Groundwater N speciation and redox control of organic N mineralization by O2 reduction to H2O2

Excess N from agriculture induces eutrophication in major river systems and hypoxia in coastal waters throughout the world. Much of this N is from headwaters far up the watersheds. In turn, much of the N in these headwaters is from ground-water discharge. Consequently, the concentrations and forms of N in groundwater are important factors affecting major aquatic ecosystems; despite this, few data exist for several species of N in groundwater and controls on speciation are ill-defined. Herein, we report N speciation for a spring and well that were selected to reflect agricultural impacts, and a spring and well that show little to no agricultural-N impact. Samples were characterized for NO₃⁻, NO₂⁻, N₂O, NH₄⁺, urea, particulate organic N(), and dissolved organic N(). These analytes were monitored in the agricultural spring for up to two years along with other analytes that we reported upon previously. For all samples, when oxidized N was present, the dominant species was NO₃⁻ (88-98% of total fixed N pool) followed by (<4-12%) and only trace fractions of the other N analytes. In the non-agriculturally impacted well sample, which had no quantifiable NO₃⁻ or dissolved O₂, comprised the dominant fraction (68%) followed by NH₄⁺ (32%), with only a trace balance comprised of other N analytes. Water drawn from the well, spring and a wetland situated in the agricultural watershed also were analyzed for dissolved N₂ and found to have a fugacity in excess of that of the atmosphere. H₂O₂ was analyzed in the agricultural spring to evaluate the O₂/H₂O₂ redox potential and compare it to other calculated potentials. The potential of the O₂/H₂O₂ couple was close in value to the NO₃⁻/NO₂⁻ couple suggesting the important role of H₂O₂ as an O₂-reduction intermediate product and that O₂ and NO₃⁻ are reduced concomitantly. The O₂/H₂O₂ and NO₃⁻/NO₂⁻ couples also were close in value to a cluster of other inorganic N and Fe couples indicating near partial equilibrium among these species. Urea mineralization to NO₂⁻ was found to approach equilibrium with the reduction of O₂ to H₂O₂. By modeling as amide functional groups, as justified by recent analytical work, similar thermodynamic calculations support that mineralization to NO₂⁻ proceeds nearly to equilibrium with the reduction of O₂ to H₂O₂ as well. This near equilibration of redox couples for urea- and -oxidation with O₂-reduction places these two couples within the oxidized redox cluster that is shared among several other couples we have reported previously. In the monitored agricultural spring, [NO₃⁻] was lower in the summer than at other times, whereas [N₂O] was higher in the summer than at other times, perhaps reflecting a seasonal variation in the degree of denitrification reaction progress. No other N analytes were observed to vary seasonally in our study. In the well having no agricultural-N impact, C_org/N_org = 5.5, close to the typical value for natural aqueous systems of about 6.6. In the agricultural watershed C_org/N_org varied widely, from ∼1.2 to ?9.     

Fate of organic carbon reaching the deep sea floor: a status report

The rates of organic carbon oxidation by O₂, NO₃^?, MnO₂, Fe₂O₃ and SO₄^? have been calculated for five pelagic Pacific and Atlantic sites using simple diffusion-reaction models. O₂ everywhere oxidizes > 90% of the raining C_org; the fraction oxidized by the secondary oxidants decreases as the rain rate of organic C to the seafloor decreases. A large fraction of the C_org escaping oxidation by O₂ is oxidized by the secondary oxidants. Hence while these oxidants play a small role in remineralization, they are important in regulating the burial of organic matter and the consequent removal from the oceans of reduced carbon and nutrients.     

Remineralization Ratios in the Subtropical North Pacific Gyre

Based on a new mixing model of two end-members, the water column remineralization ratios of P/N/C_org - O₂ = 1/13 ± 1/135 ± 18/170 ± 9 are obtained for the Hawaii Ocean Time-series (HOT) data set at station ALOHA. The traditional Redfield ratios of P/N/C_org/–O₂ = 1/16/106/138 have standard deviations of more than 50%, when they are based on the average composition of phytoplankton. Apparently, the remineralization processes in the water column have smoothed out the observed large variability of plankton compositions. A new molar formula for the remineralized plankton may be written as ₁₃₅H₂₈₀O₁₀₅N₁₃P or C₂₅(CH₂O)₁₀₁(CH₄)₉(NH₃)₁₃(H₃PO₄). Oxidation of this formula results inC₂₅(CH₂O)₁₀₁(CH₄)₉(NH₃)₁₃(H₃PO₄) + 170O₂ 135CO₂ + 132H₂O + 13NO₃ ^- + H₂PO₄ ^- + 14H⁺.For comparison, remineralization using Redfield's formula gives:(CH₂O)₁₀₆(NH₃)₁₆(H₃PO₄) + 138O₂ 106CO₂ + 122H₂O + 16NO₃ ^-+ H₂PO₄ ^- + 17H⁺     

环境介质中高氯酸盐污染及微生物修复技术研究进展

高氯酸盐(ClO4-)是一种有毒的无机阴离子,其环境污染问题引起了广泛关注,控制与修复高氯酸盐污染环境成为新的研究热点,其中微生物修复技术最具应用前景。国外已开展环境中高氯酸盐污染现状的调查工作,利用微生物修复技术去除高氯酸盐取得了一定的成果,但我国的相关研究较少。文章综述了近年来国内外高氯酸盐的污染现状及微生物修复高氯酸盐的最新研究进展。由于高氯酸盐的高水溶性和低吸附性,当前研究最多的是高氯酸盐水体污染,这些水体通过饮用水(源水)或食物链直接或间接地对人类健康造成影响。在微生物修复方面,从有机电子供体,无机电子供体(H2、Fe0等),电子受体(O2、NO3-、SO24-)及微生物的生长环境因素(pH值、温度、氧化还原电位、盐度)等方面总结了各因素对微生物修复技术去除高氯酸盐效果的影响,以期为我国开展微生物处理技术在高氯酸盐污染修复领域的实践应用提供参考。     

Behavior of stable isotopes of dissolved oxygen,dissolved inorganic carbon and nitrate in groundwater at a former wood treatment facility containing hydrocarbon contamination

The speciation and mobility of a variety of chemical species in groundwater are strongly influenced by redox and pH conditions. Dissolved O₂ (DO) and dissolved inorganic C (DIC) concentrations are significant controls of these conditions, respectively. It is not always clear what the major processes are that influence changes in the concentration of DO and DIC across a groundwater flowpath. The combined use of the stable isotope compositions of DO (δ¹⁸O–DO) and DIC (δ¹³C–DIC) has the potential to help investigators discriminate between sources and sinks of DO and DIC in groundwater systems.     

Loading and fate of particulate organic carbon from the Himalaya to the Ganga-Brahmaputra delta

We use the evolution of river sediment characteristics and sedimentary C_org from the Himalayan range to the delta to study the transport of C_org in the Ganga-Brahmaputra system and especially its fate during floodplain transit.A detailed characterisation of both mineral and organic particles for a sampling set of river sediments allows taking into account the sediment heterogeneity characteristic of such large rivers. We study the relationships between sediment characteristics (mineralogy, grain size, specific area) and C_org content in order to evaluate the controls on C_org loading. Contributions of C3 and C4 plants are estimated from C_org stable isotopic composition (δ¹³C_org). We use the evolution of δ¹³C_org values from the Himalayan range to the delta in order to study the fate of C_org during floodplain transit.Ganga and Brahmaputra sediments define two distinct linear relations with specific area. In spite of 4-5 times higher specific area, Ganga sediments have similar C_org content, grain size and mineralogy as Brahmaputra sediments, indicating that specific area does not exert a primary control on C_org loading. The general correlation between the total C_org content and Al/Si ratio indicates that C_org loading is mainly related to: (1) segregation of organic particles under hydrodynamic forces in the river, and (2) the ability of mineral particles to form organo-mineral aggregates.Bed and suspended sediments have distinct δ¹³C_org values. In bed sediments, δ¹³C_org values are compatible with a dominant proportion of fossil C_org derived from Himalayan rocks erosion. Suspended sediments from Himalayan tributaries at the outflow of the range have low δ¹³C_org values (−24.8‰ average) indicating a dominant proportion of C3 plant inputs. In the Brahmaputra basin, δ¹³C_org values of suspended sediments are constant along the river course in the plain. On the contrary, suspended sediments of the Ganga in Bangladesh have higher δ¹³C_org values (−22.4‰ to −20.0‰), consistent with a significant contribution of C4 plant derived from the floodplain. Our data indicate that, during the plain transit, more than 50% of the recent biogenic C_org coming from the Himalaya is oxidised and replaced by floodplain C_org. This renewal process likely occurs during successive deposition-erosion cycles and river course avulsions in the plain.     

Variation and paleoclimatic significance of organic carbon isotopes of Ili loess in arid Central Asia

As an indicator for terrestrial paleovegetation, the stable isotopic composition of total organic matter (δ¹³C_org) in loess sediments has been widely used for paleoclimatic reconstruction in western Europe, the Great Plains of North America and the Chinese Loess Plateau (CLP). However, little is known about the variation and paleoclimatic significance of the loess δ¹³C_org in arid Central Asia (ACA). We report δ¹³C_org data from an Axike (AXK) loess/paleosol profile from the eastern Ili Basin, eastern Central Asia. Along the profile, the δ¹³C_org values were more negative in the paleosol layers observed in the field and were confirmed by environmental magnetic proxies and a higher concentration of total organic carbon (TOC), consistent with results for western Europe and the northwestern CLP. Our results demonstrate that the loess δ¹³C_org in this region documents mainly the response of δ¹³C of locally predominant C₃ plants to paleoclimatic variation, especially paleoprecipitation. Our results also suggest that the loess δ¹³C_org values in the area have the potential for quantitative paleoprecipitation reconstruction on the basis of detailed δ¹³C_org results from modern plants and surface soils in the future.     

Attenuation of landfill leachate at two uncontrolled landfills

Attenuation characteristics of landfill leachate were examined for two uncontrolled landfills in Korea. The two landfills containing municipal wastes without appropriate bottom liner and leachate treatment system have different landfill age, waste volume, and most importantly different hydrogeologic settings. One landfill (Cheonan landfill) is situated in an open flat area while the other (Wonju landfill) is located in a valley. Variations of various parameters including dissolved organic carbon (DOC), dissolved oxygen (DO), alkalinity, pH, electrical conductivity (EC), redox potential (ORP), ammonia (NH₃), nitrate (NO₃⁻), sulfate (SO₄²⁻), and chloride (Cl⁻) were examined along groundwater flow path. All these parameters were analyzed every month for a year. In the interior of the landfills, typical anaerobic conditions revealed by low DO and NO₃ concentrations, negative ORP values, high NH₃, alkalinity, and Cl⁻ concentrations were observed. Generally, higher levels of contaminants (DOC, NH₃, and Cl⁻) were detected in the dry season while they were greatly lowered in the wet season. Significantly, large decrease of Cl^- concentration in the wet season indicates that the dilution or mixing is one of dominant attenuation mechanisms of leachate. But detailed variation behaviors in the two landfills are different and they were largely dependent on permeability of surface and subsurface layers. The intermediately permeable surface of the landfills receives part of direct rainfall infiltration but most rainwater is lost to fast runoff. The practically impermeable surface of clayey silt (paddy field) at immediately adjacent to the Cheonan landfill boundary prevented direct rainwater infiltration and hence redox condition of the ground waters were largely affected by that of the upper landfill and the less permeable materials beneath the paddy fields prohibited dispersion of the landfill leachate into down gradient area. In the Wonju landfill, there are three different permeability divisions, the landfill region, the sandy open field and the paddy field. Roles of the landfill and paddy regions are very similar to those at the Cheonan. The very permeable sandy field receiving a large amount of rainwater infiltration plays a key role in controlling redox condition of the down gradient area and contaminant migration. This paper reports details of the attenuation and redox conditions of the landfill leachates at the two uncontrolled landfills.     

Lacustrine sedimentary record of early Aptian carbon cycle perturbation in western Liaoning,China

The early Aptian abrupt carbon isotope excursion in marine carbonate and sedimentary organic matter reflects a major perturbation in the global carbon cycle. However, until now almost all the evidences of this event came from marine deposits. Here we present organic-carbon isotope (δ¹³C_org) data from the non-marine Jehol Group in western Liaoning, China. The lacustrine δ¹³C_org curve is marked by a relative long-lasting δ¹³C_org minimum followed by two stages of positive δ¹³C_org excursions that are well correlated with contemporaneous marine records. The carbon isotope correlation shows that the lacustrine strata of the Jehol Group were deposited at the same time of the early Aptian Oceanic Anoxic Event (OAE1a). The relative long-lasting δ¹³C_org minimum supports the hypothesis that volcanic CO₂ emission may have played the main role in triggering the negative δ¹³C excursion and global warming at the onset of this event. In addition, the onset of δ¹³C_org minimum is concomitant with the radiation of the Jehol Biota, implying that the evolutionary radiation of the Jehol Biota may have been closely related with the increase in atmospheric CO₂ and temperature.     

Oxidation and Origin of Organic Matter in Surficial Eastern Mediterranean Hemipelagic Sediments

Aerobic mineralisation of C_org in surface sedimentsof the deep (>2000 m water depth) eastern Mediterranean Sea has been quantified by analysis of detailedbox core C_org concentration versus depth profiles and the modelling environment for early diageneticproblems MEDIA. The reactive fraction comprises 60–80% of the total C_org reachingthe sediments and is largely oxidised within the surficial 10 cm. A non-reactive C _orgfraction (G_NR) dominates at depths >10 cm, and makes up20–40% of the total C _org flux to the sediments. First-order rateconstants for decomposition of the reactive fraction calculated from theC _org profiles range from 5.4 × 10^-3 to8.0 × 10^-3 y^-1 to 8.0 × 10^-3 y^-1. Total mineralization rates in thesurface sediment are between 1.7 and 2.6 mol C cm^-2 y^-1 and thus are typical for oligotrophic, deep-seaenvironments. The low fluxes and rapid remineralisation of C _org are accompanied by²¹⁰Pb_excess surface mixed layers which are only 2 cm deep, among the thinnest reported for oxygenated marine sediments.Model results indicate a mismatch between the C _org profiles and O₂ microprofileswhich were measured onboard ship. This can be attributed to a combination of decompression artefactsaffecting onboard measurement of the O₂ profiles or the leakage ofoxygen into the core during handling on deck. Furthermore, the used D_b values, based on ²¹⁰Pb, may not befully appropriate; calculations with higher D_b values improve the O₂ fits. The surficial sediment¹³C _org values of -22 become less negative with increasing depth and decreasing C _orgconcentrations. The major ¹³C change occurs in the top 3 to 4 cm and coincides with the interval weremost of the organic carbon oxidation takes place. This indicates that the reactive fractionof organic matter, commonly assumed to be marine, has a more negative ¹³C _orgthan the refractory fraction, usually held to be terrestrial. Palaeoproductivity estimates calculated from thesediment data by means of literature algorithms yield low surface productivities(12–88 gC m^-2 y^-1), which are in good agreement with field measurements of primary productivity in otherstudies. Such values are, however, significantly lower than those indicated by recent productivitymaps of the area derived from satellite imagery (>100 gC m^-2 y^-1).     

Early diagenetic remineralization of sedimentary organic C in the Gulf of Papua deltaic complex (Papua New Guinea): Net loss of terrestrial C and diagenetic fractionation of C isotopes

Oceania supplies ∼40% of the global riverine flux of organic carbon, approximately half of which is injected onto broad continental shelves and processed in shallow deltaic systems. The Gulf of Papua, on the south coast of the large island of New Guinea, is one such deltaic clinoform complex. It receives ∼4 Mt yr⁻¹ particulate terrestrial organic carbon with initial particle C_org loading ∼0.7 mg m⁻². C_org loading is reduced to ∼0.3 mg m⁻² in the topset-upper foreset zones of the delta despite additional inputs of mangrove and planktonic detritus, and high net sediment accumulation rates of 1-4 cm yr⁻¹. Carbon isotopic analyses (δ¹³C, Δ¹⁴C) of ΣCO₂ and C_org demonstrate rapid (<100 yr) remineralization of both terrestrial (δ¹³C <−28.6) and marine C_org (δ¹³C ∼−20.5) ranging in average age from modern (bomb) (Δ¹⁴C ∼60) to ∼1000 yr (Δ¹⁴C ∼−140). Efficient and rapid remineralization in the topset-upper foreset zone is promoted by frequent physical reworking, bioturbation, exposure, and reoxidation of deposits. The seafloor in these regions, particularly <20 m, apparently functions as a periodically mixed, suboxic batch reactor dominated by microbial biomass. Although terrestrial sources can be the primary metabolic substrates at inshore sites, relatively young marine C_org often preferentially dominates pore water ΣCO₂ relative to bulk C_org in the upper foreset. Thus a small quantity of young, rapidly recycled marine organic material is often superimposed on a generally older, less reactive terrestrial background. Whereas the pore water ΣCO₂ reflects both rapidly cycled marine and terrestrial sources, terrestrial material dominates the slower overall net loss of C_org from particles in the topset-upper foreset zone (i.e. recycled marine C_org leaves little residue). Preferential utilization of C_org subpools and diagenetic fractionation of C isotopes supports the reactive continuum model as a conceptual basis for net decomposition kinetics. Early diagenetic fractionation of C isotopes relative to the bulk sedimentary C_org composition can produce changes in ¹⁴C activity independent of radioactive decay. In the Gulf of Papua topset-upper foreset, Δ¹⁴C of pore water ΣCO₂ averaged ∼ 300‰ greater than C_org sediment between ∼1-3 m depth in deposits. Diagenetic fractionation and decomposition aging of sedimentary C_org compromises simple application of ¹⁴C for determination of sediment accumulation rates in diagenetically reactive deposits.     

Influence of the biological carbon pump effect on the sources and deposition of organic matter in Fuxian Lake,a deep oligotrophic lake in southwest China

Biological carbon pumping (BCP) is a key process in which dissolved inorganic carbon in terrestrial aquatic ecosystems is utilized by aquatic autotrophs for photosynthesis and transformed into autochthonous organic matter (AOC). However, the mechanisms underlying BCP and the amount of generated AOC deposited effectively, are still poorly understood. Therefore, we conducted a systematic study combining modern hydrochemical monitoring and a sediment trap experiment in Fuxian Lake (Yunnan, SW China), the second-deepest plateau, oligotrophic freshwater lake in China. Temperature, pH, EC (electrical conductivity), DO (dissolved O₂), [HCO₃⁻], [Ca²⁺], SI_c, partial CO₂ (pCO₂) pressure, and carbon isotopic compositions of HCO₃⁻ (δ¹³C_DIC) in water from Fuxian Lake all displayed distinct seasonal and vertical variations. This was especially apparent in an inverse correlation between pCO₂ and DO, indicating that variations of hydrochemistry in the lake water were mainly controlled by the metabolism of the aquatic phototrophs. Furthermore, the lowest C/N ratios and highest δ¹³C_org were recorded in the trap sediments. Analyses of the C/N ratio demonstrated that the proportions of AOC ranged from 30% to 100% of all OC, indicating that AOC was an important contributor to sedimentary organic matter (OC). It was calculated that the AOC flux in Fuxian Lake was 20.43 t C km⁻² in 2017. Therefore, AOC produced by carbonate weathering and aquatic photosynthesis could potentially be a significant carbon sink and may have an important contribution to solving the lack of carbon sinks in the global carbon cycle.

     

Paired δ13Ccarb and δ13Corg records of the Ordovician on the Yangtze platform,South China

During the Ordovician, huge biological revolutions and environmental changes happened in Earth’s history, including the Great Ordovician Biodiversification Event, global cooling and so on, but the cause of these events remains controversial. Herein, we conducted a paired carbon isotopic analysis of carbonate (δ¹³C_carb) and organic matter (δ¹³C_org) through the Ordovician in the Qiliao section on the Yangtze platform of South China. Our results showed that the δ¹³C_carb trend of the Qiliao section can be correlated with local and global curves. The δ¹³C_org trend seems is less clear than the δ¹³C_carb trend for stratigraphic correlations, but some δ¹³C_org positive excursions in the Middle and Upper Ordovician may be used for correlation studies. These carbon isotopic records may have global significance rather than local significance, revealing several fluctuations to the global carbon cycle during the Ordovician. Several known δ¹³C_carb and δ¹³C_org negative and positive excursions have been recognised in this study, including the early Floian Negative Inorganic Carbon (δ¹³C_carb) Excursion (EFNICE), as well as the early Floian Positive Organic Carbon (δ¹³C_carb) Excursion, the mid-Darriwilian Inorganic Carbon (δ¹³C_carb and δ¹³C_org) Excursion (MDICE), and the early Katian Guttenberg Inorganic Carbon (δ¹³C_carb and δ¹³C_org) Excursion (GICE). These positive excursions and a smooth decline trend of δ¹³C_org values during the early to mid-Floian may imply multiple episodes of enhanced organic carbon burial that began at the early Floian stage, probably resulting in further decline in atmospheric pCO₂ and then global cooling.     

Stable isotope geochemistry of coals, humic kerogens and related natural gases

Isotope systematics are well defined for conventional sapropelic, Type I/II kerogens and their associated bacterial and thermogenic natural-gas products. These geochemical tools are used to estimate source type, maturity and depositional environment, and as a correlation technique. In many cases the natural gas signatures in near-surface samples and drill cuttings can be used to classify or predict a deeper lying source rock or reservoir.Corresponding interpretative schemes for coals, Type III kerogens and their associated hydrocarbons are progressing quickly. The shift in attention to humic sources is driven primarily by depletion of conventional oil and gas resources and the economic and societal requirements of coal and coal-bed methane.Carbon, hydrogen and nitrogen stable isotope variations can be large between different coals and humic kerogens. These differences can often be recognized in their bulk δ¹³C_org, δD_org and δ¹⁵N_org values. Isotope signatures of coals can be diagnostic of several factors, including deposit age, type, geographic location, maturity and generation history. However, these characteristic isotopic variations are substantially better defined by the C-, H- and N-isotope ratios of the separate maceral groups, such as vitrinite, exinite and inertinite. This new application of stable isotopes, at the maceral and compound levels, have great potential to improve the interpretative precision over conventional whole coal or bulk techniques.Hydrocarbon gases, including coal gases, derived from coals and humic kerogens can be distinguished from Type I/II sources, based on their molecular rations, i.e., C₁/(C₂ + C₃) and by comparing their stable isotope compositions, especially δ¹³C_CH4 and δD_CH4. The δ¹³C_C2H6 can also be valuable, but ethane is generally present in small amount (<1 vol. %) and requires     

Hydrogeochemical characterization of major factors affecting the quality of shallow groundwater in the coastal area at Kimje in South Korea

This study has evaluated the main hydrogeochemical characteristics that affect the quality of shallow groundwater in the coastal area at Kimje in South Korea. In this area, the chemical composition of groundwater is mostly classified into Na⁺?Cl^? and Ca²⁺+Mg²⁺?NO₃^-+Cl^? types. These types are affected by three major factors: seawater intrusion, fertilizers and redox processes. The Na⁺?Cl^? type, which is generally localized in the coastal area, shows typical characteristics of groundwater affected not only by modern seawater but also by old seawater residing in the reclaimed land. In contrast, the Ca²⁺+Mg²⁺?NO₃^-+Cl^? type, which is usually found inland, is very contaminated by fertilizers. As groundwater flows from the inland area to the coast, the redox condition changes from an oxic condition to a suboxic/anoxic condition. In addition, the reclamation has caused a large amount of underlying organic matter. These effects provide optimum conditions for the occurrence of redox processes in the coastal area.     

新疆罗北洼地湖相沉积物有机碳同位素的变化序列及其古环境意义

测定了新疆罗布泊地区湖相沉积物CK-2钻孔样品的总有机碳含量（TOC）及其同位素组成、碳酸盐含量和C/N比值等环境代用指标,以及石膏矿物的质谱-铀系年龄。测试结果表明,20～9kaB.P.期间沉积物δ¹³C_org.在-23.4‰～-16.1‰之间波动且阶段性明显,与TOC呈现良好的相关关系,整体变化趋势同南极Dome C冰芯中记录的全球大气CO₂浓度一致;C/N比值表明有机碳来源主要是陆生高等植物。因此大气CO₂浓度变化是影响20～9kaB.P.期间罗布泊湖相沉积物δ¹³C_org.值变化的主导因素,周围山体上C₃/C₄植物相对生物量的变化则是另一重要因素。依据δ¹³C_org.的变化序列将此时间段湖区古环境的演化分成6个阶段:20.0～14.1kaB.P.期间受到末次盛冰期的影响,气温偏低,湖水丰沛;14.1～13.3kaB.P.是一个气候不稳定期,冷暖波动较频繁,但以暖为趋势;13.3～12.8kaB.P.期间经历了一段冷期,于12.8kaB.P.结束了末次冰期,随后气候开始转暖至11.8kaB.P.;其后气温再次变冷并维持到10kaB.P.;最后从10kaB.P.进入全新世暖期。δ¹³C_org.序列明显向偏负方向变化,表明该地区变暖的趋势相当明显。罗布泊地区日益干旱化是全球气候变化的结果,尤其是受到全球CO₂浓度的不断升高所制约。     

Coupling between Pbex and organic matter in sediments of a nutrient-enriched lake: An example from Lake Chenghai, China

Sediment cores were collected from deep-water areas of Lake Chenghai, China in June 1997. The vertical profile of ¹³⁷Cs activity gives reliable geochronological results. The results also indicate that sediment accumulation rates in deep-water areas of Lake Chenghai were relatively constant in recent decades, averaging 0.43 g cm^− 2 y^− 1, despite a variable organic carbon influx. ²¹⁰Pb_eq (= ²²⁶Ra) activity was relatively constant also, with an average value of 54.3 ± 3.2 Bq kg^− 1. Vertical profiles of ²¹⁰Pb_ex (= ²¹⁰Pb_total − ²²⁶Ra) decreased exponentially, resulting in somewhat lower sediment accumulation rates (0.3 g cm^− 2 y^− 1). These lower rates are likely less reliable, as the relatively large fluctuations in ²¹⁰Pb_ex activities correlate closely to the organic carbon (C_org) content of the sediments. For example, the vertical profile of ²¹⁰Pb_ex activity displays peaks at mass depths of 3.7-4.7 g cm^− 2 (10-12 cm) and 10-11 g cm^− 2(25-28 cm), similar to the maxima in the vertical profile of C_org. This phenomenon must be related to the delivery of particulate organic matter (POM) from the water to the sediments, or to watershed soil erosion. Since the mean atomic ratios of H_org / C_org and C_org / N_org in Lake Chenghai sediments are 5.5 and 7.0, respectively, indicating that POM was predominantly derived from the remains of authigenic algae, this eliminates watershed erosion rates as a primary control on lake sedimentation rates as resolved by ²¹⁰Pb_ex. Sedimentation fluxes (F(C_org)) of particulate organic carbon since 1970 varied between 60 to 160 g m^− 2 y^− 1, and appeared to closely influence variations in ²¹⁰Pb_ex concentrations. For example, sedimentation fluxes of ²¹⁰Pb_ex (F(²¹⁰Pb_ex)) showed maxima in the years 1972-1974 and 1986-1989, likely reflecting historical variations of lake biological productivity or carbon preservation.     

Soil organic matter as an important contributor to Late Quaternary sediments of the tropical West African continental margin

The contribution of soil organic matter (SOM) to continental margins is largely ignored in studies on the carbon budget of marine sediments. Detailed geochemical investigations of late Quaternary sediments (245-0 ka) from the Niger and Congo deep-sea fans, however, reveal that C_org/N_tot ratios and isotopic signatures of bulk organic matter (δ¹³C_org) in both fans are essentially determined by the supply of various types of SOM from the river catchments thus providing a fundamentally different interpretation of established proxies in marine sciences. On the Niger fan, increased C_org/N_tot and δ¹³C_org (up to −17‰) were driven by generally nitrogen-poor but ¹³C-enriched terrigenous plant debris and SOM from C₄/C₃ vegetation/Entisol domains (grass- and tree-savannah on young, sandy soils) supplied during arid climate conditions. Opposite, humid climates supported drainage of C₃/C₄ vegetation/Alfisol/Ultisol domains (forest and tree-savannah on older/developed, clay-bearing soils) that resulted in lower C_org/N_tot and δ¹³C_org (< −20‰) in the Niger fan record. Sediments from the Congo fan contain a thermally stable organic fraction that is absent on the Niger fan. This distinct organic fraction relates to strongly degraded SOM of old and highly developed, kaolinite-rich ferallitic soils (Oxisols) that cover large areas of the Congo River basin. Reduced supply of this nitrogen-rich and ¹²C-depleted SOM during arid climates is compensated by an elevated input of marine OM from the high-productive Congo up-welling area. This climate-driven interplay of marine productivity and fluvial SOM supply explains the significantly smaller variability and generally lower values of C_org/N_tot and δ¹³C_org for the Congo fan records. This study emphasizes that ignoring the presence of SOM results in a severe underestimation of the terrigenous organic fraction leading to erroneous paleoenvironmental interpretations at least for continental margin records. Furthermore, burial of SOM in marine sediments needs more systematic investigation combining marine and continental sciences to assess its global relevance for long-term sequestration of atmospheric CO₂.     

Heterogeneous redox conditions, arsenic mobility, and groundwater flow in a fractured-rock aquifer near a waste repository site in New Hampshire, USA

Anthropogenic sources of carbon from landfill or waste leachate can promote reductive dissolution of in situ arsenic (As) and enhance the mobility of As in groundwater. Groundwater from residential-supply wells in a fractured crystalline-rock aquifer adjacent to a Superfund site in Raymond, New Hampshire, USA, showed evidence of locally enhanced As mobilization in relatively reducing (mixed oxic-anoxic to anoxic) conditions as determined by redox classification and other lines of evidence. Redox classification was determined from geochemical indicators based on threshold concentrations of dissolved oxygen (DO), nitrate (NO ₃ ^– ), iron (Fe²⁺), manganese (Mn²⁺), and sulfate (SO ₄ ^2– ). Redox conditions were evaluated also based on methane (CH₄), excess nitrogen gas (N₂) from denitrification, the oxidation state of dissolved As speciation (As(III) and As(V)), and several stable isotope ratios. Samples from the residential-supply wells primarily exhibit mixed redox conditions, as most have long open boreholes (typically 50–100?m) that receive water from multiple discrete fractures with contrasting groundwater chemistry and redox conditions. The methods employed in this study can be used at other sites to gauge redox conditions and the potential for As mobilization in complex fractured crystalline-rock aquifers where multiple lines of evidence are likely needed to understand As occurrence, mobility, and transport.     

Controls on the geochemistry of rare earth elements along a groundwater flow path in the Carrizo Sand aquifer,Texas, USA

Groundwater samples were collected along a groundwater flow path in the Carrizo Sand aquifer in south Texas, USA. Field measurements that included pH, specific conductivity, temperature, dissolved oxygen (DO), oxidation–reduction potentials (Eh in mV), alkalinity, iron speciation, and H₂S concentrations were also conducted on site. The geochemistry (i.e., concentrations, shale-normalized patterns, and speciation) of dissolved rare element elements (REEs) in the Carrizo groundwaters are described as a function of distance along a flow path. Eh and other redox indicators (i.e., DO, Fe speciation, H₂S, U, and Re) indicate that redox conditions change along the flow path in the Carrizo Sand aquifer. Within the region of the aquifer proximal to the recharge zone, groundwaters exhibit both highly oxidizing and localized mildly reducing conditions. However, from roughly 10 km to the discharge zone, groundwaters are reducing and exhibit a progressive decrease in redox conditions. Dissolved REE geochemical behavior exhibits regular variations along the groundwater flow path in the Carrizo Sand aquifer. The changes in REE concentrations, shale-normalized patterns, and speciation indicate that REEs are not conservative tracers. With flow down-gradient, redox conditions, pH and solution composite, and adsorption modify groundwater REE concentrations, fractionation patterns, and speciation.