Estuarine benthic habitats provide an important ecosystem service regulating the nitrogen cycle.

Globally, a key ecosystem service provided by sedimentary estuarine habitats is the regulation of nutrient cycles. The nitrogen (N) cycle is driven by complex biogeochemical transformations within these sediments-including nitrogen fixation, denitrification, assimilation and anaerobic ammonia oxidation-mediated by microorganisms. Evaluating ecosystem processes and their functional value is a knowledge gap for the wet-dry tropics and even more limited for macrotidal estuaries. The capacity of these important environments to withstand and assimilate increasing nitrogenous loads as a consequence of accelerating development pressures in tropical Australia is largely unknown. Because of the critical role nitrogen cycling plays in estuarine ecosystems, identifying important habitats that underpin N cycling, particularly denitrification known to mitigate anthropogenic N inputs, is important. Detailed benthic habitat mapping of the Darwin-Bynoe region of northern Australia has provided a rare opportunity to demarcate its key habitats, such as intertidal mudflats, seagrass, mangroves, reef and saltmarsh. Combined with new measurements of benthic nitrogen fluxes, it has been possible for the first time to map these processes and develop a simple integrated functional value for N cycling across key benthic habitats of a tropical macrotidal estuary. Maps generated in this process have provided broadscale identification of the functional importance of habitats with relevance to N removal processes. The role of intertidal sediments in denitrification has been highlighted. Furthermore, the study emphasises connectivity across benthic seascapes, where multiple services are likely to interact, in supporting overall function and ecosystem health. The distillation of composite processes in this mapping format allows resource managers and scientists to communicate outputs visually with a simple classification scheme which could be superimposed with additional data to support environmental assessment and management.

Influence of life history variation and habitat on mercury bioaccumulation in a high-order predatory fish in tropical Australia.

Mercury distribution and bioaccumulation in aquatic ecosystems of tropical Australia is poorly characterised. Barramundi (Lates calcarifer), a widespread high-order predator in both fresh and coastal marine waters of the region, fulfils requirements for a bio-indicator of mercury contamination. In a study of the Mary River system of the Northern Territory, total mercury in the muscle tissue of 300 specimens gathered over four years (2013-2017, across both wet and dry seasons) was determined by direct combustion-atomic absorption spectrometry. Source of nutrition and trophic position of barramundi in the food web was also estimated via carbon and nitrogen isotopes (δ13C and δ15N), respectively, in tissue by stable isotope mass spectrometry, and determination of strontium isotopes (87Sr/86Sr) in otoliths by laser ablation-ICPMS differentiated between freshwater and saltwater residence. Results showed that fish moving into freshwater floodplain wetlands concentrated mercury in muscle tissue at approximately twice the level of those that remained in saline habitats. Resolving life histories through otolith analyses demonstrated diversity in mercury bioaccumulation for individual fish of the same migratory contingent on the floodplains. Although trophic level (δ15N), capture location, source of nutrition (δ13C), and age or size partly predicted mercury concentrations in barramundi, our results suggest that individual variability in diets, migration patterns and potentially metabolism are also influential. Using a migratory fish as a bio-indicator, and tracking its life history and use of resources, proved valuable as a tool to discern hot spots in a coastal waterway for a contaminant, such as mercury.

The emergence of marine recreational drone fishing: Regional trends and emerging concerns.

Online evidence suggests that there has been an increase in interest of using unmanned aerial vehicles or drones during land-based marine recreational fishing. In the absence of reliable monitoring programs, this study used unconventional publicly available online monitoring methodologies to estimate the growing interest, global extent, catch composition and governance of this practice. Results indicated a 357% spike in interest during 2016 primarily in New Zealand, South Africa and Australia. From an ecological perspective, many species targeted by drone fishers are vulnerable to overexploitation, while released fishes may experience heightened stress and mortality. From a social perspective, the ethics of drone fishing are being increasingly questioned by many recreational anglers and we forecast the potential for increased conflict with other beach users. In terms of governance, no resource use legislation specifically directed at recreational drone fishing was found. These findings suggest that drone fishing warrants prioritised research and management consideration.

An ICP-MS procedure to determine Cd, Co, Cu, Ni, Pb and Zn in oceanic waters using in-line flow-injection with solid-phase extraction for preconcentration.

An automated procedure including both in-line preconcentration and multi-element determination by an inductively coupled plasma mass spectrometer (ICP-MS) has been developed for the determination of Cd, Co, Cu, Ni, Pb and Zn in open-ocean samples. The method relies on flow injection of the sample through a minicolumn of chelating (iminodiacetate) sorbent to preconcentrate the trace metals, while simultaneously eliminating the major cations and anions of seawater. The effectiveness of this step is tested and reliability in results are secured with a rigorous process of quality assurance comprising 36 calibration and reference samples in a run for analysis of 24 oceanic seawaters in a 6-h program. The in-line configuration and procedures presented minimise analyst operations and exposure to contamination. Seawater samples are used for calibration providing a true matrix match. The continuous automated pH measurement registers that chelation occurs within a selected narrow pH range and monitors the consistency of the entire analytical sequence. The eluent (0.8M HNO3) is sufficiently strong to elute the six metals in 39 s at a flow rate of 2.0 mL/min, while being compatible for prolonged use with the mass spectrometer. Throughput is one sample of 7 mL every 6 min. Detection limits were Co 3.2 pM, Ni 23 pM, Cu 46 pM, Zn 71 pM, Cd 2.7 pM and Pb 1.5 pM with coefficients of variation ranging from 3.4% to 8.6% (n=14) and linearity of calibration established beyond the observed concentration range of each trace metal in ocean waters. Recoveries were Co 96.7%, Ni 102%, Cu 102%, Zn 98.1%, Cd 92.2% and Pb 97.6%. The method has been used to analyse ~800 samples from three voyages in the Southern Ocean and Tasman Sea. It has the potential to be extended to other trace elements in ocean waters.

Exploring the Link between Micronutrients and Phytoplankton in the Southern Ocean during the 2007 Austral Summer.

Bottle assays and large-scale fertilization experiments have demonstrated that, in the Southern Ocean, iron often controls the biomass and the biodiversity of primary producers. To grow, phytoplankton need numerous other trace metals (micronutrients) required for the activity of key enzymes and other intracellular functions. However, little is known of the potential these other trace elements have to limit the growth of phytoplankton in the Southern Ocean. This study, investigates whether micronutrients other than iron (Zn, Co, Cu, Cd, Ni) need to be considered as parameters for controlling the phytoplankton growth from the Australian Subantarctic to the Polar Frontal Zones during the austral summer 2007. Analysis of nutrient disappearance ratios, suggested differential zones in phytoplankton growth control in the study region with a most intense phytoplankton growth limitation between 49 and 50°S. Comparison of micronutrient disappearance ratios, metal distribution, and biomarker pigments used to identify dominating phytoplankton groups, demonstrated that a complex interaction between Fe, Zn, and Co might exist in the study region. Although iron remains the pivotal micronutrient for phytoplankton growth and community structure, Zn and Co are also important for the nutrition and the growth of most of the dominating phytoplankton groups in the Subantarctic Zone region. Understanding of the parameters controlling phytoplankton is paramount, as it affects the functioning of the Southern Ocean, its marine resources and ultimately the global carbon cycle.

PHYTOPLANKTON SELENIUM REQUIREMENTS: THE CASE FOR SPECIES ISOLATED FROM TEMPERATE AND POLAR REGIONS OF THE SOUTHERN HEMISPHERE(1).

A series of laboratory culture experiments was used to investigate the effect of selenium (Se, 0-10 nM) on the growth, cellular volume, photophysiology, and pigments of two temperate and four polar oceanic phytoplankton species [coccolithophore Emiliania huxleyi (Lohmann) W. W. Hay et H. P. Mohler, cyanobacterium Synechococcus sp., prymnesiophyte Phaeocystis sp., and three diatoms-Fragilariopsis cylindrus (Grunow) Kriegar, Chaetoceros sp., and Thalassiosira antarctica G. Karst.]. Only Synechoccocus sp. and Phaeocystis sp. did not show any requirement for Se. Under Se-deficient conditions, the growth rate of E. huxleyi was decreased by 1.6-fold, whereas cellular volume was increased by 1.9-fold. Se limitation also decreased chl a (2.5-fold), maximum relative electron transport rate (1.9-fold), and saturating light intensity (2.8-fold), suggesting that Se plays a role in photosynthesis or high-light acclimation. Pigment analysis for Antarctic taxa provided an interesting counterpoint to the physiology of E. huxleyi. For all Se-dependent Antarctic diatoms, Se limitation decreased growth rate and chl a content, whereas cellular volume was not affected. Pigment analysis revealed that other pigments were affected under Se deficiency. Photoprotective pigments increased by 1.4-fold, while diadinoxanthin:diatoxanthin ratios decreased by 1.5- to 4.9-fold under Se limitation, supporting a role for Se in photoprotection. Our results demonstrate an Se growth requirement for polar diatoms and indicate that Se could play a role in the biogeochemical cycles of other nutrients, such as silicic acid in the Southern Ocean. Se measurements made during the austral summer in the Southern Ocean and Se biological requirement were used to discuss possible Se limitation in phytoplankton from contrasting oceanographic regions.

Saccharides enhance iron bioavailability to Southern Ocean phytoplankton.

Iron limits primary productivity in vast regions of the ocean. Given that marine phytoplankton contribute up to 40% of global biological carbon fixation, it is important to understand what parameters control the availability of iron (iron bioavailability) to these organisms. Most studies on iron bioavailability have focused on the role of siderophores; however, eukaryotic phytoplankton do not produce or release siderophores. Here, we report on the pivotal role of saccharides--which may act like an organic ligand--in enhancing iron bioavailability to a Southern Ocean cultured diatom, a prymnesiophyte, as well as to natural populations of eukaryotic phytoplankton. Addition of a monosaccharide (>2 nM of glucuronic acid, GLU) to natural planktonic assemblages from both the polar front and subantarctic zones resulted in an increase in iron bioavailability for eukaryotic phytoplankton, relative to bacterioplankton. The enhanced iron bioavailability observed for several groups of eukaryotic phytoplankton (i.e., cultured and natural populations) using three saccharides, suggests it is a common phenomenon. Increased iron bioavailability resulted from the combination of saccharides forming highly bioavailable organic associations with iron and increasing iron solubility, mainly as colloidal iron. As saccharides are ubiquitous, present at nanomolar to micromolar concentrations, and produced by biota in surface waters, they also satisfy the prerequisites to be important constituents of the poorly defined "ligand soup," known to weakly bind iron. Our findings point to an additional type of organic ligand, controlling iron bioavailability to eukaryotic phytoplankton--a key unknown in iron biogeochemistry.

Mercury in 16 demersal sharks from southeast Australia: Biotic and abiotic sources of variation and consumer health implications.

Total mercury (THg) and monomethylmercury (MMHg) concentrations were determined in the tissues of demersal shark (Order Squaliformes and the Families: Scyliorhinidae, Hexanchidae) and chimaera species (Families: Chimaeridae and Rhinochimaeridae) from continental shelf and slope waters off southeast Australia, including embryos, juveniles and adults. The distribution of THg in various tissues (muscle, liver, kidney and skin), examined in ten species, shows higher levels in the muscle tissue (1.49+/-0.47mgkg(-1), ww), which accounted for between 59% and 82% of the total body burden of mercury and in the kidney (0.93+/-0.14mgkg(-1), ww) and liver (0.61+/-0.25mgkg(-1), ww) with lower levels observed in the skin (0.12+/-0.06mgkg(-1), ww). Additional THg determinations were performed in the muscle tissue of five other species allowing geographical and inter-specific comparisons. Speciation analysis demonstrated that more than 90% mercury was bound in muscle tissue as MMHg with higher percentages (>95%) observed in sharks species occupying deeper environments. Species differences were observed. Highest THg levels in the muscle tissue (up to 6.64mgkg(-1) wet weight, ww) were recorded in Proscymnodon plunketi and Centrophorus zeehaani (mean values; 4.47+/-1.20 and 3.52+/-0.07mgkg(-1), ww, respectively). Consistent with the ongoing paradigm on mercury bioaccumulation, we systematically observed THg concentrations increasing with animal size from the embryos to the larger sharks. Embryos of Etmopterus baxteri and Centroselachus crepidater had average levels 0.28 and 0.06mgkg(-1) (ww), while adult specimens reached 3.3 and 2.3mgkg(-1) (ww), respectively. THg concentrations in Australian sharks were compared with the same genus collected in other world regions. Levels were closer to data reported for East Atlantic than for the epicontinental Mediterranean margins. At a smaller geographical scale, the habitat effect on mercury concentration in sharks seems less clear. Squalid sharks occupying shelf waters showed higher mean mercury levels relative to their size (body weight, bw) than mid-slope species (0.4-6.7mgkg(-1) bw and 0.3-2.2mgkg(-1) bw, respectively). However, local regional differences (East and South Tasmania vs. Victoria) in Hg levels were not detected for the majority of taxa examined. All species, with the exception of Figaro boardmani showed values greater than 0.5mgkg(-1) (ww) and all but four were above many international regulatory thresholds (1.0mgkg(-1), ww).

Determination of aluminium in natural water samples.

The atmospheric deposition of terrestrial dust into the ocean is an important factor in controlling Earth's climate. Aluminium can be used as a tracer for the magnitude and location of dust transported from the land to surface ocean. The element is ideal for this purpose since its primary input is via aeolian dust deposition and it has a short surface water residence time. The accurate determination of dissolved aluminium in seawater is difficult due to the complexity of the matrix and the trace (nanomolar) concentrations at which the metal exists. This paper presents a critical review of the different sampling and analytical methods for the determination of the concentration of aluminium in natural waters, with particular focus on techniques successfully applied to shipboard analysis of seawater.

Flow-injection analysis with fluorescence detection for the determination of trace levels of ammonium in seawater.

A method using flow-injection, gas-diffusion, derivatisation and then fluorescent detection has been established for ammonium ion determination in seawater. The fluorescent derivative formed by reacting ortho-phthaldialdehyde (OPA) and sulfite with ammonia gives high sensitivity while removing potential interferences. This is required to measure the low concentrations of ammonium often seen in the open ocean. The experimental conditions (flow-rate, reagent concentrations, membrane configurations, etc.) were manipulated to improve performance. For a sample throughput of 30 samples h(-1), the limit of detection was 7 nM, the coefficient of variation was 5.7% at 800 nM, and the calibration curve was linear to at least 4 micromol L(-1). Interferences were minimised by a gaseous diffusion step. Volatile small molecular-weight amines as interferents were discriminated against by this method. They neither passed through the membrane as efficiently as ammonia, nor reacted as readily with OPA when sulfite was the reductant. Contamination by ammonia from laboratory and shipboard sources complicates application of the method to natural waters, especially measurement of low concentrations (<100 nM) in open-ocean waters. Steps to overcome contamination are described in detail. Some results are presented for ammonium determination in Southern Ocean and Huon Estuary (Tasmania) waters.

A compact flow injection analysis system for surface mapping of phosphate in marine waters.

The design, construction and validation of a compact, portable flow injection analysis (FIA) instrument for underway analysis of phosphate in marine waters is described. This portable system employs gas pressure for reagent propulsion and computer controlled miniature solenoid valves for precise injection of multiple reagents into a flowing stream of filtered sample. A multi-reflection flow cell with a solid state LED photometer is used to detect filterable reactive phosphate (0.2 mum) as phosphomolybdenum blue. All the components are computer controlled using software developed using the Labviewtrade mark graphical programming language. The system has the capacity for sample throughput of up to 380 phosphate analyses per hour, but in the mode described here was operated at 225 analyses per hour. Under these conditions, the system exhibited a detection limit of 0.15 muM, reproducibility of 1.95 % RSD (n=9) and a linear response (r(2)=0.9992) when calibrated in the field with standards in the range 0.81-3.23 muM. The system was evaluated for the mapping of phosphate concentrations in Port Phillip Bay, south eastern Australia, and during the course of a 150 km cruise, 542 analyses were performed automatically. In general, good agreement was observed between analyses obtained using the portable FIA system and those obtained from manual sampling and laboratory analysis.