Distribution, speciation and bioavailability of arsenic in a shallow-water submarine hydrothermal system, Tutum Bay, Ambitle Island, PNG

Abstract

Shallow-water hydrothermal vent systems can introduce large amounts of potentially toxic elements, such as arsenic (As), into coastal marine environments. The first step in understanding and describing the potential impact of these elements throughout hydrothermally influenced coastal ecosystems is to determine the element's distribution and speciation, which in turn influences the availability of the toxin for biological uptake. Shallow submarine hot springs near Ambitle Island, Papua New Guinea, are discharging as much as 1.5 kg per day of arsenic directly into a coral-reef ecosystem. We have investigated the bioavailability of the As throughout Tutum Bay by studying vent fluid, seawater, pore water, precipitates, and sediments. In addition to measuring As abundance, As speciation (As(III), As(V), and the methylated species DMA and MMA) was determined in various waters. The As concentration for discrete mineral phases in vent precipitates and sediments was determined by sequentially extracting arsenic from the easily extractable, carbonate, Fe-oxyhydroxide or hydrous ferric oxide (HFO), and residual fractions, each of which have a different bioavailability. Diffuse venting seems to play a critical role on the distribution of As throughout Tutum Bay surface sediments, which have a mean As concentration of 527 ppm while excluding the vent precipitates (range = 1483 to 52 ppm). Up to 54 ppm As were extracted from the easily extractable fraction of surface sediments (mean = 19.7 ppm), using a K 2HPO 4/KH 2PO 4 buffer at pH = 7.2. Arsenic from this fraction is considered to be the most available for biological processes, and therefore the most dangerous for biota. However, sequential extraction shows that 98.6% of the As in vent precipitates, and a mean of 93.3% in surface sediments (range = 88.2% to 96.3%), is coprecipitated with the hydrous ferric oxide (HFO) fraction. Thus, the bulk of the As being discharged into Tutum Bay is scavenged by the HFO, and should remain stable unless the physicochemical conditions surrounding the oxides change. In surface seawaters of Tutum bay, we found as much as four times the average seawater concentration of As (8.4 μg/L compared to ∼2 μg/L). The abundance of As in seawater just above the sediment/water interface is near normal, although As(III) in both surface and bottom seawater throughout Tutum Bay is substantially enriched compared to average seawater. Hydrothermal venting therefore provides bioavailable As by two major pathways throughout Tutum Bay: 1) easily-exchangeable As from hydrothermally influenced sediments to as far away as 200 m from focused venting, and 2) in surface seawaters, which may allow for biological uptake by phytoplankton and transfer up the food web.