The Geochemistry of Lake Joyce, McMurdo Dry Valleys, Antarctica

Lake Joyce is one of the least studied lakes of the McMurdo Dry Valleys. Similar to other lakes in this region, Lake Joyce is a closed-basin, permanently ice-covered, meromictic lake. We present here a detailed investigation of major ions, nutrients, and dissolved trace elements for Lake Joyce. Specifically, we investigate the role of iron and manganese oxides and hydrous oxides in trace metal cycling.Lake Joyce is characterized by fresh, oxic waters overlying an anoxic brine, primarily Na–Cl. Surface waters have a maximum nitrate concentration of 26M with a molar dissolved inorganic nitrogen to phosphorus ratio of 477. The supply of nitrogen is attributed to atmospheric deposition, possibly from polar stratospheric clouds. Dissolved phosphorus is scavenged by hydrous iron oxides. The pH is highest (10.15) just beneath the 7-m thick ice cover and decreases to a minimum of 7.29 in the redox transition zone. Dissolved Al exceeds 8M in surface waters, and appears to be controlled by equilibrium with gibbsite. In contrast, concentrations of other trace elements in surface waters are quite low (e.g., 5.4nM Cu, 0.19nM Co, <20pM La). Dissolved Fe, Mn, Ni and Cd were below our detection limits of 13 nM, 1. 8 nM, 4.7 nM and 15pM (respectively) in surface waters. There was a 6-m vertical separation in the onset of Mn and Fe reduction, with dissolved Mn appearing higher in the water column than Fe. Based on thermodynamic calculations, dissolved Mn appears to be controlled by equilibrium with hausmannite (Mn3O4). Co tracks the Mn profile closely, suggesting Co(III) is bound in the lattice of Mn oxides, whereas the Ce profile is similar, yet the Ce anomaly suggests oxidative scavenging of Ce. Release of Cu, Ni, Cd and trivalent REE appears to be controlled by pH-induced desorption from Fe and Mn oxides, although Cu (and perhaps Ni) may be scavenged by organic matter in surface waters.     

Rare earth element and strontium isotope geochemistry in Dujiali Lake,central Qinghai-Tibet Plateau,China: Implications for the origin of hydromagnesite deposits

Rare earth element (REE) and strontium isotope data (⁸⁷Sr/⁸⁶Sr) are presented for hydromagnesite and surface waters that were collected from Dujiali Lake in central Qinghai-Tibet Plateau (QTP), China. The goal of this study is to constrain the solute sources of hydromagnesite deposits in Dujiali Lake. All lake waters from the area exhibit a slight LREE enrichment (average [La/Sm]_PAAS = 1.36), clear Eu anomalies (average [Eu/Eu*]_PAAS = 1.31), and nearly no Ce anomalies. The recharge waters show a flat pattern (average [La/Sm]_PAAS = 1.007), clear Eu anomalies (average [Eu/Eu*] _PAAS = 1.83), and nearly no Ce anomalies (average [Ce/Ce*]_PAAS = 1.016). The REE+Y data of the surface waters indicate the dissolution of ultramafic rock at depth and change in the hydrogeochemical characteristics through fluid-rock interaction. These data also indicate a significant contribution of paleo-groundwater to the formation of hydromagnesite, which most likely acquired REE and Sr signatures from the interaction with ultramafic rocks. The ⁸⁷Sr/⁸⁶Sr data provide additional insight into the geochemical evolution of waters of the Dujiali Lake indicating that the source of Sr in the hydromagnesite does not directly derive from surface water and may have been influenced by both Mg-rich hydrothermal fluids and meteoric water. Additionally, speciation modeling predicts that carbonate complexes are the most abundant dissolved REE species in surface water. This study provides new insights into the origins of hydromagnesite deposits in Dujiali Lake, and contributes to the understanding of hydromagnesite formation in similar modern and ancient environments on Earth.     

Nickel, Copper, Zinc and Cadmium Cycling with Manganese in Lake Vanda (Wright Valley, Antarctica)

Lake Vanda is a closed-basin, permanently ice-covered lake located in the Wright Valley of Antarctica. The lakes more important geochemical features include the fact that it is fed by a single glacial melt water stream for only 6–8weeks out of the year; that it has remained stratified for more than a millennium; and that, like other lakes in the region, it is remote from anthropogenic influence. These, together with the fact that it is among the least biologically productive lakes in the world, make it an ideal system for examining the transport, cycling and fate of trace metals in the aquatic environment. Like others before us, we view this lake as a natural geochemical laboratory, a flask in the desert. This paper presents the first set of closely spaced, vertical, profiles for dissolved and particulate Mn, Fe, Ni, Cu, Zn and Cd in the water column. Despite the absence of an outflow, metals in the fresh upper waters of the lake have extremely low concentrations, in the pico-molar to nano-molar range, and are partitioned largely into dissolved rather than particulate phases. Efficient metal scavenging by particles from these oxygen-rich waters is indicated. Significant increases in metal concentrations begin to appear at depth, between 57 and 60m, and these increases coincide with the onset of manganese oxide dissolution in oxic, but lower pH waters. Vertical profiles suggest that the entire suite of trace metals (Ni, Cu, Zn, and Cd) is being released from manganese oxide carrier phases. Thermodynamic analysis indicates that Mn3O4 (i.e., the mineral hausmannite) may be important in metal sequestration and recycling in the deeper waters of Lake Vanda. Manganese-reducing organisms reported by Bratina etal. (1998) are active in the zone of metal release and these could also contribute to the observed cycling.     

Rare Earth Element and yttrium compositions of Archean and Paleoproterozoic Fe formations revisited: New perspectives on the significance and mechanisms of deposition

The ocean and atmosphere were largely anoxic in the early Precambrian, resulting in an Fe cycle that was dramatically different than today’s. Extremely Fe-rich sedimentary deposits—i.e., Fe formations—are the most conspicuous manifestation of this distinct Fe cycle. Rare Earth Element (REE) systematics have long been used as a tool to understand the origin of Fe formations and the corresponding chemistry of the ancient ocean. However, many earlier REE studies of Fe formations have drawn ambiguous conclusions, partially due to analytical limitations and sampling from severely altered units. Here, we present new chemical analyses of Fe formation samples from 18 units, ranging in age from ca. 3.0 to 1.8 billion years old (Ga), which allow a reevaluation of the depositional mechanisms and significance of Precambrian Fe formations. There are several temporal trends in our REE and Y dataset that reflect shifts in marine redox conditions. In general, Archean Fe formations do not display significant shale-normalized negative Ce anomalies, and only Fe formations younger than 1.9 Ga display prominent positive Ce anomalies. Low Y/Ho ratios and high shale-normalized light to heavy REE (LREE/HREE) ratios are also present in ca. 1.9 Ga and younger Fe formations but are essentially absent in their Archean counterparts. These marked differences in Paleoproterozoic versus Archean REE + Y patterns can be explained in terms of varying REE cycling in the water column.Similar to modern redox-stratified basins, the REE + Y patterns in late Paleoproterozoic Fe formations record evidence of a shuttle of metal and Ce oxides across the redoxcline from oxic shallow seawater to deeper anoxic waters. Oxide dissolution—mainly of Mn oxides—in an anoxic water column lowers the dissolved Y/Ho ratio, raises the light to heavy REE ratio, and increases the concentration of Ce relative to the neighboring REE (La and Pr). Fe oxides precipitating at or near the chemocline will capture these REE anomalies and thus evidence for this oxide shuttle. In contrast, Archean Fe formations do not display REE + Y patterns indicative of an oxide shuttle, which implies an absence of a distinct Mn redoxcline prior to the rise of atmospheric oxygen in the early Paleoproterozoic. As further evidence for reducing conditions in shallow-water environments of the Archean ocean, REE data for carbonates deposited on shallow-water Archean carbonate platforms that stratigraphically underlie Fe formations also lack negative Ce anomalies. These results question classical models for deposition of Archean Fe formations that invoke oxidation by free oxygen at or above a redoxcline. In contrast, we add to growing evidence that metabolic Fe oxidation is a more likely oxidative mechanism for these Fe formations, implying that the Fe distribution in Archean oceans could have been controlled by microbial Fe uptake rather than the oxidative potential of shallow-marine environments.     

Rare earth elements (REE) of dissolved and suspended loads in the Xijiang River, South China

The Xijiang River is the main channel of the Zhujiang (Pearl River), the second largest river in China in terms of water discharge, and flows through one of the largest carbonate provinces in the world. The rare earth element (REE) concentrations of the dissolved load and the suspended particulate matter (SPM) load were measured in the Xijiang River system during the high-flow season. The low dissolved REE concentration in the Xijiang River is attributed to the interaction of high pH and low DOC concentration. The PAAS-normalized REE patterns for the dissolved load show some common features: negative Ce anomaly, progressively heavy REE (HREE) enrichment relative to light REE (LREE). Similar to the world’s major rivers the absolute concentration of the dissolved REE in the Xijiang River are mainly pH controlled. The degree of REE partitioning between the dissolved load and SPM load is also strongly pH dependent. The negative Ce anomaly is progressively developed with increasing pH, being consistent with the oxidation of Ce (III) to Ce (IV) in the alkaline river waters, and the lack of Ce anomalies in several DOC-rich waters is presumably due to both Ce (III) and Ce (IV) being strongly bound by organic matter. The PAAS-normalized REE patterns for the dissolved load and the SPM load in rivers draining the carbonate rock area exhibit middle REE (MREE) enrichment and a distinct maximum at Eu, indicating the preferential dissolution of phosphatic minerals during weathering of host lithologies. Compared to the Xijiang River waters, the MREE enrichment with a maximum at Eu disappeared and light REE were more depleted in the South China Sea (SCS) waters, suggesting that the REE sourced from the Xijiang River must be further fractionated and modified on entering the SCS. The river fluxes of individual dissolved REE introduced by the Xijiang River into the SCS vary from 0.04 to 4.36 × 10⁴ mol a⁻¹.     

Rare earth elements in waters from the albitite-bearing granodiorites of Central Sardinia, Italy

With the aim of contributing to the knowledge of the geochemical behaviour and mobility of the rare earth element (REE) in the natural water systems, the ground and surface waters of the Ottana-Orani area (Central Sardinia, Italy) were sampled. The study area consists of albititic bodies included in Hercynian granodiorites. The waters have pH in the range of 6.0-8.6, total dissolved solid (TDS) of between 0.1 and 0.6 g/l, and major cation composition dominated by Ca and Na, whereas predominant anions are Cl and/or HCO₃.The pH and the major-element composition of the waters are the factors affecting the concentration of REE in solution. The concentrations of ∑REE+Y in the samples filtered at 0.4 μm vary between 140 and 1600 ng/l, with La of between 14 and 314 ng/l, and Yb of between <6 and 12 ng/l. A negative Ce anomaly, especially marked at high pH, is observed in the groundwaters. The surface waters show lower REE concentrations, which are independent of pH, and negligible Ce anomaly.Speciation calculations, carried out with the EQ3NR computer program, showed that the complexes with the CO₃²⁻ ligand are the dominant REE species at pH in the range of 6.7-8.6. The REE³⁺ ions dominate the speciation at pH <6.7 and only in the light REE (LREE).The relative concentrations of REE in water roughly reflect those in the aquifer host rocks. However, when concentrations of REE in water are normalised relative to the parent rocks, a preferential fractionation of heavy REE (HREE) into the water phase can be observed, suggesting the greater mobility and stability of HREE in aqueous solution.     

Geochemistry of rare-earth elements in thermal waters of Uzon-Geyzernaya hydrothermal system (Kamchatka)

Precisional analyses of the abundances of La, Ce, and major elements in thermal waters and rocks of the Uzon-Geyzernaya volcanotectonic depression, supplemented by published data on a number of modern high-temperature hydrothermal systems of Kamchatka and two other areas of the world, allowed defining genetically important patterns of rare-earth elements (REE) distribution. The La and Ce abundances positively correlate with silica contents both in fresh igneous rocks of the study areas and in the products formed by hydrothermal processes.All studied hydrothermal clays are enriched in La and Ce. The general enrichment trend is similar to the pattern of positive correlation between the La and Ce abundances. Geothermal waters display a strong relationship between REE enrichment and pH. Enhanced REE enrichment trend is observed in thermal waters with abundant SO₄^2 ? and K. The REE versus Cl and B diagrams show two individual fields reflecting the level of acidity-alkalinity of thermal waters. These data demonstrate that La and Ce concentrations in the products of modern hydrothermal systems (in fluids and secondary mineral phases) are governed by wallrock composition, anionic water composition, and pH/Eh-dependent adsorption processes.     

巢湖的稀土元素地球化学特征

采用液-液萃取法和ICP-MS测试技术对巢湖的溶解态稀土元素进行了分析。结果表明,巢湖的溶解态稀土的含量与世界淡水相当,丰水期的样品含量高于其他季节。pH值和悬浮物、胶体是控制巢湖水体中溶解态稀土含量的主要因素。巢湖的溶解态稀土的分布模式以平坦型为主,少数呈现重稀土富集。丰水期和枯水期的溶解态稀土的(La/Yb)N值从西半湖区到东半湖区呈现有规律性的逐渐增大,并且丰水期的(La/Yb)N值低于枯水期。在富营养化湖泊中,胶体和水生生物可能是造成这一现象的主要原因。     

Dissolved Al, In, and Ce in the eastern Indian Ocean and the Southeast Asian Seas in comparison with the radionuclides Pb and Po

To carry out comparative geochemical investigation of refractory and reactive metals in different oceanic settings covering different θ-S characteristics, productivity, dissolved oxygen profiles, water and sediment discharge, etc., we have determined the vertical profiles of dissolved (<0.04 μm) Al, In and Ce, as well as ²¹⁰Pb and ²¹⁰Po in the eastern Indian Ocean (from 40°S in the Southern Ocean to 8°N in the Bay of Bengal) and the Southeast Asian Seas. In the Antarctic Circumpolar Region, the concentrations of these refractory metals are very low, presumably due to very low the atmospheric input and intensified scavenging. Resemblance in the vertical profiles of these metals is often seen in some other stations. However, there are also significant differences among their distributions, for example, in the magnitude of surface enrichment caused by the external input from eolian and fluvial-coastal sources. Comparison of Al distributions in surface waters with those of atmospherically derived ²¹⁰Pb suggests the relative importance of eolian input over fluvial-coastal sources. Fluvial and coastal input appears to be insignificant for dissolved In, but may be important for Ce. The mean residence time of Al in the surface mixed layer was estimated to be ∼2 years which is similar to that of ²¹⁰Pb.In the intermediate and deep waters, the concentrations of each element vary with depth and location. The range of variation is in the order of Al>Ce>In, depending upon particle reactivity. Although dissolved Al decreases along the water trajectory by particle scavenging, variations of dissolved In and Ce are relatively small which may be due to less scavenging for both elements. Compared with significantly high (>4 pM) dissolved Ce throughout the water column in the Bay of Bengal, dissolved Al concentration remains low, suggesting that it has higher affinity to particles and hence is scavenged by sinking particulate matter. This is consistent with the observation that the dissolved Al in the Antarctic Intermediate Water (AAIW) decreases from 4 to 6 nM in the 30°S Perth Basin to <0.7 nM in the 10°S West Australia Basin along its trajectory. Using the chlorofluorocarbons (CFCs) ventilation age of AAIW (Fine, 1993), the mean residence time of Al in the intermediate and deep waters in the eastern Indian Ocean is estimated to be <17 yr, approximately the same as that of ²¹⁰Pb (10-15 yr). In the semiclosed basins of Southeast Asia, the distributions of Al, In and Ce are also very unique. In the South China Sea, there is a strong sediment source for dissolved In and Ce during the deepwater passage through the Luzon Strait.     

Rare earth elements in pore waters of marine sediments

The rare earth elements (REEs) were measured in pore waters of the upper ∼25 cm of sediment from one site off Peru and three sites on the California margin. The pore water REE concentrations are higher than sea water and show systematic down core variations in both concentration and normalized pattern. From these analyses and from comparison to other chemical species measured (dissolved Fe, Mn, Ba, oxygen, nitrate, phosphate), it is suggested that pore water REEs can be grouped into three categories: those that are from an Fe-source, those that are from a POC-source, and cerium oxide. REEs from the Fe-source appear where anoxia is reached; they have a distinctive “middle-REE (MREE) enriched” pattern. The concentrations in this source are so elevated that they dominate REE trends in the Fe-oxide reduction zone. The net result of flux from the POC-source is relative enrichment of heavy-REEs (HREEs) over light-REEs (LREEs), reflecting remineralizing POC and complexation with DOC. A common “linear” REE pattern, seen in both oxic and anoxic sediments, is associated with this POC-source, as well as a “HREE enriched” pattern that is seen in surficial sediments at the Peru site. Overall, the pore water results indicate that Mn-oxides are not an important carrier of REEs in the oceans.A REE biogeochemical model is presented which attempts to reconcile REE behavior in the water and sediment columns of the oceans. The model proposes that POC, Fe-oxide and Ce-oxide sources can explain the REE concentration profiles and relative abundance patterns in environments ranging from oxic sea water to anoxic pore water. The model is also consistent with our observation that the “Ce-anomaly” of pore water does not exceed unity under any redox condition.     

Dissolved rare earth elements in river waters draining karst terrains in Guizhou Province,China

Winter seasonal concentrations of dissolved rare earth elements (REE) of two major river systems (the Wujiang River system and the Yuanjiang River system) in karst-dominated regions in winter were measured by using a method involving solvent extraction and back-extraction and subsequent ICP-MS measurements. The dissolved REE concentrations in the rivers and their tributaries are lower than those in most of the large rivers in the world. High pH and high cation (i.e., Na⁺ + Ca²⁺) concentrations of the rivers are the most important factors controlling the concentrations of dissolved REE in the river water. The dissolved load (<0.22 μm) REE distribution patterns of high-pH river waters are very different from those of low-pH river waters. The shale (PAAS)-normalized REE patterns for the dissolved loads are characterized by light REE-enrichment and heavy REE-enrichment. Water in the upper reaches of the Wujiang River generally shows light REE-enriched patterns, while that in the middle and lower reaches generally shows heavy REE-enriched patterns. The Yuanjiang River is heavy REE enriched with respect to the light REE in the same samples. Water of the Wuyanghe River draining dolomite-dominated terrains has the highest heavy REE-enrichment. Most river water samples show the shale-normalized REE patterns with negative Ce and Eu anomalies, especially water from Wuyanghe River. Y/Ho ratios show that the water/particle interaction might have played an important role in fractionation between HREE and LREE.     

黑海西北部冷泉碳酸盐岩的沉积岩石学特征及氧化还原条件的稀土元素地球化学示踪

黑海西北部罗马尼亚大陆架(水深120m)和乌克兰陆坡(水深190m)发育冷泉碳酸盐岩结壳。XRD测试表明此结壳主要由高镁方解石和文石组成。结壳中与渗漏系统微生物活动有关的凝块和葡萄状文石等特殊的沉积组构非常发育。冷泉碳酸盐岩酸可溶部分(碳酸盐岩相矿物)的稀土元素含量很低(0.068×10-6~2.817×10-6),稀土元素页岩标准化配分模式显示罗马尼亚大陆架冷泉碳酸盐岩具有明显的Ce负异常,乌克兰陆坡冷泉碳酸盐岩具Ce的正异常,表明它们是分别在氧化和还原环境中沉积的。稀土元素和V、Cd和U等微量元素的含量在泥晶中最高,亮晶中最低,可能反映成岩过程对元素含量有控制作用。     

Dissolved organic carbon and volatile fatty acids in marine sediment pore waters

The results of a study of the contribution of microbial metabolic products to total dissolved organic carbon (DOC) levels in coastal sediments are presented. The data indicate that acidic volatile compounds make up a substantial fraction of pore water DOC's in both oxic and anoxic pore waters of coastal marine sediments. Formic, acetic and butyric acids are the principal volatile species identified at levels exceeding 10 μM. Acid concentrations are up to five times higher in anoxic pore waters than in oxic waters. Volatile organic acids show promise as indicators of diagenetic processes in marine sediments and of the ecological succession of microorganisms, in particular.     

Post-depositional redistribution processes and their effects on middle rare earth element precipitation and the cerium anomaly in sediments in the South Korea Plateau,East Sea

We sampled two box-core sediments from the slope of the eastern South Korea Plateau (SKP) in the East Sea (Sea of Japan) at water depths of 1400 and 1700 m. Two chemical fractions of extractable (hydroxylamine/acetic acid) and residual rare earth elements (REEs) together with Al, Ca, Fe, Mg, Mn, P, S, As, Mo, and U were analyzed to assess the post-depositional redistribution of REEs. Extractable Fe and Mn are noticeably abundant in the oxic topmost sediment layer (<3 cm). However, some trace elements (e.g., S, As, Mo, U) are more abundant at depth, where redox conditions are different. Analysis of upper continental crust (UCC)-normalized (La/Gd)_UCC, (La/Yb)_UCC, and (Ce/Ce^*)_UCC revealed that the extractable REE is characterized by middle REE (MREE) enrichment and a positive cerium (Ce) anomaly, different from the case of the residual fraction which shows slight enrichment in light REEs (LREEs) with no Ce anomaly. The extractable MREEs seem to have been incorporated into high-Mg calcite during reductive dissolution of Fe oxyhydroxides. In the top sediment layer, the positive Ce anomaly is attributed to Ce oxide, which can be mobilized in deeper oxygen-poor environments and redistributed in the sediment column. In addition, differential concentrations of Ce and other LREEs in pore water appear to result in variable (Ce/Ce^*)_UCC ratios in the extractable fraction at depth.     

The mobility of radium-226 and trace metals in pre-oxidized subaqueous uranium mill tailings

The exchange of ²²⁶Ra and trace metals across the tailings-water interface and the mechanisms governing their mobility were assessed via sub-centimetre resolution profiling of dissolved constituents across the tailings–water interface in Cell 14 of the Quirke Waste Management Area at Rio Algom's Quirke Mine, near Elliot Lake, Ontario, Canada. Shallow zones (<1.5 m water depth) are characterized by sparse filamentous vegetation, well-mixed water columns and fully oxygenated bottom waters. Profiles of dissolved O₂, Fe and Mn indicate that the tailings deposits in these areas are sub-oxic below tailings depths of ∼3 cm. These zones exhibit minor remobilization of Ra in the upper 5 cm of the tailings deposit; ²²⁶Ra fluxes at these sites are relatively small, and contribute negligibly to the water column activity of ²²⁶Ra. The shallow areas also exhibit minor remobilization of Ni, As, Mo and U. The release of these elements to the water cover is, however, limited by scavenging mechanisms in the interfacial oxic horizons. The presence of thick vegetation (Chara sp.) in the deeper areas (>2 m water depth) fosters stagnant bottom waters and permits the development of anoxia above the benthic boundary. These anoxic tailings are characterized by substantial remobilization of ²²⁶Ra, resulting in a relatively large flux of ²²⁶Ra from the tailings to the water column. The strong correlation between the porewater profiles of ²²⁶Ra and Ba (r²=0.99), as well as solubility calculations, indicate that the mobility of Ra is controlled by saturation with respect to a poorly ordered and/or impure barite phase [(Ra,Ba)SO₄]. In the anoxic zones, severe undersaturation with respect to barite is sustained by microbial SO₄ reduction. Flux calculations suggest that the increase in ²²⁶Ra activity in the water cover since 1995 (from <0.5 to 2.5 Bq l⁻¹) can be attributed to an increase in the spatial distribution of anoxic bottom waters caused by increased density of benthic flora. The anoxic, vegetated areas also exhibit minor remobilization with respect to dissolved As, Ni and Zn. The removal of trace metals in the anoxic bottom waters appears to be limited by the availability of free sulphide. Collectively, the data demonstrate that while the water cover over the U mill tailings minimizes sulphide oxidation and metal mobility, anoxic conditions which have developed in deeper areas have led to increased mobility of ²²⁶Ra.     

Ultra-low rare earth element content in accreted ice from sub-glacial Lake Vostok, Antarctica

This paper reports the first rare earth element (REE) concentrations in accreted ice refrozen from sub-glacial Lake Vostok (East Antarctica). REE were determined in various sections of the Vostok ice core in order to geochemically characterize its impurities. Samples were obtained from accreted ice and, for comparison, from the upper glacier ice of atmospheric origin (undisturbed, disturbed and glacial flour ice). REE concentrations ranged between 0.8-56 pg g⁻¹ for Ce and 0.0035-0.24 pg g⁻¹ for Lu in glacier ice, and between <0.1-24 pg g⁻¹ for Ce and <0.0004-0.02 pg g⁻¹ for Lu in accreted ice. Interestingly, the REE concentrations in the upper accreted ice (AC₁; characterized by visible aggregates containing a mixture of very fine terrigenous particles) and in the deeper accreted ice (AC₂; characterized by transparent ice) are lower than those in fresh water and seawater, respectively. We suggest that such ultra-low concentrations are unlikely to be representative of the real REE content in Lake Vostok, but instead may reflect phase exclusion processes occurring at the ice/water interface during refreezing. In particular, the uneven spatial distribution (on the order of a few cm) and the large range of REE concentrations observed in AC₁ are consistent with the occurrence/absence of the aggregates in adjacent ice, and point to the presence of solid-phase concentration/exclusion processes occurring within separate pockets of frazil ice during AC₁ formation. Interestingly, if the LREE enrichment found in AC₁ was not produced by chemical fractionation occurring in Lake Vostok water, this may reflect a contribution of bedrock material, possibly in combination with aeolian dust released into the lake by melting of the glacier ice. Collectively, this valuable information provides new insight into the accreted ice formation processes, the bedrock geology of East Antarctica as well as the water chemistry and circulation of Lake Vostok.     

Trace element mobility in mine waters from granitic pegmatite U–Th–REE deposits,Bancroft area,Ontario

Small, low-grade, granitic pegmatite U–Th–REE deposits are found throughout the Grenville geological province of eastern Canada. Groundwater quality at historical mining properties in the Bancroft area was investigated in order to better understand the mobility of trace elements that may pose health risks if there is renewed development of this class of mineral deposit. Groundwater samples were obtained from diamond drill holes, flowing adits and flooded mine shafts. Uranium occurs almost entirely in the dissolved (<0.45 μm) phase and is found at concentrations reaching 2579 μg/L. The Canadian maximum acceptable concentration for U in drinking water (0.02 mg/L) was exceeded in 70% of samples. Regulatory limits for ²²⁶Ra (0.5 Bq/L) and for ²¹⁰Pb (0.2 Bq/L) were generally exceeded in these samples as well. Speciation modeling indicates that over 98% of dissolved U is in the form of highly mobile uranyl-Ca–carbonate complexes known to inhibit U adsorption. Uranium concentrations in groundwater appear to be correlated with the uranothorite content of the deposits rather than with their U grade. Uranothorite may be more soluble than uraninite, the other ore mineral, because of its non-ideal composition and metamict structure. Thorium, released concomitantly with U during the dissolution of uranothorite and thorian uraninite, exhibits median and maximum total concentrations of only 0.1 and 11 μg/L, respectively. Mass balance and stoichiometric considerations indicate that almost all Th is immobilized very close to its source. The sums of total light REE (La–Gd) concentrations have median and maximum values of 6 and 117 μg/L, respectively. The sums of total heavy REE (Tb–Lu) concentrations have median and maximum values of 0.8 and 21 μg/L, respectively. Light REE are derived mainly from the dissolution of metamict allanite whereas the sources of heavy REE are widely dispersed among accessory minerals. Fractionation patterns of REE in the dissolved phase are flat or concave, with negative Ce anomalies associated with more oxic groundwaters. The data suggest preferential LREE and HREE complexation with organic and carbonate ligands in the dissolved phase, respectively. Fractionation patterns in the suspended particulate phase exhibit decreasing enrichment with atomic number from La to Gd and a flat profile from Tb to Lu. This is explained by preferential sorption of LREE and uniform sorption of HREE. Manganese particulates are the most likely sorbents. Potential health risks from Th or REE in mine waters are unlikely due to the very low mobility of these elements. Uranium, on the other hand, exhibits high mobility in shallow, oxic groundwaters and drainage from some mine adits may require mitigation.     

Comparison of the behaviour of rare earth elements in surface waters,overburden groundwaters and bedrock groundwaters in two granitoidic settings,Eastern Sweden

This work, which was done within the Swedish nuclear waste management program, was carried out in order to increase the understanding of the mobility and fate of rare earth elements (REEs) in natural boreal waters in granitoidic terrain. Two areas were studied, Forsmark and Simpevarp, one of which will be selected as a site for spent nuclear fuel. The highest REE concentrations were found in the overburden groundwaters, in Simpevarp in particular (median ∑REE 52 μg/L), but also in Forsmark (median ∑REE 6.7 μg/L). The fractionation patterns in these waters were characterised by light REE (LREE) enrichment and negative Ce and Eu anomalies. In contrast, the surface waters had relatively low REE concentrations. They were characterised either by an increase in relative concentrations throughout the lanthanide series (Forsmark which has a carbonate-rich till) or flat patterns (Simpevarp with carbonate-poor till), and had negative Ce and Eu anomalies. In the bedrock groundwaters, the concentrations and fractionation patterns of REEs were entirely different from those in the overburden groundwaters. The median La concentrations were low (just above 0.1 μg/L in both areas), only in a few samples were the concentrations of several REEs (and in a couple of rare cases all REEs) above the detection limit, and there was an increase in the relative concentrations throughout the lanthanide series. In contrast to these large spatial variations, the temporal trends were characterised by small (or non existent) variations in REE-fractionation patterns but rather large variations in concentrations. The Visual MINTEQ speciation calculations predicted that all REEs in all waters were closely associated with dissolved organic matter, and not with carbonate. In the hydrochemical data for the overburden groundwater in particular, there was however a strong indication of association with inorganic colloids, which were not included in the speciation model. Overall the results showed that within a typical boreal granitoidic setting, overburden groundwaters are enriched in REEs, organic complexes are much more important than carbonate complexes, there is little evidence of significant mixing of REEs between different water types (surface, overburden, bedrock) and spatial variations are more extensive than temporal ones.     

Geochemical processes in the Onyx River, Wright Valley, Antarctica: Major ions, nutrients, trace metals

We present data on major ions, nutrients and trace metals in an Antarctic stream. The Onyx River is located in Wright Valley (77-32 S; 161-34 E), one of a group of ancient river and glacier-carved landforms that comprise the McMurdo Dry Valleys of Antarctica. The river is more than 30 km long and is the largest of the glacial meltwater streams that characterize this relatively ice-free region near the Ross Sea. The complete absence of rainfall in the region and the usually small contributions of glacially derived tributaries to the main channel make this a comparatively simple system for geochemical investigation. Moreover, the lack of human impacts, past or present, provides an increasingly rare window onto a pristine aquatic system.For all major ions and silica, we observe increasing concentrations with distance from Lake Brownworth down to the recording weir near Lake Vanda. Chemical weathering rates are unexpectedly high and may be related to the rapid dissolution of ancient carbonate deposits and to the severe physical weathering associated with the harsh Antarctic winter. Of the nutrients, nitrate and dissolved reactive phosphate appear to have quite different sources. Nitrate is enriched in waters near the Lower Wright Glacier and may ultimately be derived from stratospheric sources; while phosphate is likely to be the product of chemical weathering of valley rocks and soils. We confirm the work of earlier investigations regarding the importance of the Boulder Pavement as a nutrient sink.Dissolved Mn, Fe, Ni, Cu, and Cd are present at nanomolar levels and, in all cases, the concentrations of these metals are lower than in average world river water. We hypothesize that metal uptake and exchange with particulate phases along the course of the river may serve as a buffer for the dissolved load. Concurrent study of these three solute classes points out significant differences in the mechanisms and sites of their removal from the Onyx River.     

Behaviour of rare earth elements at the freshwater–seawater interface of two acid mine rivers: the Tinto and Odiel (Andalucia, Spain)

The concentrations of dissolved and suspended particulate rare-earth elements (REE) are reported in acid-sulphate waters from the Odiel and Tinto rivers. Shale normalized patterns are typically convex and high REE concentrations (e.g., Ce=0.43–65 μg.l⁻¹) are present in the waters. The REE content of the suspended load is greater by a factor of up to 3000. In the Odiel river, REE patterns of the particulates are essentially convex and sub-parallel to those of the waters; speciation calculations indicate that SO₄ complexes play a dominant role in controlling the REE distributions. In the Tinto river, the REE patterns of the suspended load are slightly fractionated and a negative Ce anomaly is apparent in several samples, reflecting the local influence of phosphogypsum deposits.Contrasting with normal estuaries, REE are not intensely removed in the low chlorinity zone. A remobilization in relation to Fe reduction is observed in the Tinto river.