Magnetic anisotropy of calcite at room-temperature

The intrinsic room temperature magnetic properties of pure calcite were determined from a series of natural crystals, and they were found to be highly dependent on the chemical composition. In general, dia-, para-, and ferromagnetic components contribute to the magnetic susceptibility and the anisotropy of magnetic susceptibility (AMS). With a combination of magnetic measurements and chemical analysis these three contributions were determined and related to their mineralogical sources. The intrinsic diamagnetic susceptibility of pure calcite is − 4.46 ± 0.16 × 10^− 9 m³/kg (− 12.09 ± 0.5 × 10^− 6 SI) and the susceptibility difference is 4.06 ± 0.03 × 10^− 10 m³/kg (1.10 ± 0.01 × 10^− 6 SI). These diamagnetic properties are easily dominated by other components. The paramagnetic contribution is due to paramagnetic ions in the crystal lattice that substitute for calcium; these are mainly iron and manganese. The measured paramagnetic susceptibility agrees with the values calculated from the known concentration of paramagnetic ions in the crystals according to the Curie law of paramagnetic susceptibility. Substituted iron leads to an increase in the AMS. The paramagnetic susceptibility difference was found to correlate linearly with the iron content for concentrations between 500 and 10,000 ppm. An empirical relation was determined: (k₁ − k₃)^para (kg/m³) = Fe-content (ppm) × (1 ± 0.1) × 10^− 12 (kg/m³/ppm). The maximum susceptibility difference (Δk = k₁ − k₃) was found to be unaffected by iron contents below 100 ppm. Ferromagnetic contributions due to inclusions of ferromagnetic minerals can dominate the susceptibility. They were detected by acquisition of isothermal remanent magnetization (IRM) and their contribution to the AMS was separated by high-field measurements.     

Nature of sedimentary organic matter in the lower reaches of the Godavari River basin, India

The distribution and nature of sedimentary organic matter (OM) have been examined in sediment cores collected from the lower reaches, including estuary, of the Godavari River in order to understand sedimentation patterns, sources, and diagenesis of OM. The samples were analyzed for organic carbon (Corg), total nitrogen, amino acids and hexosamines. The observed irregular trends in Corg distribution with depth indicate the unstable nature of bed sediment in the lower reaches of the river. Yet, in the lower estuarine region, regular trends in Corg distribution with depth reflect the deposition of sediment. The atomic ratio of Corg and total nitrogen (C/N; 10.5–16.1) also supported this observation. The distribution of amino acids and diagenetic indicators (β-ala+γ-aba mol.%, AA/HA and Glc-NH₂/Gal-NH₂) in individual cores revealed the post-depositional changes in the OM. In the core sediment from the lower reaches, there was no clear cut trend in amino acid content with depth. In the estuarine region, however, amino acid content was very low (50.5 and 186.5 μg g⁻¹) in the upper layers compared to that in the lower layers (558.5 and 1099.3 μg g⁻¹). Reactivity index (range 0.3–3.7) revealed that OM in the upper few centimeters, especially in the lower estuarine region, was more reactive relative to that in the deeper layers.     

Iron speciation in interaction with organic matter: Modelling and experimental approach

The present study aims to model iron speciation when interacting with natural organic matter. Experimental data for iron speciation were achieved with insolubilized humic acid as an organic matter analogue for 1.8 × 10^− 3 M and 1.8 × 10^− 4 M iron concentrations and 2–5 pH range. Combining EPR spectroscopy and chemical analysis allowed us to fit NICA-Donnan model parameters for both organic complexation of iron and oxides precipitation.     

A method for determining both diffusion and sorption coefficients of rock medium within a few days by adopting a micro-reactor technique

Migration properties characterized by physico-chemical factors such as distribution coefficient (K_d) and diffusion coefficient (D_e) are of great concern in performance assessment of high-level radioactive waste disposal in a deep geologic environment. These coefficients are normally obtained with different sample geometries using conventional methods, i.e., crushed samples by the batch sorption method for K_d determination and block samples by the through-diffusion method for D_e. A size dependence on both K_d and D_e has been reported and an additional correction due to size difference is required to maintain consistency of the data set. A fast method was developed, hereafter referred to as the micro-channel method, to determine both the sorption coefficient (R_d) and D_e using non-crushed rock sample by adopting the micro-reactor technique. In this method, a radionuclide solution is injected into a micro-channel (20 mm length, 4 mm width, 160 μm depth), which is in contact with a plate-shaped rock sample. A part of the injected radionuclide can diffuse into the rock matrix and/or adsorb on the rock surface and this results in an inlet-outlet concentration difference. A breakthrough curve is easily obtained with a short observation period because the injection amount is extremely small and is comparable to that escaping by diffusion into the matrix. The breakthrough curve is analyzed by a two-dimensional diffusion-advection equation to evaluate R_d and D_e.In the present study, tritiated water (specific activity, 1.2 × 10⁴ Bq/mL; pH, 6) was injected into the micro-channel, and the breakthrough curve of ³H obtained. A series of experiments was carried out by changing the flow rate of the tritiated water (2.6 × 10⁻⁵–7.7 × 10⁻⁴ m/s). Rock samples were biotite granite from the Makabe area, Japan. The diffusion coefficient evaluated by least squares fitting to the numerical solutions (D_e = 1.5 × 10⁻¹¹ m²/s) agreed well with that obtained by the through-diffusion method (1.3 × 10⁻¹¹ m²/s). The breakthrough curve of Cs ([Cs] = 1.0 × 10⁻⁷ mol/L, pH 6) labeled with ¹³⁴Cs (specific activity adjusted to 4.9 × 10¹ Bq/mL) was also obtained. A nearly constant R_d value (5.5 × 10⁻² m³/kg) was found when the flow rate was less than 2.5 × 10⁻⁴ m/s. This implied that the sorption equilibrium is reached and K_d is obtained by the present method. This value was almost identical to K_d obtained by the batch sorption method (5.0 × 10⁻² m³/kg), but the testing period was very different; 1 day and 7 days, respectively. It is concluded that application of the micro-channel method provided advantages when compared with the conventional methods.     

Some parameters of rockbursts derived from underground seismological measurements

A total of 240 three-component recordings from 80 rockbursts, which occurred in various coal mines in the Ostrava-Karviná Coal Basin (Czech Republic) between 1993 and 2005, was used to examine the decrease in maximum particle velocities u_i (m/s) with a scaled distance of d = d/√E (m/√J) or d/³√E (m/³√J) and the rate of predominant frequencies of body waves. The energetic span of rockbursts was within the interval of E = 6.2 × 10³ − 5.0 × 10⁸ J, while calculated hypocentral distances d of four underground seismic stations varied from 0.6 to 7 km. The slopes b of regression straight lines for the maximum particle velocities u_i (m/s) of P- and S-waves in the bilogarithmic scale correspond to the values of − 1.004, − 1.297, − 1.183 and − 1.527. The results of the linear regression are as follows:

P_max-waves u_i = 1.184 × 10^− 4 × d^− 1.004 (m/s) (square root scaling)

P_max-waves u_i = 3.055 × 10^− 3 × d^− 1.297 (m/s) (cube root scaling)

S_max-waves u_i = 5.280 × 10^− 4 × d^− 1.183 (m/s) (square root scaling)

S_max-waves u_i = 2.397 × 10^− 2 × d^− 1.527 (m/s) (cube root scaling).

The evaluation of the abovementioned dynamic parameters was based on seismic events data gathered in the database of the regional seismic array, and calculations were carried out either by using special programs applied as part of the automated data processing in the computation center, or by usual linear regression approaches. The aim of the detailed analysis of the maximum particle velocity and predominant frequencies was a) to set up input data from underground seismological observations for laboratory experiments dealing with the comparison of rock mass behaviour under modeled laboratory conditions simulating manifestation of rockbursts, and b) to incorporate particle velocity into the design of support in order to control damage and evident devastation of workings by rockbursts. The investigation of peak particle velocities was based on the recognition that they are the best criterion to assess vibration damage to surface structures and in mines.     

Source and flux of POC in two subtropical karstic tributaries with contrasting land use practice in the Yangtze River Basin

Elemental (C/N ratio) and C isotope composition (δ¹³C) of particulate organic C (POC) and organic C content (OC) of total suspended solids (TSS) were determined for two subtropical karstic tributaries of the Yangtze River, the Wujiang (the eighth largest tributary) and Yuanjiang (the third largest tributary). For the latter, two headwaters, the karstic Wuyanghe and non-karstic Qingshuijiang were studied. The Wujiang catchment is subject to intensive land use, has low forest coverage and high soil erosion rate. The δ¹³C of POC covered a range from −30.6‰ to −24.9‰, from −27.6‰ to −24.7‰, and from −26.2‰ to −23.3‰ at the low-water stage, while at the high-water stage varied in a span between −28.6‰ and −24.4‰, between −27.7‰ and −24.5‰, and between −27.6‰ and −24.2‰ for the Wujiang, Wuyanghe, and Qingshuijiang, respectively. The combined application of C isotopes, C/N ratio, OC, and TSS analyses indicated that catchment soil was the predominant source of POC for the Wujiang while for the Wuyanghe and Qingshuijiang, in-stream processes supplied the main part of POC in winter and summer. A significant increase in δ¹³C value (1.4‰) of POC was found in the Wujiang during summer, and was attributed to the enhanced soil erosion of the dry arable uplands close to the riverbanks of the main channel. Based on a conservative estimate, POC fluxes were 3.123 × 10¹⁰, 0.084 × 10¹⁰, and 0.372 × 10¹⁰ g a⁻¹ while export rates of POC were 466, 129, and 218 mg m⁻² a⁻¹ for the Wujiang, Wuyanghe, and Qingshuijiang, respectively. The POC export rate for the karstic Wujiang, with intensive land use, was 2–3 higher than that of the karstic Wuyanghe or of the non-karstic Qingshuijiang where soil erosion was minor. Such high values imply rapid degradation of related karstic ecosystems impacted by intensive land use activities, and pose a potential threat to the health of the Three Gorges Reservoir.     

11 Å tobermorite from cement bypass dust and waste container glass: A feasibility study

A novel one-step hydrothermal synthesis of 11 Å tobermorite, a cation exchanger, from a unique combination of waste materials is reported. 11 Å tobermorite was prepared from stoicheiometric quantities of cement bypass dust and waste container glass at 100 °C in water. The product also comprised 10 wt.% calcite and trace quartz as residual parent phases from the cement bypass dust. In a batch sorption study at 20 °C the uptakes of Cd²⁺ and Pb²⁺ by the waste-derived tobermorite product were found to be 171 mg g^− 1 and 467 mg g^− 1, respectively, and in both cases the removal process could be described using a simple pseudo-second-order rate model (k₂ = 2.30 × 10^− 5 g mg^− 1 min^− 1 and 5.09 × 10^− 5 g mg^− 1 min^− 1, respectively). The sorption characteristics of the 11 Å tobermorite are compared with those of other waste-derived sorbents and potential applications are discussed.     

Comparison of methods for the estimation of pyrite oxidation rate in a waste rock pile at Mine Doyon site, Quebec, Canada

Several methods were evaluated and compared for the estimation of pyrite oxidation rates (POR) in waste rock at Mine Doyon, Quebec, Canada. Methods based on data collected in situ, such as the interpretation of temperature and oxygen concentration profiles (TOP) measured in the waste rock pile and pyrite mass balance (PMB) on solid phase samples were compared with the oxygen consumption measurements (OCM) in closed chamber in the laboratory. A 1-D analytical solution to a gas and heat transport equation used temperature and oxygen profiles (TOP) measured in the pile for the preliminary POR estimates at a site close to the slope of the pile (Site 6) and in the core of the pile (Site 7). Resulting POR values were 1.1 × 10^− 9 mol(O₂) kg^− 1 s^− 1 and 1.0 × 10^− 10 mol(O₂) kg^− 1 s^− 1 for the slope site and the core site, respectively. Oxidation rates based on pyrite mass balance (PMB) calculations for solid samples were 2.21 × 10^− 9 mol(O₂) kg^− 1 s^− 1 and 2.03 × 10^− 9 mol(O₂) kg^− 1 s^− 1, respectively, for the same slope and core sites, but the difference between sites was within the error margin. The OCM measurements in the laboratory on fresh waste rock samples yielded higher POR values than field methods, with average oxidation rate of 6.7 × 10^− 8 mol(O₂) kg^− 1 s^− 1. However, the OCM results on weathered and decomposed material from the rock stockpile (average oxidation rate 3.4 × 10^− 9 mol(O₂) kg^− 1 s^− 1) were consistent with results from the field-based estimates. When POR values based on fresh material are excluded, the remaining POR values for all methods range from 1.0 × 10^− 10 to 3.4 × 10^− 9 mol(O₂) kg^− 1 s^− 1. The lowest estimated value (1.0 × 10^− 10 mol(O₂) kg^− 1 s^− 1) was based on TOP estimates in the interior of the pile where oxygen transport was limited by diffusion from the surface. These results suggest that small-scale OCM laboratory experiments may provide relatively representative values of POR in the zones of waste rock piles in which oxygen transport is not dominated by diffusion.     

Temporal and spatial variations in water discharge and sediment load in the Alaknanda and Bhagirathi Rivers in Himalaya, India

The Alaknanda and Bhagirathi Rivers originate in the mountainous regions of the Himalayas (Garhwal) and result in high sediment yields causing flood hazards downstream of the Ganga River and high sediment flux to the Bay of Bengal. The rivers are perennial, since runoff in these rivers is controlled by both precipitation and glacial melt. In the present study, three locations in the upper reaches of the Ganga River were monitored for 1 yr (daily observations of, more than >1000 samples) for suspended sediment concentrations. In addition, more than one hundred samples were collected from various locations of the Alaknanda and Bhagirathi Rivers at different periods to observe spatial and temporal variations in river suspensions. Further, multi-annual data (up to 40 yrs) of water flow and sediment concentrations were used for inferring the variations in water flow and sediment loads on longer time scales. In most previous studies of Himalayan Rivers, there has been a general lack of long term water flow and sediment load data. In the present study, we carried out high frequency sampling, considered long term discharge data and based on these information, discussed the temporal and spatial variations in water discharge and sediment loads in the rivers in the Himalayan region. The results show that, >75% of annual sediment loads are transported during the monsoon season (June through September). The annual physical weathering rates in the Alaknanda and Bhagirathi River basins at Devprayag are estimated to be 863 tons km⁻² yr⁻¹ (3.25 mm yr⁻¹) and 907 tons km⁻² yr⁻¹ (3.42 mm yr⁻¹) respectively, which are far in excess of the global average of 156 tons km⁻² yr⁻¹ (0.58 mm yr⁻¹).     

Magnetic fabric variations in Mesozoic black shales, Northern Siberia, Russia: Possible paleomagnetic implications

A 28-m-long section situated on the coast of the Arctic Ocean, Russia (74°N, 113°E) was extensively sampled primarily for the purpose of magnetostratigraphic investigations across the Jurassic/Cretaceous boundary. The section consists predominantly of marine black shales with abundant siderite concretions and several distinct siderite cemented layers. Low-field magnetic susceptibility (k) ranges from 8 × 10^− 5 to 2 × 10^− 3 SI and is predominantly controlled by the paramagnetic minerals, i.e. iron-bearing chlorites, micas, and siderite. The siderite-bearing samples possess the highest magnetic susceptibility, usually one order of magnitude higher than the neighboring rock. The intensity of the natural remanent magnetization (M₀) varies between 1 × 10^− 5 and 6 × 10^− 3 A/m. Several samples possessing extremely high values of M₀ were found. There is no apparent correlation between the high k and high M₀ values; on the contrary, the samples with relatively high M₀ values possess average magnetic susceptibility and vice versa. According to the low-field anisotropy of magnetic susceptibility (AMS), three different groups of samples can be distinguished. In the siderite-bearing samples (i), an inverse magnetic fabric is observed, i.e., the maximum and minimum principal susceptibility directions are interchanged and the magnetic fabric has a distinctly prolate shape. Triaxial-fabric samples (ii), showing an intermediate magnetic fabric, are always characterized by high M₀ values. It seems probable that the magnetic fabric is controlled by the preferred orientation of paramagnetic phyllosilicates, e.g., chlorite and mica, and by some ferromagnetic mineral with anomalous orientation in relation to the bedding plane. Oblate-fabric samples (iii) are characterized by a bedding-controlled magnetic fabric, and by moderate magnetic susceptibility and M₀ values. The magnetic fabric is controlled by the preferred orientation of phyllosilicate minerals and, to a minor extent, by a ferrimagnetic fraction, most probably detrital magnetite. Considering the magnetic fabric together with paleomagnetic component analyses, the siderite-bearing, and the high-NRM samples (about 15% of samples) were excluded from further magnetostratigraphic research.     

High-field cantilever magnetometry as a tool for the determination of the magnetocrystalline anisotropy of single crystals

Cantilever torque magnetometry is utilized widely in physics and material science for the determination of magnetic properties of thin films and semiconductors. Here, we report on its first application in rock magnetism, namely the determination of K₁ and K₂ of single crystal octahedra of natural magnetite. The design of cantilever magnetometers allows optimization for the specific research question at hand. For the present study, a cantilever magnetometer was used that enables measurement of samples with a volume up to 64 mm³. It can be inserted into an electromagnet with a maximum field of 2 T. The cantilever spring is suitable for torque values ranging from 7.5 × 10^− 7 N·m to 5 × 10^− 6 N·m. The torque is detected capacitively; the measured capacitance is converted into torque by using a calibrated feedback coil. The magnetometer allows in-situ rotation of the sample in both directions and is, therefore, also suitable to analyze rotational hysteresis effects.The evaluation of the magnetite anisotropy constants involved Fourier analysis of the torque signal on the magnetite crystals' (001) and (110) planes. The absolute anisotropy constant has been computed using the extrapolation-to-infinite-field method. The value of K₁ at room temperature is determined at − 1.28 × 10⁴ [J m^− 3] (± 0.13, i.e. 10%) and that of K₂ at − 2.8 × 10³ [J m^− 3] (± 0.1, i.e. 2%). These values concur with earlier determinations that could not provide an instrumental error, in contrast with this work.The cantilever magnetometer performs four times faster than other torque magnetometers used for rock magnetic studies. This makes the instrument also suitable for magnetic fabric analysis.     

Biodegradation of C-labeled low molecular organic acids using three biometer methods

Low molecular weight organic acids (LMWOA) are produced in soil by various biological and chemical processes and can exhibit substantial metal complexing and dissolution capacity. The reactivity of these compounds in the soil environment is dependent on their non-complexed concentration in the soil solution. Adsorption of LMWOA has been shown to reduce their concentration in the soil solution; however, little is known about the reduction of LMWOA concentration due to microbial degradation. To examine the extent of microbial degradation in reducing LMWOA concentration in the soil solution, three-biometer methods were used: a soil biometer flask, an in-situ field biometer and a soil column biometer. Four soil horizons were used with each method. To each soil sample, 2.0×10⁻⁶ moles of organic acid containing 3.7×10⁴ Bq total activity was applied. The ¹⁴C-radiolabeled aliphatic and aromatic acids studied included oxalic, malonic, succinic, and phthalic acid. Evolved ¹⁴CO₂ was trapped in 0.5 mol l⁻¹ NaOH and measured using liquid scintillation counting. Labeled acids degraded rapidly within the first 5 days for the Ap1, Ap2, and BA horizons, with a generally slower rate of ¹⁴CO₂ evolution being observed for the Bt1 horizon. The % degradation of labeled acid was substantially greater for the soil biometer flask method, compared to the field and soil column biometer methods. The average % degradation for the soil biometer flask was 67% for all soil horizons and organic acids, compared to 14% for the field biometer and 13% for the soil column biometer. Results indicate that substantial microbial degradation of organic acids can occur within a relatively short time period and the biometer method selected can influence the % acid degraded. Based on primary results, the soil column biometer method better approximated microbial degradation under field conditions, as evaluated using the field biometer.     

Correlation between dissolved He concentration and Cl in groundwater at Äspö, Sweden

Tunnel excavation at Äspö Island, Sweden, has caused severe groundwater disturbance, gradually extending deeper into the tunnel as present-day Baltic seawater intrudes through fractures connecting to the surface. However, the paleo-hydrogeochemical conditions have remained in the deep highly saline waters that have avoided mixing. A correlation has been observed between dissolved ⁴He concentration and Cl⁻ ion concentration, measured every two years from 1995 to 2001 at Äspö. Groundwater mixing conditions can be examined by the correlations between 1/Cl, ³⁶Cl/Cl, and ³H concentrations. Subsurface production is responsible for the majority of the ³⁶Cl and excess dissolved ⁴He of interstitial groundwater in fractures. The secular equilibrium ratio of ³⁶Cl/Cl in rock was theoretically estimated to be (5.05 ± 0.82) × 10⁻¹⁴ based on the neutron flux intensity, a value comparable to the measured ³⁶Cl/Cl ratio in rock and groundwater. The degassing crustal ⁴He flux was estimated to be 2.9 × 10⁻⁸  1.3 × 10⁻⁶ (ccSTP/cm²a) using the HTO diffusion coefficient for the Äspö diorite. The ⁴He accumulation rate ranges from 6.8 × 10⁻¹⁰ (for the in situ accumulation rate) to 7.0 × 10⁻⁹ (ccSTP/(g_water · a) considering both ⁴He in situ production and the degassing flux, assuming ⁴He is accumulated constantly in groundwater. By comparing the subsurface ³⁶Cl increase with ⁴He concentrations in groundwater, the ⁴He accumulation rate was determined from data for groundwater arriving at the secular equilibrium of ³⁶Cl/Cl. The ⁴He accumulation rate was found to be (1.83 ± 0.72) × 10⁻⁸ ccSTP/(g_water · a) without determining the magnitude of degassing ⁴He flux.     

Rates of Deglaciation during the Last Glaciation and Holocene in the Cordillera Vilcanota-Quelccaya Ice Cap Region, Southeastern Perú

Moraine chronology is combined with digital topography to model deglacial rates of paleoglacier volumes in both the Huancané Valley on the west side of the Quelccaya Ice Cap and the Upismayo Valley on the northwest side of the Cordillera Vilcanota. The fastest rates of deglaciation (39×10⁻⁵ to 114×10⁻⁵ km³ yr⁻¹ and 112×10⁻⁵ to 247×10⁻⁵ km³ yr⁻¹ for each valley, respectively) were calculated for the most recent paleoglaciers, corresponding to the last few centuries. These results are consistent with observations in the Venezuelan Andes showing high rates of deglaciation since the Little Ice Age. These rates also fall within the range of 20th century rates of deglaciation measured on the Quelccaya Ice Cap (29×10⁻⁵ to 220×10⁻⁵ km³ yr⁻¹, Brecher and Thompson, 1993; Thompson, 2000). These results imply that rates of deglaciation may fluctuate significantly over time and that high rates of deglaciation may not be exclusive to the late 20th century. Equilibrium line altitude (ELA) depressions for the ice volumes of the last glaciation modeled here were computed as 230 m for the Quelccaya Ice Cap and 170 m for the Cordillera Vilcanota. Maximum ELA depressions are lower than previously published: <500 m for the Cordillera Vilcanota and <400 m for the Quelccaya Ice Cap. These lower values could imply a topographic control over paleoglacier extent.     

Sources and transport of carbon and nitrogen in the River Sava watershed, a major tributary of the River Danube

Carbon and nitrogen dynamics were examined throughout the River Sava watershed, a major tributary of the River Danube, in 2005 and 2006. The River Sava exported 2.1 × 10¹¹ mol C/yr as dissolved inorganic carbon (DIC), and emitted 2.5 × 10¹⁰ mol C/yr as CO₂ to the atmosphere. Stable carbon isotope ratios indicate that up to 42% of DIC originated from carbonate weathering and 23% from degradation of organic matter. Loads of dissolved and particulate organic carbon increased with discharge and export rates were calculated to be 2.1 × 10¹⁰ mol C/yr and up to 4.1 × 10⁹ mol C/yr, respectively. Isotopic compositions (δ¹³C and δ¹⁵N) and C/N ratios indicated that soil organic matter was the dominant source of particulate organic matter for 59% of the samples. Eighteen percent of the samples were dominated by plankton, 12% by periodic inputs of fresh terrestrial plant detritus with C/N > 15, and about 11% of the samples were dominated by the contribution of aquatic vascular plants. Nitrate inputs were controlled by land use in the River Sava watershed. δ¹⁵N_NO3 values <6‰ were found in predominantly forested watersheds, while values >6‰ typically represented watersheds with a higher percentage of agricultural and/or urban land use. Elevated δ¹⁵N_NO3 values (up to +25.5‰) at some sites were probably due to the combined effects of low-flow and inputs from sewage and/or animal waste.     

Organic matter degradation in sediments of the York River estuary: Effects of biological vs. physical mixing

We investigated the influence of biological and physical seabed disturbance on the degradation of bulk organic matter and source specific lipid biomarker compounds by measuring downcore changes in bulk elemental composition, bulk stable isotopic (δ¹³C and δ¹⁵N) signatures, and lipid biomarker compounds in sediment cores collected from two sites in the York River, a subestuary of the Chesapeake Bay, USA. One site (LY) is influenced by biological mixing (bioturbation), restricted to the upper 15-20 cm, while the other site (POD) experiences intense, episodic physical mixing events that penetrate 50-100 cm into the sediment. We utilized a suite of auxiliary measurements to constrain the sources of organic matter, depositional environments, and general ages of the cores. Diagenetic modeling of total organic carbon and total nitrogen in sediments yielded higher apparent rate constants for POD than LY suggesting that the physical mixing regime promotes enhanced degradation of bulk organic matter. Apparent rate constants for select lipids representing distinct sources of organic matter were also higher at POD than LY for all but the most labile (i.e., diatom-derived fatty acids) biomarkers. Differences in stanol/stenol ratios also supported enhanced diagenesis of stenols at POD. The source-specific biomarkers, while useful in qualitatively identifying the sources of sedimentary organic matter, likely do not represent the full spectrum of its reactivity. However, based on our results, we hypothesize that the intense sediment disturbance at POD promotes degradation of more recalcitrant organic material, due to prolonged exposure to oxygen and other electron acceptors (e.g., NO₃⁻, Mn and Fe oxides). In contrast, the degradation of more labile constituents is equally facilitated by biological and physical disturbance.     

How depositional conditions control input, composition, and degradation of organic matter in sediments from the Chilean coastal upwelling region

In a comprehensive study, we compared depositional conditions, organic matter (OM) composition, and organic carbon turnover in sediments from two different depositional systems along the Chilean continental margin: at ∼23° S off Antofagasta and at ∼36° S off Concepción. Both sites lie within the Chilean coastal upwelling system and have an extended oxygen minimum zone in the water column. However, the northern site (23° S) borders the Atacama Desert, while the southern site (36° S) has a humid hinterland. Eight surface sediment cores (up to 30 cm long) from water depths of 126-1350 m were investigated for excess ²¹⁰Pb (²¹⁰Pb_xs) activity, total organic and total inorganic carbon concentrations (TOC and TIC, respectively), C/N-ratios, organic carbon isotopic compositions (δ¹³C), chlorin concentrations, Chlorin Indices (CI), and sulfate reduction rates (SRR). Sediment accumulation rates obtained from ²¹⁰Pb-analysis were similar in both regions (0.04-0.15 cm yr⁻¹ at 23° S, 0.10-0.19 cm yr⁻¹ at 36° S), although total ²¹⁰Pb_xs fluxes indicated that the vertical particle flux was higher at 36° S than at 23° S. We propose that sediment focusing in isolated deposition centers led to high sediment accumulation rates at 23° S. Furthermore, there were no indications for sediment mixing at 23° S, while bioturbation was intense at 36° S. δ¹³C-values (−24.5‰ to −20.1‰ vs. VPDB) and C/N-ratios (molar, 8.6-12.8) were characteristic of a predominantly marine origin of the sedimentary OM in both investigated areas. The extent of OM alteration in the water column was partly reflected in the surface sediments as chlorin concentrations decreased and C/N-ratios and CI increased with increasing water depth of the sampling site. SRR were lower at 23° S (areal SRR 0.12-0.60 mmol m⁻² d⁻¹) than at 36° S (areal SRR 0.82-1.18 mmol m⁻² d⁻¹), which was partly due to the greater water depth of most of the sediments investigated in the northern region and consistent with a lower quality of the sedimentary OM at 23° S. Reaction rate constants for TOC degradation that were obtained from measured SRR (k_SRR; 0.0004-0.0022 yr⁻¹) showed a good correspondence to k_TOC that were derived from the depth profiles of TOC (0.0003-0.0014 yr⁻¹). Both, k_SRR and k_TOC, reflect differences in OM composition. At 36° S they were related to the degradation state of bulk OM (represented by C/N-ratios), whereas near 23° S they were related to the freshness of a small fraction of labile OM (represented by CI). Our study shows that although rates of organic carbon accumulation were similar in both investigated sites, the extent and kinetics of organic carbon degradation were closely linked to differing depositional conditions.     

Mercury gas emissions from La Soufrière Volcano, Guadeloupe Island (Lesser Antilles)

Quantifying mercury (Hg) emissions from active volcanoes is of particular interest for better constraining the global cycle and environmental impact of this highly toxic element. Here we report on the abundance of total gaseous (TGM = Hg⁰_(g) + Hg^II_(g)) and particulate (Hg_(p)) mercury in the summit gas emissions of La Soufrière andesitic volcano (Guadeloupe island, Lesser Antilles), where enhanced degassing of mixed hydrothermal-magmatic volatiles has been occurring since 1992 from the Southern summit crater. We demonstrate that Hg in volcanic plume occurs predominantly as gaseous mercury, with a mean TGM/Hg_(p) mass ratio of ~ 63. Combining the mean TGM/H₂S mass ratio of the volcanic plume (~ 3.2 × 10^− 6), measured close to the source vent, with the H₂S plume flux (~ 0.7 t d^− 1), determined simultaneously, allows us to estimate a gaseous mercury emission rate of 0.8 kg yr^− 1 from La Soufrière summit dome. Somewhat lower TGM/S_tot mass ratio in fumarolic gases from the source vent (4.4 × 10^− 7) suggests that plume chemical composition is not well represented by the emission source (fumaroles) due to chemical processes prior to (or upon) discharge. Current mercury emission from La Soufrìere volcano represents a very small contribution to the estimated global volcanic budget for this element.     

Elucidation of different forms of organic carbon in marine sediments from the Atlantic coast of Spain using thermal analysis coupled to isotope ratio and quadrupole mass spectrometry

Analysis of river, estuary and marine sediments from the Atlantic coast of Spain using thermogravimetry–differential scanning calorimetry–quadrupole mass spectrometry–isotope ratio mass spectrometry (TG–DSC–QMS–IRMS) was used to (a) distinguish bulk chemical hosts for C within a sediment and humic acid fraction, (b) track C pools with differing natural C isotope ratios and (c) observe variation with distance from the coast. This is the first application of such a novel method to the characterisation of organic matter from marine sediments and their corresponding humic acid fractions. Using thermal analysis, a labile, a recalcitrant and a refractory carbon pool can be distinguished. Extracted humic fractions are mainly of recalcitrant nature. The proportion of refractory carbon is greatest in marine sediments and humic acid fractions. Quadrupole mass spectrometry confirmed that the greatest proportion of m/z 44 (CO₂) and m/z 18 (H₂O) were detected at temperatures associated with recalcitrant carbon (510–540 °C). Isotope analysis detected progressive enrichment in δ¹³C for the sediment samples with an increase in marine influence. Isotopic heterogeneity in the refractory organic matter in marine sediments could be due to products of anthropogenic origin or natural combustion products. Isotope homogeneity of humic acids confirms the presence of terrigenous C in marine sediments, allowing the terrestrial input to be characterised.     

Cu and Fe associated with humic acids in sediments of a tropical coastal lagoon

The amount of Cu and Fe associated with humic acids was estimated in five sediment cores from a tropical coastal lagoon (Piratininga Lagoon, Rio de Janeiro, Brazil). Core samples were analysed for humic acid contents, total Fe and Cu content. Fe and Cu associated with humic acids were also measured. Results show amounts of humic acids ranging from 0.7 to 21.7% of the dry weight of sediment (average 4.6%, standard deviation 4.4%). Concentrations of Fe and Cu ranged from 0.3 to 6.0% (average 2.2%, S.D. 1.2%) and from <1.0 to 65.0 μg g⁻¹ (average 28.6 μg g⁻¹, S.D. 16.4 μg g⁻¹), respectively. The results of strongly bound metals show that while humic acids are the main carrier for Cu, Fe does not seems to be significantly associated with this organic matter.