污灌区地下水硝酸盐污染来源的氮同位素示踪

为了识别石家庄市南部污灌区地下水硝酸盐污染来源, 采集5种潜在污染源和19组地下水样用于化学和氮同位素分析.灌溉污水NH₄+的δ15N值较低(4.0‰), 施化肥土壤和粪堆下土壤NO₃-的δ15N值分别为1.4‰和12.4‰; 仅施厩肥的蔬菜种植区下伏近30 m厚包气带沉积物NO₃-的δ15N分布显示, 来自动物粪便的NO₃-已运移到11.5 m以下包气带, 均值10.9‰; 污水灌溉农田下伏厚层包气带沉积物样品分析结果指示, 土壤层下伏包气带沉积物δ15N值变幅较小, 均值5.7‰.污灌区内除一深井外, 其他水井地下水硝酸盐浓度变化在52.6~124.5 mg/L之间, 均值79.72 mg/L, δ15N值变化在5.3‰~8.3‰之间, 均值7.0‰.污灌区地下水的δ15N值较污灌区土壤层下伏包气带沉积物的δ15N值高, 表明地下水NO₃-除了来自灌溉的污水外, 还有δ15N值更高的其他来源, 这些来源主要是人和动物粪便.利用线性混合模型计算, 污灌区地下水NO₃-来自灌溉的污水, 约占76%, 而来自人和动物粪便的NO₃-约占24%.为控制污灌区地下水NO₃-浓度进一步增长, 不仅要加强污水灌溉管理, 还要加强人和动物粪便的管理.      

Application of multiple-isotope and groundwater-age data to identify factors affecting the extent of denitrification in a shallow aquifer near a river in South Korea

The extent of denitrification in a small agricultural area near a river in Yangpyeong, South Korea, was determined using multiple isotopes, groundwater age, and physicochemical data for groundwater. The shallow groundwater at one monitoring site had high concentrations of NO₃-N (74–83 mg L^?1). The δ¹⁵N-NO₃ values for groundwater in the study area ranged between +9.1 and +24.6‰ in June 2014 and +12.2 to +21.6‰ in October 2014. High δ¹⁵N-NO₃ values (+10.7 to +12.5‰) in both sampling periods indicated that the high concentrations of nitrate in the groundwater originated from application of organic fertilizers and manure. In the northern part of the study area, some groundwater samples showed elevated δ¹⁵N-NO₃ and δ¹⁸O-NO₃ values, which suggest that nitrate was removed from the groundwater via denitrification, with N isotope enrichment factors ranging between ?4.8 and ?7.9‰ and O isotope enrichment factors varying between ?3.8 and ?4.9‰. Similar δD and δ¹⁸O values of the surface water and groundwater in the south appear to indicate that groundwater in that area was affected by surface-water infiltration. The mean residence times (MRTs) of groundwater showed younger ages in the south (10–20 years) than in the north (20–30 years). Hence, it was concluded that denitrification processes under anaerobic conditions with longer groundwater MRT in the northern part of the study area removed considerable amounts of nitrate. This study demonstrates that multi-isotope data combined with physicochemical data and age-dating information can be effectively applied to characterize nitrate contaminant sources and attenuation processes.     

Role of degree of saturation in denitrification of unsaturated sand specimens

Nitrate contamination of groundwater arises from anthropogenic activities, such as, fertilizer and animal manure applications and infiltration of wastewater/leachates. During migration of wastewater and leachates, the vadose zone (zone residing above the groundwater table), is considered to facilitate microbial denitrification. Particle voids in vadose zone are deficient in dissolved oxygen as the voids are partially filled by water and the remainder by air. Discontinuities in liquid phase would also restrict oxygen diffusion and therefore facilitate denitrification in the vadose/unsaturated soil zone. The degree of saturation of soil specimen (S _r) quantifies the relative volume of voids filled with air and water. Unsaturated specimens have S _r values ranging between 0 and 100 %. Earlier studies from naturally occurring nitrate losses in groundwater aquifers in Mulbagal town, Kolar District, Karnataka, showed that the sub-surface soils composed of residually derived sandy soil; hence, natural sand was chosen in the laboratory denitrification experiments. With a view to understand the role of vadose zone in denitrification process, experiments are performed with unsaturated sand specimens (S _r = 73–90 %) whose pore water was spiked with nitrate and ethanol solutions. Experimental results revealed 73 % S _r specimen facilitates nitrate reduction to 45 mg/L in relatively short durations of 5.5–7.5 h using the available natural organic matter (0.41 % on mass basis of sand); consequently, ethanol addition did not impact rate of denitrification. However, at higher S _r values of 81 and 90 %, extraneous ethanol addition (C/N = 0.5–3) was needed to accelerate the denitrification rates.     

Redox-driven changes in porewater chemistry in the unsaturated zone of the chalk aquifer beneath unlined cattle slurry lagoons

Farm waste stores such as cattle slurry lagoons are widespread in the UK and many overly important aquifers. Stores can be serious risks to water quality because they are important sources of N species, organic C and pathogenic microbes. At two sites on the Chalk aquifer of southern England, inclined boreholes were drilled and cored to obtain aquifer material from directly beneath unlined slurry stores. Vertical boreholes were also drilled adjacent to the slurry stores to determine any lateral movement of contaminants. Interstitial porewaters were analysed for major and minor ions and S isotopes. At the second site, unsaturated zone gases were sampled from the inclined hole. Infiltration of slurry into the unsaturated zone caused significantly elevated concentrations of metals such as Cu and Ni at both sites. Sulphate reduction was occurring at Site 1, as evidenced by SO₄ concentrations decreasing from 150 to 50 mg/l and enhanced ratios of δ³⁴S–SO₄ and δ¹⁸O–SO₄. Ammonium-N also leaches along with dissolved organic C which were found 17 m below ground surface at concentrations up to 400 and 260 mg/l, respectively. Contaminant concentrations were similar in the porewaters from both the inclined and vertical boreholes. At Site 2, higher contaminant concentrations were found in the inclined borehole compared with the vertical borehole. Organic C concentrations were considerably lower than at Site 1, ranging from 10 to 70 mg/l. Ammonium–N concentrations reached a maximum concentration of 25 mg/l, however NO₃-N concentrations were up to 500 mg/l and SO₄ concentrations were generally higher than Site 1. Data for N₂/Ar and δ¹⁵N–N₂ from the gas samplers show a peak of 102 and 2.2‰, respectively, at 14 m below ground level indicating denitrification was taking place. Evidence from δ³⁴S–SO₄ and δ¹⁸O–SO₄ suggest that some SO₄ reduction was taking place simultaneously. From CH₄ and NH₃ detected at depth it is suggested that slurry contamination, emanating from early use of the store, has passed through the top 18 m of the unsaturated zone at Site 2. The presence of high concentrations of NO₃ and lower concentrations of organic C suggests that this lagoon has formed a relatively impermeable seal at its base within the first few years of its lifetime. The anoxic conditions at both sites may have mobilised U from N–P–K fertilisers. Both sites are continuing to impact on the porewater chemistry and pose a risk of groundwater contamination.     

Carbon and nitrogen isotope,and mineral inclusion studies on the diamonds from the Pozanti–Karsanti chromitite,Turkey

The Pozanti–Karsanti ophiolite (PKO) is one of the largest oceanic remnants in the Tauride belt, Turkey. Micro-diamonds were recovered from the podiform chromitites, and these diamonds were investigated based on morphology, color, cathodoluminescence, nitrogen content, carbon and nitrogen isotopes, internal structure and inclusions. The diamonds recovered from the PKO are mainly mixed-habit diamonds with sectors of different brightness under the cathodoluminescence images. The total δ¹³C range of the PKO diamonds varies between ??18.8 and ??28.4‰, with a principle δ¹³C mode at ??25‰. Nitrogen contents of the diamonds range from 7 to 541 ppm with a mean value of 171 ppm, and the δ¹⁵N values range from ??19.1 to 16.6‰, with a δ¹⁵N mode of ??9‰. Stacking faults and partial dislocations are commonly observed in the Transmission Electron Microscopy foils whereas inclusions are rather rare. Combinations of (Ca_0.81Mn_0.19)SiO₃, NiMnCo-alloy and nano-sized, quenched fluid phases were observed as inclusions in the PKO diamonds. We believe that the ¹³C-depleted carbon signature of the PKO diamonds derived from previously subducted crustal matter. These diamonds may have crystallized from C-saturated fluids in the asthenospheric mantle at depth below 250 km which were subsequently carried rapidly upward by asthenospheric melts.     

Nitrogen recycling in subducted mantle rocks and implications for the global nitrogen cycle

The nitrogen concentrations [N] and isotopic compositions of ultramafic mantle rocks that represent various dehydration stages and metamorphic conditions during the subduction cycle were investigated to assess the role of such rocks in deep-Earth N cycling. The samples analyzed record low-grade serpentinization on the seafloor and/or in the forearc wedge (low-grade serpentinites from Monte Nero/Italy and Erro Tobbio/Italy) and two successive stages of metamorphic dehydration at increasing pressures and temperatures (high-pressure (HP) serpentinites from Erro Tobbio/Italy and chlorite harzburgites from Cerro del Almirez/Spain) to allow for the determination of dehydration effects in ultramafic rocks on the N budget. In low-grade serpentinites, δ¹⁵N_air values (?3.8 to +3.5 ‰) and [N] (1.3–4.5 μg/g) are elevated compared to the pristine depleted MORB mantle (δ¹⁵N_air ~ ?5 ‰, [N] = 0.27 ± 0.16 μg/g), indicating input from sedimentary organic sources, at the outer rise during slab bending and/or in the forearc mantle wedge during hydration by slab-derived fluids. Both HP serpentinites and chlorite harzburgites have δ¹⁵N_air values and [N] overlapping with low-grade serpentinites, indicating no significant loss of N during metamorphic dehydration and retention of N to depths of 60–70 km. The best estimate for the δ¹⁵N_air of ultramafic rocks recycled into the mantle is +3 ± 2 ‰. The global N subduction input flux in serpentinized oceanic mantle rocks was calculated as 2.3 × 10⁸ mol N₂/year, assuming a thickness of serpentinized slab mantle of 500 m. This is at least one order of magnitude smaller than the N fluxes calculated for sediments and altered oceanic crust. Calculated global input fluxes for a range of representative subducting sections of unmetamorphosed and HP-metamorphosed slabs, all incorporating serpentinized slab mantle, range from 1.1 × 10¹⁰ to 3.9 × 10¹⁰ mol N₂/year. The best estimate for the δ¹⁵N_air of the subducting slab is +4 ± 1 ‰, supporting models that invoke recycling of subducted N in mantle plumes and consistent with general models for the volatile evolution on Earth. Estimates of the efficiency of arc return of subducted N are complicated further by the possibility that mantle wedge hydrated in forearcs, then dragged to beneath volcanic fronts, is capable of conveying significant amounts of N to subarc depths.     

Assessing nitrate origin in a volcanic aquifer using a dual isotope approach

Identifying the origin of nitrate is important for the control and management of groundwater quality in aquifer systems. In the southern Apennines (Italy), the Mount Vulture volcanic aquifer is a large and valuable resource of potable and mineral water supply. Unfortunately, signs of anthropogenic impact, especially nitrogen contamination, have recently become evident. In this study, and for the first time, stable isotope ratios (δ¹⁵N and δ¹⁸O) of NO₃ ^? were determined in groundwater to identify their origins and evaluate the presence of transformation processes. The Mount Vulture groundwaters are meteoric in origin, as demonstrated by measurements of δD and δ¹⁸O, and can be divided into two distinct areas based on their NO₃ ^? content. In the southeastern area, characterized by active agricultural land use, the high NO₃ ^? content and the δ¹⁵N–NO₃ isotopic values are due to anthropogenic contamination (inorganic fertilizer). In groundwaters from the western area, the NO₃ ^? contents below 4 mg/L and the δ¹⁵N–NO₃ values can be associated at organic soil N. Evidence for local denitrification may be assumed in a few groundwater samples of the western area showing relatively heavy δ¹⁵N values and low concentrations of nitrate. Finally, the low measured δ¹⁸O values indicate that nitrification occurred in both investigated areas.     

Formation of carbonate concretions in surface sediments of two mud mounds,offshore Costa Rica: a stable isotope study

The surface sediments of two mud mounds (“Mound 11” and “Mound 12”) offshore southwest Costa Rica contain abundant authigenic carbonate concretions dominated by high-Mg calcite (14–20 mol-% MgCO₃). Pore fluid geochemical profiles (sulfate, sulfide, methane, alkalinity, Ca and Mg) indicate recent carbonate precipitation within the zone of anaerobic oxidation of methane (AOM) at variable depths. The current location of the authigenic carbonate concretions is, however, not related to the present location of the AOM zone, suggesting mineral precipitation under past geochemical conditions as well as changes in the flow rates of upward migrating fluids. Stable oxygen and carbon isotope analysis of authigenic carbonate concretions yielded δ¹⁸O_carbonate values ranging between 34.0 and 37.7 ‰ Vienna standard mean ocean water (VSMOW) and δ¹³C_carbonate values from ?52.2 to ?14.2 ‰ Vienna Pee Dee belemnite (VPDB). Assuming that no temperature changes occurred during mineral formation, the authigenic carbonate concretions have been formed at in situ temperature of 4–5 °C. The δ¹⁸O_carbonate values suggest mineral formation from seawater-derived pore fluid (δ¹⁸O_porefluid = 0 ‰ VSMOW) for Mound 12 carbonate concretions but also the presence of an emanating diagenetic fluid (δ¹⁸O_porefluid ≈5 ‰) in Mound 11. A positive correlation between δ¹³C_carbonate and δ¹⁸O_carbonate is observed, indicating the admixing of two different sources of dissolved carbon and oxygen in the sediments of the two mounds. The carbon of these sources are (1) marine bicarbonate (δ¹³C_porefluid ≈0 ‰) and (2) bicarbonate which formed during the AOM (δ¹³C_porefluid ≈?70 ‰). Furthermore, the δ¹⁸O_porefluid composition, with values up to +4.7 ‰ Vienna standard mean ocean water (VSMOW), is interpreted to be affected by the presence of emanating, freshened and boron-enriched fluids. Earlier, it has been shown that the origin of ¹⁸O-enriched fluids are deep diagenetic processes as it was indicated by the presence of methane with thermogenic signature (δ¹³C_CH4 = ?38 ‰). A combination of present geochemical data with geophysical observations indicates that Mounds 11 and 12 represent a single fluid system interconnected by deep-seated fault(s).     

Fluid-induced breakdown of white mica controls nitrogen transfer during fluid–rock interaction in subduction zones

ABSTRACT

In order to determine the effects of fluid–rock interaction on nitrogen elemental and isotopic systematics in high-pressure metamorphic rocks, we investigated three different profiles representing three distinct scenarios of metasomatic overprinting. A profile from the Chinese Tianshan (ultra)high-pressure–low-temperature metamorphic belt represents a prograde, fluid-induced blueschist–eclogite transformation. This profile shows a systematic decrease in N concentrations from the host blueschist (~26 μg/g) via a blueschist–eclogite transition zone (19–23 μg/g) and an eclogitic selvage (12–16 μg/g) towards the former fluid pathway. Eclogites and blueschists show only a small variation in δ¹⁵N_air (+2.1 ± 0.3‰), but the systematic trend with distance is consistent with a batch devolatilization process. A second profile from the Tianshan represents a retrograde eclogite–blueschist transition. It shows increasing, but more scattered, N concentrations from the eclogite towards the blueschist and an unsystematic variation in δ¹⁵N values (δ¹⁵N = + 1.0 to +5.4‰). A third profile from the high-P/T metamorphic basement complex of the Southern Armorican Massif (Vendée, France) comprises a sequence from an eclogite lens via retrogressed eclogite and amphibolite into metasedimentary country rock gneisses. Metasedimentary gneisses have high N contents (14–52 μg/g) and positive δ¹⁵N values (+2.9 to +5.8‰), and N concentrations become lower away from the contact with 11–24 μg/g for the amphibolites, 10–14 μg/g for the retrogressed eclogite, and 2.1–3.6 μg/g for the pristine eclogite, which also has the lightest N isotopic compositions (δ¹⁵N = + 2.1 to +3.6‰).

Overall, geochemical correlations demonstrate that phengitic white mica is the major host of N in metamorphosed mafic rocks. During fluid-induced metamorphic overprint, both abundances and isotopic composition of N are controlled by the stability and presence of white mica. Phengite breakdown in high-P/T metamorphic rocks can liberate significant amounts of N into the fluid. Due to the sensitivity of the N isotope system to a sedimentary signature, it can be used to trace the extent of N transport during metasomatic processes. The Vendée profile demonstrates that this process occurs over several tens of metres and affects both N concentrations and N isotopic compositions.     

Hydrogen and Oxygen Isotope Study on the Water-Rock Interaction of the Yinshan (Cu-) Pb-Zn-Ag Ore Deposit, Jiangxi Province

The δ18O values of vein quartz of different stages from the Yinshan ore deposit are constant around 16‰ and the calculated δ18OH2O values attain 8‰± ; the δDH2O values of fluid inclu-sions in vein quartz are constant at about-60‰. From the surface down to 1200 m below the δ18O values of altered rocks gradually decrease from 15‰± to 11‰± . Various water-rock inversion calculations indicate that the ore fluids were formed by the interaction between meteoric water and phyllite at 350℃ and the effective W/ R value of around 0.1. When the water-rock exchange in the upper mineralization system took place, the effective W / R value increased to 5.0 or more. As a result, an evolution and mineralization model of a buffered open system with two-stage water-rock interactions is proposed in this study.     

Assessment of bacterial biomass in the highly contaminated urban Nanming River,Guiyang, SW China

High anthropogenic N loads and abundant bacteria are characteristic of highly contaminated urban rivers. To better understand the dispersal and accumulation of bacteria, we determined contents and isotopic compositions of suspended particulate organic matter (SPOM) and bacteria in a highly contaminated urban river (the Nanming) and effluents in winter and summer of 2013. Relative to SPOM, bacterial biomass in the river was depleted in ¹³C and ¹⁵N and its C/N ratio was lower (δ¹³C: ? 33.2‰ ± 3.1‰; δ¹⁵N: ? 1.5‰ ± 1.2‰; C/N: 4.8 ± 0.6), while effluents showed higher ¹³C and ¹⁵N contents and C/N ratios (δ¹³C: ? 25‰ ± 2.1‰; δ¹⁵N: + 8.5‰ ± 1.1‰; C/N: 8.1 ± 1.2). Source recognition of SPOM was based on carbon isotopes because they are conservative and distinct between end-members (effluent detritus and bacterial biomass). Using a mixing model, bacterial biomass in the river was calculated to account for < 20% and < 56% of bulk suspended particulate organic nitrogen in winter and summer, respectively. An N budget showed that bacterial N was a small proportion of total nitrogen (< 7.4%) in the riverwater.     

Effects of agricultural practices on nitrogen distribution in unsaturated soils

Nitrogen fertilizer consumption is very common in the agricultural practices. Nitrogen application could be an important source of groundwater N pollution. Normally, nitrogen can pass through the unsaturated zone to pollute the groundwater. Different agricultural practices have different cultivation methods, accordingly different fertilization and irrigation techniques. Hence, the agricultural practice determines the environment of the unsaturated zone, which subsequently determines the extent of groundwater N pollution. To verify the pollution modes and transformation mechanisms of nitrogen, both in situ and laboratory tests were conducted at four different sites to study the effects of agricultural practices on nitrogen distribution in unsaturated zones. The inorganic nitrogen in soil is extracted by potassium chloride solution, and the soil utilization form and pollution type are identified by δ¹⁵N by comparing with the known standard values. The experimental results indicate that continual fertilization and sewage irrigation in these agricultural regions were the primary sources of nitrogen in the unsaturated zone. In the soils planted with rice, δ¹⁵N–NH₄ ⁺ was relatively elevated due to ammonium volatilization. In the unsaturated zone of rice–wheat rotation fields, NO₃ ^?–N and δ¹⁵N were both elevated because of manure fertilizer. Meanwhile, denitrification also occurred in the hypoxic environment due to the high soil water content.     

Cretaceous–Neogene basin control on the formation of uranium deposits in South China: evidence from geology,mineralization ages,and H–O isotopes

ABSTRACT

The South China Uranium Province (SCUP) contains the largest number of discovered uranium deposits in China. This province includes seven uranium mineralization belts, at Wuyishan, Taoshan–Zhuguang, Chenzhou–Qinzhou, Gan–Hang, Xixia–Luzong, Mufushan–Hengshan, and Xuefengshan–Jiuwandashan. The uranium deposits can be classified according to their ore-hosting rocks into four general types: granite-, volcanic-, black-shale-, and sandstone-related. These uranium deposits crop out at the peripheries of Cretaceous–Neogene (K–N) redbed basins or are connected to the basins by NE–SW- to NNE–SSW-trending regional faults. Most of the volcanic-related uranium deposits were formed during the mid-Cretaceous (118 to 88 Ma); granite-related deposits have a wider range of ages from 124 to 11 Ma; the black-shale-related deposits have ages of 120 to 7 Ma; sandstone-related deposits yield ages of 111 to 22.5 Ma. As such, these four types of uranium deposits in South China have similar ages, irrespective of location, and are similar in age to K–N redbed basins in this region. δD_VSMOW(fluid) and δ¹⁸O_VSMOW(fluid) values of the volcanic-related uranium deposits generally range from – 105.9‰ to – 38.0‰ and – 11.1‰ to +5.3‰, respectively. The black-shale-related uranium deposits yield δD_VSMOW(fluid) and δ¹⁸O_VSMOW(fluid) values of – 74.5‰ to – 33.0‰ and – 4.4‰ to 9.3‰, respectively. However, the granite-related uranium deposits have a much wider range of δD_VSMOW(fluid) and δ¹⁸O_VSMOW(fluid) values from – 104.4‰ to – 23.1‰ and – 9.4‰ to +7.3‰, respectively. H–O isotopic compositions of the SCUP ore-forming fluids are similar to those of basinal fluids, again demonstrating the link between the uranium deposits and the basins. The spatial–temporal relationships and fluid isotopic similarities between the K–N basins and uranium mineralization indicate that the uranium deposits of the SCUP are genetically related to the K–N redbed basins, and are unconformity-related uranium deposits.     

A reinterpretation of the crustal N‐isotope record: evidence for a 15N‐enriched Archean atmosphere?

A new compilation of N‐isotope and abundance data for metasedimentary rocks, and hyrdothermal micas that proxy for bulk crust, show systematic patterns. (1) δ¹⁵N values of kerogen in Precambrian cherts are more negative relative to siliciclastic counterparts, probably due to a mantle hydrothermal component. (2) There is a secular trend from average δ¹⁵N 15.3 ± 1.8‰ in Archean shales, through intermediate values in the Proterozoic, to Phanerozoic counterparts where δ¹⁵N averages +3.5‰. (3) Hydrothermal micas in metamorphic hydrothermal systems of Palaeozoic and Mesozoic age that proxy for crust have δ¹⁵N within the range of contemporaneous sedimentary rocks. (4) Hydrothermal micas track the secular trend of δ¹⁵N for kerogen from 2.7 Ga to the Phanerozoic. (5) Within Precambrian datasets δ¹⁵N does not increase with decreasing N content; accordingly, high δ¹⁵N values cannot stem either from metamorphism or form Rayleigh fractionation. (6) Previous studies show isotopic shifts during metamorphism are only +1 to +3‰ up to amphibolite facies. Values of 10–24‰ are attributed to a high δ¹⁵N Archean atmosphere, a residual signature of CI carbonaceous chondrites where δ¹⁵N is +30‰ to + 42‰.     

Traces of brine and hydrocarbon migration in carbon,oxygen, and sulfur isotopic compositions of reservoir rocks in the Talakan petroleum field,Southwestern Yakutia

Dolomites from the productive Osa horizon (upper subformation of the Lower Cambrian Bilir Formation) in the Talakan petroleum field show a prominent 1–2‰ decrease in δ¹⁸O (from 23–24 to 21–22‰), which presumably marks a zone of relatively high water/rock ratios. Productive boreholes are characterized by moderate δ³⁴S values (from 25.1 to 30.6‰) and negative correlation between δ³⁴S in anhydrite and δ¹⁸O in associated dolomite, which points to a partial sulfate reduction during catagenesis. In nonproductive borehole, δ³⁴S values increase significantly (from 31.4 to 35.6‰) and show positive correlation with δ¹⁸O in dolomite. Rocks recovered by nonproductive borehole possibly recrystallized during early diagenesis, and, correspondingly lost their permeability and capacity to form pores. Limestones and dolomites of the Osa horizon have a carbon isotopic composition within the range of normal marine carbonates (δ¹³C = 0 ± 1 ‰), which does not indicate a significant role of organic matter in postsedimentary recrystallization of carbonate sediments. A positive δ¹³C excursion up to 4.5‰ recorded in the lower subformation of the Bilir Formation presumably occurred at the sedimentation stage under conditions of high rates of bioproductivity and organic matter burial in sediments.     

Chemical Dynamics and Evaluation of Biogeochemical Processes in Alpine River Kamniška Bistrica, North Slovenia

Biogeochemical processes were investigated in alpine river—Kamni?ka Bistrica River (North Slovenia), which represents an ideal natural laboratory for studying anthropogenic impacts in catchments with high weathering capacity. The Kamni?ka Bistrica River water chemistry is dominated by HCO₃ ^?, Ca²⁺ and Mg²⁺, and Ca²⁺/Mg²⁺ molar ratios indicate that calcite weathering is the major source of solutes to the river system. The Kamni?ka Bistrica River and its tributaries are oversaturated with respect to calcite and dolomite. pCO₂ concentrations were on average up to 25 times over atmospheric values. δ¹³C_DIC values ranged from ?12.7 to ?2.7 ‰, controlled by biogeochemical processes in the catchment and within the stream; carbonate dissolution is the most important biogeochemical process affecting carbon isotopes in the upstream portions of the catchment, while carbonate dissolution and organic matter degradation control carbon isotope signatures downstream. Contributions of DIC from various biogeochemical processes were determined using steady state equations for different sampling seasons at the mouth of the Kamni?ka Bistrica River; results indicate that: (1) 1.9–2.2 % of DIC came from exchange with atmospheric CO₂, (2) 0–27.5 % of DIC came from degradation of organic matter, (3) 25.4–41.5 % of DIC came from dissolution of carbonates and (4) 33–85 % of DIC came from tributaries. δ¹⁵N values of nitrate ranged from ?5.2 ‰ at the headwater spring to 9.8 ‰ in the lower reaches. Higher δ¹⁵N values in the lower reaches of the river suggest anthropogenic pollution from agricultural activity. Based on seasonal and longitudinal changes of chemical and isotopic indicators of carbon and nitrogen in Kamni?ka Bistrica River, it can be concluded that seasonal changes are observed (higher concentrations are detected at low discharge conditions) and it turns from pristine alpine river to anthropogenic influenced river in central flow.     

Microscale Simultaneous Measurement of Carbon and Nitrogen Isotopes on Natural Diamond

Simultaneous analysis of carbon and nitrogen isotope ratios by SIMS was applied for the first-time to a natural diamond from the Kelsey Lake kimberlite, State Line Distinct, Colorado (UWD-1). This in situ procedure is faster, reduces sample size for analysis, and measures both isotope ratios from a single ~ 10 μm diameter pit, a critical advantage for zoned diamonds. The carbon isotope ratio (expressed as δ¹³C_VPDB) of the bulk UWD-1 crystal, determined by the conventional combustion method in the present study, is -5.9‰ ± 0.2‰ (VPDB, 2s). Nitrogen mass fraction ([N]) and isotope ratio (expressed as δ¹⁵N_Air) were determined by stepwise combustion and gas-source mass-spectrometry, resulting in 553 ± 64 μg g^-1 and -6.7‰ ± 1.1‰ (Air, 2s), respectively. Secondary ions of ¹²C₂^-, ¹²C¹³C^-, ¹²C¹⁴N^-, and ¹²C¹⁵N^- were simultaneously measured by SIMS using three Faraday cups and one electron multiplier. The spot-to-spot reproducibility of δ¹³C and δ¹⁵N values for the UWD-1 (178 spots on sixteen chips, 10 μm spots), were 0.3‰ and 1.6‰, respectively (2s). While ¹²C¹⁴N^-/¹²C₂^- ratios, which are an indicator for [N], varied up to 12% among these sixteen chips, such variation did not correlate with either δ¹³C or δ¹⁵N values. We propose that UWD-1 is a suitable reference sample for microscale in situ analysis of δ¹³C and δ¹⁵N values in diamond samples.     

Geochemical evidence of microbial activity within ooids

Ooid formation remains elusive despite their importance as palaeoclimatic indicators and important contributors to global carbonate budget. Based on stable isotopes, nutrient and elemental analyses on solid components and ooidal leachates, this study supports the notion of microbial involvement in the development of ooids from Great Bahama Bank. Carbon and nitrogen isotopic analyses on organic fractions identified geochemical signatures of microbial activity. The δ¹³C values for organic carbon in the bulk (?11·9 to ?16·9‰); intercrystalline/intracrystalline (?11·9 to 16·7‰); and intracrystalline phases (?12·4 to ?17·7‰) were similar and, except for the more enriched values of ooids from Butterfly Beach, were within the range of photosynthesisers. The δ¹⁵N values for the bulk (+0·5 to ?0·2‰); intercrystalline/intracrystalline (?0·3‰ to ?0·7‰) and intracrystalline organic matter (?0·3 to ?1·7‰) showed a narrow range consistent with nitrogen fixation. While positive δ¹⁵N and δ¹⁸O values of the leached from the ooids provided evidence of denitrification, the carbonate associated sulphate δ³⁴S_CAS of the bulk sediments (+19·2 to +19·6‰) and δ³⁴S of the leachates (+16·6 to +18·3‰) provided weak indication of sulphate reduction, suggesting either that high concentrations of isotopically enriched S are overriding bio‐signatures of sulphate reduction or that microbes are preferentially using as an electron acceptor. In contrast, the elevated sulphate concentrations of the leachates suggest the occurrence of microbial sulphide oxidation within ooids. The high Mg/Ca of the leachates and scanning electron microscope analyses provide putative evidence of amorphous calcium carbonate and a formative role in CaCO₃ precipitation. Together, these findings indicate that a redox dependent microbial consortium may influence CaCO₃ precipitation in the form of ooid accretion, cementation and micritization. It is also inferred that ooid deposits are not suitable indicators of palaeoclimate because ooids are affected throughout their life by a complex chain of abiotic and biological processes which can lead to large geochemical offsets.     

Extreme <Superscript>15</Superscript>N Depletion in Seagrasses

Seagrass beds form an important part of the coastal ecosystem in many parts of the world but are very sensitive to anthropogenic nutrient increases. In the last decades, stable isotopes have been used as tracers of anthropogenic nutrient sources and to distinguish these impacts from natural environmental change, as well as in the identification of food sources in isotopic food web reconstruction. Thus, it is important to establish the extent of natural variations on the stable isotope composition of seagrass, validating their ability to act as both tracers of nutrients and food sources. Around the world, depending on the seagrass species and ecosystem, values of seagrass N normally vary from 0 to 8?‰ δ¹⁵N. In this study, highly unusual seagrass N isotope values were observed on the east coast of Qatar, with significant spatial variation over a scale of a few metres, and with δ¹⁵N values ranging from +2.95 to ?12.39?‰ within a single bay during March 2012. This pattern of variation was consistent over a period of a year although there was a seasonal effect on the seagrass δ¹⁵N values. Seagrass, water column and sediment nutrient profiles were not correlated with seagrass δ¹⁵N values and neither were longer-term indicators of nutrient limitation such as seagrass biomass and height. Sediment δ¹⁵N values were correlated with Halodule uninervis δ¹⁵N values and this, together with the small spatial scale of variation, suggest that localised sediment processes may be responsible for the extreme isotopic values. Consistent differences in sediment to plant ¹⁵N discrimination between seagrass species also suggest that species-specific nutrient uptake mechanisms contribute to the observed δ¹⁵N values. This study reports some of the most extreme, negative δ¹⁵N values ever noted for seagrass (as low as ?12.4?‰) and some of the most highly spatially variable (values varied over 15.4?‰ in a relatively small area of only 655 ha). These results are widely relevant, as they demonstrate the need for adequate spatial and temporal sampling when working with N stable isotopes to identify food sources in food web studies or as tracers of anthropogenic nutrients.     

The Use of Stable Sulfur, Oxygen and Hydrogen Isotope Ratios as Geochemical Tracers of Sulfates in the Podwiśniówka Acid Drainage Area (South-Central Poland)

The paper presents the results of determinations of stable S and O isotopes of dissolved sulfates and O and H stable isotopes of waters from three ponds, that is, Marczakowe Do?y acid pond, Marczakowe Do?y fish pond and Podwi?niówka acid pit pond, located in the Holy Cross Mountains (south-central Poland). The δ³⁴S_V-CDT and δ¹⁸O_V-SMOW of SO₄ ^2? in waters of three ponds (n = 14) varied from ?16.2 to ?9.5 ‰ (mean of ?13.6 ‰) and from ?8.1 to ?3.2 ‰ (mean of ?4.8 ‰), respectively. The mean δ³⁴S–SO₄ ^2? values were closer to those of pyrite (mean of ?25.4 ‰) and efflorescent sulfate salts (mean of ?25.6 ‰), recorded previously in the Podwi?niówka quarry, than to sulfates derived from other anthropogenic or soil and bedrock sources. The SO₄ ^2? ions formed by bacterially induced pyrite oxidation combined with bacterial (dissimilatory) dissolved sulfate reduction, and presumably with subordinate mineralization of carbon-bonded sulfur compounds, especially in both Marczakowe Do?y ponds. In addition, the comparison of δ¹⁸O–SO₄ ^2? and δ¹⁸O–H₂O values indicated that 75–100 % of sulfate oxygen was derived from water. Due to the largest size, the Podwi?niówka acid pit pond revealed distinct seasonal variations in both δ¹⁸O–H₂O (?9.2 to ?1.6) and δD–H₂O (?29.7 to ?71.3) values. The strong correlation coefficient (r ² = 0.99) was noted between δ¹⁸O–H₂O and δD–H₂O values, which points to atmospheric precipitation as the only source of water. The sediments of both acid ponds display different mineral inventory: the Marczakowe Do?y acid pond sediment consists of schwertmannite and goethite, whereas Podwi?niówka acid pit pond sediment is composed of quartz, illite, chlorite and kaolinite with some admixture of jarosite reflecting a more acidic environment. Geochemical modeling of two acid ponds indicated that the saturation indices of schwertmannite and nanosized ε-Fe₂O₃ (Fe³⁺ oxide polymorph) were closest to thermodynamic equilibrium state with water, varying from ?1.44 to 3.05 and from ?3.42 to 6.04, respectively. This evidence matches well with the obtained mineralogical results.