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The global distribution of dissolved cadmium (Cd) in the world’s oceans is generally well understood. However, information on seasonal variability of this and other trace metals in the open ocean is difficult to obtain and, therefore, our understanding is limited. Here, we present a 3-year time series of field measurements of dissolved and particulate Cd and phosphate (PO4) from a transect across the subtropical convergence, south-eastern New Zealand. In the final year of study, the bioactive trace metals (iron, Fe; zinc, Zn; cobalt, Co) and nutrients (nitrate, NO3; silicate, Si(OH)4) were also measured to identify their influence on Cd cycling in the region. Cadmium varied seasonally from 0.009 to 0.137nM in the sub-Antarctic surface waters (SASW). Zinc in SASW varied between 0.03 and 0.011nM, which is low enough to suggest Zn limitation year-round. The seasonal input of dissolved Fe may stimulate phytoplankton growth in summer where microplankton (especially diatoms) dominate the phytoplankton distribution. The Cd:PO4 ratio also varied strongly with season (0.015×10–3 to 0.05×10–3). This seasonal variation in the Cd:PO4 ratio is productivity driven as revealed in the characteristic trend in the Cd:PO4 ratio, particulate Cd and chlorophyll-a measurements. The high seasonal variability between Cd and PO4 complicates the application of the Cd proxy for the reconstruction of historical PO4 concentrations in SASW.

Stable isotope analyses of fatty acids in environmental waters provides important information as to their source(s). Analysis is often confounded due to low concentrations of fatty acids and/or a complex sample matrix requiring separation of the target analyte. The purpose of this study was to validate a method to extract fatty acids from natural waters using solid phase extraction (SPE) before compound specific isotope analysis (CSIA). Three SPE cartridges and multiple eluting solvents were tested to determine the efficiency, isotopic fractionation, and reproducibility of each extraction technique. Our results indicated that surface-modified styrene divinylbenzene cartridges, when eluted with methanol, caused negligible fractionation of the hydrogen isotopes and minimal fractionation of the carbon isotopes, but that isotopic fractionation occurred when compounds were only partially eluted from SPE cartridges. Compounds were also extracted from landfill leachate using both SPE and liquid–liquid extraction (LLE). The hydrogen isotope composition (δ2H) of compounds extracted from water using either method were within experimental precision and the carbon isotope composition (δ13C) of all but one fatty acid were within experimental precision. Therefore, these experiments prove the aforementioned SPE methods to be a convenient and precise method to extract fatty acids from natural waters before CSIA.

The isotope enrichment of nitrate due to uptake by phytoplankton has previously been measured in a variety of ways, both in the field over time or space, and in vitro. This study provided an unusual opportunity to measure the isotopic fractionation of nitrate over an extended spatial scale. Results are presented from the Otago Continental shelf, New Zealand. δ15N-PON and [NO3–] was correlated using Rayleigh distillation equations to obtain isotope enrichment factors for the uptake of nitrate. The decrease in nitrate concentration during advection landward across the shelf was consistent with removal by phytoplankton, with an average enrichment factor (ϵ) of 8.2 per mil, as calculated using the Rayleigh accumulated product equation. The spatial evolution of δ15N-PON and [NO3–] across the Otago continental shelf led to the conclusion that cross-shelf advection is the predominant process bringing nutrients to the shelf. No Rayleigh distillation-type process is observable from monthly observations. However, in subantarctic surface water (SASW), a seasonal variation in δ15N-PON was seen that was in the opposite phase to that expected for isotopic enrichment of the nutrient pool. In SASW, δ15N-PON peaked at 4‰ in winter months and fell to –2‰ in the spring and summer.

Methamphetamine HCl was synthesized using three variations of the hydriodic acid/red phosphorus (HI/Pred) synthetic route. A Plackett-Burman experimental design was used to determine how reaction parameters affected the isotopic composition of the product. Isotope ratio mass spectrometry results showed only the source of precursor 13C was significant in determining product δ 13C; the manufacturer, reaction temperature, time, scale, and source of HI were not significant. The precursor was also the main determinant of product δ 2H, with smaller contributions from the HI source for one method. From precursor to product, large δ 2H depletion occurred for most samples. Deuterium nuclear magnetic resonance spectroscopy (2H NMR) was used to investigate the specific site of this. Significant fraction of deuterium was observed only at the benzylic position, the site of hydrogen addition during synthesis. Methamphetamine synthesized from ephedrine was shown to be depleted in this position.

Iron (Fe) is a critical nutrient in marine systems and the organic complexation of Fe is a central factor of the marine biogeochemistry of Fe. In the present study, total dissolved Fe and its organic speciation were measured in filtered seawater samples (99.9%) by natural organic ligands, which were found to occur in excess of the dissolved Fe concentration at 1.29 ± 0.33 nm (equivalent to an excess over Fe of ~1.0 nm), and with a complex stability of log⁡ K ′ FeL,F e 3+ --> K′FeL,Fe3+ = 22.67 ± 0.22. The total ligand concentrations were consistently higher (~0.5 nm) in the ST and STC waters than in the SA waters. Our Fe data imply that the regional currents may be an important vehicle for transporting the elevated Fe across the front.

Blue Lake is an abandoned, water-filled alluvial gold-mine pit in Central Otago, New Zealand. Alluvial gold mining is generally considered to be chemically benign, unless mercury is added to assist gold separation. The major element, trace metal and isotopic composition of the pit lake was compared to nearby, unaffected streams. Blue Lake was found to be enriched in the major cations, with levels that were 2–5 times higher than in unaffected streams. Furthermore, Cu, Ni and Zn concentrations exceeded 10 nmol L–1 in Blue Lake; these levels were 2–30 times higher than those in nearby, unaffected streams. Processes affecting the lake’s characteristics include evaporative concentration, and the oxidation and dissolution of locally derived sulfide and sulfate minerals. Localised acidification in surface and ground waters around the lake leads to the mobilisation of Zn and Ni, resulting in lake waters being strongly enriched in these trace metals (concentrations greater than 40 nmol L–1), whereas surrounding stream waters have much lower Ni and Zn concentrations (less than 5 nmol L–1). Ongoing evaporative concentration, and the continuing mobilisation of trace metals, implies that metal enrichment in lake waters will continue to occur. The present study demonstrated that the ‘benign’ process of alluvial gold mining can have significant chemical consequences in resulting water bodies.