The rare earth elements in rivers, estuaries, and coastal seas and their significance to the composition of ocean waters

Elderfield, H.; Upstill‐Goddard, Robert C.; Sholkovitz, Edward R.

doi:10.1016/0016-7037(90)90432-k

Cited by 953 publications

(522 citation statements)

References 45 publications

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“…As a result of abandoned mine workings, the River Nent is contaminated with Zn and Pb (Macklin and Dowset 1989), which, probably as a result of grazer mortality, has in turn resulted in the formation of an algal bloom in the river (Say and Whitton 1981). Additional samples were taken from the River Luce and Crosswater of Luce in SW Scotland, where peat-rich moorland overlies Ordovician greywackes and siltstones (see Sholkovitz [1976] and Elderfield et al [1990] for other studies of the metal chemistry of the River Luce; Robson and Neal [1997] for data on the River Tweed).…”

Section: Sampling and Analysismentioning

confidence: 99%

Role of colloids and fine particles in the transport of metals in rivers draining carbonate and silicate terrains

Hill

Aplin

2001

Limnology & Oceanography

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We have used cross flow filtration (CFF) to determine the pools of fine particulate (0.1-0.45 m), colloidal (1,000 Dalton to 0.1 m), and dissolved (Ͻ1,000 Dalton) metals in seven rivers that are all relatively rich in organic matter but have differing pH, alkalinity, and ionic strength. The metal content of Ͻ0.45-m filtered river water primarily reflects a mixing of two metal pools with differing elemental compositions: a truly dissolved pool and a colloidal pool. Fine particulate metals contribute Ͻ10% of the total metal load of Ͻ0.45-m filtered water. Colloidal metals generally comprise at least the following percentages of the metal load of Ͻ0.45-m filtered water: Ͼ50% of Fe, Al, and trace metals; 30% Mn, 25% Ca and Mg; 15% Na and K; and a few percent Si. We believe that these figures are minima because recovery experiments with the CFF apparatus suggest that whilst recoveries of pure metal salt solutions are close to 100%, only 70% of particle-reactive metals are recovered from metal salt solutions spiked with humic acid. We propose that the metal composition of riverine colloids is primarily controlled by element mobility during weathering. In organic-rich soils with low acid-neutralizing capacity, low pH solutions drive the dissolution of aluminosilicates and oxides. Uptake of Al, Fe, and trace metals onto colloidal organic matter helps to maintain low activities of dissolved metals and enhances mineral dissolution. Colloids derived from these soils are thus enriched in Al, Fe, Mn, and trace metals, resulting in high concentrations of these elements in Ͻ0.45-m filtered water. In carbonate-rich soils, rapid neutralization of rainwater by carbonate minerals restricts the mobilization of aluminosilicates and oxides. Compared to colloids from rivers draining silicate terrains, colloids in carbonate-rich systems have higher total loadings of metals, are enriched in alkali and alkaline earth metals, but are depleted in Al, Fe, and trace metals.Quantifying weathering processes and the subsequent transport of elements to the ocean is a fundamental aim of geochemistry. Although the abundance of dissolved elements has been commonly and pragmatically quantified by filtering water at 0.45 m, it is well known that sub-0.1-m colloidal phases, such as organic matter and oxides, interact strongly with dissolved metals (for reviews see Buffle 1988;Stumm 1992Stumm , 1993Gustafsson and Gschwend 1997). Several previous studies suggest that colloids can be important metal carriers in freshwater (e.g., Giesy and Briese 1977;Reuter and Perdue 1977;Hoffmann et al. 1981;Salbu et al. 1985;Tanizaki et al. 1992;Dai and Martin 1995;Ross and Sherrell 1999), and it is likely that the loss of metals from estuarine water is related to the coagulation of colloids (Sholkovitz 1976;Boyle et al. 1977).This paper reports the results of a study aimed at determining the importance of colloids as metal carriers in a series of rivers of widely varying pH and ionic strength. Cross flow filtration (CFF) is developed as a method of fraction-1...

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Section: Sampling and Analysismentioning

confidence: 99%

Role of colloids and fine particles in the transport of metals in rivers draining carbonate and silicate terrains

Hill

Aplin

2001

Limnology & Oceanography

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“…For most elements, however, partition is the same in blackwater and whitewater samples Dissolved REE concentrations in blackwater rivers are generally in the range of 0.1-1 mg L -1 for La, Ce and Nd, and below 0.1 µg L -1 for the other REE; concentrations are even lower in Rio Solimões (Tables 4 and 5). Graphs of REE in solution, normalized to the NASC average shale standard 12 , show an almost horizontal line for a typical blackwater sample (RN5), except for the small enrichment of Ce; samples from Rio Solimões (RS5) present a bellshaped curve ( Figure 5). However, if samples from Solimões are normalized against a chondrite standard 13 , a typical horizontal line is found ( Figure 6).…”

Section: Flat Membrane Ultrafiltrationmentioning

confidence: 99%

A contribution to the chemical characterization of rivers in the Rio Negro Basin, Brazil

Küchler¹,

Miekeley²,

Forsberg³

2000

J. Braz. Chem. Soc.

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Water samples were collected in Middle Amazonia from the Amazon River, Rio Negro and 17 tributaries of Rio Negro. The analyses consisted of pH, conductivity, and dissolved organic (DOC) measurements, as well as plasma source mass spectrometry (ICP-MS). Factor analysis revealed three factors, which explained 94% of the total variance. A plot of factor scores presented a cluster containing mostly samples from the Rio Negro Basin. Ultrafiltration tests confirmed that organics from the Rio Negro have higher molecular mass than in the Amazon, and that some metals are associated with these compounds. Heavy rare-earth elements (REE) are enriched relative to light REE in the dissolved fraction of most rivers of the Negro Basin; the opposite occurred in suspended matter.

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“…The (La/Yb) cn ratios of river waters are generally low, probably because the stabilities of REE carbonate complexes become greater as the atomic number increases (Kosterin, 1959;McLennan and Taylor, 1979). The negative Ce anomaly is essentially caused by the removal of Ce as CeO 2 under oxidizing conditions (e.g., Piper, 1974;Elderfield et al, 1981;Liu et al, 1988), although the anomaly also partly depends on the pH value of solution (de Baar et al, 1985;Liu et al, 1988;Elderfield et al, 1990). It is generally considered that the REE 10 -5 Fig.…”

Section: Rees Of Hydrothermal Fluids Of Meteoric Water Originmentioning

confidence: 99%

Rare Earth Elements as an Indicator to Origins of Skarn Deposits: Examples of the Kamioka Zn‐Pb and Yoshiwara‐Sannotake Cu(–Fe) Deposits in Japan

Kato

1999

Resource Geology

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: Systematic data of rare earth elements (REEs) are presented in order to put some constraints on the origin of hydrothermal fluids responsible for two contrastive skarn deposits in Japan; the Kamioka Zn‐Pb and Yoshiwara‐Sannotake Cu(‐Fe) deposits. Carbon and oxygen isotopic studies have demonstrated that the hydrothermal fluids responsible for the Kamioka Zn‐Pb deposits are of meteoric water origin whereas those for the Yoshiwara‐Sannotake Cu(‐Fe) deposits are of magmatic water origin. The REE abundances of epidote skarn derived from aluminous rocks, garnet and clinopyroxene in calcic exoskarn derived from limestone, and interstitial calcite associated with sulfide minerals were determined for these contrastive skarn deposits by inductively‐coupled plasma mass spectrometry (ICP‐MS). A significant difference in the REE concentrations is not found between epidote skarn and aluminous original rock (plagioclase‐clinopyroxene rock, called Inishi rock) from the Kamioka Zn‐Pb deposits, indicating that the REEs are generally immobile during the formation of epidote skarn, and that the REE concentrations of the hydrothermal fluid are considerably low relative to the aluminous original rock. In contrast, the epidote skarn exhibits enrichment of Eu with increasing total REE concentrations relative to the aluminous original rock (quartz diorite) in the Yoshiwara‐Sannotake Cu(‐Fe) deposits, implying a contribution of magmatic fluid derived from granitoids during the skarn formation. Limestone generally has much lower REE concentrations related to surrounding aluminous rocks, and thus the REE concentrations of garnet and clinopyroxene in calcic exoskarn, originated from limestone, are variable due to the interaction with the hydrothermal fluids. The chondrite‐normalized REE patterns of garnet, clinopyroxene, and interstitial calcite exactly provide useful information on origins of hydrothermal fluids. The REE patterns of these minerals from the Kamioka Zn‐Pb deposits show lower (Pr/Yb)cn ratios, and negative Ce and Eu anomalies inherited from limestone with the decrease of This suggests that the hydrothermal fluids responsible for the Kamioka Zn‐Pb deposits were depleted in REEs, and were not magmatic water in origin, but presumably meteoric one. In striking contrast, the REE patterns of exoskarn minerals and calcite from the Yoshiwara‐Sannotake Cu(‐Fe) deposits exhibit a positive Eu anomaly, and high (Pr/Yb)cn ratios with the considerable increase of σREE and the disappearance of negative Ce anomaly, implying that the fluids were dominantly of magmatic origin. The REE indices are very likely to be an excellent indicator to origins of the skarn deposits.

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The rare earth elements in rivers, estuaries, and coastal seas and their significance to the composition of ocean waters

Cited by 953 publications

References 45 publications

Role of colloids and fine particles in the transport of metals in rivers draining carbonate and silicate terrains

Role of colloids and fine particles in the transport of metals in rivers draining carbonate and silicate terrains

A contribution to the chemical characterization of rivers in the Rio Negro Basin, Brazil

Rare Earth Elements as an Indicator to Origins of Skarn Deposits: Examples of the Kamioka Zn‐Pb and Yoshiwara‐Sannotake Cu(–Fe) Deposits in Japan

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