REE Patterns in Geochemistry

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rare-earth-elements REE chondrite-normalized Eu-anomaly

Core Idea

The rare earth elements (La through Lu, plus Y) form a coherent geochemical group with smoothly varying ionic radii, making their chondrite-normalized abundance patterns powerful diagnostic tools. Because all REE are trivalent (except Eu2+ and Ce4+ under specific conditions), their relative behavior during geological processes reflects systematic size-dependent partitioning rather than dramatic chemical differences. The slope of the REE pattern (LREE/HREE ratio) indicates the depth and degree of melting (garnet retains HREE). Anomalies at Eu (controlled by plagioclase fractionation in the crust) and Ce (controlled by redox in marine environments) provide additional process-specific information. REE patterns are among the most widely used geochemical fingerprints in igneous, sedimentary, and environmental geochemistry.

Explainer

The rare earth elements are the geochemist's most versatile pattern-recognition tool. Their coherent geochemical behavior -- all trivalent, similar bonding properties, smoothly decreasing ionic radius from La to Lu -- means that any deviation from a smooth chondrite-normalized pattern records a specific geological process.

Chondrite normalization removes the odd-even abundance variation (the Oddo-Harkins effect, where even-Z elements are more abundant) inherited from stellar nucleosynthesis. After normalization, any remaining pattern is geological. A flat pattern at 10x chondrite indicates a source with chondritic REE ratios. A steep LREE-enriched pattern indicates either a LREE-enriched source or a process that preferentially concentrated LREE. The slope of the pattern, quantified by La_N/Yb_N (where N = chondrite-normalized), ranges from ~1 (flat, like MORB) to >30 (steep, like kimberlites).

The two diagnostic anomalies -- Eu and Ce -- arise from unique redox chemistry. Europium can exist as Eu2+ in reducing conditions (silicate melts, lower crust). Eu2+ has the same charge and similar radius to Ca2+ and enters plagioclase readily. Plagioclase fractionation produces negative Eu anomalies in evolved magmas and complementary positive Eu anomalies in cumulate anorthosites. The magnitude of the Eu anomaly quantifies the role of plagioclase in the magmatic history. Cerium can be oxidized to Ce4+ in surface environments, making it insoluble and causing it to be removed from seawater onto oxide surfaces. Seawater has a pronounced negative Ce anomaly; marine precipitates inherit this signature.

In sedimentary geochemistry, REE patterns trace provenance. Sediments derived from felsic continental sources have negative Eu anomalies, LREE enrichment, and high total REE. Sediments from mafic sources have flatter patterns without Eu anomalies. Marine authigenic minerals (phosphorites, carbonates, iron formations) inherit the REE pattern of the seawater from which they precipitated, preserving a record of marine chemistry -- including Ce anomalies as a proxy for ocean oxygenation -- through geological time.

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