Geochemistry of the Rare Earth Elements in Natural Terrestrial Waters：A Review of What Is Currently Knows

The range of observed chemical compositions of natural terrestrial waters varies greatly especially when compared to the essentially constant global composition of the oceans.The concentrations of the REEs in natural terrestrial waters also exhibit more variation than what was reported in seawater,In terrestrial waters ,pH values span the range from acid up to alkaline,In addition,terrestrial waters can range from very dilute waters through to highly concentrated brines.The REE concentrations and their behavior in natural terrestrial waters reflect these compositional ranges,Chemical weathering of rocks represents the source of the REEs to natural terrestrial waters and ,consequently,the REE signature of rocks can impart their REE signature to associated waters,In addition,Because of the typical low solubilities of the REEs both surface and solution complexation can be important in fractionating REEs in aqueous solution.Both of these processes are important in all natural terrestrial waters,however,their relative importance varies as a function of the overall solution composition,In alkaline waters,for example,Solution complexation of the REEs with carbonate ions appears to control their aqueous distributions whereas in acid waters,the REE signature of the labile fraction of the REEs is readily leached from the rocks.In circumneutral pH waters,both processes appear to be important and their relative significance has not yet been determined.     

Geochemistry of Tertiary tholeiites and picrites from Qeqertarssuaq (Disko Island) and Nuussuaq, West Greenland with implications for the mineral potential of comagmatic intrusions

Tertiary continental flood basalts on Qeqertarssuaq and Nuussuaq in West Greenland contain ～3?km of picrites and variably contaminated tholeiites. The picrites are in the Naujánguit member of the Vaïgat Formation and they have 7–29?wt% MgO, La/Sm?=?0.9–2.1, and ¹⁴³Nd/¹⁴⁴Nd?=?0.51263–0.51307. They appear to have crystallised from high-Mg parental magmas (14.4–16.4?wt% MgO) with isotope and trace element ratios similar to recent Icelandic picrites. Discrete horizons of tholeiites, including the Asûk and?Kûgánguaq, have elevated SiO₂ (50–58 wt%), La/Sm?=?3–7, ⁸⁷Sr/⁸⁶Sr?=?0.70550–0.71224, and low ¹⁴³Nd/¹⁴⁴Nd?=?0.51234–0.51174. These lavas have low Cu and Ni abundances (typically 10–50?ppm Ni or Cu), and in the case of the Asûk on Qeqertarssuaq, they contain droplets of native iron. The low Cu and Ni contents are attributed to scavenging by magmatic sulphides formed in response to crustal contamination of picritic magmas. Two contamination trends are recognised, one to a sediment end-member with high Th/Nb and Archaean model Nd ages, and the other to a meta-igneous component with high La/Sm, low Th/Nb and Rb/Nb, and Proterozoic source ages. Overall, ²⁰⁶Pb/²⁰⁴Pb varies from 16.47–21.68. Both contamination trends are associated with low Cu and Ni, and high SiO₂, and it is argued that the magmatic sulphides were triggered by the increases in silica, rather than simply by the introduction of additional crustal-derived sulphur. Geochemically, the Asûk and Kûgánguaq rocks resemble the most contaminated Nadezhdinsky lavas of the Siberian Trap, which are widely regarded as the source of the Ni and Cu mineralisation in the giant Noril'sk deposits. Mass balance considerations indicate that the parental liquids to the contaminated magmas contained sufficient Ni, Cu, S and platinum group elements to form substantial magmatic sulphide deposits. However, unlike the lavas at Noril'sk, the contaminated (low Cu and Ni) West Greenland basalts are in isolated units with no evidence for a gradual recovery in Ni and Cu abundances with height in the lava column. Comparison with Noril'sk suggests that although significant quantities of metals were scavenged by sulphides in West Greenland, the metal contents of the sulphides may not have been upgraded by continued interaction with subsequent magma batches.     

Evidence for freeze–thaw events and their implications for rock weathering in northern Canada

Discussions regarding weathering in cold environments generally centre on mechanical processes and on the freeze–thaw mechanism in particular. Despite the almost ubiquitous assumption of freeze–thaw weathering, unequivocal proof of interstitial rock water actually freezing and thawing is singularly lacking. Equally, many studies have used the crossing of 0 °C, or values close to that, as the basis for determining the number of ‘freeze–thaw events’. In order to assess the weathering regime at a site in northern Canada, temperatures were collected at the surface, 1 cm and 3 cm depth for sets of paving bricks, with exposures both vertical and at 45°, orientated to the four cardinal directions. Temperature data were collected at 1 min intervals for 1 year. These data provide unequivocal proof for the occurrence of the freezing and thawing of water on and within the rock (freeze–thaw events). The freeze event is evidenced by the exotherm associated with the release of latent heat as the water actually freezes. This is thought to be the ?rst record of such events from a ?eld situation. More signi?cantly, it was found that the temperature at which freezing occurred varied signi?cantly through the year and that on occasion the 1 cm depth froze prior to the rock surface. The change in freeze temperature is thought to be due to the chemical weathering of the material (coupled with on‐going salt inputs via the melting of snowfall), which, it is shown, could occur throughout the winter despite air temperatures down to ?30 °C. This ?nding regarding chemical weathering is also considered to be highly signi?cant. A number of thermal stress events were also recorded, suggesting that rock weathering in cold regions is a synergistic combination of various chemical and mechanical weathering mechanisms. Copyright © 2003 John Wiley & Sons, Ltd.     

L'archivage des activités humaines par les neiges et glaces polaires : le cas du plomb

The investigation of the occurrence of lead in dated snow and ice from Greenland and Antarctica has played a major role in our understanding of the history of the pollution of the atmosphere of our planet by this metal. Such studies have however proved to be very demanding, mainly because of the extreme purity of polar snow and ice. Reliable measurements can be obtained only if ultra-clean and highly sensitive procedures are used, as pioneered by Clair Patterson. The Greenland data show evidence of large-scale pollution of the atmosphere of the Northern Hemisphere for lead as early as two millennia ago during Greco–Roman times, especially because of mining and smelting activities in southern Spain. It peaked at the end of the 1960s, with lead concentrations in snow about 200 times higher than natural values, before declining during recent times because of the fall in the use of leaded gasoline. Lead pollution in Antarctica was already significant at the end of the 19th century as a consequence of whaling activities, the traffic of coal-powered ships crossing the Cape Horn, and mining activities in South America, South Africa and Australia. After declining because of the opening of the Panama Canal, the great economic depression and World War II, it reached a maximum during the 1980s, with lead concentrations 20 times higher than natural values. Other studies focus on past natural variations of lead in ancient ice dated from the last climatic cycles. To cite this article: C. Boutron et al., C. R. Geoscience 336 (2004).     

Dust production and the release of iron oxides resulting from the aeolian abrasion of natural dune sands

Global dust trajectories indicate that signi?cant quantities of aeolian‐transported iron oxides originate in contemporary dryland areas. One potential source is the iron‐rich clay coatings that characterize many sand‐sized particles in desert dune?elds. This paper uses laboratory experiments to determine the rate at which these coatings can be removed from dune sands by aeolian abrasion. The coatings impart a red colour to the grains to which previous researchers have assigned variable geomorphological signi?cance. The quantities of iron removed during a 120 hour abrasion experiment are small (99 mg kg^?1) and dif?cult to detect by eye; however, high resolution spectroscopy clearly indicates that ferric oxides are released during abrasion and the re?ectance of the particles alters. One of the products of aeolian abrasion is ?ne particles (<10 µm diameter) with the potential for long distance transport. Copyright © 2004 John Wiley & Sons, Ltd.     

Rock albedo and monitoring of thermal conditions in respect of weathering: some expected and some unexpected results

Broadly speaking, there is, at least within geomorphic circles, a general acceptance that rocks with low albedos will warm both faster and to higher temperatures than rocks with high albedos, reflectivity influencing radiative warming. Upon this foundation are built notions of weathering in respect of the resulting thermal differences, both at the grain scale and at the scale of rock masses. Here, a series of paving bricks painted in 20 per cent reflectivity intervals from black through to white were used to monitor albedo‐influenced temperatures at a site in northern Canada in an attempt to test this premise. Temperatures were collected, for five months, for the rock surface and the base of the rock, the blocks being set within a mass of local sediment. Resulting thermal data did indeed show that the dark bricks were warmer than the white but only when their temperatures were equal to or cooler than the air temperature. As brick temperature exceeded that of the air, so the dark and light bricks moved to parity; indeed, the white bricks frequently became warmer than the dark. It is argued that this ‘negating’ of the albedo influence on heating is a result of the necessity of the bricks, both white and black, to convect heat away to the surrounding cooler air; the darker brick, being hotter, initially convects faster than the white as a product of the temperature difference between the two media. Thus, where the bricks become significantly hotter than the air, they lose energy to that air and so their respective temperatures become closer, the albedo influence being superceded by the requirement to equilibrate with the surrounding air. It is argued that this finding will have importance to our understanding of weathering in general and to our perceptions of weathering differences between different lithologies. Copyright © 2005 John Wiley & Sons, Ltd.     

Vegetation changes in the Jornada Basin from 1858 to 1998

Notes made by land surveyors in 1858 were utilized to estimate cover of grasses and shrubs on the Jornada Experimental Range (JER) and the Chihuahuan Desert Range Research Center (CDRRC) in the northern Chihuahuan Desert in southern New Mexico, USA. Portions of these areas have been previously assessed for historical vegetation dynamics but the entire 84,271 ha assessed in the 19th century has not been examined in total. In 1858, fair to very good grass cover occurred on 98% and 67% of the JER and CDRRC, respectively. Shrubs were present throughout both properties but 45% of the JER and 18% of the CDRRC were shrub free. Reconnaissance surveys, made to determine carrying capacity for livestock were made in 1915–1916 and 1928–1929 on the JER and in 1938 on the CDRRC, show that shrubs had made large increases in area occupied at the time of the surveys. Vegetation type maps were made of both properties in 1998. Mesquite (Prosopis glandulosa) was the primary dominant on 59% of the JER in 1998 and creosotebush (Larrea tridentata) was the primary dominant on 27% of the area. On the CDRRC mesquite and creosotebush were primary dominants on 37% and 46% of the area, respectively. Grass cover has decreased greatly with the increase in shrubs and only shrub control efforts have maintained the once abundant black grama (Bouteloua eriopoda) as a primary dominant on 1% or less of the area on both properties.     

Groundwater control of mangrove surface elevation: Shrink and swell varies with soil depth

We measured monthly soil surface elevation change and determined its relationship to groundwater changes at a mangrove forest site along Shark River, Everglades National Park, Florida. We combined the use of an original design, surface elevation table with new rod-surface elevation tables to separately track changes in the mid zone (0–4 m), the shallow root zone (0–0.35 m), and the full sediment profile (0–6 m) in response to site hydrology (daily river stage and daily groundwater piezometric pressure). We calculated expansion and contraction for each of the four constituent soil zones (surface [accretion and erosion; above 0 m], shallow zone [0–0.35 m], middle zone [0.35–4 m], and bottom zone [4–6]) that comprise the entire soil column. Changes in groundwater pressure correlated strongly, with changes in soil elevation for the entire profile (Adjusted R² = 0.90); this relationship was not proportional to the depth of the soil profile sampled. The change in thickness of the bottom soil zone accounted for the majority (R² = 0.63) of the entire soil profile expansion and contraction. The influence of hydrology on specific soil zones and absolute elevation change must be considered when evaluating the effect of disturbances, sea level rise, and water management decisions on coastal wetland systems.     

Pronounced occurrence of long-chain alkenones and dinosterol in a 25,000-year lipid molecular fossil record from Lake Titicaca, South America

Our analysis of lipid molecular fossils from a Lake Titicaca (16° S, 69° W) sediment core reveals distinct changes in the ecology of the lake over an ∼25,000-yr period spanning latest Pleistocene to late Holocene time. Previous investigations have shown that over this time period Lake Titicaca was subject to large changes in lake level in response to regional climatic variability. Our results indicate that lake algal populations were greatly affected by the changing physical and chemical conditions in Lake Titicaca. Hydrocarbons are characterized by a combination of odd-numbered, mid- to long-chain (C₂₁-C₃₁) normal alkanes and alkenes. During periods when lake level was higher (latest Pleistocene, early Holocene, and late Holocene), the C₂₁n-alkane, and the C₂₅ and C₂₇ alkenes dominate hydrocarbon distributions and indicate contribution from an algal source, potentially the freshwater alga Botryococcus braunii. The C₃₀ 4 α-methyl sterol (dinosterol) increases sharply during the mid-Holocene, suggesting a greatly increased dinoflagellate presence at that time. Long-chain alkenones (LCAs) become significant during the early Holocene and are highly abundant in mid-Holocene samples. There are relatively few published records of LCA detection in lake sediments but their occurrence is geographically widespread (Antarctica, Asia, Europe, North America). Lake Titicaca represents the first South American lake and the first low-latitude lake in which LCAs have been reported. LCA abundance and distribution may be related to the temperature-dependent response of an unidentified algal precursor. Although the LCA unsaturation indices cannot be used to determine absolute Lake Titicaca temperatures, we suspect that the published LCA U₃₇^K unsaturation calibrations can be applied to infer relative temperatures for early to mid-Holocene time when LCA concentrations are high. Using these criteria, the U₃₇^K unsaturation indices suggest relatively warmer temperatures in the mid-Holocene. In contrast to previous speculation, lipid analysis provides little evidence of a greatly increased presence of aquatic plants during the mid-Holocene. Instead, it appears that a few algal species were dominant in the lake. Based on the dramatic rise in abundances of LCAs and dinosterol during the early to mid-Holocene, we suspect that the algal producers of these compounds rose in response to a combination of physical and chemical changes in the lake. These include temperature, salinity, and alkalinity changes that occurred as lake level dropped sharply during a multi-millennial drought affecting the Central Andean Altiplano.     

Oxygen and sulfur isotope systematics of sulfate produced by bacterial and abiotic oxidation of pyrite

To better understand reaction pathways of pyrite oxidation and biogeochemical controls on δ¹⁸O and δ³⁴S values of the generated sulfate in acid mine drainage (AMD) and other natural environments, we conducted a series of pyrite oxidation experiments in the laboratory. Our biological and abiotic experiments were conducted under aerobic conditions by using O₂ as an oxidizing agent and under anaerobic conditions by using dissolved Fe(III)_aq as an oxidant with varying δ¹⁸O_H2O values in the presence and absence of Acidithiobacillus ferrooxidans. In addition, aerobic biological experiments were designed as short- and long-term experiments where the final pH was controlled at ∼2.7 and 2.2, respectively. Due to the slower kinetics of abiotic sulfide oxidation, the aerobic abiotic experiments were only conducted as long term with a final pH of ∼2.7. The δ³⁴S_SO4 values from both the biological and abiotic anaerobic experiments indicated a small but significant sulfur isotope fractionation (∼−0.7‰) in contrast to no significant fractionation observed from any of the aerobic experiments. Relative percentages of the incorporation of water-derived oxygen and dissolved oxygen (O₂) to sulfate were estimated, in addition to the oxygen isotope fractionation between sulfate and water, and dissolved oxygen. As expected, during the biological and abiotic anaerobic experiments all of the sulfate oxygen was derived from water. The percentage incorporation of water-derived oxygen into sulfate during the oxidation experiments by O₂ varied with longer incubation and lower pH, but not due to the presence or absence of bacteria. These percentages were estimated as 85%, 92% and 87% from the short-term biological, long-term biological and abiotic control experiments, respectively. An oxygen isotope fractionation effect between sulfate and water (ε¹⁸O_SO4-H2O) of ∼3.5‰ was determined for the anaerobic (biological and abiotic) experiments. This measured value was then used to estimate the oxygen isotope fractionation effects between sulfate and dissolved oxygen in the aerobic experiments which were −10.0‰, −10.8‰, and −9.8‰ for the short-term biological, long-term biological and abiotic control experiments, respectively. Based on the similarity between δ¹⁸O_SO4 values in the biological and abiotic experiments, it is suggested that δ¹⁸O_SO4 values cannot be used to distinguish biological and abiotic mechanisms of pyrite oxidation. The results presented here suggest that Fe(III)_aq is the primary oxidant for pyrite at pH < 3, even in the presence of dissolved oxygen, and that the main oxygen source of sulfate is water-oxygen under both aerobic and anaerobic conditions.