Applied Geochemistry (v.23, #10)

Lac Pavin (French Massif Central) is a permanently stratified lake: the upper water layers (mixolimnion, from 0 to 60 m depth) are affected by seasonal overturns, whereas the bottom water layers (monimolimnion, from 60 to 90 m depth) remain isolated and are never mixed. Hence, they are capable of storing important quantities of dissolved gases, mainly CO2. With the aim of better constraining the water balance and of gaining new insights into the carbon cycle of Lac Pavin, an isotopic approach is used. The δ 18 O H 2 O profiles lead the authors to give a new evaluation of the evaporation flow rate (8 L s−1), and to propose and characterize two sub-surface springs. The sub-surface spring located at the bottom of the lake can be deduced from the 1% isotopic difference between the upper water layers (mean δ 18 O H 2 O value: −7.3‰) and the bottom water layers ( δ 18 O H 2 O = - 8.4 ‰ ). It is argued that this sub-surface spring has isotopic and chemical characteristics similar to those of the magmatic CO2-rich spring (i.e. Fontaine Goyon, δ 18 O H 2 O = - 9.4 ‰ ), and we calculate its flow rate of 1.6 L s−1. The second sub-surface spring is located around 45 m depth, with a composition close to those of the water surface streams ( δ 18 O H 2 O < - 7.6 ‰ ).Methane (4 mM) and dissolved inorganic carbon concentrations (≈14 mM) allow the re-estimation of the relative DIC contributions in the bottom of the lake (90 m depth): 1/3 deriving from methanogenesis (δ 13CDIC  ≈ +7‰) and 2/3 from the magmatic CO2-rich spring (δ 13CDIC  ≈ −5‰). Above 80 m depth, the variations in DIC concentrations (ranging from 0.5 to 10 mM) and δ 13CDIC values (ranging from −6.5‰ to 4.4‰) are partly explained by the usual methanotrophy, organic matter oxidation, photosynthesis and CO2 equilibrium with atmosphere. The unusually high δ 13CDIC values in the upper water layers (ranging from −6‰ to 0‰) compared to the expected δ 13CDIC values assuming only organic matter oxidation, demonstrate the leakage of 13C-enriched DIC from the bottom water layers of Lac Pavin (δ 13CDIC values ranging from −5‰ to 3‰).

The use of radioactive isotopes plays a very important role in dating groundwater, providing an apparent age of the systems in the framework of the aquifers conceptual modelling making available important features about the water fluxes, such as recharge, horizontal flow rates and discharge. In this paper, special emphasis has been put on isotopic constraints in the use of δ 13C and 14C content as a dating tool in some hot (76 °C) and cold (17 °C) CO2-rich mineral waters discharging in the Vilarelho da Raia–Pedras Salgadas region (N-Portugal). The radiocarbon content determined in these CO2-rich mineral waters (14C activity from 4.3 up to 9.9 pmc) is incompatible with the systematic presence of 3H (from 1.7 to 7.9 TU). The δ 13C values of the studied CO2-rich mineral waters indicate that the total C in the recharge waters is being masked by larger quantities of CO2 (14C-free) introduced from deep-seated (upper mantle) sources. This paper demonstrates that a good knowledge of mineral water systems is essential to allow hydrologists to make sound conclusions on the use of C isotopic data in each particular situation.

Radon and progeny (214Pb and 214Bi) in urban water-supply systems of São Paulo State, Brazil by Daniel Marcos Bonotto; Priscilla Cardoso Padron-Armada (2829-2844).
Many water-supply systems in South America utilize the waters of the Guarani aquifer at least as part of their networks. However, there is little present knowledge in Brazil of the factors affecting Rn presence in the water supplied for end-users, despite the economic importance of Guarani aquifer. 222Rn analyzes of 162 water samples were performed at 8 municipalities in São Paulo State, Brazil, with the aim of investigating the major factors affecting its presence in solution. The 222Rn activity concentration ranged from 0.04 up to 204.9 Bq/L, with three samples exceeding the World Health Organization maximum limit of 100 Bq/L. Aeration was confirmed as the most important factor for Rn release, as expected due to its gaseous nature. Accumulation in pipes and stratification in the water column were other significant factors explaining the data obtained in some circumstances. The Rn daughters 214Pb and 214Bi were also determined in a set of selected samples and their presence was directly related to the occurrence of Rn dissolved in water.

Stable O and C isotope data of 110 Upper Pliensbachian-Lower Bajocian belemnites have been obtained and used to attempt a reconstruction of palaeotemperature and its variation in two epicontinental depositional environments from the Western Balkan mountains (Bulgaria). The samples were collected from 3 sections with high-resolution ammonite subdivision. Initially taphonomic, cathodoluminescence and geochemical analyses were used for evidence of diagenetic alteration. Non-luminescent parts of the belemnite rostra have been sampled for isotope analyses and 76 samples, having δ 18O < −4‰ (PDB), δ 13C > −0.5‰ (PDB), Fe < 250 ppm, Mn < 50 ppm, Sr > 950 ppm and Sr/Mn ratio > 80 were used for palaeotemperature interpretations. The O and C isotope data generally exhibit little stratigraphical variability with minor fluctuations, however, there are prominent positive C isotope excursions and coeval negative O isotope shifts detected in the Lower Toarcian Tenuicostatum, Falciferum and Bifrons Zones. The O isotope data, interpreted in terms of palaeotemperature, revealed relatively high seawater temperatures during the Toarcian, Aalenian and Early Bajocian, with detectable temperature rises during the Early Toarcian (maximum value of 29.6 °C). Both C isotope maxima and O isotope minima are used as evidence of the Early Toarcian anoxic event reported from many localities of the same age and in similar facies in Western Europe. In the study the latter is recognized as 3 episodes, which are closely related with the seawater temperature maxima. This isotope record pattern is considered as a consequence of a global Tethyan transgression during the Early Toarcian.

Sources of organic carbon in the Portuguese continental shelf sediments during the Holocene period by D. Burdloff; M.F. Araújo; J.-M. Jouanneau; I. Mendes; A.M. Monge Soares; J.M.A. Dias (2857-2870).
Organic C (OC) and total N (TN) concentrations, and stable isotope ratios (δ 13C) in muddy deposit sediments of the Northern and Southern Portuguese continental shelf were used to identify sources of fine-sized organic matter (<63 μm) during the Holocene period. Sedimentary columns off the Guadiana (core CRIDA 05), Tagus (core MD 992332) and Douro (core KSGX 57) estuaries are characterised by elemental and isotopic values that reflect distinct sources of organic matter (OC/TN and δ 13C ranging, respectively, from 8.5 to 21 and from −22.4‰ to −27‰). Intense supplies to the Guadiana continental shelf of fine terrigenous particles during the Younger-Dryas Event are closely linked with higher OC/TN values and lower δ 13C ratios. During the postglacial transgression phase, an increasing contribution of marine supplies (up to 80%) occurred. Higher δ 13C (up to −22.4‰) values and low OC/TN ratios (down to 8.5) are found as the sea level approaches the current one. The Upper Holocene records emphasize the return to enhanced terrestrial supplies except for the Little Climatic Optimum between the 11th and 15th centuries AD. This climatic event is especially obvious in the three cores as a return to marine production and a decrease in terrestrial sediment supply to the continental shelf. The return to a cooling event, the Little Ice Age, between the 15th and 19th centuries AD, is mirrored by decreased terrigenous supplies in core KSGX 57. Gradually increasing sedimentation in estuaries, as well as formation of coastal dune fields, have been hypothesized on the basis of increasing δ 13C and decreasing OC, TN and OC/TN values.

Separating contributions from natural and anthropogenic sources in atmospheric methane from the Black Sea region, Romania by Stela Cuna; Elise Pendall; John B. Miller; Pieter P. Tans; Ed Dlugokencky; James W.C. White (2871-2879).
The Danube Delta-Black Sea region of Romania is an important wetland, and this preliminary study evaluates the significance of this region as a source of atmospheric CH4. Measurements of the mixing ratio and δ13C in CH4 are reported from air and water samples collected at eight sites in the Danube Delta. High mixing ratios of CH4 were found in air (2500–14,000 ppb) and dissolved in water samples (∼1–10 μmol L−1), demonstrating that the Danube Delta is an important natural source of CH4. The intercepts on Keeling plots of about −62‰ show that the main source of CH4 in this region is microbial, probably resulting primarily from acetate fermentation. Atmospheric CH4 and CO data from the NOAA/ESRL (National Oceanic and Atmospheric Administration/Earth System Research Laboratory) were used to make a preliminary estimate of biogenic CH4 at the Black Sea sampling site at Constanta (BSC). These data were used to calculate ratios of CH4/CO in air samples, and using an assumed CH4/CO anthropogenic emissions ratio of 0.6, fossil fuel emissions at BSC were estimated. Biogenic CH4 emissions were then estimated by a simple mass balance approach. Keeling plots of well-mixed air from the BSC site suggested a stronger wetland source in summer and a stronger fossil fuel source in winter.

Comparative behaviour of recently deposited radiostrontium and atmospheric common strontium in soils (Vosges mountains, France) by L. Pourcelot; P. Stille; D. Aubert; N. Solovitch-Vella; F. Gauthier-Lafaye (2880-2887).
The vertical distribution of atmospheric 87Sr/86Sr isotope ratios in soil is compared to the distribution of recent atmospheric 90Sr deposition. 87Sr/86Sr isotope ratios of soil leachates are correlated with 90Sr activities. Samples from the uppermost part of a soil profile have low 87Sr/86Sr ratios and high 90Sr activities. Samples from the deeper part of the soil profile, however, have high 87Sr/86Sr but low 90Sr activities. This points to mixing between an atmospheric and a geogenic component. Mixing calculations indicate that 50–80% of the Sr in the topsoil of a small catchment in the Vosges mountains is of atmospheric origin. Similarly 87Sr/86Sr of roots point to the presence of an atmospheric and geogenic component. 87Sr/86Sr ratios of soil leachates and corresponding roots are very similar indicating, that the roots integrate at each level of the soil profile the leachable Sr of the corresponding soil.

Mineralogical sources of the buffer capacity in a granite catchment determined by strontium isotopes by Christina Weyer; Gunnar Lischeid; Luc Aquilina; Anne-Catherine Pierson-Wickmann; Charlotte Martin (2888-2905).
The role of different minerals in base cation release and thus the increase of buffering capacity of groundwater against acid deposition is controversially discussed in the literature. The 87Sr/86Sr ratios and base cation concentration were investigated in whole rock leachates, mineral separates, precipitation, soil solution, groundwater and stream water samples in the Lehstenbach catchment (Germany) to identify the weathering sequence of the granite bedrock. Three different approaches were followed in parallel. It was assumed that the contribution of different minerals to base cation supply of the groundwater with increasing weathering intensity would be observed by investigating (1) unweathered rock leachates, deep groundwater and shallow groundwater, (2) groundwater samples from new groundwater wells, reflecting the initial weathering of the drilled bedrock, and groundwater from wells that were drilled in 1988, (3) stream water during baseflow, dominated by deep groundwater, and stream water during high flow, being predominantly shallow groundwater. Whereas the first approach yielded consistent patterns, there was some evidence that groundwater from the new wells initially reflected contamination by the filter gravel rather than cation release in an initial stage of weathering. Time series samples of stream water and groundwater solute concentrations and isotope ratios turned out to reflect varying fractions of soil water and precipitation water at baseflow and high flow conditions rather than varying contributions of different minerals that prevail at different stages of granite weathering.The early phase of weathering was clearly dominated by base cation release from biotite weathering and to a lesser extent by apatite dissolution. Feldspars contributed to base cation release as well, but could not be regarded as endmembers of the mixing diagram. There was no clear evidence for a contribution from calcite. Correspondingly, base cation input by atmospheric deposition and liming had only minor effects on groundwater buffer capacity.

The fluorite-bearing hydrothermal mineralization in Sardinia mainly occurs within Paleozoic volcanic and metasedimentary rocks. Only 3 occurrences are located in volcanic and siliciclastic Cenozoic rocks. Most Sardinian fluorites exhibit relatively high rare earth and Y (REY) contents, strong positive Y anomalies, slightly negative Ce and generally positive Eu anomalies. These features indicate that the REY were mobilized mainly from non-carbonate rocks. Neither Sr nor Nd isotopes can be used to date radiometrically the Sardinian fluorites. However, the measured Sr-isotope ratios of the fluorites hosted by Paleozoic rocks fit mixing lines in the 1000/Sr versus 87Sr/86Sr plot once recalculated at 280 Ma, suggesting that the age inferred for the correction probably represents that of the formation of the fluorite mineralization. Mixing likely occurred between diluted surficial waters and brines circulating mainly through the Lower Paleozoic metasedimentary basement. The Cenozoic fluorites exhibit chemical and isotopic features similar to those of the Paleozoic fluorites, except the Nuraghe Onigu fluorite displaying a possible contribution of Sr from Cenozoic magmatic rocks. The initial εNd values of the Paleozoic fluorites fit the age proposed for the formation of the deposits. Moreover, the values suggest that radiogenic Nd was provided to the fluids from the Ordovician siliciclastic basement, except for 3 deposits where the potential source rocks of Nd were mainly Ordovician acidic magmatic rocks. The initial εNd values of the Cenozoic fluorites suggest a provenance of Nd essentially from the leaching of Variscan granitoids.

The biogeochemistry of atmospherically derived Pb in the boreal forest of Sweden by Jonatan Klaminder; Richard Bindler; Ingemar Renberg (2922-2931).
The use of stable Pb isotopes for tracing Pb contamination within the environment has strongly increased our understanding of the fate of airborne Pb contaminants within the boreal forest. This paper presents new stable Pb isotope (206Pb/207Pb ratio) measurements of solid soil samples, stream water (from a mire outlet and a stream draining a forest dominated catchment) and components of Picea abies (roots, needles and stemwood), and synthesizes some of the authors’ recent findings regarding the biogeochemistry of Pb within the boreal forest. The data clearly indicate that the biogeochemical cycling of Pb in the present-day boreal forest ecosystem is dominated by pollution Pb from atmospheric deposition. The 206Pb/207Pb ratios of the mor layer (O-horizon), forest plants and stream water (mainly between 1.14 and 1.20) are similar to atmospheric Pb pollution (1.14–1.19), while the local geogenic Pb of the mineral soil (C-horizon) has high ratios (>1.30). Roots and basal stemwood of the analyzed forest trees have higher 206Pb/207Pb ratios (1.15–1.30) than needles and apical stemwood (1.14–1.18), which indicate that the latter components are more dominated by pollution derived Pb. The low 206Pb/207Pb ratios of the mor layer suggest that the upward transport of Pb as a result of plant uptake is small (<0.04 mg m−2  a−1) in comparison to atmospheric inputs (∼0.5 mg m−2  a−1) and annual losses with percolating soil-water (∼2 mg m−2  a−1); consequently, the Pb levels in the mor layer are now decreasing while the pool of Pb in the mineral soil is increasing. Streams draining mires appear more strongly affected by pollution Pb than streams from forested catchments, as indicated by Pb concentrations about three times higher and lower 206Pb/207Pb ratios (1.16 ± 0.01 in comparison to 1.18 ± 0.02). To what extent stream water Pb levels will respond to the build-up of Pb in deeper mineral soil layers remains uncertain.

Bioavailability of sediment-borne lead for ragworms (Hediste diversicolor) investigated by lead isotopes by Sylvie Philippe; Céline Leterme; Sandric Lesourd; Lucie Courcot; Udo Haack; Jacinthe Caillaud (2932-2944).
The Seine estuary possesses a heavily industrialised catchment area that contrasts significantly with that possessed by the smaller Authie estuary. For both of these northern French estuaries, Pb isotopic compositions and concentrations have been determined on specimens of Hediste diversicolor (ragworms) and on HCl leachates performed on related mudflat sediment. Three sampling campaigns were completed in 2003. As expected, the reactive Pb obtained by 1 M HCl leaching, shows higher concentrations and a more anthropogenic signature in samples from the Seine estuary than in samples from the Authie. However, neither of the two sites is free from the influence of anthropogenic Pb. Possible contaminant sources are discussed through comparisons with previously published data. For the more highly contaminated Seine estuary, most of the ragworm Pb signatures are similar to those of the sediments. In contrast, ragworms from the Authie site exhibit a higher proportion of anthropogenic Pb than the corresponding sediments. Various hypotheses are discussed to explain this significant discrepancy: (1) analytical artifacts, (2) migration of ragworm populations, (3) diet and feeding behaviour, and as the most likely explanation (4) an unsuitable leaching method for the extraction of bioavailable Pb.The possibility of using Pb isotopes as a tool for bioavailability studies on sediments or soils is discussed.

Naturally occurring stable and radioactive isotopes were used as environmental tracers to investigate contaminant metal mobilization processes in a metal smelter dump mainly consisting of slag. Water emerging from the dump at a spring is heavily contaminated by metals. The smelter dump contains minor amounts of flue dust, a material which shows a high potential for metal mobilization. Nearby dumps mainly consist of low-grade ore. Concentration patterns of 238U, 226Ra and 210Pb determined in sediment deposited close to the contaminated spring reveal the flue dust to be the major local metal source rather than the slag or the low-grade ore. Contamination pathways inside the dump were investigated using hydrological, chemical and isotopic data. Strong negative correlation between water discharge and metal concentration in the spring water suggests, besides short-term dilution of the metal concentration by direct rainwater runoff, distinct long-term dilution of the spring water by groundwater being discharged at a significantly increased rate as a result of heavy rains. δ18O and δD signatures of rain, local groundwater and spring water confirm the importance of groundwater derived from the local aquifer. Another hydrological component with importance for metal mobilization was found to be water that is recharged in the dump itself. Tritium analysis allowed an assessment of the probable residence time of that water component in the smelter dump. Since that water component seems to represent a major local contamination pathway the findings of the study are of substantial importance for site remediation planning. As a primary result it could be stated that covering the dump would not result in any noteworthy short-term improvement of the spring water quality. First significant effects would only be visible after 2–3 decades at the earliest.

The determination of rare earth elements (REEs), Th and U in seaweeds of various species and in ambient surface seawater were performed by inductively coupled plasma mass spectrometry. The seaweeds and the seawater samples were collected at 10 different coastal areas of Niigata Prefecture in Japan twice a year (spring and autumn) in 2004 and 2005. Results showed that concentration of REEs in seaweed species from Niigata Prefecture were about 103 times higher than those in seawater, and the enrichment factors of REEs were larger in heavy REE than light REE. A significant concentration difference of REEs, Th and U was found among species even in the same phylum. Undaria pinnatifida had the highest concentration of U. Considering that U. pinnatifida has low concentrations of REEs among typical brown algae, different REEs and U uptake mechanisms are suggested. The concentration of REEs, Th and U did not vary remarkably between sampling points and/or seasons.

Estimates of uncertainty in the prediction of past climatic variables by D. Lucy; I. Robertson; R.G. Aykroyd; A.M. Pollard (2961-2965).
Fitting a regression line to a set of measurements to investigate the relationship between a proxy estimate of past climate and known climatic parameters is a routine procedure. It is generally accepted that the higher the correlation between parameters, the more reliable the reconstruction. However, there is a lack of published work upon what correlation is the minimum acceptable value. Simulated data was used to demonstrate that the relationship between proxy values and the climatic data are adversely affected by falling correlation, to the point where, in a training set consisting of 100 pairs of temperature and tree-ring proxies, the mean 95% confidence interval width for the reconstructed temperature exceeds the total range of temperatures in the training set at or below r  = 0.65. This correlation is typical of that used in many climate-proxy reconstructions, and it suggests that understanding of past climate variability may be somewhat constrained.