Iron Isotope Variations in Coastal Seawater Determined by Multicollector ICP-MS

In this paper, we applied a reliable technique for measuring Fe isotope variations in coastal seawater at nanomolar levels. Iron was directly pre-concentrated from acidified seawater samples onto a nitrilotriacetic acid chelating resin and further purified using anion-exchange resin. Sample recovery, determined using a standard addition method, was essentially quantitative. Iron was then determined using a high-resolution multicollector ICP-MS (Neptune) coupled to an ApexQ desolvation introduction system. The external precision for δ⁵⁶Fe values was 0.11‰ (2s) when using total a Fe quantity between 25 and 100 ng. We initially applied this technique to measure the Fe isotope composition of dissolved Fe from several coastal environments in the north-eastern United States and we observed a range of δ⁵⁶Fe values between -0.9‰ and 0.1‰ relative to the IRMM-14 reference material. Iron isotope compositions of several reference water materials for inter-laboratory comparisons were also reported. Our results suggest that iron in coastal seawater, derived from benthic diagenesis and/or groundwater has negative Fe isotopic signatures that are distinct from other iron sources such as atmospheric deposition and rivers.     

A study of rare earth element (REE)–SiO2 variations in felsic liquids generated by basalt fractionation and amphibolite melting: a potential test for discriminating between the two different processes

The origin of felsic magmas (>63% SiO₂) in intra-oceanic arc settings is still a matter of debate. Two very different processes are currently invoked to explain their origin. These include fractional crystallization of basaltic magma and partial melting of lower crustal amphibolite. Because both fractionation and melting can lead to similar major element, trace element and isotopic characteristics in felsic magmas, such lines of evidence have been generally unsuccessful in discriminating between the two processes. A commonly under-appreciated aspect of rare earth element (REE) solid–liquid partitioning behavior is that D _REE for most common igneous minerals (especially hornblende) increase significantly with increasing liquid SiO₂ contents. For some minerals (e.g., hornblende and augite), REE partitioning can change from incomptatible (D < 1) at low liquid SiO₂ to compatible (D > 1) at high liquid SiO₂. When this behavior is incorporated into carefully constrained mass-balance models for mafic (basaltic) amphibolite melting, intermediate (andesitic) amphibolite melting, lower or mid to upper crustal hornblende-present basalt fractionation, and mid to upper crustal hornblende-absent basalt fractionation the following general predictions emerge for felsic magmas (e.g., ∼63 to 76% SiO₂). Partial melting of either mafic or intermediate amphibolite should, regardless of the type of melting (equilibrium, fractional, accumulated fractional) yield REE abundances that remain essentially constant and then decrease, or steadily decrease with increasing liquid SiO₂ content. At high liquid SiO₂ contents LREE abundances should be slightly enriched to slightly depleted (i.e., C _l/C _o ∼ 2 to 0.2) while HREE abundances should be slightly depleted (C _l/C _o ∼ 1 to 0.2). Lower crustal hornblende-bearing basalt fractionation should yield roughly constant REE abundances with increasing liquid SiO₂ and exhibit only slight enrichment (C _l/C _o ∼ 1.2). Mid to upper crustal hornblende-bearing basalt fractionation should yield steadily increasing LREE abundances but constant and then decreasing HREE abundances. At high liquid SiO₂ contents LREE abundances may range from non-enriched to highly enriched (C _l/C _o ∼ 1 to 5) while HREE abundances are generally non-enriched to only slightly enriched (C _l/C _o ∼ 1 to 2). Hornblende-absent basalt fractionation should yield steadily increasing REE abundances with increasing liquid SiO₂ contents. At high SiO₂ contents both LREE and HREE are highly enriched (C _l/C _o ∼ 3 to 4). It is proposed that these model predictions constitute a viable test for determining a fractionation or amphibolite melting origin for felsic magmas in intra-oceanic arc environments where continental crust is absent. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.

National scale evaluation of groundwater chemistry in Korea coastal aquifers: evidences of seawater intrusion

Pollution of groundwater by seawater intrusion poses a threat to sustainable agriculture in the coastal areas of Korea. Therefore, seawater intrusion monitoring stations were installed in eastern, western, and southern coastal areas and have been operated since 1998. In this study, groundwater chemistry data obtained from the seawater intrusion monitoring stations during the period from 2007 to 2009 were analyzed and evaluated. Groundwater was classified into fresh (<1,500 μS/cm), brackish (1,500–3,000 μS/cm), and saline (>3,000 μS/cm) according to EC levels. Among groundwater samples (n = 233), 56, 7, and 37% were classified as the fresh, brackish, and saline, respectively. The major dissolved components of the brackish and saline groundwaters were enriched compared with those of the fresh groundwater. The enrichment of Na⁺ and Cl⁻ was especially noticeable due to seawater intrusion. Thus, the brackish and saline groundwaters were classified as Ca–Cl and Na–Cl types, while the fresh groundwater was classified as Na–HCO₃ and Ca–HCO₃ types. The groundwater included in the Na–Cl types indicated the effects of seawater mixing. Ca²⁺, Mg²⁺, Na⁺, K⁺, SO₄ ²⁻, and Br⁻ showed good correlations with Cl⁻ of over r = 0.624. Of these components, the strong correlations of Mg²⁺, SO₄ ²⁻, and Br⁻ with Cl⁻ (r ≥ 0.823) indicated a distinct mixing between fresh groundwater and seawater. The Ca/Cl and HCO₃/Cl ratios of the groundwaters gradually decreased and approached those of seawater. The Mg/Cl, Na/Cl, K/Cl, SO₄/Cl, and Br/Cl ratios of the groundwaters gradually decreased, and were similar to or lower than those of seawater, indicating that Mg²⁺, Na⁺, K⁺, SO₄ ²⁻, and Br⁻, as well as Cl⁻ in the saline groundwater can be enriched by seawater mixing, while Ca²⁺ and HCO₃ ⁻ are mainly released by weathering processes. The influence of seawater intrusion was evaluated using threshold values of Cl⁻ and Br⁻, which were estimated as 80.5 and 0.54 mg/L, respectively. According to these criteria, 41–50% of the groundwaters were affected by seawater mixing.     

Measurement of the Isotopic Composition of Molybdenum in Geological Samples by MC‐ICP‐MS using a Novel Chromatographic Extraction Technique

A novel preconcentration method is presented for the determination of Mo isotope ratios by multi‐collector inductively coupled plasma‐mass spectrometry (MC‐ICP‐MS) in geological samples. The method is based on the separation of Mo by extraction chromatography using N‐benzoyl‐N‐phenylhydroxylamine (BPHA) supported on a microporous acrylic ester polymeric resin (Amberlite CG‐71). By optimising the procedure, Mo could be simply and effectively separated from virtually all matrix elements with a single pass through a small volume of BPHA resin (0.5 ml). This technique for separation and enrichment of Mo is characterised by high selectivity, column efficiency and recovery (~ 100%), and low total procedural blank (~ 0.18 ng). A ¹⁰⁰Mo‐⁹⁷Mo double spike was mixed with samples before digestion and column separation, which enabled natural mass‐dependent isotopic fractionation to be determined with a measurement reproducibility of  < 0.09‰ (δ^98/95Mo, 2s) by MC‐ICP‐MS. The mean δ^98/95Mo_{SRM 3134} (NIST SRM 3134 Mo reference material; Lot No. 891307) composition of the IAPSO seawater reference material measured in this study was 2.00 ± 0.03‰ (2s, n = 3), which is consistent with previously published values. The described procedure facilitated efficient and rapid Mo isotopic determination in various types of geological samples.     

Submarine groundwater discharge is an important net source of light and middle REEs to coastal waters of the Indian River Lagoon, Florida, USA

Porewater (i.e., groundwater) samples were collected from multi-level piezometers across the freshwater-saltwater seepage face within the Indian River Lagoon subterranean estuary along Florida’s (USA) Atlantic coast for analysis of the rare earth elements (REE). Surface water samples for REE analysis were also collected from the water column of the Indian River Lagoon as well as two local rivers (Eau Gallie River, Crane Creek) that flow into the lagoon within the study area. Concentrations of REEs in porewaters from the subterranean estuary are 10-100 times higher than typical seawater values (e.g., Nd ranges from 217 to 2409 pmol kg⁻¹), with submarine groundwater discharge (SGD) at the freshwater-saltwater seepage face exhibiting the highest REE concentrations. The elevated REE concentrations for SGD at the seepage face are too high to be the result of simple, binary mixing between a seawater end-member and local terrestrial SGD. Instead, the high REE concentrations indicate that geochemical reactions occurring within the subterranean estuary contribute substantially to the REE cycle. A simple mass balance model is used to investigate the cycling of REEs in the Indian River Lagoon and its underlying subterranean estuary. Mass balance modeling reveals that the Indian River Lagoon is approximately at steady-state with respect to the REE fluxes into and out of the lagoon. However, the subterranean estuary is not at steady-state with respect to the REE fluxes. Specifically, the model suggests that the SGD Nd flux, for example, exported from the subterranean estuary to the overlying lagoon waters exceeds the combined input to the subterranean estuary from terrestrial SGD and recirculating marine SGD by, on average, ∼100 mmol day⁻¹. The mass balance model also reveals that the subterranean estuary is a net source of light REEs (LREE) and middle REEs (MREE) to the overlying lagoon waters, but acts as a sink for the heavy REEs (HREE). Geochemical modeling and statistical analysis further suggests that this fractionation occurs, in part, due to the coupling between REE cycling and iron redox cycling within the Indian River Lagoon subterranean estuary. The net SGD flux of Nd to the Indian River Lagoon is ∼7-fold larger than the local effective river flux to these coastal waters. This previously unrecognized source of Nd to the coastal ocean could conceivably be important to the global oceanic Nd budget, and help to resolve the oceanic “Nd paradox” by accounting for a substantial fraction of the hypothesized missing Nd flux to the ocean.     

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.     

High-resolution coral records of rare earth elements in coastal seawater: biogeochemical cycling and a new environmental proxy

In this study we have used laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), to produce a high resolution coral record of rare earth elements (REE), Mn and Ba from coastal Porites corals from the Great Barrier Reef of Australia. Validation of the LA-ICP-MS technique indicated that the method provides accurate and reproducible (RSD = 13-18%) analysis of low concentration REE in corals (∼1 to 100 ppb). The REE composition in coral samples was found to closely reflect that of the surrounding seawater and distribution coefficients of ∼1-2 indicated minimal fractionation of the series during incorporation into coral carbonate. To explore the idea that coral records of REE can be used to investigate dissolved seawater composition, we analyzed two coastal corals representing a total of ∼30 yr of growth, including a 10-yr overlapping period. Comparable results were obtained from the two samples, particularly in terms of elemental ratios (Nd/Yb) and the Ce anomaly. Based on this evidence and results from the determination of distribution coefficients, we suggest that useful records of seawater REE composition can be obtained from coral carbonates. When compared to the REE composition of a mid shelf coral, coastal corals showed a significant terrestrial influence, characterized by higher REE concentrations (greater than 10 times) and light REE enrichment. The REE composition of coastal seawater inferred from the coral record was dependent on seasonal factors and the influence of flood waters. REE fractionation displayed a strong seasonal cycle that correlated closely with Mn concentration. We suggest that higher Nd/Yb ratios and higher Mn concentrations in summer result from scavenging of heavy REE by particulate organic ligands and Mn reductive dissolution respectively, both processes displaying higher rates during periods of high primary productivity. The Ce anomaly also displayed a strong seasonal cycle showing an enhanced anomaly during summer and during flood events. This is consistent with the Ce anomaly being primarily controlled by the abundance of Ce oxidizing bacteria. Based on these arguments, we suggest that the coral record of dissolved REE and Mn may be regarded as a useful proxy for biological activity in coastal seawater.     

Isotopic and geochemical identifications of groundwater salinisation processes in Salalah coastal plain,Sultanate of Oman

A detail investigation was carried out to improve the current knowledge of groundwater salinisation processes in coastal aquifers using hydrochemical and isotopic parameters. Data of major ions for 40 wells located in the Salalah plain aquifer, Sultanate of Oman, were collected during pre-monsoon 2004 and analysed. The groundwater changes along the general flow path towards the coast from fresh (EC < 1500 μS/cm), brackish (EC: 1500–3000 μS/cm) and saline (EC > 3000 μS/cm). Results of inverse modeling simulations using PHREEQC show that dissolution of halite may be the main source of Cl and Na in the study area. Ionic delta calculation indicates that the depletion of Na and K and enrichment of Ca and Mg in groundwater were probably attributed to reverse ion exchange reactions. During a sampling campaign conducted in October 2015, 11 groundwater samples were collected for Cl, Br and isotopic analysis (²H/¹⁸O). Molar Cl/Br ratios in fresh groundwater were higher than those of seawater, indicating the impact of halite dissolution on the groundwater quality. For saline groundwater, these ratios were less than those of seawater, showing the influence of anthropogenic input from agriculture on the same. Relatively depleted isotopic signature of all groundwater samples show that the monsoon precipitation is the main source of groundwater recharge in the study area.     

Geochemistry of Suspended Particulate Matter (SPM) in the Murray-Darling River System: A Conceptual Isotopic/Geochemical Model for the Fractionation of Major, Trace and Rare Earth Elements

A conceptual isotopic/geochemical model is presented to explain the variation of major, trace and rare earth element (REE) geochemistry and Sr isotope systematics in suspended particulate matter (SPM) as a function of particle/colloid size. This conceptual model is an extension of a previous investigation of the origin of SPM in the Murray-Darling River system (MDRS) that utilised Sr isotope systematics to examine aspects of SPM (particle/colloid) origin, structure and mineralogy. The geochemical processes that give rise to the often coherent trends in major, trace and REE geochemistry and Sr isotopic signature as a function of particulate (<1 μm) and colloidal (>1 μm) size in the MDRS have been identified using an enhanced SPM size fractionation technique as a basis to not only obtain a broad range of particle/colloid size ranges, but also to provide sufficient material for subsequent geochemical and isotopic analysis. The conceptual isotopic/geochemical model proposed here contains three major components: (i) the differential weathering of micas and alkali (K-) feldspars to form the majority of the particulate (<1 μm) fractions (high 87Sr/86Sr ratio), which have a geochemical and Sr isotopic signature that closely resembles precursor mineralogies, (ii) the differential weathering of Na, Ca-feldspars (plagioclase) which decompose to form clay minerals in the colloidal (>1 μm) fractions (low 87Sr/86Sr ratio), with a range of geochemical signatures related to the relative proportions of inorganic and organic constituents, and (iii) the presence of natural organic matter as coatings on the particulate (<1 μm) and colloidal (>1 μm) matter and possibly as organo-colloids which exert an increasing influence in particular on bulk colloid geochemistry with decreasing colloid size. This conceptual isotopic/geochemical model also accounts for the distinct variation in major, trace and REE geochemistry and Sr isotopic systematics between the particulate (<1 μm) and colloidal (>1 μm) fractions, the variation being primarily a function of the distinctly different precursor mineralogies of the SPM fractions and geochemical fractionation during the weathering and transport. Additionally, this model explains a systematic fractionation of REE apparent within colloidal (>1 μm) fractions. Statisitcal (hierachical cluster) analysis of two particulate and three colloidal fractions from 23 samples from the MDRS is used as a basis to investigate geochemical and mineralogical associations within the particulate and colloidal size fractions and to provide additional supporting evidence for the conceptual isotopic/geochemical model. This revised version was published online in July 2006 with corrections to the Cover Date.     

Evaluation of groundwater quality in coastal areas: implications for sustainable agriculture

Seawater intrusion is a problem in the coastal areas of Korea. Most productive agricultural fields are in the western and southern coastal areas of the country where irrigation predominantly relies on groundwater. Seawater intrusion has affected agricultural productivity. To evaluate progressive encroachment of saline water, the Korean government established a seawater intrusion monitoring well network, especially in the western and southern part of the peninsula. Automatic water levels and EC monitoring and periodic chemical analysis of groundwater help track salinization. Salinization of fresh groundwater is highly associated with groundwater withdrawal. A large proportion of the groundwaters are classified as Na–Cl and Ca–Cl types. The Na–Cl types represent effects of seawater intrusion. The highest EC level was over 1.6 km inland and high Cl values were observed up to 1.2 km inland. Lower ratios of Na/Cl and SO₄/Cl than seawater values indicate the seawater encroachment. A linear relation between Na and Cl represents simple mixing of the fresh groundwater with the seawater. The saline Na–Cl typed groundwaters showed Br/Cl ratios similar to or less than seawater values. The Ca–HCO₃ type groundwaters had the highest Br/Cl ratios. Substantial proportions of the groundwaters showed potential for salinity and should be better managed for sustainable agriculture.     

The geochemical characteristics of aqueous rare-earth elements in shallow karst groundwater in Guiyang City,China

Fifty-seven shallow groundwater samples were collected from Guiyang karst basin, China, to analyze the aqueous rare-earth elements in low-water seasons and it is shown that the total amount of rare-earth elements (ΣREE) in karst groundwater is exceedingly low compared with that in carbonate rocks or weathering crusts of carbonate rocks, and ranges from 0.01 to 0.43, from 0.03 to 0.27, from 0.03 to 0.19 and from 0.05 to 1.38 μg·L-1 for dolomite, dolomitic & limestone, limestone and clastic rock aquifer, respectively. Both distributions and contents of rare-earth elements (REE) in karst groundwater reflect the lithology of host rocks or weathering crusts of carbonate rocks through which groundwater flows. The chondrite-normalized patterns show a non-flat profile with higher enrichment of slightly light rare-earth elements (LREE) than heavy rare-earth elements (HREE), prominent fractionation between LREE and HREE, negative Ce anomalies and negative or positive Eu anomalies. There is more obvious fractionation between LREE and HREE in groundwater than that in carbonate rocks and their weathering crusts due to high contents of HCO3? and PH in groundwater. In shallow karst groundwater, REE(CO3)n2n-3 (n=1 and 2) is the main inorganic species of REE. But for a clastic rock aquifer, both REESO4+ and REECO3+ are the main inorganic species of REE. Species of REE in groundwater is closely associated with the hydrochemical type of groundwater which is predominated by the lithology of host rocks, groundwater-rock interaction and weathering-pedogenesis of carbonate rocks.     

Rare earth elements in the sedimentary cycle: A summary

The relative and absolute concentrations of rare earth elements (REE) in authigenic and biogenic phases of deep-sea sediments are quite different. Competition between these phases for REE has resulted in fractionation from the parent material, the latter consisting predominantly of terrigenous material, but with a contribution from marine volcanism. The strongest feature of this fractionation is a depletion of Ce, relative to La, in CaCO₃, opalline silica, phillipsite, phosphorite, barite, and montmorillonitic clays; and a Ce enrichment in Fe/Mn nodules. The distribution of REE in different masses of seawater strongly reflects their fractionation in sediments. Whereas the relative concentration of REE in rivers resembles that of shale, their removal from seawater by authigenic and biogenic phases results in: (1) a decrease of their total concentration; (2) a depletion of Ce; and (3) an enrichment of heavy REE relative to light REE. The order of fractionation for water masses in the Atlantic Ocean is:Antarctic intermediate water > North Atlantic deep water > Antarctic bottom water> shelf water > river water ～ shale.The shale-normalized pattern for the sum of REE in the authigenic and biogenic phases of pelagic sediment and in seawater resembles that of an admixture of shale and basalt corresponding presumably to the realtive inputs from continents and marine volcanism respectively. The estimated rate of accumulation of each REE in the sediment, however, is approximately 12 times the estimated rate of input of REE from these two sources.     

Hydrochemical characteristics and quality assessment of shallow groundwater in a coastal area of Southwest Bangladesh

In this study, the hydrochemical characteristics of shallow groundwater in a coastal region (Khulna) of southwest Bangladesh have been evaluated based on different indices for drinking and irrigation uses. Water samples were collected from 26 boreholes and analyzed for major cations and anions. Other physico-chemical parameters like pH, electrical conductivity (EC), and total dissolved solids were also measured. Most groundwater is slightly alkaline and largely varies in chemical composition, e.g. EC ranges from 962 to 9,370 μs/cm. The abundance of the major ions is as follows: Na⁺ > Ca²⁺ > Mg²⁺ > K⁺ = Cl⁻ > HCO₃ ⁻ > SO₄ ²⁻ > NO₃ ⁻. Interpretation of analytical data shows two major hydrochemical facies (Na⁺–K⁺–Cl⁻–SO₄ ²⁻ and Na⁺–K⁺–HCO₃ ⁻) in the study area. Salinity, total hardness, and sodium percentage (Na%) indicate that most of the groundwater samples are not suitable for irrigation as well as for domestic purposes and far from drinking water standard. Results suggest that the brackish nature in most of the groundwaters is due to the seawater influence and hydrogeochemical processes.     

Rare Earth Element Patterns in the Karst Terrains of Guizhou Province, China: Implication for Water/Particle Interaction

The authors determine the concentrations of dissolved (<0.22 μm) rare earth elements (REE) and suspended particulate matter (SPM) of typical karst rivers in Guizhou Province, China during the high-flow period. The concentrations of acid-soluble REE extracted from SPM using diluted hydrochloric acid are also obtained to investigate water/particle interaction in the river water. The dissolved REE contents in the river water are extremely low in the rivers of the study. The dissolved REE distribution patterns normalized by the Post Archean Australia Shale (PAAS) in the karst rivers are not flat, show slight enrichment of heavy REE to light REE, and also have significant negative Ce and Eu anomalies. The acid-soluble REE appears to have similar distribution patterns as characterized by MREE enrichment and slight LREE depletion, with unremarkable Ce and Eu anomalies. The PAAS-normalized REE distribution patterns of SPM are flat with negative Eu anomalies. The contents and distribution patterns of REE in the SPM are closely related to the lithological character of the source rocks. The SPM contains almost all the REE produced in the process of surficial weathering. This demonstrates that particle-hosted REE are the most important form of REE occurrence. REE fractionation, which takes place during weathering and transport, leads to an obvious HREE enrichment in the dissolved loads relative to the SPM. Y/Ho ratio can be used to shed light on REE behaviors during water/particle interaction.     

The role of apatite fractionation and REE distribution in alkaline rocks from Mt. Etna, Sicily

Summary Melt inclusions in olivine and apatite, and REE distribution of apatite were studied in one of the least differentiated members of the oldest alkaline succession of Mt. Etna. Apatite occurs both as microphenocrysts and as inclusions in olivine crystals, even in the most Mg-rich ones (Fo₈₂). In addition phenocrysts and groundmass are composed of plagioclase, clinopyroxene, olivine and magnetite. Apatite is fluor-apatite, with rather homogeneous major element (measured by electron microprobe, EMP) and REE (measured by laser-ablation microprobe, LAM, and by secondary ion mass spectrometer, SIMS) contents. REE are enriched when compared to the whole rock, with contents in olivine-hosted apatite lower than or the same as those of the microphenocryst cores; these in turn show lower REE values than their edges. Distribution coefficients, calculated from LAM data of microphenocryst edges and whole rock analyses, are higher for LREE (8–12) than for HREE (5–4). In the SiO₂ vs. P₂O₅ diagram melt inclusions and whole rock samples define a trend that is consistent with continuous apatite extraction from a “high P” basalt magma. Finally, whole rock data show LREE/HREE (La/Lu)_n enrichment ratios from hawaiites to mugearites (=1.14), consistent with apatite fractionation, lower than those documented for lavas of the “low P” type (enrichment ratio = 1.34–1.37), where conditions for apatite saturation were not established. Received January 2, 2000; revised version accepted April 2, 2001     

Trace element mobility in dolomitic argillites of the Mesoproterozoic Belt-Purcell Supergroup, Western North America

The Belt-Purcell Supergroup comprises dolomite-rich stratigraphic units in a dominantly siliciclastic succession, where sedimentation spans 1400-1470 Ma. Dolomitic units are variable mixtures of co-sedimented argillite and primary carbonate post-depositionally converted to secondary dolomite. Based on rare earth element (REE) relationships three distinct REE patterns are identified in the dolomite-rich units: Type 1 (T1d; d = dolomitic sample) with REE patterns parallel to post-Archean Upper Continental Crust (PA-UCC), albeit at lower absolute abundances due to dilution by carbonate content; Type 2 (T2d) with Heavy REE (HREE) enrichment but Light REE (LREE) depletion relative to T1d; and Type 3 (T3d) with enrichment in LREE and HREE relative to T1d, but erratic Middle REE (MREE) patterns. There is a progressive increase of ΣREE from T1d through T2d to T3d, whereas for ΣLREE/ΣHREE T2d < T1d < T3d. T1d-T2d and T3d represent three different “snapshots” of a continuous process.In terms of timing, dolomitization of calcite primary sediment in all samples likely took place broadly during burial diagenesis, as inferred for most Proterozoic dolomites. T1d is easily explained by provenance: however, T2d and T3d cannot be related to provenance, weathering or sedimentary sorting processes to explain higher concentrations of HREE referenced to PA-UCC and consequently developed in the sediment from a T1d precursor. The same three REE signatures have been described in previous studies in counterpart siliciclastic counterparts throughout the Belt-Purcell Supergroup at three different locations. Mobility of normally stable REE is accompanied by mobility of normally isochemical high field strength elements (HFSE) in T2d and T3d to give REE/REE, HFSE/HFSE, REE/HFSE and Y/HREE fractionations. No specific REE-HFSE signatures are apparent in the carbonate-rich units as compared to their non-dolomitic siliciclastic counterparts. This unusual mobility of REE and HFSE reflected in T2d and T3d is attributed to alkaline oxidizing post-depositional brines. Salinity was derived from seawater-sediment reactions, dissolution of evaporite minerals, and the smectite-illite transformation, whereas alkaline oxidizing conditions were promoted by groundwater interaction with mafic units in the basin, CO₂ introduced into the system during episodic rifting with mantle degassing, and interaction of syn-sedimentary mafic intrusions with carbonate units at early stages of BPS deposition. Intermittent brine activity, inducing T2d and T3d patterns, spanned >1 Ga as recorded by secondary monazite grains with age distributions that correspond to large scale tectono-thermal events in Laurentia.Post-depositional processes and redistribution of carbonate can have an impact on transitional stratigraphic contacts between dolomitic and siliciclastic units which may have been incorrectly described as primary due to sedimentary environment changes.     

Salinity mapping of coastal groundwater aquifers using hydrogeochemical and geophysical methods: a case study from north Kelantan,Malaysia

Integrated hydrogeochemical and geophysical methods were used to study the salinity of groundwater aquifers along the coastal area of north Kelantan. For the hydrogeochemical investigation, analysis of major ion contents of the groundwater was conducted, and other chemical parameters such as pH and total dissolved solids were also determined. For the geophysical study, both geoelectrical resistivity soundings and reflection seismic surveys were conducted to determine the characteristics of the subsurface and groundwater contained within the aquifers. The pH values range from 6.2 to 6.8, indicating that the groundwater in the study area is slightly acidic. Low content of chloride suggests that the groundwater in the first aquifer is fresh, with an average concentration of about 15.8 mg/l and high geoelectrical resistivity (>45 ohm m). On the other hand, the groundwater in the second aquifer is brackish, with chloride concentration ranging from 500 mg/l to 3,600 mg/l and very low geoelectrical resistivity (<45 ohm m) as well as high concentration of total dissolved solids (>1,000 mg/l). The groundwater in the third aquifer is fresh, with chloride concentrations generally ranging from 2 mg/l to 210 mg/l and geoelectrical resistivity of greater than 45 ohm m. Fresh and saltwater interface in the first aquifer is generally located directly in the area of the coast, but, for the second aquifer, both hydrogeochemical and geoelectrical resistivity results indicate that the fresh water and saltwater interface is located as far as 6 km from the beach. The considerable chloride ion content initially suggests that the salinity of the groundwater in the second aquifer is probably caused by the intrusion of seawater. However, continuous monitoring of the chloride content of the second aquifer indicated no significant changes with time, from which it can be inferred that the salinity of the groundwater is not affected by seasonal seawater intrusion. Schoeller diagrams illustrate that sulphate concentrations of the groundwater of the second aquifer are relatively low compared to those of the recent seawater. Therefore, this result suggests that the brackish water in the second aquifer is probably from ancient seawater that was trapped within the sediments for a long period of time, rather than due to direct seawater intrusion.     

“寨背式”离子吸附型稀土矿床多类型稀土矿化及其成因

赣南寨背离子吸附型稀土矿床产于寨背复式花岗岩体的风化壳中,自20世纪80年代发现以来一直以轻稀土型开采,近年在轻稀土型花岗岩风化壳中发现了重稀土矿。为了探讨轻稀土型花岗岩风化过程中重稀土元素的迁移、分馏和富集机制,本文选择了区内三个具有代表性的风化壳钻孔(ZK1、ZK2和ZK4)对其进行了全相和离子交换相稀土元素地球化学研究。结果显示：钻孔ZK4中离子交换相稀土含量介于14.90×10^-6～835.8×10^-6之间,并富集轻稀土(LREE/HREE=2.28～10.78);钻孔ZK1中离子交换相稀土含量达1470×10^-6(9件样品均值),具有从轻稀土型向重稀土型过渡的配分特征(LREE/HREE=1.30～1.65),并且剖面自上而下显示轻、重稀土逐渐富集的趋势;钻孔ZK2中离子交换相稀土含量为492.4×10^-6(8件样品均值),自上而下稀土配分类型从轻稀土型过渡至重稀土型(LREE/HREE=0.43～2.25),且轻稀土富集在全风化层上部而重稀土则富集在下部。三个钻孔的Nb/Ta和Zr/Hf...     

Do Archean chemical sediments record ancient seawater rare earth element patterns?

Rare earth elements (REE) concentrations of Archean and Proterozoic chemical sediments are commonly used as proxies to study secular trends in the geochemistry of Precambrian seawater. In addition, similarities in the REE signatures of Archean chemical sediments and modern seawater have led researchers to argue that some Archean rocks originated as biochemical precipitates (i.e., microbial carbonates) in shallow marine (e.g., peritidal) environments. However, terrestrial waters, including river water and groundwater, also commonly exhibit REE fractionation patterns that resemble modern seawater. Here, we present the seawater-like REE data for groundwaters from central México as additional evidence that these patterns are not unique to the marine environment. The shale-normalized REE patterns of the groundwaters are compared to those of modern seawater (open ocean and nearshore), Holocene reefal microbial carbonates and corals, and Archean chemical sediments using statistical means (i.e., ANOVA and Wilcoxon analyses) in order to quantify the similarities and/or differences in the REE patterns. Shale-normalized (SN) Ce anomalies and measures of REE fractionation [i.e., (La/Yb)_SN, (Pr/Yb)_SN, (Nd/Yb)_SN, and (Gd/Yb)_SN] of the central México groundwater samples are statistically indistinguishable from those of modern seawater. Moreover, except for differences in the Ce anomalies, which are lacking in Archean chemical sediments, the REE patterns of the central México groundwaters are also statistically similar to REE patterns of Archean chemical sediments, especially those of the 3.45 Ga Strelley Pool Chert. Consequently, we suggest that without additional information, it may be premature to unequivocally conclude that Archean chemical sediments record REE signatures of an Archean ocean.     

Rare earth elements in corals from the Isla de Sacrificios Reef,Veracruz, Mexico

Rare earth elements (REE) analysis was carried out in two coral species Diploria strigosa and Copophyllia natans from Isla de Sacrificios Reef (ISR) (19° 10′ 51.6″N; 96° 5′ 45.6″W) Veracruz, Mexico. Both corals were cut at the top, middle and bottom parts to detect possible differences in REE concentrations related to water masses and sediment inputs. An enrichment in heavy rare elements (HREE) compared to light rare elements (LREE) at the top of Diploria strigosa and Copophyllia natans, evidenced by (La/Lu)_SN <0.5, (La/Yb)_SN <0.5 and (Pr/Yb)_SN <0.5 is observed. This HREE enrichment in both corals is probably due to the high pH and CO₃^2? content in the seawater. A negative Ce anomaly is observed throughout Diploria strigosa and Copophyllia natans, probably linked with well oxygenated, highly oxidative modern shallow waters, and high nutrients related to suspended matter. Positive Eu anomalies in both corals are due to development of the ISR in shallow waters. Ce/Ce* vs. (Pr/Yb)_SN diagram suggests the input of terrigenous material, as all samples have Ce/Ce* and Pr/Yb values outside the seawater range signature. However, the Nd/Yb and (Nd/Yb)_SN suggest that the top of Diploria strigosa and Copophyllia natans are associated with coastal waters at about 50 m depth.