Greywater irrigation as a source of organic micro-pollutants to shallow groundwater and nearby surface water.

Increased water demands due to population growth and increased urbanisation have driven adoption of various water reuse practices. The irrigation of greywater (water from all household uses, except toilets) has been proposed as one potential sustainable practice. Research has clearly identified environmental harm from the presence of micro-pollutants in soils, groundwater and surface water. Greywater contains a range of micro pollutants yet very little is known about their potential environmental fate when greywater is irrigated to soil. Therefore, this study assessed whether organic micro-pollutants in irrigated greywater were transferred to shallow groundwater and an adjacent surface waterway. A total of 22 organic micro-pollutants were detected in greywater. Six of these (acesulfame, caffeine, DEET, paracetamol, salicylic acid and triclosan) were selected as potential tracers of greywater contamination. Three of these chemicals (acesulfame, caffeine, DEET) were detected in the groundwater, while salicylic acid was also detected in adjacent surface water. Caffeine and DEET in surface water were directly attributable to greywater irrigation. Thus the practice of greywater irrigation can act as a source of organic micro-pollutants to shallow groundwater and nearby surface water. The full list of micro-pollutants that could be introduced via greywater and the risk they pose to aquatic ecosystems is not yet known.

Irrigated greywater in an urban sub-division as a potential source of metals to soil, groundwater and surface water.

Increased water demands in dry countries such as Australia, have led to increased adoption of various water reuse practices. Irrigation of greywater (all water discharged from the bathrooms, laundry and kitchen apart from toilet waste) is seen as a potential means of easing water demands; however, there is limited knowledge of how greywater irrigation impacts terrestrial and aquatic environments. This study compared four greywater irrigated residential lots to adjacent non-irrigated lots that acted as controls. Accumulation and potential impacts of metals in soil, groundwater and surface water, as a result of greywater irrigation, were assessed by comparing measured concentrations to national and international guidelines. Greywater increased concentrations of some metals in irrigated soil and resulted in As, B, Cr and Cu exceeding guidelines after only four years of irrigation. Movement of metals from the irrigation areas resulted in metal concentrations in groundwater (Al, As, Cr, Cu, Fe, Mn, Ni and Zn) and surface water (Cu, Fe and Zn) exceeding environmental quality guidelines again within four years. These results are unlikely to be universally applicable but indicate the need to consider metals in greywater in order to minimize potential adverse environmental effects from greywater irrigation.

Phosphorus as a limiting factor on sustainable greywater irrigation.

Water reuse through greywater irrigation has been adopted worldwide and has been proposed as a potential sustainable solution to increased water demands. Despite widespread adoption, there is limited domestic knowledge of greywater reuse. There is no pressure to produce low-level phosphorus products and current guidelines and legislation, such as those in Australia, may be inadequate due to the lack of long-term data to provide a sound scientific basis. Research has clearly identified phosphorus as a potential environmental risk to waterways from many forms of irrigation. To assess the sustainability of greywater irrigation, this study compared four residential lots that had been irrigated with greywater for four years and adjacent non-irrigated lots that acted as controls. Each lot was monitored for the volume of greywater applied and selected physic-chemical water quality parameters and soil chemistry profiles were analysed. The non-irrigated soil profiles showed low levels of phosphorus and were used as controls. The Mechlich3 Phosphorus ratio (M3PSR) and Phosphate Environmental Risk Index (PERI) were used to determine the environmental risk of phosphorus leaching from the irrigated soils. Soil phosphorus concentrations were compared to theoretical greywater irrigation loadings. The measured phosphorus soil concentrations and the estimated greywater loadings were of similar magnitude. Sustainable greywater reuse is possible; however incorrect use and/or lack of understanding of how household products affect greywater can result in phosphorus posing a significant risk to the environment.

Experimental and theoretical studies of the redox potentials of cyclic nitroxides.

The redox potentials of 25 cyclic nitroxides from four different structural classes (pyrrolidine, piperidine, isoindoline, and azaphenalene) were determined experimentally by cyclic voltammetry in acetonitrile, and also via high-level ab initio molecular orbital calculations. It is shown that the potentials are influenced by the type of ring system, ring substituents and/or groups surrounding the radical moiety. For the pyrrolidine, piperidine, and isoindolines there is excellent agreement (mean absolute deviation of 0.05 V) between the calculated and experimental oxidation potentials; for the azaphenalenes, however, there is an extraordinary discrepancy (mean absolute deviation of 0.60 V), implying that their one-electron oxidation might involve additional processes not considered in the theoretical calculations. This recently developed azaphenalene class of nitroxide represents a new variant of a nitroxide ring fused to an aromatic system and details of the synthesis of five derivatives involving differing aryl substitution are also presented.

Chemical discrimination by a kinetic model of organic photooxidation in a heterosupramolecular assembly.

The photooxidation of range of common organic pollutants in a dye-sensitised photoelectrochemical cell (DS-PEC) is reported. A photoanode was prepared by the chemisorption of a photosensitiser, cis-bis-(2,2)-bipyridine)-(4,4'-bis-(methyl)phosphonato-2,2'-bipyridine)ruthenium(II) dichloride ([Ru(bpy)2(dmpbpy]2+), to a nanoporous nanocrystalline TiO2 thin film on a conducting glass substrate. The photoanode was coupled to a platinum electroplated fluorine doped tin oxide glass substrate in a two electrode assembly and the cell cavity was filled with an aqueous solution of organic pollutants and irradiated with lambda>420 nm to give a measurable photocurrent. In addition to the ability of this cell to photooxidise a range of chemically diverse organic pollutants, the application of a kinetic model to observed photocurrent transients allowed the study of interfacial electron transfer processes. Through the mathematical fit of a five-parameter double exponential decay function, evidence to support numerous interfacial reactions for the oxidation process were identified. Rapid oxidation of species in close proximity to the photooxidation centre was proposed as the kinetically fast interfacial process with a first-order rate constant of the order 0.4 s(-1). The slower process was attributed to the diffusion of oxidisable species from the solution bulk to the surface prior to oxidation with a first-order rate constant of the order 0.01 s(-1). Theoretical profiling of the kinetic events supported the biphasic assignment of interfacial processes and indicated that non-exhaustive oxidation occurs for the solution concentrations examined.

Modification of TiO2 for enhanced surface properties: finite Ostwald ripening by a microwave hydrothermal process.

The effect of microwave modification of colloidal TiO2 suspensions under extended periods of treatment is presented. The nanoparticulate TiO2 is compared and contrasted to similar convection hydrothermally treated TiO2 and a commercial titania product, namely Degussa P25. Microwave-treated samples were analyzed by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and Raman spectroscopy to determine their physicochemical characteristics. Comparative surface area analyses were performed by N2 adsorption and calculated from a Brunauer-Emmett-Teller (BET) isotherm. The complementary techniques of XRD and TEM showed good correlation between observed and calculated particle sizes (by application of the Scherrer equation), with the material being highly crystalline anatase TiO2, as identified by XRD and Raman. This investigation identified that extended periods of microwave hydrothermal treatment do not greatly enhance the crystallinity and primary grain size. Treatment of >180 min has a negative effect on crystallite growth; however, treatment up to this time had a significant effect on the material's surface area. The limiting regime of Ostwald ripening for hydrothermal treatment is discussed in relation to the mechanism of microwave treatment, that is, rapid heating to temperature and extremely rapid rates of crystallization. The effect of these property modifications are further discussed in relation to photocatalytic and photoelectrochemical applications of TiO2 nanoparticles.

Two-dimensional crystal growth and stacking of bis(phthalocyaninato) rare earth sandwich complexes at the 1-phenyloctane/graphite interface.

Initial stages of two-dimensional crystal growth of the double-decker sandwich complex Lu(Pc*)2 [Pc* = 2,3,9,10,16,17,23,24-octakis(octyloxy)phthalocyaninato] have been studied by scanning tunneling microscopy at the liquid/solid interface between 1-phenyloctane and highly oriented pyrolytic graphite. High-resolution images strongly suggest alignment of the double-decker molecules into monolayers with the phthalocyanine rings parallel to the surface. Domains were observed with either hexagonal or quadrate packing motifs, and the growing interface of the layer was imaged. Molecular resolution was achieved, and the face of the phthalocyanine rings appeared as somewhat diffuse circular features. The alkyl chains are proposed to be interdigitating to maintain planar side-by-side packing.

Photoelectrochemical measurements of a heterosupramolecular system under visible light irradiation.

A photochemical system utilising a modular approach characterised through interpretation of photoelectrochemical measurements is discussed. A photoanode was prepared by the chemisorption of a photosensitiser, cis-bis-(2,2'-bipyridine)-(4,4'-bis-(methyl)phosphonato-2,2'-bipyridine)ruthenium(II) dichloride (RuL2L'2+), to a mixed nanoporous nanocrystalline RuO2:TiO2 thin film, calcined on a fluorine doped SnO2 conducting glass substrate. Similarly, an electron relay molecule, 1-ethyl-1'-(2-phosphonoethyl)-4,4'-bipyridinium dichloride (EVP), was covalently bound to a platinum electroplated nanoporous nanocrystalline TiO2 thin film, and the electrodes connected in a photoelectrocatalytic cell (PCC). Irradiation with lamda > 420 nm gave a measurable photocurrent. Interpretation of the photocurrents obtained from this assembly provides a means for understanding photochemical reactions under low light intensities. Optimised conditions of the electrolyte solution were determined to be pH = 5 and illumination yielded eta = 0.0036% with an apparent quantum yield (AQY)= 1.6%.