Applied Geochemistry (v.20, #3)

Characterization of the hydrogen isotopic composition of individual n-alkanes in terrestrial source rocks by Yongqiang Xiong; Ansong Geng; Changchun Pan; Deyong Liu; Pingan Peng (455-464).
In order to characterize the H isotopic compositions of individual lipid compounds from different terrestrial depositional environments, the δD values of C-bound H in individual n-alkanes from typical terrestrial source rocks of the Liaohe Basin and the Turpan Basin, China, were measured using gas chromatography–thermal conversion–isotope ratio mass spectrometry (GC–TC–IRMS). The analytical results indicate that the δD values of individual n-alkanes in the extracts of terrestrial source rocks have a large variation, ranging from −140‰ to −250‰, and are obviously lighter than the δD of marine-sourced n-alkanes. Moreover, a trend of depletion in 2H(D) was observed for individual n-alkanes from different terrestrial depositional environments, from saline lacustrine to freshwater paralic lacustrine, and to swamp. For example, the δD values of n-alkanes from a stratified saline lacustrine environment vary from −140‰ to −200‰, δD for n-alkanes from swamp facies range from −200‰ to −250‰, while those from freshwater paralic lacustrine–lacustrine environments fall between the δD values of the end members. The shift toward lighter δD from saltwater to freshwater environments indicates that the source water δD is the major controlling factor for the H isotopic composition of individual compounds. In addition, H exchange between formation water and sedimentary organic matter may possibly be important in regard to the δD of individual n-alkanes. Therefore, other lines of geochemical evidence must be considered when depositional paleoenvironments of source rocks are reconstructed based on the H isotopic composition of individual n-alkanes.

Hydrogeochemical evolution and C isotope study of groundwaters from “Mina Fe” U deposit (Salamanca, Spain): implications for processes in radwaste disposal by L. Pérez del Villar; A. Garralón; A. Delgado; E. Reyes; J.S. Cózar; P. Gómez; R. Núñez; L. Sánchez; J. Raya (465-485).
Within the framework of the ENRESA natural analogue programme, the U ore deposit of “Mina Fe”, western Spain, has been studied as a natural analogue of radioactive spent fuel behaviour after burial, in spite of being an extremely perturbed geological environment due to mining activities. The main objectives of this project are to determine the hydrogeochemical evolution of the system and identify the main water/rock interaction processes that control the physicochemical variables (pH and Eh) of groundwaters, including the role-played by the organic matter.The hydrogeochemical results from 3 consecutive groundwater sampling campaigns, separated by a phase of restoration works, indicate that the groundwater of the site shows an evolutionary trend from Ca – SO 4 2 - acid oxidising waters towards alkaline-reducing waters, though their evolution with respect to the alkaline and alkaline-earth elements is not clear. The SO 4 2 - -acid waters are the result of the oxidation processes affecting the primary sulphide-rich U mineralisation, while the alkaline-reducing waters result from the buffer capacity of carbonates from fracture filling materials, as the δ 13C values of DIC demonstrate. The reducing character of these waters mainly results from the microbiologically mediated partial oxidation of the abundant organic matter existing in the clayey walls of the major faults at the site, since other dissolved inorganic redox pairs are insufficient to explain the in situ measured redox potential. Thus, the high content in DOC of these waters is also explained, since the soil at the site is poorly developed. DOC, DIC or both can be responsible for the high U concentration measured in these groundwaters, in spite of its reducing character.The restoration works performed in the exploitation quarry have also restored the aforementioned evolutionary trend, which was the normal evolution of groundwater in the site before mining. Finally, the results are discussed in terms of the geochemical processes expected in a radioactive disposal site after closure.

Sequential leaching methods have been used to determine the mineralogical distribution of some trace elements for environmental purposes, such as radiological contamination of soils and sediments, bioavailability studies and natural analogues of deep geological radwaste disposals. In this context, a 7-step-sequential leaching protocol is applied to Fe(III)–U(VI)-rich fracture filling materials from the oxidised zone of the “Mina Fe” U deposit to identify and evaluate the main sinks of natural nuclides and other analogue trace elements, since it is crucial in the performance assessment of a nuclear waste repository.After a careful characterisation of the samples, the analytical data from each leaching step were statistically analysed and then interpreted in light of the mineralogical and geochemical features of the samples. Precise knowledge of the mineralogical distribution of trace elements by sequential leaching methods is quite complex, mainly due to cross-contamination throughout the different steps of the experiments. Thus, the results obtained suggest that U is retained as U-minerals, mainly oxides, closely associated with crystalline Fe-oxyhydroxides. Though Ce and La also form independent compounds, such as Ce oxides and La–Nd phosphates, they are mainly retained by the amorphous Mn-oxyhydroxides. However, the crystalline Mn-oxyhydroxides are the main sink for Ni and crystalline Fe-oxyhydroxides mainly retain P.

A photosynthetic microbial community promotes the bio-precipitation of hydrozincite [Zn5(CO3)2(OH)6], containing tens to thousands of mg kg−1 of Pb, Cd, Cu, and Ni, in the Rio Naracauli, a streamlet polluted by mine tailings. Major variations in chemical and physical parameters occur in the waters as a consequence of hydrozincite precipitation induced by an initial environmental change (including a pH increase) produced by microbial activity. Specifically, the pH increases from 6.4 to 7.7 during hydrozincite precipitation, while at the same time the HCO 3 - concentration decreases. High concentrations of heavy metals (Zn 350 mg l−1, Cd 3.3 mg l−1, Pb 1.1 mg l−1 and Ni 0.17 mg l−1) were found upstream from the region of bio-precipitation in the outflow of tailings ponds. All metal concentrations decrease significantly immediately after the bio-precipitation of hydrozincite and continue to decrease further downstream.According to theoretical calculations, the main chemical species of Zn, Cd and Pb are Zn2+, Cd 2+ and Pb2+ in the upper reaches of Naracauli Creek, while further downstream ZnCO 3 0 , CdCO 3 0 , and PbCO 3 0 complexes prevail. The saturation index with respect to hydrozincite shows an oversaturation of up to 30 times the equilibrium value.Bulk partition coefficients between solution and hydrozincite show that K D(Pb/Zn)  >  K D(Cu/Zn)  >  K D(Ba/Zn)  >  K D(Ni/Zn)  >  K D(Cd/Zn)  >  K D(Sr/Zn) (K D(Me/Zn)  = (Me/Zn)s/(Me2+/Zn2+)aq where (Me/Zn)s represents the ratio between trace metal Me to Zn in hydrozincite, (Me2+/Zn2+)aq represents the ratio in associated water, and Me stands for Cd2+, Pb2+, Ni2+, Cu2+, Sr2+ and Ba2+). Heavy metals appear to be strongly bound in hydrozincite, because only small quantities of these are removed by cation exchange.These results may have implications for the development of remediation methods for waters contaminated with heavy metals.

Did an extensive forest ever develop on the Chinese Loess Plateau during the past 130 ka?: a test using soil carbon isotopic signatures by Weiguo Liu; Hong Yang; Yunning Cao; Youfeng Ning; Li Li; Jie Zhou; Zhisheng An (519-527).
Pleistocene vegetation history on the Chinese Loess Plateau has been traditionally investigated using palynological methods, and questions remain regarding whether an extensive broadleaf deciduous forest ever developed on the loess table under favorable climatic conditions. The authors have employed a C isotope approach to address this question by comparing δ13C values in soil organic matter from different loess ecological domains with known source vegetation to the C isotope values obtained from a paleosol section that can be dated back to 130 ka. The C isotopic compositions of modern soils from the loess table and the loess–desert transition gave δ13C values of −24.5‰ to −18.2‰ and −25.7‰ to −20.7‰, respectively. These C isotopic ratios are consistent with the standing modern vegetation that is dominated by a mixture of C3 and C4 plants and can be distinguished from that in the patchy forest areas where exclusive C3 trees yield a narrow δ13C value range from −26.9‰ to −25‰ (average −26.1‰). Obtained δ13C compositions from paleosols and loess sediments in the Lantian and the Luochuan profiles vary from −24‰ to −16.9‰, indicating a grass-dominated steppe with shifting C3 and C4 contributions controlled mainly by paleoclimatic changes during the late Pleistocene. The present results suggest no extensive forest coverage on the loess table during the past 130 ka even under the most suitable conditions for forest development. This conclusion supports the explanation of natural causes for the development of only patchy forests on the modern loess table and provides critical historical information toward the vegetation restoration project that is currently underway on the Chinese Loess Plateau.

Freshly precipitated hydrous oxides of Al (flocs) are important sorbents of heavy metal ions and are used in water treatment processes. The addition of chelating agents or polyelectrolytes can increase the efficiency of heavy metal removal by flocs. The polymer polyethylenimine is commonly used as a flocculant aid in water treatment and has been modified with phthalic acid. Adsorption studies have shown that the addition of millimolar concentrations of polyelectrolyte increases the removal of Cd ions from a 29.7 μM aqueous solution by aluminium flocs from ca. 40% to up to 75%. Experiments in which the pH was varied demonstrated that the observed enhancement of Cd adsorption is caused by a shift of the pH edge to lower pH values in the presence of polyelectrolyte. Maximum polyelectrolyte adsorption occurs between pH 6 and pH 7, corresponding to the point of enhanced Cd adsorption in the presence of polyelectrolyte. The enhancement of Cd adsorption observed below pH 7 is therefore likely to be due to the formation of a ternary surface complex. At pH values above pH 8 the polyelectrolyte forms a stable complex with Cd and Al ions in solution causing floc dissolution and decreased Cd adsorption.

Thermal analysis (TG–DTA) and isotopic characterization (13C–15N) of humic acids from different origins by Ornella Francioso; Daniela Montecchio; Paola Gioacchini; Claudio Ciavatta (537-544).
Thermal analyses (TG–DTA), elemental composition and isotope analyses (13C and 15N) were performed on humic acids (HA) from peats, leonardites and lignites, in order to investigate their structure and the changes taking place during the humification process. Thermal analyses showed structural differences between HA samples in relation to their coalification rank. In particular the lignite HA were characterized by a more stable chemical composition at high temperatures.The δ 13C and δ 15N values can provide information on the biogeochemical processes involved in HA formation. In particular, peat HA were linked to anoxic environments that enable plant residues to persist in their structure. In contrast, leonardite and lignite HA formation seems to be governed by different biogeochemical processes from those responsible for peat diagenesis. However, the isotopic analyses did not provide any distinction between leonardite and lignite HA. On the basis of the data presented in this study, it may be concluded that TG–DTA and isotope ratio measurements are powerful tools for investigating the formation pathway of humic substances from coals.

Applications of Mango’s light hydrocarbon parameters to petroleum from Tarim basin, NW China by Chunming Zhang; Sitian Li; Hongjing Zhao; Jun Zhang (545-551).
Light hydrocarbons in oils from the Tarim basin, NW China, were analyzed by GC. The light hydrocarbon parameters proposed by Mango revealed the distributions of the oils as two main types, marine and terrigenous sources. The Mango parameter K 1 not only displays a remarkable invariance (∼1) in most of the oils, but also shows significant variations (ranging from 1.20 to 1.54) in the oils occurring in the eastern part of the Tazhong Fault Uplift (EPTFU) located in the center of the Tarim basin. This variation of the K 1 value may indicate different petroleum systems in the areas which are superimposed in the EPTFU. Parameter K 2 proposed by Mango shows a significant variation between the two main oil types. The marine oils are characterized by relatively low values of K 2 (average 0.23) and the terrigenous oils by relatively high K 2 values (average 0.35), with general invariance within the same oil set. A plot of (P 3  +  P 2  +  N 2) vs. ( N 1 6 ) based on the model proposed by Mango can be used not only to discriminate between the two main genetic oils from the Tarim basin, but also to classify the marine oils from the Lunnan area into two sub-types, which may indicate two sub-petroleum systems existing in the area.

Seven coal and carbonaceous mudstone samples were collected from outcropping Jurassic coal beds, on the margin of the Dingxi Basin, Northwestern China. The n-alkane distributions in all of the samples are characterised by high concentrations of the C19–C29 homologues, and very much lower amounts outside of this range. C23 or C24 are usually the most abundant n-alkanes. Straight chain n-alkanes from C23 to C29 show moderate odd-to-even C number predominances (CPI range: 1.26–2.70). Long-chain acyclic n-alkan-2-ones, n-alkan-3-ones and n-alkan-4-ones ranging from C15 to C33 with moderate odd-to-even C number predominances, were detected together with one isoprenoid methyl ketone (6,10,14-trimethylpentadecan-2-one) in all of the samples. The C number distributions of the three series of alkanones show a similar distribution to that of the n-alkanes, but the correspondence is not sufficient to substantiate a product–precursor relationship. It can be concluded that the n-alkan-2-ones are a mixture of the products of microbially-mediated β-oxidation of corresponding n-alkanes in the sediments and from the microbial oxidation of higher plant-derived n-alkanes prior to incorporation in the sediments. The n-alkan-3-ones and n-alkan-4-ones were formed from microbially mediated oxidation of the corresponding n-alkanes in the γ and δ positions, respectively. Generation of the ketones from higher plant n-fatty alcohols and n-alkanoic acids could be a possible way to form some of the ketones observed, but it can only play a minor role in the samples analysed.

Constructed and natural wetlands can accumulate elevated levels of Se; however, few data are available on cost-effective methods for remobilization and removal of Se from these areas. A field experiment was conducted to assess the effectiveness of flooding on the removal of Se from dry surface sediments. The 83-m2 flood-experiment plot contained 10 monitoring wells, a water-quality minimonitor (continuous measurement of pH, specific conductance, water temperature, and dissolved O2), a down-hole Br electrode, and 2 pressure transducers. Flooding was initiated on August 27, 2002, and a Br tracer was added to water delivered through a pipeline to the flood plot during the first 1.2 h. Standing water depth in the flood plot was maintained at 0.3 m through September 1, 2002. The Br tracer data indicate a dual porosity system that includes fracture (mud cracks) and matrix flow components. Mean vertical water velocities for the matrix flow component were estimated to range from 0.002 to 0.012 m/h. Dissolved (less than 0.45 μm) Se increased from pre-flood concentrations of less than 10 μg/L to greater than 800 μg/L during flooding in samples from deep (2.0 m below land surface) ground water. Selenium concentrations exceeded 5500 μg/L in samples from shallow (0.8 m below land surface) ground water. Ratios of Se to Br in water samples indicate that Se moved conservatively during the experiment and was derived from leaching of near-surface sediments. Cumulative Se flux to the deep ground water during the experiment ranged from 9.0 to 170 mg/m2. Pre- and post-flood surface soil sampling indicated a mean Se flux of 720 mg/m2 through the top 15 cm of soil. Ground-water samples collected 8 months after termination of the flood experiment contained Se concentrations of less than 20 μg/L. The minimonitor data indicate a rapid return to chemically reducing conditions in the deep ground water, limiting the mobility of the Se dissolved in the water pulse introduced during the flood experiment. Ratios of Se to Br in deep ground-water samples collected 8 months after the experiment confirmed the removal of Se from the aqueous phase. Based on the median Se flux rate estimated during the experiment of 0.65 mg/h/m2 (n  = 52), 7 flooding cycles would be required to meet the 4 μg/g remediation goal in surface soils from the SLWMA wetland.

Closed pyrolyses were performed on the Boom Clay kerogen to simulate the weak thermal stress applied during the in situ CERBERUS heating experiment (80 °C for 5 a). Two stronger thermal stresses, encompassing the range generally considered for the long-term disposal of high-activity nuclear waste (80 °C for 1 ka and 120 °C for 3 ka), were also simulated. Quantitative and qualitative studies were carried out on the products thus generated with a focus on the C12+ fraction, especially on its polar components. It thus appeared that the soluble C12+ fractions generated during these simulation experiments comprise a wide variety of polar O- and/or N-containing compounds, including carboxylic acids and phenols. The nature and/or the relative abundance of these polar compounds exhibit strong variations, with the extent of the thermal stress, reflecting the primary cracking of different types of structures with different thermal stability and the occurrence of secondary degradation reactions. These observations support the idea that the compounds, generated upon exposure of the Boom Clay kerogen to a low to moderate thermal stress, may affect the effectiveness of the geological barrier upon long-term storage of high-activity nuclear waste.

36Cl in modern groundwater dated by a multi-tracer approach (3H/3He, SF6, CFC-12 and 85Kr): a case study in quaternary sand aquifers in the Odense Pilot River Basin, Denmark by J.A. Corcho Alvarado; R. Purtschert; K. Hinsby; L. Troldborg; M. Hofer; R. Kipfer; W. Aeschbach-Hertig; H. Arno-Synal (599-609).
36Cl produced by thermonuclear bomb testing has been proposed as an additional tool to date or at least to identify recent groundwater components. In order to investigate the behaviour of 36Cl in shallow groundwater a multi-tracer approach (3H/3He, SF6, CFC-12 and 85Kr) was used to characterise and date the groundwater of a quaternary sands aquifer which is located on the Island of Funen near the city of Odense, Denmark. Recharge to the semi-confined shallow aquifer occurs through permeable sand windows and fractured tills at the surface. Locally, however, mixing with older pre-bomb water from the underlying limestone aquifer may occur. The integrated analyses of the available tracer data allowed a well constrained age structure determination of the investigated water system.The 36Cl/Cl ratios measured in groundwater were used to reconstruct the fallout rates for radioactive 36Cl at Odense. The calculated fallout values exceeded the fallout estimated based on data from the Dye-3 ice core in Greenland. Recycling of the bomb peak fallout seems to be the most probable reason of the high values measured. The local extent of this process is difficult to quantify, which impedes the use of 36Cl for dating.

This paper presents new data on the baseline concentrations of U, Th and K in 2389 stream sediments over the whole Campania region. These data, based on systematic sampling and analysis, are compared with those obtained by gamma-ray spectrometry surveys.Variations in the U, Th and K concentration in the surficial environment of the Campania region appear to be related to bedrock lithology. Generally, high U, Th and K values in stream sediments correspond well with the occurrence of volcanic rocks in the central-western part of the region, whereas low values are found in areas characterized by silico-clastic and carbonate deposits, occurring mostly in the southern and eastern part of the region. Gamma-ray spectrometry maps show a similar pattern, although the distribution of the highest radioactivity levels define more restricted areas than the ones resulting from mapping stream sediment geochemistry. Particularly high 40K radioactivity levels delimit all the known eruptive centers (Roccamonfina, Campi Flegrei and Somma–Vesuvius), including the fissural sources of Campania Ignimbrites, much better than U and Th radioactivity. One of the concerns for human health in the Campania region is the total gamma radiation and Rn potential related mostly to alkaline volcanics of the Neapolitan volcanological province. In particular, geothermal activity occurring in all the Campanian volcanic areas represents a potential hazard for Rn gas.

Concentrations of total Hg and methylmercury (MMHg) in riparian soil, mine-waste calcine, sediment, and moss samples collected from abandoned Hg mines in Wanshan district, Guizhou province, China, were measured to show regional dispersion of Hg-contamination. High total Hg and MMHg concentrations obtained in riparian soils from mined areas, ranged from 5.1 to 790 mg kg−1 and 0.13 to 15 ng g−1, respectively. However, total Hg and MMHg concentrations in the soils collected from control sites were significantly lower varying from 0.1 to 1.2 mg kg−1 and 0.10 to 1.6 ng g−1, respectively. Total Hg and MMHg concentrations in sediments varied from 90 to 930 mg kg−1 and 3.0 to 20 ng g−1, respectively. Total Hg concentrations in mine-waste calcines were highly elevated ranging from 5.7 to 4400 mg kg−1, but MMHg concentrations were generally low ranging from 0.17 to 1.1 ng g−1. Similar to the high Hg concentrations in soil and sediments, moss samples collected from rocks ranged from 1.0 to 95 mg kg−1 in total Hg and from 0.21 to 20 ng g−1 in MMHg. Elevated Hg concentrations in mosses suggest that atmospheric deposition might be an important pathway of Hg to the local terrestrial system. Moreover, the spatial distribution patterns of Hg contamination in the local environment suggest derivation from historic Hg mining sites in the Wanshan area.

Release, transport and attenuation of metals from an old tailings impoundment by M.C. Moncur; C.J. Ptacek; D.W. Blowes; J.L. Jambor (639-659).
The oxidation of sulfide minerals from mine wastes results in the release of oxidation products to groundwater and surface water. The abandoned high-sulfide Camp tailings impoundment at Sherridon, Manitoba, wherein the tailings have undergone oxidation for more than 70 a, was investigated by hydrogeological, geochemical, and mineralogical techniques. Mineralogical analysis indicates that the unoxidized tailings contain nearly equal proportions of pyrite and pyrrhotite, which make up to 60 wt% of the total tailings, and which are accompanied by minor amounts of chalcopyrite and sphalerite, and minute amounts of galena and arsenopyrite. Extensive oxidation in the upper 50 cm of the tailings has resulted in extremely high concentrations of dissolved SO4 and metals and As in the tailings pore water (pH < 1, 129,000 mg L−1 Fe, 280,000 mg L−1 SO4, 55,000 mg L−1 Zn, 7200 mg L−1 Al, 1600 mg L−1 Cu, 260 mg L−1 Mn, 110 mg L−1 Co, 97 mg L−1 Cd, 40 mg L−1 As, 15 mg L−1 Ni, 8 mg L−1 Pb, and 3 mg L−1 Cr). The acid released from sulfide oxidation has been extensive enough to deplete carbonate minerals to 6 m depth and to partly deplete Al-silicate minerals to a 1 m depth. Below 1 m, sulfide oxidation has resulted in the formation of a continuous hardpan layer that is >1 m thick. Geochemical modeling and mineralogical analysis indicate that the hardpan layer consists of secondary melanterite, rozenite, gypsum, jarosite, and goethite. The minerals indicated mainly control the dissolved concentrations of SO4, Fe, Ca and K. The highest concentrations of dissolved metals are observed directly above and within the massive hardpan layer. Near the water table at a depth of 4 m, most metals and SO4 sharply decline in concentration. Although dissolved concentrations of metals and SO4 decrease below the water table, these concentrations remain elevated throughout the tailings, with up to 60,600 mg L−1 Fe and 91,600 mg L−1 SO4 observed in the deeper groundwater. During precipitation events, surface seeps develop along the flanks of the impoundment and discharge pore water with a geochemical composition that is similar to the composition of water directly above the hardpan. These results suggest that shallow lateral flow of water from a transient perched water table is resulting in higher contaminant loadings than would be predicted if it were assumed that discharge is derived solely from the deeper primary water table. The abundance of residual sulfide minerals, the depletion of aluminosilicate minerals in the upper meter of the tailings and the presence of a significant mass of residual sulfide minerals in this zone after 70 a of oxidation suggest that sulfide oxidation will continue to release acid, metals, and SO4 to the environment for decades to centuries.

This paper describes the geochemical testing of mine tailings sourced from the Black Swan Ni Mine located near Kalgoorlie, Western Australia. Acid–base accounting was used to provide an indication of the acid generating capacity of two kinds of mining tailings: disseminated-ore tailings from the Cygnet Tailings Dam Storage Facility (CTDSF) and massive-ore tailings from the Silver Swan Tailings Dam Storage Facility (SSTDSF). All of the tailings in SSTDSF have acid generating potential which is consistent with previous research reports. New findings in this paper reveal that approximately 16% of the tailings in CTDSF have the potential to be acid generating. In contrast, previous reports state that the disseminated-ore tailings are classified as non-acid forming. Most of the potential acid generating tailings in the CTDSF are found in the upper-middle sections of the tailings profile, but some are located at the bottom of the tailings dam. The upper-middle section of the tailings is oxidized because these tailings have interacted with atmospheric O2 and rain and surface water. Oxidation of the bottom tailings in the CTDSF may be due to infiltration of ground water into hidden fractures under the east bank of CTDSF, which caused these tailings to oxidize under closed and reduced conditions.The acid drainage in the tailings dam storage facility was observed 3 a, after the development of the Black Swan Nickel project. This delayed production of acid drainage was likely due to the slow rates of acid neutralization provided by alteration gouge minerals such as Mg/Fe-carbonates (magnesite–siderite series) associated with the Ni ores. The acid drainage leaking from the tailings dams has contaminated neighboring ground water via increased acidity and heavy metals.Because of the potential acid generation in some of the disseminated ore tailings, it is inadvisable to use disseminated ore tailings as cover materials in the storage facility to isolate the underlying potentially-acid-forming tailings from O2 and water, as proposed by previous research reports.