Hg in the hydrothermal fluids and gases in Baia di Levante, Vulcano, Italy

Abstract

The importance of fluid and gaseous mercury (Hg) emissions from hydrothermal systems in the shallow, coastal ocean is poorly constrained. However, there are indicators that they could be a significant natural Hg source. We evaluated the hydrothermal Hg emissions around Vulcano Island, Aeolian Arc, Italy, which is host to a marine shallow-water hydrothermal system (MSWHS) in Baia di Levante. Fluids were collected with porewater probes, and gases were collected into Tedlar© bags. Total Hg (THg) concentrations in the hydrothermal fluids ranged from 2.9 to 2888 pM. The concentrations of volatile Hg were below 8 pM and trended positively with increasing temperature. Monomethyl Hg (MMHg) was not detected. Total Hg in the gases ranged from 0.03 to 1.82 μmol/m3.High concentrations of THg were associated with low Cl-concentrations, low pH-values, and high K/Cl and Mg/Cl ratios. Concentrations of THg in the hydrothermal fluids resulted from mixing between meteoric water, seawater, condensed fumarolic vapor, and a deep hydrothermal fluid. However, not all low-Cl fluids were high THg samples. Samples taken along the coast of the La Fossa crater contained substantially less THg (2.9 to 29.4 pM), despite similar hydrothermal indicators as those in the Baia di Levante samples. These data support subsurface circulation models, which discuss the downslope flow of condensed La Fossa crater gases to the coast. In the hydrothermally active area of Baia di Levante, concentrations of THg were elevated relative to background surface seawater, ranging from 40 to 5110 pM. In comparison, the remainder of the bay ranged from 0.8 to 2.4 pM.The flux of Hg to the atmosphere from surface waters was calculated through dissolved Hg concentrations. The flux at each sampled site ranged from 0 to 19.6 pmol/m2/hr. The highest flux rates were determined for those areas with visible hydrothermal activity, particularly those with high gaseous emission rates. Surface water concentrations declined rapidly away from point sources, indicating atmospheric emission, dilution through mixing, or scavenging and sedimentation. In hydrothermally active areas, Baia di Levante sediments contained THg concentrations of 2.42 nmol/g and 49.52 nmol/g, which were significantly above background (0.03 nmol/g).The largest gaseous point source, Bambino, released >2 L of gas per second. Although, Hg concentrations in the gas were low (113 to 122 nmol/m3) relative to other measured point sources near the beach (1768 to 1817 nmol/m3), due to the volume of discharge, surface water concentrations were elevated (131 pM).The Hg present in the hydrothermal system of Vulcano contributes Hg to the atmosphere and local seawater as a natural source.