Arsenic, barium, germanium, tin, dimethylsulfide and nutrient biogeochemistry in Charlotte Harbor, Florida, a phosphorus-enriched estuary

Concentrations of dissolved nutrients (NO 3, PO 4, Si), germanium species, arsenic species, tin, barium, dimethylsulfide and related parameters were measured along the salinity gradient in Charlotte Harbor. Phosphate enrichment from the phosphate industry on the Peace River promotes a productive diatom bloom near the river mouth where NO 3 and Si are completely consumed. Inorganic germanium is completely depleted in this bloom by uptake into biogenic opal. The Ge Si ratio taken up by diatoms is about 0·7 × 10 −6, the same as that provided by the river flux, confirming that siliceous organisms incorporate germanium as an accidental trace replacement for silica. Monomethylgermanium and dimethylgermanium concentrations are undetectable in the Peace River, and increase linearly with increasing salinity to the seawater end of the bay, suggesting that these organogermanium species behave conservatively in estuaries, and are neither produced nor consumed during estuarine biogenic opal formation or dissolution. Inorganic arsenic displays slight removal in the bloom. Monomethylarsenic is produced both in the bloom and in mid-estuary, while dimethylarsenic is conservative in the bloom but produced in mid-estuary. The total production of methylarsenicals within the bay approximately balances the removal of inorganic arsenic, suggesting that most biological arsenic uptake in the estuary is biomethylated and released to the water column. Dimethylsulfide increases with increasing salinity in the estuary and shows evidence of removal, probably both by degassing and by microbial consumption. An input of DMS is observed in the central estuary. The behavior of total dissolvable tin shows no biological activity in the bloom or in mid-estuary, but does display a low-salinity input signal that parallels dissolved organic material, perhaps suggesting an association between tin and DOM. Barium displays dramatic input behavior at mid-salinities, probably due to slow release from clays deposited in the harbor after catastrophic phosphate slime spills into the Peace River.