matter, likely to be mainly a terrestrial source rock with a partial contribution from a marine source. These gases may have migrated to the near-surface environment, where they represent an admixture of thermally generated hydrocarbon gases from mixed sources and maturity. The maturity scale (δ¹³C versus Log Ro %) applied to the surface sediment samples of the Jamnagar area indicated the source material to be capable of generating oil and gas. The detection of thermogenic alkane gases in near-surface sediments offers the possibility of hydrocarbons at depth in Saurashtra.     

Altitudinal shift in stable hydrogen isotopes and microbial tetraether distribution in soils from the Southern Alps,NZ: Implications for paleoclimatology and paleoaltimetry

The Southern Alps are an ideal locality for studying patterns of isotopic fractionation associated with orographic precipitation. We have evaluated whether altitudinal change is reflected in the stable hydrogen isotopic composition (δ²H) of stream water, plant stem water and leaf wax lipids (n-alkanes) from living plants and soils, as well as in soil temperature. Samples were collected along an altitudinal transect from the windward side of the Southern Alps to Lake Hawea in the rain shadow. The results indicate that δ²H values of stem water overlap with stream water, demonstrating a gradual decrease with elevation that complied with modeled Rayleigh distillation, reflecting an isotopic lapse rate of −18.0 (± 1.1, 1σ)‰/km. Leaf and soil n-alkanes shared similar δ²H values and were ²H depleted relative to stem/stream waters. The values for soil n-alkanes indicated an isotopic lapse rate of −21.8 (± 2.0, 1σ)‰/km, consistent with precipitation data and long term observations. MBT/CBT derived soil temperature values based on the relative distribution of microbial tetraether lipids were similar to midsummer temperature observations, displaying an elevational decrease rate of −5.6 (± 1.5, 1σ) °C/km, consistent with regional and global observations.The results indicate that sedimentary lipid δ²H and microbial tetraether temperature estimates captured altitudinal trends in the isotopic composition of precipitation and mean temperature and further support their application in the reconstruction of past climate and surface uplift histories. However, notable differences in isotopic composition and temperature estimates between in situ soils and those with downslope transport of material emphasize the importance of facies analysis when interpreting past systems.     

Comparison of dissolved inorganic and organic carbon yields and fluxes in the watersheds of tropical volcanic islands,examples from Guadeloupe (French West Indies)

Organic matter is an important factor that cannot be neglected when considering global carbon cycle. New data including organic matter geochemistry at the small watershed scale are needed to elaborate more constrained carbon cycle and climatic models. The objectives are to estimate the DOC and DIC yields exported from small tropical watersheds and to give strong constraints on the carbon hydrodynamic of these systems. To answer these questions, we have studied the geochemistry of eleven small watersheds around Basse-Terre volcanic Island in the French West Indies during different hydrological regimes from 2006 to 2008 (i.e. low water level versus floods). We propose a complete set of carbon measurements, including DOC and DIC concentrations, δ¹³C data, and less commonly, some spectroscopic indicators of the nature of organic matter. The DOC/DIC ratio varies between 0.07 and 0.30 in low water level and between 0.25 and 1.97 during floods, indicating that organic matter is mainly exported during flood events. On the light of the isotopic composition of DOC, ranging from ? 32.8 to ? 26.2‰ during low water level and from ? 30.1 to ? 27.2‰ during floods, we demonstrate that export of organic carbon is mainly controlled by perennial saprolite groundwaters, except for flood events during which rivers are also strongly influenced by soil erosion. The mean annual yields ranged from 2.5 to 5.7 t km^? 2 year^? 1 for the DOC and from 4.8 to 19.6 t km^? 2 year^? 1 for the DIC and exhibit a non-linear relationship with slopes of watersheds. The flash floods explain around 60% of the annual DOC flux and between 25 and 45% of the DIC flux, highlighting the important role of these extreme meteorological events on global carbon export in small tropical volcanic islands. From a carbon mass balance point of view the exports of dissolved carbon from small volcanic islands are important and should be included in global organic carbon budgets.     

Terrestrial stable isotope records of Late Quaternary paleoclimates in the eastern Mediterranean region

Terrestrial stable isotope records (¹³C/¹²C, ¹⁸O/¹⁶O, and D/H ratios) of late Quaternary paleoclimates in the eastern Mediterranean region are reviewed. Significant paleoclimatic reconstructions come from a variety of isotopic studies. Paleogroundwaters, although they cannot be accurately dated, show oxygen and hydrogen isotopic compositions highly depleted in heavier isotopes compared to modern meteoric waters in arid regions of southern Israel, Sinai and northeastern Africa and attest to a major difference in climatic regime some time in the Pleistocene. Th-U dating of land snails showing a similar ¹⁸O depletion indicates ages of 100,000 yr and ≥300,000 yr for this climatic regime in the Negev Desert of southern Israel. Carbon isotope records of organic matter have not been studied extensively in the region, except for the record of Holocene land snails in the Negev. These document a southward shift in pure C₃ plant communities in the middle and early Holocene relative to their present distribution and indicate wetter conditions at those times. An oxygen isotope curve for the Holocene, reflecting changes in the isotopic composition of precipitation, has been established from analysis of carbonate materials—land snail shells and speleothems. The curve indicates a depletion of ca. 2‰ in ¹⁸O centered around 7000 cal yr bp, with modern levels being reached by 5000 cal yr bp. Carbon isotope analysis of soil carbonates in paleosols developed in loess in the Negev show the existence of dramatic north–south climatic gradients at the times of formation of the soils (ca. 13,000, 28,000, and ≥37,000 ¹⁴C yr bp), as occur also today due to the waning influence of Mediterranean to the south. Some isotopic methods, widely used in other regions, have received little or no attention in the eastern Mediterranean region. These include oxygen and hydrogen isotopes in wood, phosphate oxygen and organic carbon in bones and teeth, and carbon in soil organic matter.     

Late Pleistocene vegetation change in Korea and its possible link to East Asian monsoon and Dansgaard–Oeschger (D–O) cycles

Late Pleistocene carbon isotope (δ¹³C) records from a paleolithic sedimentary sequence collected from Baeki, Hongcheon, central Korea, show long-term changes with superimposed short-term isotopic excursions. The δ¹³C value of the sedimentary organic matter, a proxy for past vegetation change, varied from ? 26‰ to ? 23‰ for the period between 30 and 90 ka, with a long-term variation similar to insolation changes. High-amplitude (? 1‰ to approximately ? 1.5‰) fluctuations superimposed on the long-term changes in the δ¹³C values decreased during stronger summer monsoon intervals but increased during the weakened summer monsoon. This millennial-scale pattern is generally similar to Greenland Dansgaard–Oeschger (D–O) cycles. The possible connection between the Hongcheon area, Korea and high latitudes may be explained by atmospheric circulation changing in response to the D–O oscillations in the Northern Hemisphere.     

Tracking the fate of dung-derived carbohydrates in a temperate grassland soil using compound-specific stable isotope analysis

Carbohydrates are major organic components of dung and are likely to contribute substantially to increased carbon stocks in manured soils. To investigate this hypothesis, a field-scale experiment was conducted on a temperate grassland site in Devon, UK. C₄ dung (bulk δ¹³C value ?12.6‰) was applied to a temperate grassland C₃ soil (bulk δ¹³C value ?30.3‰) in April and the surface soil beneath cow pats sampled at seven dates over a year. Total carbohydrates were extracted as their monosaccharide components and analysed as the alditol acetates using gas chromatography. The δ¹³C values of the major monosaccharides glucose (?11.5 ±0.6‰), xylose (?10.4 ±0.4‰), arabinose (?10.4 ±0.5‰) and galactose (?8.3 ±1.6‰) extracted from the C₄ dung via acid hydrolysis were indicative of their source. Their weighted mean δ¹³C value was ?10.8‰, 1.8‰ more ¹³C-enriched than the bulk dung value. The δ¹³C values of individual monosaccharides recovered by acid hydrolysis in the 0–1 cm and 1–5 cm soil horizons beneath C₄ cow pats, compared with control soils determined over 372 days, allowed assessment of the extent of incorporation and fluxes of dung-derived monosaccharides. A maximum of 60% of the dung C in soil was derived from carbohydrates after 56 days, declining to around 20% after 372 days. Incorporation dynamics varied between monosaccharide species. Glucose, xylose and arabinose behaved in a similar manner because of their predominantly plant cell wall derived provenance in the dung, whilst dung-derived galactose and mannose appeared to have a microbial source in the soil. The dynamics of total dung-derived monosaccharides in the top 5 cm was comparable to incorporation and flux of bulk dung C, previously estimated using bulk δ¹³C values. The movement of dung-derived carbohydrates into the soil was inequivalent between the 0–1 cm and 1–5 cm horizons. The lack of a significant difference in concentration, but the evidence for the persistence of dung-derived monosaccharides in soil based on δ¹³C values, indicated replacement of existing pools in the soil, suggesting that the ability of this particular soil to sequester further C derived from carbohydrates was limited.     

The impact of severe biodegradation on the molecular and stable (C,H, N,S) isotopic compositions of oils in the Alberta Basin,Canada

Although the effects of biodegradation on the composition and physical properties of crude oil have been well studied, effects of in-reservoir petroleum biodegradation on molecular and isotopic compositions of crude oils are not yet clearly understood. The Alberta Basin, in western Canada, is one of the world’s largest petroleum accumulations and constitutes an ideal example of a natural suite of sequentially biodegraded oils. The basin hosts moderately to severely biodegraded petroleum, regionally distributed and in single, more or less continuous, oil columns. In this study, a series of oil samples from the Alberta heavy oil and oil sands provinces, with varying degrees of biodegradation, were analyzed to assess the impact of progressive biodegradation on the molecular and C, H, N, and S isotopic compositions of oils. The results of the molecular characterization of the hydrocarbon fraction of the studied oils show that the oils have suffered biodegradation levels from 2 to 10⁺ (toward the Alberta–Saskatchewan border) on the Peters and Moldowan scale of biodegradation (abbreviated PM 2 to PM 10) and from tens to hundreds on the Manco scale. Within single reservoirs, increasing biodegradation was observed from top to bottom of the oil columns at all sites studied. The whole oil stable isotopic compositions of the samples varied in the ranges δ¹³C = −31.2‰ to −29.0‰, δ²H = −147‰ to −133‰, δ¹⁵N = 0.3–4.7‰ and δ³⁴S = 0.4–6.4‰. The maximum differences between δ values of samples (Δ) within single oil columns were Δ¹³C = 1.4‰, Δ²H = 7‰, Δ¹⁵N = 1.7‰ and Δ³⁴S = 1.0‰. Regional variations in the isotopic compositions of oil samples from different wells (averaged values from top to bottom) were 1.2‰ for δ¹³C, 12‰ for δ²H, 4.1‰ for δ¹⁵N and 5.5‰ for δ³⁴S and hence generally significantly larger variations were seen than variations observed within single oil columns, especially for N and S. It appears that even severe levels of biodegradation do not cause observable systematic variations in carbon, nitrogen or sulfur isotope composition of whole oils. This indicates that sulfur and nitrogen isotopic compositions may be used in very degraded oils as indicators for oil charge from different source rock facies.     

Chemostratigraphy and detrital zircon geochronology of the Neoproterozoic Khorbusuonka Group,Olenek Uplift,Northeastern Siberian platform

This study provides ⁸⁷Sr/⁸⁶Sr, δ¹³C and δ¹⁸O data from the best-preserved limestone and dolomite of the Ediacaran carbonate-dominated Khorbusuonka Group of the Olenek Uplift, NE Siberian Craton, as well as detrital zircon geochronological data from both underlying and overlying sandstones. The Maastakh Formation is characterized by ⁸⁷Sr/⁸⁶Sr ratios of ca. 0.70822 and δ¹³C values between + 4.8 and + 6.0‰. ⁸⁷Sr/⁸⁶Sr ratios in limestones of the Khatyspyt Formation are fairly uniform, ranging from 0.70783 to 0.70806. The carbon isotopic composition slowly decreases from bottom (+ 3.7‰) to top (− 0.2‰) of section. The Sr isotopic composition of the Turkut Formation varies from 0.70824 to 0.70914, value of δ¹³C is about zero: − 0.7…+0.7 ‰. The youngest population of detrital zircons from Maastakh Formation indicates that these rocks were formed not later than 630 Ma. U–Pb detrital zircons data of Kessyusa Group has a single peak at about 543 Ma, which is almost identical to the earlier dating. Based on biostratigraphy and isotopic data, the Sr isotopic compositions from the Khatyspyt Formation (⁸⁷Sr/⁸⁶Sr = 0.70783–0.70806) represent the composition of seawater at 560–550 Ma. Such low values of ⁸⁷Sr/⁸⁶Sr ratio in Ediacaran water were probably caused by the quick opening of Iapetus Ocean.     

Soil evidence for historical human-induced land degradation in West Iceland

Human impacts have been severe on Icelandic soils and vegetation. In order to assess human impact on soils soil quality, soil organic C (SOC), soil bulk density (BD), soil moisture content (SMC), soil mass, and SOC sequestration were measured from two Histosol cores in West Iceland. The cores cover a period from around 665 BC to present, capturing the initial human settlement of Iceland in AD 871. Tephrochronology allowed for a reliable correlation and comparison between the two cores. The initial settlement had profound impacts on the soil quality, causing decreased SOC concentration and SMC, and increased vegetation degradation, soil exposure, eolian deposition, and BD. The total SOC pool was 34.6 kg C m² at one of the sites, of which 60.1% was formed during historic times, driven by increased soil mass deposition from surrounding eroded areas. The SOC pool was 43.7 kg C m² at the other site, of which 31.4% was formed during historic time, constrained by water cycling and decomposition.     

Nanhuan manganese deposits within restricted basins of the southeastern Yangtze Platform,China: Constraints from geological and geochemical evidence

The Nanhuan manganese deposits in the southeastern Yangtze Platform occur in the black shale series in the lower part of the Datangpo Formation. In order to constrain the genesis of the deposits, a detailed study was undertaken that involved field observations, major and trace element analyses, organic carbon analyses, and isotope analyses (C, O, S). The major findings are as follows. (1) The ore-bearing rock series, morphology of the ore bodies, and characteristics of ores in several deposits are similar. The ore minerals are rhodochrosite and manganocalcite. The gangue minerals are mainly quartz, feldspar, dolomite, and illite. Minor apatite and bastnaesite occur in the manganese ores. (2) The ores are enriched in Ca and Mg, whereas they are depleted in Si, Al, K, and Ti compared to wall rocks. The ores normalized to average Post-Archean Australian shale (PAAS) are enriched in Co, Mo, and Sr. The chondrite-normalized rare earth element (REE) patterns for ores and wall rocks are between those of typical hydrogenous and hydrothermal type manganese deposits. Additionally, the ores have positive Ce anomalies with an average Ce/Ce* of 1.23 and positive Eu anomalies with an average Eu/Eu* of 1.18 (normalized to PAAS). (3) The average content of organic carbon is 2.21% in the samples, and the average organic carbon isotopic value (δ¹³C_V-PDB) is − 33.44‰. The average inorganic carbon isotopic value (δ¹³C_V-PDB) of carbonates in Gucheng is − 3.07‰, while the values are similar in the other deposits with an average of − 8.36‰. The oxygen isotopic compositions (δ¹⁸O_V-PDB) are similar in different deposits with an average of − 7.72‰. (4) The sulfur isotopic values (δ³⁴S_V-CDT) of pyrite are very high and range from + 37.9‰ to + 62.6‰ (average of 52.7‰), which suggests that the pyrite was formed in restricted basins where sulfate replenishment was limited. The sulfate concentrations in the restricted basins were extremely low and enriched in δ³⁴S, which resulted in the very high δ³⁴S values for the pyrite that formed in the manganese deposits. Therefore, a terrigenous weathering origin for manganese can be excluded; otherwise, the sulfate would have been introduced into the basins together with terrigenous manganese, which would have decreased the δ³⁴S values of pyrites. The manganese, which originated from hydrothermal processes, was enriched in the restricted and anoxic basins, and then, it was oxidized to manganese oxyhydroxide in the overlying oxic waters whereby the products precipitated into the sediments. The manganese oxyhydroxide in the sediment was then reduced to Mn^2 + and released to the pore waters during the process of diagenesis. Some organic carbon was oxidized to CO₃^2 −, which made the depletion of ¹³C in manganese carbonates. Therefore, we suggest that the Nanhuan manganese deposits are hydrothermal–sedimentary/diagenetic type deposits.     

The Cu isotopic signature of granites from the Lachlan Fold Belt,SE Australia

This contribution reports our preliminary work to determine Cu isotope ratios for various granite rocks and examine the Cu isotope systematics within granite suites. A chemical procedure, modified from Maréchal [Maréchal, C.N., Télouk, P. and Albarède, F., 1999. Precise analysis of copper and zinc isotopic compositions by plasma-source mass spectrometry. Chemical Geology, 156(1–4): 251–273.], was used to separate Cu from rock matrix. Quantitative recovery (100.6 ± 1.6%), with a low total procedural blank (2.65 ± 0.66 ng) for Cu, has been achieved, allowing Cu isotopic measurements on samples with as little as 10 ppm Cu. The Cu isotope ratios (δ⁶⁵Cu relative to NIST SRM 976) of 32 rock samples, ranging from mafic to felsic compositions, from 3 batholiths (2 I-type, 1 S-type) from the Lachlan Fold Belt in southeastern Australia, vary from ? 0.46‰ to 1.51‰. Most of them cluster around zero, with mean values for the I-type and S-type granites of 0.03 ± 0.15‰ and ? 0.03 ± 0.42‰ (2 sigma) respectively. These data, together with Cu isotope ratios of two loess samples, provide preliminary evidence that the baseline Cu isotopic composition of the crystalline part of upper continental crust is close to zero. The tight clustering of Cu isotope ratios of rocks from the I-type suites suggests that high-temperature magmatic processes do not produce significant Cu isotope fractionation. However, two granites with abnormally heavy Cu isotope signatures (up to 1.51‰) appears to be the result of localized hydrothermal alteration. Measurable variation in Cu isotopic composition of the S-type granite may reflect isotopic heterogeneity in the sedimentary source region as a result of redox processes or may be due to hydrothermal overprinting. Thus, Cu isotope geochemistry may be a useful tracer for studying hydrothermal alteration and source heterogeneity of granitic rocks.     

Silicon isotopes in allophane as a proxy for mineral formation in volcanic soils

Weathering of basaltic ash in volcanic areas produces andosols, rich in allophane and ferrihydrite. Since the rate of mineral formation is very useful in climate and geochemical modelling, this study investigates Si isotope compositions of allophane as a proxy for mineral formation. Allophane formed in contrasting conditions in five Icelandic soil profiles displays silicon isotope signatures lighter than the basalt in less weathered soils (?0.64 ± 0.15‰), and heavier in more weathered organic-rich soils (+0.23 ± 0.10‰). The fate of the dissolved Si in those volcanic soils strongly depends on Al availability. In organic-rich soils, most of Al is humus-complexed, and the results support that Si precipitates as opaline silica by super-saturation, leaving an isotopically heavier dissolved Si pool to form allophane with uncomplexed Al. This study highlights that Si isotopes can be useful to record successive soil processes involved in mineral formation, which is potentially useful in environmental paleo-reconstruction.     

Influence of maceral content on δ13C and δ15N in a Middle Pennsylvanian coal

Using density-gradient centrifugation, within-sample heterogeneity in C/N, δ¹³C, and δ¹⁵N was determined for a sample of the Blue Gem coal bed (Middle Pennsylvanian, Duckmantian (Westphalian B), Breathitt Formation) and related to maceral (petrographically identifiable organic component) composition. Relatively pure macerals were separated by density, with purities up to 99% in the case of vitrinite in fractions around 1.3 g/mL. Lower density fractions (∼ 1.2 g/mL) contain predominantly liptinite (∼ 75%) but also significant amounts of vitrinite (∼ 20%). Denser fractions contain increasing amounts of inertinite, with several fractions between 1.37 and 1.44 g/mL containing > 98% total inertinite. Within these denser fractions, semifusinite concentrated at lower densities than did fusinite. The separation of macerals by density allowed a more detailed evaluation of the isotopic composition of relatively pure macerals within a single coal. δ¹³C becomes increasingly heavy across the density gradient, with δ¹³C values being lightest in the liptinites, followed by vitrinite, and then semifusinite and fusinite; by contrast, δ¹⁵N becomes lighter across the same density range. C/H increases with density, reflecting a general decrease in aliphatic components and increase in aromatic components. C/N follows a similar pattern, ranging from < 40 to over 100, increasing significantly at densities > 1.32, the point at which inertinite macerals begin to predominate over vitrinite.The isotopic composition of macerals reflects chemical composition, which in turn reflects: 1) the original composition of plant tissues from which the macerals originated; 2) early diagenetic changes; and 3) changes during coalification. Macerals derived from lipid-rich precursor materials (liptinites) have more depleted δ¹³C values (∼ 2‰) relative to those derived from woody tissues (vitrinite). Fusinized material, derived from fossil charcoal, has δ¹³C values enriched by ∼ 0.5‰ compared with the vitrinite, consistent with the results from combustion experiments using modern plant tissues. Vitrinite fractions have enriched δ¹⁵N values relative to inertinite fractions, which may reflect early diagenetic changes in woody tissues involving preferential loss of ¹⁴N, possibly due to bacterial activity during the peat-forming stage. Due to the within-sample variability in carbon isotopic composition reported here, it is suggested that chemostratigraphic studies based on Type III kerogen (including both dispersed organic matter and coals) carefully consider the associated effects of variability in maceral composition.     

Soil organic carbon quantity,chemistry and thermal stability in a mountainous landscape: A Rock–Eval pyrolysis survey

Mountain soils store huge amounts of carbon which may be highly vulnerable to the strong land use and climate changes that mountain areas currently experience worldwide. Here, we tested the Rock–Eval (RE) pyrolysis as a proxy technique to (i) quantify soil organic carbon (SOC) stocks, (ii) bring insights into SOC bulk chemistry and (iii) investigate biogeochemical stability at the landscape scale in a mountain area of the French calcareous Prealps. A total of 109 soils from 11 eco-units representing the variety of ecosystems of the study area were analyzed with RE pyrolysis. RE pyrolysis showed an excellent predictive performance (R² = 0.99) for SOC content even in calcareous soils. The technique revealed specific chemical fingerprints for some eco-units and soil types, with decreasing hydrogen index values from Anthroposols (425 ± 62 mg HC/g SOC) to Umbrisols, Leptosols (311 ± 49 mg HC/g SOC) and to Cambisols (278 ± 35 mg HC/g SOC), associated with an increase in SOC maturation. Newly developed RE pyrolysis indices revealed the high stability of SOC in most eco-units developed on Cambisols (acidic grasslands, alpine meadows, bushy facies) and a significantly lower stability of SOC in mountain ridges, sheepfold areas and coniferous forest soils. The persistence of SOC in this mosaic of ecosystems may depend not only on its chemistry or thermal stability, but also on local environmental factors such as climatic conditions or pH, especially for high altitude soils. Overall, RE pyrolysis appears as an appropriate tool for landscape scale carbon inventories and could become a standardized proxy for assessing the vulnerability of SOC stocks.     

Accumulation of terrestrial organic carbon on an active continental margin offshore southwestern Taiwan: Source-to-sink pathways of river-borne organic particles

Sediment samples (213 sites) collected from the tectonic-active continental margin, offshore southwestern Taiwan were analyzed for grain sizes, organic carbon, nitrogen and carbon isotopic composition to obtain mass accumulation rate of terrestrial organic carbon and carbon budget to evaluate fate of terrestrial organic carbon from small mountainous rivers on the continental margin offshore southwestern Taiwan. Terrestrial organic carbon accumulation rates range from 0.29 to 45.6 g C m⁻² yr⁻¹ with a total accumulation budget of 0.063 Mt yr⁻¹, which accounts for less than 13% of total river particulate organic carbon loads exported from the adjacent rivers, the Gaoping (a.k.a., Kaoping), Erhjen and Tsengwen rivers. This low burial efficiency of terrestrial organic carbon demonstrated that a majority of river-borne particles together with organic materials was moved away from the study area.For the river-borne particles from the Gaoping river, a pair of depocenters in the upper slope flanking the Gaoping submarine canyon are the locations where the maximum TC_org accumulation rate were observed which hold up to 45% (0.016 Mt yr⁻¹) of the calculated accumulation found in the study region. On the other hand, the occurrence of higher-fraction terrestrial organic carbon in the upper and middle Gaoping submarine canyon suggests that a majority of particulate organic carbon of the Gaoping river was transported directly into the deep-sea basin through the Gaoping submarine canyon. Our results demonstrated that active margin with narrow shelf and slope is not an efficient sink for the large amount of terrigenous organic carbon supplied by the small rivers, but, a transient environment for these river derived particles.     

Effect of low-molecular-weight organic acids on the distribution of mobilized Al between soil solution and solid phase

Low-molecular-weight (LMW) organic acids occur widely in soils. Results in pure mineral systems and podzols suggest that LMW organic acids can promote the dissolution of Al from kaolinite, Al oxides and soils, but limited information is available concerning the role of these organic acids on Al mobilization in variable charge soils as yet. This paper deals with the effect of LMW organic acids on Al mobilization and mobilized Al distributed between the solution phase and exchangeable sites in two acidic variable charge soils. The results indicated that LMW organic acids accelerated Al mobilization through proton- and ligand- promoted reactions. The ability of different organic acids to mobilize Al followed the order: citric acid > oxalic acid > malonic acid > malic acid > tartaric acid > salicylic acid > lactic acid > maleic acid. This order was in general agreement with the magnitude of the stability constants of Al–organic acid complexes. The ratio of soluble Al to exchangeable Al also increased as the stability constants increased. These results showed that the organic acids with strong Al-complexation capacity were most effective in Al mobilization, whereas the weak organic acids promoted the retention of mobilized Al by the soil exchangeable sites. Increase in both organic acid concentration and solution pH promoted Al mobilization and also increased the ratio of soluble Al to exchangeable Al due to the increase in the concentration of the effective organic ligands, especially in the strong organic acid systems. These findings may have their practical significance for establishing more effective amelioration procedures for variable charge soils with increased acidity and higher mobility of Al.     

Copper and iron isotope fractionation in mine tailings at the Laver and Kristineberg mines,northern Sweden

Previous research has shown that Cu and Fe isotopes are fractionated by dissolution and precipitation reactions driven by changing redox conditions. In this study, Cu isotope composition (⁶⁵Cu/⁶³Cu ratios) was studied in profiles through sulphide-bearing tailings at the former Cu mine at Laver and in a pilot-scale test cell at the Kristineberg mine, both in northern Sweden. The profile at Kristineberg was also analysed for Fe isotope composition (⁵⁶Fe/⁵⁴Fe ratios). At both sites sulphide oxidation resulted in an enrichment of the lighter Cu isotope in the oxidised zone of the tailings compared to the original isotope ratio, probably due to preferential losses of the heavier Cu isotope into the liquid phase during oxidation of sulphides. In a zone with secondary enrichment of Cu, located just below the oxidation front at Laver, δ⁶⁵Cu (compared to ERM-AE633) was as low as −4.35 ± 0.02‰, which can be compared to the original value of 1.31 ± 0.03‰ in the unoxidised tailings. Precipitation of covellite in the secondary Cu enrichment zone explains this fractionation. The Fe isotopic composition in the Kristineberg profile is similar in the oxidised zone and in the unoxidised zone, with average δ⁵⁶Fe values (relative to the IRMM-014) of −0.58 ± 0.06‰ and −0.49 ± 0.05‰, respectively. At the well-defined oxidation front, δ⁵⁶Fe was less negative, −0.24 ± 0.01‰. Processes such as Fe(II)–Fe(III) equilibrium and precipitation of Fe-(oxy)hydroxides at the oxidation front are assumed to cause this Fe isotope fractionation. This field study provides additional support for the importance of redox processes for the isotopic composition of Cu and Fe in natural systems.