Sources, presence and potential effects of contaminants of emerging concern in the marine environments of the Great Barrier Reef and Torres Strait, Australia.

Current policy and management for marine water quality in the Great Barrier Reef (GBR) in north-eastern Australia primarily focusses on sediment, nutrients and pesticides derived from diffuse source pollution related to agricultural land uses. In addition, contaminants of emerging concern (CECs) are known to be present in the marine environments of the GBR and the adjacent Torres Strait (TS). Current and projected agricultural, urban and industrial developments are likely to increase the sources and diversity of CECs being released into these marine ecosystems. In this review, we evaluate the sources, presence and potential effects of six different categories of CECs known to be present, or likely to be present, in the GBR and TS marine ecosystems. Specifically, we summarize available monitoring, source and effect information for antifouling paints; coal dust and particles; heavy/trace metals and metalloids; marine debris and microplastics; pharmaceuticals and personal care products (PPCPs); and petroleum hydrocarbons. Our study highlights the lack of (available) monitoring data for most of these CECs, and recommends: (i) the inclusion of all relevant environmental data into integrated databases for building marine baselines for the GBR and TS regions, and (ii) the implementation of local, targeted monitoring programs informed by predictive methods for risk prioritization. Further, our spatial representation of the known and likely sources of these CECs will contribute to future ecological risk assessments of CECs to the GBR and TS marine environments, including risks relative to those identified for sediment, nutrients and pesticides.

Formation of Zn- and Fe-sulfides near hydrothermal vents at the Eastern Lau Spreading Center: implications for sulfide bioavailability to chemoautotrophs.

BACKGROUND: The speciation of dissolved sulfide in the water immediately surrounding deep-ocean hydrothermal vents is critical to chemoautotrophic organisms that are the primary producers of these ecosystems. The objective of this research was to identify the role of Zn and Fe for controlling the speciation of sulfide in the hydrothermal vent fields at the Eastern Lau Spreading Center (ELSC) in the southern Pacific Ocean. Compared to other well-studied hydrothermal systems in the Pacific, the ELSC is notable for unique ridge characteristics and gradients over short distances along the north-south ridge axis. RESULTS: In June 2005, diffuse-flow (< 50 degrees C) and high-temperature (> 250 degrees C) vent fluids were collected from four field sites along the ELSC ridge axis. Total and filtered Zn and Fe concentrations were quantified in the vent fluid samples using voltammetric and spectrometric analyses. The results indicated north-to-south variability in vent fluid composition. In the high temperature vent fluids, the ratio of total Fe to total Zn varied from 39 at Kilo Moana, the most northern site, to less than 7 at the other three sites. The concentrations of total Zn, Fe, and acid-volatile sulfide indicated that oversaturation and precipitation of sphalerite (ZnS(s)) and pyrite (FeS2(s)) were possible during cooling of the vent fluids as they mixed with the surrounding seawater. In contrast, most samples were undersaturated with respect to mackinawite (FeS(s)). The reactivity of Zn(II) in the filtered samples was tested by adding Cu(II) to the samples to induce metal-exchange reactions. In a portion of the samples, the concentration of labile Zn2+ increased after the addition of Cu(II), indicating the presence of strongly-bound Zn(II) species such as ZnS clusters and nanoparticles. CONCLUSION: Results of this study suggest that Zn is important to sulfide speciation at ELSC vent habitats, particularly at the southern sites where Zn concentrations increase relative to Fe. As the hydrothermal fluids mix with the ambient seawater, Zn-sulfide clusters and nanoparticles are likely preventing sulfide oxidation by O2 and reducing bioavailability of S(-II) to organisms.

Pseudopolarographic determination of Cd2+ complexation in freshwater.

Pseudopolarography was used to detect Cd2+ complexes in samples collected at several locations along the Potomac River in June and September, 2004. Irrespective of site and sampling time, no weak inorganic Cd2+ species were present. However, up to two stable Cd(2+)-organic complexes were detected at each site. These unknown Cd2+ complexes were characterized by their half-wave potential (E1/2). The E1/2 values indicated certain Cd2+ complexes were common at different sites during each sampling but different complexes were observed in June and September. A Cd2+ chelate scale, generated from model ligands, was used to estimate the thermodynamic stability constants (K(THERM)) of the unknown complexes, which ranged from log K(THERM) = 21.5-32.0. Pseudopolarography did not recover all Cd2+ in the samples. This was partly attributed to highly stable Cd-sulfide species; owing to the presence of acid volatile sulfide at concentrations greater than total dissolved Cd2+. These electrochemically inert species may be multinuclear Cd-sulfide clusters and/ or nanoparticles with K(THERM) values that exceed the detection window of pseudopolarography (log K(THERM) > 34.4).