Relative macrofaunal biomass reduced under an enriched salmon farm, Pelorus Sound, Aotearoa-New Zealand.

We compared changes in the benthos associated with discharges from a salmon farm at a low-flow location in Pelorus Sound, Aotearoa-New Zealand to the Pearson and Rosenberg model (PRM). As predicted by PRM, benthic enrichment resulted in significant increases in abundance of small, opportunistic macrofauna beneath salmon farm cages. In contrast, at reference sites we found fewer but larger, rare species. When estimates for biomass were calculated from macrofaunal size-classes, reference sites averaged 4.86 times more biomass and 4.35 times greater diversity than farm sites - results also consistent with the PRM. Farm sites favoured deposit feeders at the expense of suspension feeders and grazers. We discuss the significance of large rare species that contributed most to reference biomass estimates that appear under threat from multiple anthropogenic stressors.

Rapid treatment of vessels fouled with an invasive polychaete, Sabella spallanzanii, using a floating dock and chlorine as a biocide.

Chlorine solution was added to the water encapsulated within a proprietary 'floating dock' to treat a vessel infested with the invasive polychaete Sabella spallanzanii. The chlorine was added as sodium dichloroisocyanurate ('dichlor') at an initial concentration of 200 mg l(-1) of free available chlorine (FAC). This concentration killed 99% of S. spallanzanii in their tubes during a 4-h exposure in laboratory tests (EC99 160 mg FAC l(-1)). The concentration of FAC in the floating dock declined to ~50 mg l(-1) after 4 h and < 10 mg l(-1) after 16 h. Residual FAC was neutralised with thiosulphate at completion of exposure. A sample of 30 S. spallanzanii individuals collected from the hull after treatment all showed morphological damage and 28 showed no response to touch. Re-examination of the hull after 6 d found no live worms or other fouling organisms. This method provides a cost-effective, rapid means of treating hull fouling.

Entrapped Sediments as a Source of Phosphorus in Epilithic Cyanobacterial Proliferations in Low Nutrient Rivers.

Proliferations of the benthic mat-forming cyanobacteria Phormidium have been reported in rivers worldwide. Phormidium commonly produces natural toxins which pose a health risk to animal and humans. Recent field studies in New Zealand identified that sites with Phormidium proliferations consistently have low concentrations of water column dissolved reactive phosphorus (DRP). Unlike other river periphyton, Phormidium mats are thick and cohesive, with water and fine sediment trapped in a mucilaginous matrix. We hypothesized that daytime photosynthetic activity would elevate pH inside the mats, and/or night time respiration would reduce dissolved oxygen. Either condition could be sufficient to facilitate desorption of phosphates from sediment incorporated within mats, thus allowing Phormidium to utilize it for growth. Using microelectrodes, optodes and pulse amplitude modulation fluorometry we demonstrated that photosynthetic activity results in elevated pH (>9) during daytime, and that night-time respiration causes oxygen depletion (<4 mg L-1) within mats. Water trapped within the mucilaginous Phormidium mat matrix had on average 320-fold higher DRP concentrations than bulk river water and this, together with elevated concentrations of elements, including iron, suggest phosphorus release from entrapped sediment. Sequential extraction of phosphorus from trapped sediment was used to investigate the role of sediment at sites on the Mangatainoka River (New Zealand) with and without Phormidium proliferations. Deposition of fine sediment (<63 µm) was significantly higher at the site with the most extensive proliferations and concentrations of biological available phosphorus were two- to four- fold higher. Collectively these results provide evidence that fine sediment can provide a source of phosphorus to support Phormidium growth and proliferation.

A source mixing model to apportion PAHs from coal tar and asphalt binders in street pavements and urban aquatic sediments.

Present-day and more than 30 years old road and footpath pavements from Auckland, New Zealand were analysed for PAHs to test the hypothesis that coal tar based pavement binders contribute to unusually high PAH concentrations in adjacent stream and estuarine sediments. Total PAH (∑(28)PAH) concentrations in the dichloromethane-soluble fraction ("binder"), comprising 5-10% of pavement mass, were as high as 200,000 mgkg(-1) (10,000 mgkg(-1) in binder+aggregate). Older and deeper pavement layers were strongly pyrogenic, whereas pavement layers from recently sealed roads had a more petrogenic composition and more than 1000 times lower ∑(28)PAH concentrations. Source identification analysis using three PAH isomer ratio pairs (benz(a)anthracene/(benz(a)anthracene+chrysene); benzo(a)pyrene/(benzo(a)pyrene+benzo(e)pyrene); and indeno(1,2,3-cd)pyrene/(indeno(1,2,3-cd)pyrene+benzo(g,h,i)perylene) revealed low PAH (bitumen) pavements to have consistently lower isomer ratios than high PAH (coal tar) samples. Moreover, pavement data for one isomer ratio (e.g. benzo(a)pyrene/(benzo(a)pyrene+benzo(e)pyrene) were highly correlated with those of another isomer ratio (e.g. benz(a)anthracene/(benz(a)anthracene+chrysene) and were bounded at their lower and higher extremes by the characteristics of pure bitumen and coal tar, respectively, suggesting that PAH composition of a given pavement sample could be accounted for by conservative mixing between coal tar and bitumen as source materials. A concentration-weighted mixing model, with coal tar and bitumen as source materials, explained more than 80% of the variance in isomer ratios and enveloped the entire PAH compositional and concentration range encountered. PAH composition and concentrations in adjacent stream sediments (> 15 mgkg(-1) dry weight) were consistent with diluted coal tar material as a principal PAH source. Due to the very high PAH concentrations of coal tar, a coal tar content of as little as 0.01% of total sediment mass can account for more than 90% of PAH concentrations in adjacent stream sediments.

Heavy metal stabilization in contaminated road-derived sediments.

There is increasing interest in the stabilization of heavy metals in road-derived sediments (RDS), to enable environmentally responsible reuse applications and circumvent the need for costly landfill disposal. To reduce the mobility of heavy metals (i.e. Cu, Pb and Zn) the effectiveness of amendments using phosphate, compost and fly ash addition were investigated using batch leaching experiments. In general, phosphate amendments of RDS were found to be ineffective at stabilizing heavy metals, despite being used successfully in soils. Phosphate amendment resulted in enhanced concentrations of dissolved organic carbon (DOC), which increased the solubilisation of heavy metals via complexation. Amendment with humified organic matter (compost) successfully stabilized Cu and Pb in high DOC leaching RDS with an optimum loading of 15-20% (w/w). Compost, however, was ineffective at stabilizing Zn. Increasing the pH by amending RDS/compost blends with 2.5-15% (w/w) coal fly ash resulted in the stabilization of Zn, Cu and Pb. However, above a pH of approximately 7.5 and 8 enhanced leaching of organic matter resulted in an increase in leached Cu and Pb, respectively. Accordingly, the optimum level of fly ash amendment for the RDS/compost blends was estimated to be ca. 10%. Boosted regression trees analysis (BRT) of the data revealed that DOC accounted for 56% and 65% of the Cu and Pb leaching, respectively, whereas pH only accounted for ca. 18% of Cu and Pb leaching. RDS sample characteristics (i.e. metal concentrations, size fractionation and organic matter content) were more important at reconciling the leaching concentrations of copper Cu (27%) than Pb (16%). The most important parameter explaining Zn leaching was pH. Overall, the choice of a suitable stabilization agent/s depends on the composition of RDS with respect to the amount of organic matter present, and the sorption chemistry of the heavy metal of interest.

Antifouling sesterterpenes from the New Zealand marine sponge Semitaspongia bactriana.

Three antifouling (AF) sesterterpenes have been isolated from the New Zealand marine sponge Semitaspongia bactriana with toxicity against the diatom Nitzschia closterium and bryozoan Bugula neritina. The three metabolites have been characterised by spectroscopic techniques as 7E,12E,20Z-variabilin (1), cavernosolide (2) and lintenolide A (3) (also called spongianolide C) and have low micromolar activity against our two test species. The gamma-hydroxybutenolide containing sesterterpenes (2 and 3) show the most promise, with relative stability and suitable lipophilicity for incorporation of either these metabolites, or synthetic analogues, as biocides to produce paints or plastics with AF properties.

Polymer building blocks: self-assembly of silver(I) cyclotriphosphazene cationic columns.

The multimodal ligand hexakis(2-pyridyloxy)cyclotriphosphazene (L) and its 4-methyl-2-pyridyloxy analogue (MeL) react with Ag(I) to afford {[AgL]+}infinity supramolecular cationic columns via self-assembly, with the anions occupying the intercolumnar channels. In contrast, the reaction of MeL with Cu(I) yields a dimetallic Cu(II) complex containing mu-OH and mu-4-methyl-2-pyridyloxylato bridges.

Copper(II) chloride complexes with multimodal ligands based on the cyclotriphosphazene platform.

The reaction of hexakis(2-pyridyloxy)cyclotriphosphazene (L) and hexakis(4-methyl-2-pyridyloxy)cyclotriphosphazene (MeL) with copper(ii) chloride afford the complexes [CuLCl(2)], [(CuCl(2))(2)(MeL)], [CuLCl]PF(6) and [Cu(MeL)Cl]PF(6). The single-crystal X-ray structure of [CuLCl(2)] shows the copper ion to be in a square based pyramidal distorted trigonal bipyramidal (SBPDTBP) environment (tau= 0.47) with L acting as a kappa(3)N donor, coordinating via the nitrogen atoms from two non-geminal pyridyloxy pendant arms, a nitrogen atom in the phosphazene ring and two chloride ions. In the dimetallic complex, [(CuCl(2))(2)(MeL)], the geometry about both (symmetry related) copper(ii) centres is also SBPDTBP (tau= 0.57) with a 'N(3)Cl(2)' donor set. In the monocation of [CuLCl]PF(6), L acts as a kappa(5)N donor, bonding to the copper(ii) centre through the nitrogen atoms of four pyridyloxy pendant arms, a phosphazene ring nitrogen atom and a chloride ion to give an elongated rhombic octahedral coordination sphere. The phosphazene ring atoms remain virtually coplanar in all three structures as a consequence of the phenoxy-hinge, which links the pyridine pendant donors to the cyclotriphosphazene platform, allowing the formation of six-membered chelate rings. The spectroscopic (mass spectral, EPR and electronic) and magnetic properties of the complexes are discussed. The EPR and variable temperature magnetic susceptibility results for the dicopper complex, [(CuCl(2))(2)(MeL)], point to a very weak electronic interaction between the metal atoms.

Inhomogeneous distribution of polycyclic aromatic hydrocarbons in different size and density fractions of contaminated sediment from Auckland Harbour, New Zealand: an opportunity for mitigation.

Polycyclic aromatic hydrocarbons (PAHs) in sediment from Auckland Harbour (New Zealand) are not distributed evenly throughout bulk sediment, but highly concentrated in coarser, low-density fractions. Concentrations of 24 PAHs, measured in sediment that was separated into six size fractions that were furthermore separated into two density sub-fractions by flotation in sodium-polytungstate solution (rho = 2.15 g cm(-3)), varied between 4-103 microg g(-1)dw among grain size fractions and 2-998 microg g(-1)dw for density sub-fractions. Highest PAH concentrations were measured in the low density, 125-250 microm fraction. All sediment fractions had a similar relative PAH composition, dominated by >3-ring PAHs, suggesting a common pyrogenic origin. Low density material had 10-200 times higher PAH concentrations and 10-100 times higher organic carbon (OC) content, yet differences in OC content only partially accounted for variations in PAH concentration. Low density particles contributed more than 75% of the Sigma PAH, while comprising only 3% of bulk sediment dry weight. This may have significant utility for contaminant mitigation efforts in Auckland Harbour.