Rare earth element behavior during groundwater–seawater mixing along the Kona Coast of Hawaii

Groundwater and seawater samples were collected from nearshore wells and offshore along the Kona Coast of the Big Island of Hawaii to investigate rare earth element (REE) behavior in local subterranean estuaries. Previously we saw that submarine groundwater discharge (SGD) is the predominant flux of terrestrial waters to the coastal ocean along the arid Kona Coast of Hawaii. Groundwater and seawater samples were filtered through 0.45 μm and 0.02 μm pore-size filters to evaluate the importance of colloidal and soluble (i.e., truly dissolved ionic species and/or low molecular weight [LMW] colloids) fractions of the REEs in the local subterranean estuaries. Mixing experiments using groundwater collected immediately down gradient from a wastewater treatment facility (WWTF) proximal to the Kaloko-Hanokohau National Historic Park, and more “pristine” groundwater from a well constructed in a lava tube at Kiholo Bay, were conducted with local seawater to study the effect of solution composition (i.e., pH, salinity) on the concentrations and fractionation behavior of the REEs as groundwater mixes with seawater in Kona Coast subterranean estuaries. The mixed waters were also filtered through 0.45 or 0.02 μm filters to ascertain the behavior of colloidal and soluble fractions of the REEs across the salinity gradient in each mixing experiment. Concentrations of the REEs were statistically identical (two-tailed Student t-test, 95% confidence) between the sequentially filtered sample aliquots, indicating that the REEs occur as dissolved ionic species and/or LMW colloids in Kona Coast groundwaters. The mixing experiments revealed that the REEs are released to solution from suspended particles or colloids when Kona Coast groundwater waters mix with local seawater. The order of release that accompanies increasing pH and salinity follows light REE (LREE) > middle REE (MREE) > heavy REE (HREE). Release of REEs in the mixing experiments is driven by decreases in the free metal ion activity in solution and the concomitant increase in the amount of each REE that occurs in solution as dicarbonato complexes [i.e., Ln(CO3)2-] as pH increases across the salinity gradient. Input-normalized REE patterns of Kona Coast groundwater and coastal seawater are nearly identical and relatively flat compared to North Pacific seawater, indicating that SGD is the chief source of these trace elements to the ocean along the Kona Coast. Additionally, REE concentrations of the coastal seawater are b