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2015
Bundy, RM, Abdulla HAN, Hatcher PG, Biller DV, Buck KN, Barbeau KA.  2015.  Iron-binding ligands and humic substances in the San Francisco Bay estuary and estuarine-influenced shelf regions of coastal California. Marine Chemistry. 173:183-194.   10.1016/j.marchem.2014.11.005   AbstractWebsite

Dissolved iron (dFe) and organic dFe-binding ligands were determined in San Francisco Bay, California by competitive ligand exchange adsorptive cathodic stripping voltammetry (CLE-ACSV) along a salinity gradient from the freshwater endmember of the Sacramento River (salinity <2) to the mouth of the estuary (salinity >26). A range of dFe-binding ligand classes was simultaneously determined using multiple analytical window analysis, involving titrations with multiple concentrations of the added ligand,salicylaldoxime. The highest dFe and ligand concentrations were determined in the low salinity end of the estuary, with dFe equal to 131.5 nmol L-1 and strong ligand (log K-Fel, Fe'(cond) >= 12.0) concentrations equal to 139.5 nmol L-1. The weakest ligands (log K-Fel, Fe'(cond) < 10.0) were always in excess of dFe in low salinity waters, but were rapidly flocculated within the estuary and were not detected at salinities greater than 7. The strongest ligands (log K-Fel, Fe'(cond) > 11.0) were tightly coupled to dFe throughout the estuary, with average excess ligand concentrations ([L]-[dFe]) equal to 0.5 nmol L-1. Humic-like substances analyzed via both CLE-ACSV and proton nuclear magnetic resonance in several samples were found to be a significant portion of the dFe-binding ligand pool in San Francisco Bay, with concentrations ranging from 559.5 mu g L-1 to 67.5 mu g L-1 in the lowest and highest salinity samples, respectively. DFe-binding ligands and humic-like substances were also found in benthic boundary layer samples taken from the shelf near the mouths of San Francisco Bay and Eel River, suggesting estuaries are an important source of dFe-binding ligands to California coastal shelf waters. (C) 2014 Elsevier B.V. All rights reserved.

2014
Earley, PJ, Swope BL, Barbeau K, Bundy R, McDonald JA, Rivera-Duarte I.  2014.  Life cycle contributions of copper from vessel painting and maintenance activities. Biofouling. 30:51-68.   10.1080/08927014.2013.841891   AbstractWebsite

Copper-based epoxy and ablative antifouling painted panels were exposed in natural seawater to evaluate environmental loading parameters. In situ loading factors including initial exposure, passive leaching, and surface refreshment were measured utilizing two protocols developed by the US Navy: the dome method and the in-water hull cleaning sampling method. Cleaning techniques investigated included a soft-pile carpet and a medium duty 3M((TM)) pad for fouling removal. Results show that the passive leach rates of copper peaked three days after both initial deployment and cleaning events (CEs), followed by a rapid decrease over about 15days and a slow approach to asymptotic levels on approximately day 30. Additionally, copper was more bioavailable during a CE in comparison to the passive leaching that immediately followed. A paint life cycle model quantifying annual copper loading estimates for each paint and cleaning method based on a three-year cycle of painting, episodic cleaning, and passive leaching is presented.

2012
Buck, KN, Moffett J, Barbeau KA, Bundy RM, Kondo Y, Wu JF.  2012.  The organic complexation of iron and copper: an intercomparison of competitive ligand exchange-adsorptive cathodic stripping voltammetry (CLE-ACSV) techniques. Limnology and Oceanography-Methods. 10:496-515.   10.4319/lom.2012.10.496   AbstractWebsite

Characterization of the speciation of iron and copper is an important objective of the GEOTRACES Science Plan. To incorporate speciation measurements into such a multinational program, standard practices must be adopted that allow data from multiple labs to be synthesized. Competitive ligand exchange-adsorptive cathodic stripping voltammetry (CLE-ACSV) is the primary technique employed for measuring metal-binding ligands and determining metal speciation in seawater. The determination of concentrations and conditional stability constants of metal-binding ligands is particularly challenging, as results can be influenced both by experimental conditions and interpretation of titration data. Here, we report an investigation between four laboratories to study the speciation of iron and copper using CLE-ACSV. Samples were collected on the GEOTRACES II intercomparison cruise in the North Pacific Ocean in May 2009 at 30 degrees N, 140 degrees W. This intercomparison was carried out shipboard and included an assessment of the viability of sample preservation by freezing. Results showed that consensus values could be obtained between different labs, but that some existing practices were problematic and require further attention in future work. A series of recommendations emerged from this study that will be useful in implementing multi-investigator programs like GEOTRACES.

2007
Hopkinson, BM, Barbeau KA.  2007.  Organic and redox speciation of iron in the eastern tropical North Pacific suboxic zone. Marine Chemistry. 106:2-17.   10.1016/j.marchem.2006.02.008   AbstractWebsite

The organic and redox speciation of iron was examined in the strongly layered upper water column of the eastern tropical North Pacific, including oxic and sub oxic waters, in a region 100- 1300 km offshore. Suboxic conditions ([O-2] < 5 mu M) were found to affect the organic speciation of iron, and reduced dissolved iron, Fc(II), was present in the suboxic zone, but conditions were not sufficiently reducing to convert all iron to Fe(II). Dissolved iron concentrations in the suboxic zone were similar to concentrations found in oxic regions. Using a competitive ligand exchange-adsorptive cathodic stripping voltammetry (CLE-ACSV) method, natural ligands were found to have distinct characteristics in the oxic and suboxic waters with stronger ligands found in the suboxic zone. It is unusual to find stronger ligands below the euphotic zone, but their strength, logK(Fe'L) = 12.1-12.8, is within the range determined for surface ligands in other regions. These strong ligands may be the result of the unique chemistry of the suboxic zone stabilizing reduced or labile compounds, or they may be actively produced by microbes to enhance iron uptake. No onshore-offshore trends in ligand strength or concentration were detected suggesting the ligands may result from the inherent chemistry of the suboxic zone or production from denitrifiers, rather than the resident suboxic zone population of Prochlorococcus which were more abundant nearshore. A luminol-chemiluminescence based flow injection analysis (FIA) technique capable of detecting picomolar concentrations of Fe(II) was used to assess the redox state of iron in the suboxic zone and overlying oxic waters at a station 1300 km offshore. An elevated signal equivalent to 0.12-0.15 nM Fe(II), 21-24% of dissolved iron, was found only in the suboxic waters. Oxidation kinetics suggest that this Fe(II) is most likely produced by an in-situ process, as opposed to being transported from shelf sediment. The luminol-chemiluminescence Fe(II) method was systematically tested for inferences from reduced species potentially present in the suboxic zone to validate our Fe(II) results. Several species, V(IV) and V(111), produced significant signals, but considerations of the reducing state of the suboxic zone make it unlikely that reduced V is present. With additional information on the identity of the suboxic zone species provided by analysis of signal decay rate, it was determined that Fe(II) was the most reasonable source of the signal, and at minimum the chemiluminescence data allows us to set limits on the Fe(II) concentration in the offshore suboxic water column. (C) 2006 Elsevier B.V. All rights reserved.

1994
Barbeau, K, Wollast R.  1994.  Microautoradiography (with Combined Liquid Scintillation) Applied to the Study of Trace-Metal Uptake by Suspended Particles - Initial Results Using NI-63 as a Tracer. Limnology and Oceanography. 39:1211-1222. AbstractWebsite

We report the development of a microautoradiographic method for the study of trace metal-particle interactions in natural waters. This technique, in combination with conventional liquid scintillation counting methods, was applied to surface water samples from the Belgian coastal zone and Scheldt estuary. Ni-63 was used as the metallic radio-tracer. Ni partitioning in our experimental system was shown to be a primarily abiotic process, driven by passive sorption reactions and limited in extent on a 24-h time scale by the slow reaction kinetics of Ni. Small particles (< 1 mum) were important as sorption sites, while large particles exhibited variable and particle-specific scavenging potential.