Controls on species distribution and biogeochemical cycling in nitrate-contaminated groundwater and surface water, southeastern Australia.

A detailed study of groundwater and surface water nitrate over four seasons across an area of varied landuse provided insights into the mechanisms that underlie accumulation and transport of nitrate. High nitrate concentrations found in a significant percentage of surface water and shallow groundwater samples are due to anthropogenic contamination. Statistics (PCA, ANOVA, parsimonious model and general linear regression) were used to explore the relationship between NO3- and land use, and confirmed that areas of high NO3- concentration are associated with dairy pasture and horticulture. Seasonally, NO3- levels are greater during winter, the wettest part of the year. Values of δ15N showed that most nitrate is sourced from livestock waste, with a smaller contribution from synthetic fertilizer. Direct wash-off of animal waste from dairy farms results in higher NO3- concentrations in surface water than in groundwater. Denitrification is an important NO3- attenuation mechanism which reduces NO3- to NH4, as demonstrated by the PCA analysis, which showed positive correlation of NO3- concentrations with dissolved oxygen and negative correlations with NH4+, Fe2+and Mn2+; the latter two species may act as the electron donors necessary for reduction of NO3-. The often high NO3- concentrations in shallow groundwater are decreased by denitrification, which can occur at relatively shallow depths (<3 m). The relatively small NO3- concentrations in deeper groundwater are due partly to denitrification, but more to originally lower NO3- concentrations, as the age of deeper groundwater shows that it was recharged before agriculture was established in the study area. Overall, the study demonstrates the usefulness of hydrogeochemical characterisation and multivariate statistics in the evaluation of impacts of agricultural land-use on regional N cycling. In particular, the results show that efforts to mitigate NO3- pollution from farms should concentrate more on wash-off of animal waste than the contribution of nitrogenous synthetic fertilizer.

Physicochemical properties and trace organic compounds in a dairy processor's aerobic bioreactor.

Wastewater samples were taken from an aerobic bioreactor, operated by a dairy processor in southeastern Australia to reduce nutrient and pollutant loads. Samples were taken over a two-year period, to determine whether trace organic compounds or physicochemical analyses of the wastewater could be used to discriminate the water taken before, during and after processing of the wastewater in the bioreactor. Multivariate analyses of the physicochemical data suggested that nitrate, pH and total dissolved nitrogen best described the infeed wastewater entering the bioreactor, while organic and particulate phosphorus concentrations where predominantly responsible for describing the composition of the content of the bioreactor. Gas chromatography-mass spectrometry data of organic compounds within the wastewater samples were also analysed via multivariate analyses. The analyses found that the compound 4-nitrophenol was associated with ammonia concentrations and mixed liquor wastewater. Therefore, 4-nitrophenol may possibly be used to act as an indicator of anaerobicity in aerobic bioreactors.

Seasonal and wastewater stream variation of trace organic compounds in a dairy processing plant aerobic bioreactor.

Bioreactors are often an integral part of dairy factory efforts to reduce the biological oxygen demand of their wastewater. In this study, infeed, mixed liquor and supernatant samples of an aerobic bioreactor used by a dairy factory in South-Eastern Australia were analyzed for nutrients and organic compounds using gas chromatography-mass spectrometry and physicochemical analyses. Despite different concentrations of organic inputs into the bioreactor, nutrients and trace organic compounds were reduced significantly (i.e. average concentration of trace organic compounds: infeed=1681 µg/L; mixed liquor=257 µg/L; supernatant=23 µg/L). However, during one sampling period the bioreactor was adversely affected by the organic loading. Trace organic compounds in the samples were predominantly fatty acids associated with animal products. The analyses suggest that it is possible to trace a disruptive input (i.e. infeed with high organic carbon concentrations) into an aerobic bioreactor by measuring concentrations of fatty acids or ammonia.

Characterization of organic particulates present in milk factory process waters used for reuse along with aerobically digested effluent wastewater.

Wastewater from a dairy processor is being reused and recycled both within the plant and for irrigation. Flash pyrolysis GC-MS was used to examine nitrogen and phenol containing compounds (M.W.=35 to 450 g/mol) in the particulate fraction of the milk condensate, combined clean wastewater and aerobic bioreactor effluent. For comparison, the particulates were also prepared for standard GC-MS analyses using conventional solvent extraction methods. Compounds detected by pyrolysis GC-MS were found mostly in the bioreactor with the amino acid arginine (220 mg/kg) and the amino acid derivative 1-methyl-5-oxo-L-proline methyl ester (130 mg/kg) found at the highest concentrations. In comparison, sterols detected in the effluent were found at higher concentrations when using solvent extraction indicating some degradation with pyrolysis GC-MS. However, with few exceptions, particulates were generally found not to act as passive collectors capable of concentrating less water soluble chemicals.

Crystal structure of the gold nanoparticle [N(C8H17)4][Au25(SCH2CH2Ph)18].

We report the crystal structure of the thiolate gold nanoparticle [TOA+][Au25(SCH2CH2Ph)18-], where TOA+ = N(C8H17)4+. The crystal structure reveals three types of gold atoms: (a) one central gold atom whose coordination number is 12 (12 bonds to gold atoms); (b) 12 gold atoms that form the vertices of an icosahedron around the central atom, whose coordination number is 6 (five bonds to gold atoms and one to a sulfur atom), and (c) 12 gold atoms that are stellated on 12 of the 20 faces of the Au13 icosahedron. The arrangement of the latter gold atoms may be influenced by aurophilic bonding. Together they form six orthogonal semirings, or staples, of -Au2(SCH2CH2Ph)3- in an octahedral arrangement around the Au13 core.

Solvent-free, direct synthesis of supramolecular nano-capsules.

The single step direct synthesis of pyrogallol[4]arene via a solvent free protocol yields the pure product as a self-assembled nano-capsule, comprised of six macrocyclic building blocks.

Association and orientation of C70 on complexation with calix[5]arene.

Calix[5]arene and C70 in p-xylene form a ball-and-socket supramolecular complex with the C5 axis of the fullerene tilted 40 degrees relative to the symmetry axis of the calixarene, the extended structure is comprised of well-separated zigzag sheets of C70 molecules.