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Apart from its central role in photosynthesis, one of the most dramatic effects of light in marine and freshwater systems is its ability to generate reactive chemical intermediates. Of these, hydrogen peroxide is one of the more stable and easily detected. Aspects of the generation and decay of hydrogen peroxide in the Port Hacking River estuary, New South Wales, have been investigated in a number of field and laboratory studies. Peroxide concentrations in surface waters in the early morning are relatively uniform over the estuary and typically less than 35 nM, whereas concentrations in mid-afternoon in excess of 100 nM have been observed. Variation of peroxide concentration with depth in the deep basins of Port Hacking is dependent on the extent of structure within the water column, with little mixing of surface- generated peroxide into poorly-illuminated bottom waters under stratified conditions. Laboratory studies confirmed that light induces the production of hydrogen peroxide, the initial rate of production increasing with increasing molar absorptivity of the filtered water sample. Filtration of samples had little effect on the generation of hydrogen peroxide but dramatically reduced the rate of decay of photogenerated hydrogen peroxide.