Chemical relationships in waters and sediments of some urban streams, with particular reference to heavy metals and phosphorus

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This thesis describes two studies of the chemistry of freshwater streams in the Sydney basin. The first was a survey of 86 waterways, sampled under low conditions. Samples were generally low in salinity, soft, of poor buffering capacity and dominated by sodium and chloride. C0-dominance by calcium, magnesium and (bi)carbonate occured in a number of particular cases. Multivariate analyses indicated three groups, separated primarily by levels of dissolved nutrients, trace metals, turbidity and colour. Groupings were associated strongly with the type of catchment. Streams in areas relatively unaffected by human influence had notable uniformity in chemistry, while those from developed catchments were varied. Heavy metal contamination was relatavely low, although a few of the samples displayed inordinately large levels of one or more metals. In such cases the more extreme measurements of phosphorus and nitrogen were also seen. The findings were consistant with occasional or localised elevation of contaminant levels. The second study invloved monitoring of three Hawkesbury Sandstone streams. Sampling of surface waters, interstial waters and sediments was performing at irregular intervals over a two year period at three stations within each site. The streams predominantly existed under low conditions and showed similar major ion chemistries to the majority of the survey samples. Levels of calcium and total carbonate, plus heavy metals and nutrients were generally higher in the urbanised creeks, comapred to the reference strema. During a heavy storm, high levels of nutrients, suspended solids and colour were detected in all surface waters at peak-flow, as well as alkaline pH, oxidising redox, and reduced conductivity, alkalinity and hardness. The sandy sediments were characterised by very low levels of organic matter and cation exchange capacity. Sequential extractions identified that the sums of secondary phase lead, zinc and copper were over nine, four and two times that of the corresponding residual, respectively. Greatest proportions of zinc and lead were associated with coatings of iron and maganese oxides, or coarse waste particles. Copper was preferentially associated with organic matter. Concentration gradients between interstitial and surface waters were rare and release of sedimentary constituents should occur from the upper-most particulates. Poor water and sediment qualities were often observed in the urban sites. Poor water quality was also seen on occassion in the reference stream. However, since poor sediment quality was not detected at those times and interstitial waters for all sites displayed high within-site variability, surface waters were considered the most reliable short-term indicator of condition for Hawkesbury Sandstone streams. Multidimensional scaling showed that all streams had distinct water and sediment chemistries. High levels of temporal and spatial variability were apparant within the urbanised sites - particularly in interstitial waters - mostly due to concentrations of heavy metals, phosphorus and suspended solids. Seasonal differences were detected, but only in terms of the level of variability between summer and winter samples.
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