Assessing the oxidising effect of NaNO3 and NaNO2 from disposed Eurobitum bituminised radioactive waste on the dissolved organic matter in Boom Clay

In Belgium, compatibility studies are performed in view of the final disposal of nitrate-containing bituminised intermediate-level radioactive waste in Boom Clay, which is considered as a potential host formation. Due to the presence of large amounts of nitrate in the waste, a slow release of nitrate (and to a smaller extent also nitrite) into the Boom Clay is expected. Nitrate and/or nitrite reduction by redox-active components of the host rock may cause a geochemical perturbation of the clay and subsequently might affect its barrier function against the migration of radionuclides. This paper therefore addresses the possible oxidation of one of the main redox-active components of the Boom Clay, i.e. dissolved organic matter, by nitrate and nitrite. For this, abiotic and microbially mediated nitrate and nitrite reduction was studied during long-term batch tests (2–2.5 years) in Boom Clay pore water, containing 155 ± 15 mg C/l present as humic and fulvic acids. Changes in the reducing capacity of the DOM due to oxidation were assessed successfully using two oxidants, namely ferricyanide and ferric citrate. The results of these experiments indicate that an abiotic reaction between DOM and nitrate does not occur or is characterised by very slow kinetics. On the other hand, a slow microbial nitrate reduction to nitrite was observed and the associated oxidation of DOM was confirmed by a decrease in the (partial) reducing capacity of DOM for ferric citrate. In contrast to nitrate, nitrite was shown to oxidise DOM both abiotically and mediated by microbes through (chemo)denitrification, although these reactions also seem to occur only at a rather slow rate. No significant change in the maximally obtainable reducing capacity of DOM (using ferricyanide) was detected during any of the observed reactions, suggesting that the impact of such a slow heterotrophic nitrate reduction is very limited.     

Studying the migration behaviour of selenate in Boom Clay by electromigration

For the disposal of high-level waste (HLW) in a deep geological formation as Boom Clay, safety assessment studies have shown that long lived ⁷⁹Se is one of the more critical fission products. Therefore, the knowledge of its migration properties (diffusion, retention) through the geological barrier (Boom Clay) is of paramount importance. The migration behaviour of selenium strongly depends on its speciation. Under reducing conditions, selenide would be the dominant species and selenium migration would mainly be controlled by the low solubility of Se(−II)-bearing minerals. However Se species are often found in redox disequilibrium and more oxidized species might also coexist. Therefore, the study of selenate migration requires attention, as it might be the most mobile selenium species in the host rock. Electromigration experiments performed with a ⁷⁵Se-labeled selenate in Boom Clay indicate a high mobility for this species. The apparent diffusion coefficient (D_app) of selenate in Boom Clay is estimated from electromigration experiments performed under different electric fields. Using two independent approaches, the value of D_app for selenate is shown to fall in the range from 1.7×10⁻¹¹ to 6.2×10⁻¹¹ m² s⁻¹. Moreover, no reduction of selenate in Boom Clay was observed.     

洱海沉积物间隙水中溶解有机质的地球化学特性

对洱海沉积物间隙水中溶解有机质(DOM)含量、紫外可见吸收、荧光以及分子量等的垂直分布特征进行了研究。结果表明,DOC含量在沉积物水界面明显富集,随后急剧下降,6cm处达到最小值,随后呈上升趋势。DOC与吸光度值、荧光发射光谱强度之间具有一定的线性相关关系。DOM的E3/E4值范围在1～6之间,绝大多数在1～35之间。表征DOM中腐殖质来源的指标荧光指数值处于148～159之间,说明DOM以陆源输入为主。此外,洱海沉积物间隙水DOM分子量分布呈多峰分布模式,重均分子量(M_w)值在1462～1953Da之间,数均分子量(M_n)值在547～900Da之间,多分散性系数ρ值在202～305之间。随着沉积深度增大,M_w和M_n有略微的增大趋势,但变化不大。沉积物的氧化还原条件、微生物活动以及铁、锰氧化物等在沉积剖面的差异是控制间隙水中DOM各种地球化学特性的主要因素。     

沉积环境有机质及在铀成矿中的作用研究

通过系统研究,将沉积环境有机质分为可确定或未确定的高相对分子质量有机物质、简单物质和腐殖质3个主要部分,一般称为非腐殖质和腐殖质2个部分.非腐殖质系指那些可被列入单独的化合物类别中的有机化合物,主要包括糖、脂类和氨基酸;腐殖质系指那些很难确定的不能再分成其他化合物的有机化合物,据其溶解性质和颜色特征,腐殖质分为黄腐酸、...     

Hydrogeological modeling of radionuclide transport in low permeability media: a comparison between Boom Clay and Ypresian Clay

Deep low-permeability clay layers are considered as suitable environments for disposal of high-level radioactive waste. In Belgium, the Boom Clay is the reference host formation and the Ypresian Clay an alternative host formation for research and safety and feasibility assessment of deep disposal of nuclear waste. In this study, two hydrogeological models are built to calculate the radionuclide fluxes that would migrate from a potential repository through these two clay formations. Transport parameter heterogeneity is incorporated in the models using geostatistical co-simulations of hydraulic conductivity, diffusion coefficient and diffusion accessible porosity. The calculated radionuclide fluxes in the two clay formations are compared. The results show that in the Ypresian Clay larger differences between the fluxes through the lower and the upper clay boundary occur, larger total output radionuclide amounts are calculated and a larger effect of parameter heterogeneity on the calculated fluxes is observed, compared to the Boom Clay.     

Organic pollutants associated with macromolecular soil organic matter: Mode of binding

A study of ether-linked moieties in macromolecular bound residues of polycyclic aromatic hydrocarbons (PAH) generated in bioremediation experiments was performed using high temperature hydrolysis degradation with subsequent analysis of the products by GC-MS. This hydrolysis reaction was specifically designed to cleave ether bonds including relatively stable diarylether structures. Among the reaction products, aromatic alcohols representing typical microbiologically derived metabolites of PAH were found in addition to natural compounds. Thus, parts of the bound residues appeared to be linked within the macromolecular material by ether bonds. Model experiments with an oxidoreductase enzyme and aromatic alcohols indicate the formation of these ether bonds to be an enzyme-catalysed process.     

Dissolved organic matter tracers reveal contrasting characteristics across high arsenic aquifers in Cambodia:A fluorescence spectroscopy study

Organic matter in the environment is involved in many biogeochemical processes,including the mobilization of geogenic trace elements,such as arsenic,into groundwater.In this paper we present the use of fluorescence spectroscopy to characterize the dissolved organic matter(DOM)pool in heavily arsenicaffected groundwaters in Kandal Province,Cambodia.The fluorescence DOM(fDOM)characteristics between contrasting field areas of differing dominant lithologies were compared and linked to other hydrogeochemical parameters,including arsenic and dissolved methane as well as selected sedimentary characteristics.Absorbance-corrected fluorescence indices were used to characterize depth profiles and compare field areas.Groundwater fDOM was generally dominated by terrestrial humic and fulvic-like components,with relatively small contributions from microbially-derived,tryptophan-like components.Groundwater fDOM from sand-dominated sequences typically contained lower tryptophan-like,lower fulvic-like and lower humic-like components,was less bioavailable,and had higher humification index than clay-dominated sequences.Methane concentrations were strongly correlated with fDOM bioavailability as well as with tryptophan-like components,suggesting that groundwater methane in these arsenic-prone aquifers is likely of biogenic origin.A comparison of fDOM tracers with sedimentary OM tracers is consistent with the hypothesis that external,surface-derived contributions to the aqueous DOM pool are an important control on groundwater hydrogeochemistry.     

Molecular Weight Distribution of Dissolved Organic Matter in Lake Hongfeng Determined by High Performance Size Exclusion Chromatography （HPSEC） With On-Line UV-Vis Absorbance and Fluorescence Detection

1IntroductionDissolvedorganicmatter (DOM)isamixtureoforganicsubstancesconsistingmainlyofhighmolecularweightpolymericcompounds (KenandLee,1 974) .Itplaysanimportantroleincarboncyclingandbiogeochemicalmobilizationoftracemetalsandorganiccompoundsintheaquaticenvi ronment (BeffleandLeppard ,1 995) .InrecentyearsmanyresearchershavepaidattentiontothesecomplexesbasedontheMWDofDOM ,sincethefateandtransportoftracechemicalsareinfluencedbyitsmolecularsize (Chiouetal.,1 986) .Themolecularweightorfrac…     

Diagenesis of organic matter in a 400 m organic rich sediment core from offshore Namibia using solid state 13C NMR and FTIR

Although rates and mechanisms of early diagenesis have been well studied, the effects of microbial metabolism on the molecular composition of the sedimentary organic matter (SOM) over long periods of time need more investigation. In this study, we characterize the early diagenesis of marine SOM from organic rich sediments of the Ocean Drilling Program site 1082 located off Namibia, in the vicinity of the Benguela coastal upwelling system. We used both Fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance spectroscopy (¹³C NMR) to assess the quantitative partitioning of the organic carbon into major compound classes (aliphatic, aromatic, ester, carboxylic, amide and carbons from carbohydrates). Then, we calculate the SOM composition in the main biomolecules (proteins, carbohydrates, lipids and lignin) on the basis of previous ¹³C NMR based estimates of the molecular composition of the organic mixtures. Results show that the SOM is still labile at 7 m below the seafloor (mbsf) and composed of about 25% proteins and 15% carbohydrates. With increasing depth, the protein content exponentially decreases to 13% at 367 mbsf, whereas the carbohydrate content decreases linearly to 11%. The lignin and lipid content consistently represent around 10% and 40% of the SOM, respectively, and show an increase with depth, due mostly to selective enrichment as the more labile components are lost by degradation. Thus, these components of the SOM are considered refractory at the depth scale considered. The calculated remineralization rates are extremely slow ranging from 5.6 mol C m⁻³ ky⁻¹ at the top of the core to 0.2 mol C m⁻³ ky⁻¹ according to the organic carbon flux to the seafloor. Knowing the labile carbon losses, we propose a method to calculate the initial TOC before the diagenesis took place.     

Carbon isotope fractionation in various forms of biogenic organic matter: I. Partitioning of carbon isotopes between the main polymers of higher plant biomass

Partitioning of carbon isotopes between main polymers of biomass of higher plants was investigated by the example of the structural polymers of wheat plant: lignin, hemicellulose, and cellulose representing the ligno-carbohydrate complex, starch and proteins representing storage compounds, and the lipid fraction. Biopolymers account from 80% (grasses) to 95% (trees) of the biomass of higher plants and are of geochemical interest as biological precursors for the terrigenous organic matter (OM) of sediments and sedimentary rocks. The biomass of algae is also dominated (∼80%) by polymers: proteins, carbohydrates, and lipids. The isotopic heterogeneity of the organs and parts of plants is controlled by carbon isotope composition (from −33.3 to −25.9‰) in biopolymers and their distribution: among various parts of plants. The carbohydrates: starch and hemicellulose are isotopically heaviest (−25.9 and −26.2‰), proteins are slightly poorer in ¹³C (up to −27.3‰), and lipids (−33.3‰) and lignin (−32.6‰) are isotopically light components of the biomass. The regularity of carbon isotopes partitioning among the large complexes of the biomass of higher plants is reflected in the existence of a common linear trend of δ¹³C values of biopolymers versus the ranges of thermodynamic β-factor values calculated by the method of isotopic bond numbers for the whole set of monomers in the composition of each polymer studied. The carbohydrates of grain and straw (starch, xylan, and cellulose) form a common C6–C5 pool of the isotopically heaviest polymers of the higher plant biomass (wheat). No significant isotopic effects were observed at the transformation between C6–C5 monomers and their transport between plant organs during grain ripening.     

Fingerprinting of soil organic matter as a proxy for assessing climate and vegetation changes in last interglacial palaeosols (Veldwezelt, Belgium)

Soil characteristics in palaeosols are an important source of information on past climate and vegetation. Fingerprinting of soil organic matter (SOM) by pyrolysis-GC/MS is assessed as a proxy for palaeo-reconstruction in the complex of humic layers on top of the Rocourt pedosequence in the Veldwezelt-Hezerwater outcrop (Belgian loess belt). The fingerprints of the extractable SOM of different soil units are related to total organic carbon content, δ¹³C and grain-size analysis. Combined results indicate that the lower unit of the humic complex reflects a stable soil surface, allowing SOM build-up, intensive microbial activity and high decomposition. Higher in the profile, decomposition and microbial activity decrease. This is supported by a shift in the isotopic signal, an increased U ratio and evidence of wildfires. Although the chemical composition of the extracted SOM differed greatly from recent SOM, fingerprinting yielded detailed new information on SOM degree of decomposition and microbial contribution, allowing the reconstruction of palaeo-environmental conditions during pedogenesis.     

Formation of solid bituminous matter in pegmatites: Constraints from experimentally formed organic matter on microporous silicate minerals

The formation of solid bituminous matter (SBM) on surfaces of microporous silicates was experimentally studied at pressure and temperature conditions typical of late-stage magmatic and hydrothermal processes. Aliquots of microporous silicate minerals (zorite and kuzmenkoite-Mn, Lovozero Alkaline Massif, Kola Peninsula, Russia) were exposed to solid or liquid organic carbon sources (natural brown coal and liquid 1-hexene for synthesis purposes) in a 0.1 M NaCl-solution for 7 days, at constant pressure (50 MPa), and at three individual temperatures (200, 275, and 300 °C). No thermal decomposition of the solid organic sources happened at 200 °C and only a thin film of brown coal derivatives on the silicates’ surfaces and no formation of SBM were observed at 275 °C and 300 °C. But solid bituminous matter on the surfaces of both microporous silicates were detected in experiments with liquid 1-hexene as organic carbon source and at temperatures of 275 °C and 300 °C with a more pronounced formation of SBM at 300 °C compared to 275 °C. The aromatic and aliphatic hydrocarbons, as well as alcoholic compounds of the experimentally produced SBM are similar, if not even partly identical, with natural SBM occurrences of the Khibiny and Lovozero Massifs, Kola Peninsula, Russia, and from the Viitaniemi granitic pegmatite, Finland, as shown by FT-IR and ¹H NMR spectroscopy. This strengthens the hypothesis of formation of natural solid bituminous matter by catalytic reactions between microporous Ti-, Nb- and Zr-silicates and hydrocarbons at postmagmatic hydrothermal conditions.     

Biogeochemical characteristics of settling particulate organic matter in Lake Superior: A seasonal comparison

To assess settling particulate organic matter (POM) seasonality and its availability to the benthic community, settling particulate matter was studied in terms of mass fluxes and main biogeochemical characteristics (including organic carbon (OC), nitrogen, and stable carbon and nitrogen isotopic values) at two Lake Superior offshore sites over the course of a year. Fourier transform infrared spectroscopy (FTIR) and hydrolysis, extraction, and derivatization were used to provide further compositional information. Carbon and nitrogen content, isotopic and wet chemical data, and FTIR spectra show that summer particulate material is mainly autochthonous, with higher proportions of amide and carbohydrate. FTIR shows that spring particulate material contains relatively high proportions of clay minerals, indicating major sources from sediment resuspension and/or spring runoff. Distinct amino acid distributions at the two sites, revealed by principal component analysis (PCA) based on amino acid mol% composition, possibly result from differences in OM sources and the degree of degradation occurring at the two sites. Carbohydrate (PCHO), total hydrolyzable amino acid (THAA) and FTIR data suggest that the nutritional value of bulk POM to benthic heterotrophs should be lower in spring than summer-fall, although both periods exhibited high sinking fluxes of total mass and OC. Due to sediment resuspension events and an oxic water column, organic matter eventually buried in Lake Superior’s sediments has probably experienced extensive alteration due to several cycles through the water column and the bacterially-active sediment-water interface.     

The former presence of organic matter caused its later absence: Burn‐down of organic matter in oceanic red beds enhanced by bioturbation (Eocene Variegated Shale,Carpathians)

Eocene oceanic red beds that formed in a well‐oxygenated setting at low sedimentation rates below the calcite compensation depth are effectively barren of organic carbon in the present state. Recurrent distal low‐erosive turbidites preserve the bioturbated zone underneath that documents seasonal and long‐term fluctuating accumulation of considerable amounts of organic matter on the sea floor as evidenced by Scolicia ; the producers of this trace fossil exploited nutritious organic matter conserved in turbidite‐buried sea floor deposits. Over the long‐term, slow average sedimentation of (hemi)pelagic oxic (red) mud led to long oxygen exposure times and low burial of organic matter. Consequently, trace fossils representing persistent sediment‐feeding modes are of small size. Although the food‐limited setting appears appropriate for producers of graphoglyptids, such ‘stationary’ burrows have not been encountered because seasonal deposition of organic matter fostered at least temporary surface layer feeding organisms, for instance producers of Nereites irregularis that intensively reworked the sediment and, hence, hindered graphoglyptid production. These findings confirm palaeoceanographic modelling results that suggest upwelling in the study area during the Eocene.     

Distribution of sedimentary organic matter in Anisian carbonate series of S Poland: evidence of third-order sea-level fluctuations

The stratigraphic distribution of sedimentary organic matter in Anisian carbonate series of southern Poland is studied with respect to relative sea-level fluctuations. Palynofacies patterns clearly reflect transgressive–regressive trends that are interpreted in terms of third-order cyclicity. Major flooding phases are detected by maximum abundance of marine plankton in the upper Bithynian and Pelsonian. Transgressive and highstand deposits are recognized by changes in the terrestrial input of organic particles and the relative percentages and diversity of the plankton group. The palynological data support the sequence stratigraphic interpretation based on sedimentological features and geochemical signatures. The corresponding eustatic signals of sedimentary and organic facies are discussed. The study highlights the potential of palynofacies analysis for sequence stratigraphical interpretation.     

Carbon and nitrogen pools in Padanian soils (Italy): Origin and dynamics of soil organic matter

Carbon and nitrogen elemental (C-N, wt%) and isotopic (δ¹³C-δ¹⁵N, ‰) investigation has been carried out on alluvial and deltaic soils from the Padanian plain (northern Italy), an area interested by intensive agricultural activities, to refine previous inferences on depositional facies, pedogenetic processes and anthropogenic influences. Soil analysis, carried out by EA-IRMS, have been focused on inorganic and organic fractions properly speciated by a thermally-based method, whereas further insights on the organic matter constituents have been obtained by sequential fractionation. The bulk EA-IRMS analyses reveal a remarkable compositional heterogeneity of the investigated soils (TC 0.89 to 11.93?wt%, TN 0.01 to 0.78?wt%, δ¹³C_TC -1.2 to -28.2‰, δ¹⁵N -1.2 to 10.0‰) that has to be explained as an integration between inorganic and organic pools. The latter have been subdivided in Non-Extractable Organic Matter (NEOM, δ¹³C -16.3 to -28.6‰) and in extractable fractions as Fulvic (FA, δ¹³C -24.7 to -27.5‰, δ¹⁵N 0.6 to 5.7‰) and Humic (HA, δ¹³C -24.6 to -27.0‰, δ¹⁵N 1.0 to 9.7‰) Acids, which have been used to infer soil dynamics and Soil Organic Matter (SOM) stability processes. Results indicate that SOM at depth of 100?cm was generally affected by microbial reworking, with the exception of clayey and peaty deposits in which biological activity seems inhibited. Peaty and clayey soils display an organic fraction loss of ca. 20% toward the surface, suggesting deterioration possibly induced by intensive agricultural activities. These latter may be the cause of the ubiquitous losses of organic fraction throughout the investigated area over the last seventy years, evaluated by the comparison with historical data on corresponding topsoils. The obtained insights are very important because these soils are carbon (and nitrogen) sinks that are vulnerable and can be degraded, loosing agricultural productivity and potentially contributing to greenhouse gases fluxes.     

A natural cement analogue study to understand the long-term behaviour of cements in nuclear waste repositories: Maqarin (Jordan)

The geological storage of nuclear waste includes multibarrier engineered systems where a large amount of cement-based material is used. Predicting the long term behaviour of cement is approached by reactive transport modelling, where some of the boundary conditions can be defined through studying natural cement analogues (e.g. at the Maqarin natural analogue site). At Maqarin, pyrometamorphism of clay biomicrites and siliceous chalks, caused by the in-situ combustion of organic matter, produced various clinker minerals. The interaction of infiltrating groundwater with these clinker phases resulted in a portlandite-buffered hyperalkaline leachate plume, which migrated into the adjacent biomicrite host rock, resulting in the precipitation of hydrated cement minerals.In this study, rock samples with different degrees of interaction with the hyperalkaline plume were investigated by various methods (mostly SEM-EDS). The observations have identified a paragenetic sequence of hydrous cement minerals, and reveal how the fractures and porosity in the biomicrite have become sequentially filled. In the alkaline disturbed zone, C-A-S-H (an unstoichiometric gel of Ca, Al, Si and OH) is observed to fill the pores of the biomicrite wallrock, as a consequence of reaction with a high pH Ca-rich fluid circulating in fractures. Porosity profiles indicate that in some cases the pores of the rock adjacent to the fractures became tightly sealed, whereas in the veins some porosity is preserved. Later pulses of sulphate-rich groundwater precipitated ettringite and occasionally thaumasite in the veins, whereas downstream in the lower pH distal regions of the hyperalkaline plume, zeolite was precipitated.Comparing our observations with the reactive transport modelling results reveals two major discrepancies: firstly, the models predict that ettringite is precipitated before C-A-S-H, whereas the C-A-S-H is observed as the earlier phase in Maqarin; and, secondly, the models predict that ettringite acts as the principal pore-filling phase in contrast to the C-A-S-H observed in the natural system. These discrepancies are related to the fact that our data were not available at the time the modelling studies were performed. However, all models succeeded in reproducing the porosity reduction observed at the fracture–rock interface in the natural analogue system.     

Compositions and sources of extractable organic matter in Mesopotamian marshland surface sediments of Iraq: II. Polar compounds

The concentrations of polar organic compounds including n-alkanoic acids, n-alkanols, steroids and triterpenoids were determined in extracts of shallow sediments from the Mesopotamian marshlands of Iraq. The sediments were collected by a stainless steel sediment corer, extracted with a dichloromethane and methanol mixture (3:1 v:v) by ultrasonic agitation and then analyzed by gas chromatography–mass spectrometric (GC–MS). The analysis results showed that the n-alkanoic acids ranged from C₈ to C₂₀ with concentrations of 7.8 ± 1.2 μg/g sample, whereas the concentrations of n-alkanols, which ranged from C₁₂ to C₃₉ were from 28.6 ± 4.3 to 121.7 ± 18.3 μg/g sample. The steroids and triterpenoids included stenols, stanols, stenones, stanones, tetrahymanol, tetrahymanone and extended ββ-hopanes. The total concentrations of steroids and triterpenoids ranged from 26.8 ± 4.1 to 174.6 ± 26.2 μg/g and from 0.74 ± 0.11 to 11.2 ± 1.7 μg/g sample, respectively. The major sources of these lipids were from natural vegetation, microbial (plankton) residues and bacteria in the sediments, with some contribution from anthropogenic sources (livestock, sewage and petroleum). Further studies of these wetlands are needed to characterize the input rate, transformation and diagenesis of the organic matter and to assess its various sources.     

Compositions and sources of extractable organic matter in Mesopotamian marshland surface sediments of Iraq. I: aliphatic lipids

Shallow surface sediment samples from the Mesopotamian marshlands of Iraq were collected and analyzed to determine the distribution, concentrations and sources of aliphatic lipid compounds (n-alkanes, n-alkanols, n-alkanoic acids, and methyl n-alkanoates) and molecular markers of petroleum in these wetlands. The sediments were collected using a stainless steel sediment corer, dried, extracted with a dichloromethane/methanol mixture and then analyzed by gas chromatography-mass spectrometry (GC–MS). The aliphatic lipid compounds included n-alkanes, n-alkanoic acids, n-alkanols and methyl n-alkanoates with concentrations ranged from 6.8 to 31.1 μg/g, 4.1 to 5.0 μg/g, 5.9 to 7.7 μg/g and from 0.3 to 5.9 μg/g, respectively. The major sources of aliphatic lipids were natural from waxes of higher plants (24–30%) and microbial residues (42–30%), with a significant contribution from anthropogenic sources (27–30%, petroleum), based on the organic geochemical parameters and indices. Further studies are needed to characterize the rate, accumulation and transformation of various organic matter sources before and after re-flooding of these wetlands.