The effect of seawater magnesium on natural fluorescence during estuarine mixing,and implications for tracer applications

Natural fluorescence, which is thought to result from low molecular weight humic and fulvic compounds, can be used as a tracer to distinguish between individual river waters. Natural fluorescence exhibits conservative mixing with seawater, except for a slight fluorescence increase which is sometimes observed in the low salinity range (0–5‰). This increase is not due to the inner filter effect (internal quenching). Laboratory experiments can reproduce this low-salinity natural fluorescence increase. Of the major seawater ions, only magnesium can cause a similar natural fluorescence increase. Variation in sample pH, ionic strength, or particle content cannot explain the natural fluorescence increase, nor does it appear to be related to the estuarine flocculation of humic material. Addition of seawater magnesium to the fluorescent material with subsequent loss of hydrogen ions could enhance fluorescence by adding crosslinking to the structure. Replacement of a fluorescence-depressing metal like copper or iron by magnesium could also enhance fluorescence, essentially by removing the quenching effect of the metal. Experimental data in this study are consistent with both of these possible mechanisms. Calcium also enhances fluorescence, however the effect of seawater calcium during estuarine mixing is not as apparent as the magnesium effect. The implications of this low-salinity natural fluorescence increase with respect to estuarine and coastal tracer applications depend on whether individual rivers mix in the high or low salinity region of an estuary or coastal area.