Description: The effect of phototrophic biofilm activity on advective transport of cadmium (Cd), copper (Cu), nickel (Ni), and lead (Pb) in sandy sediments was examined using percolated columns. Cd and Ni in the effluent exhibited clear diel cycles in biofilm-containing columns, with concentrations at the end of dark periods exceeding those during illumination by up to 4.5- and 10-fold for Ni and Cd, respectively. Similar cycles were not observed for Pb or Cu. Breakthrough of the latter metals was greatly retarded and incomplete relative to Cd and Ni, and trends in biofilm treatments did not differ greatly from those in control columns. Inhibition of photosystem II by DCMU (3-(3,4-dichlorophenyl)-1,1-dimethylurea) proved that diel cycles of Cd and Ni were controlled by oxygenic photosynthesis, and microsensor measurements showed that metal cycles closely matched metabolic activity-driven pH variations. The sorption edge pH for the sand/biofilm substrate followed the order Ni 〉 Cd 〉 Cu 〉 Pb, and for Ni and Cd, was within the pH 7–10 range observed in the biofilm-containing column. Adsorption dynamics over the light periods matched pH increases, but desorption during dark periods was incomplete and slower than the rate of change of pH. Over a diel cycle, desorption was less than adsorption, resulting in net binding of dissolved metals due to the biofilm metabolic activity. Extraction with selective reagents indicated that the adsorbed metals were readily exchangeable, and potentially bioavailable. Thus, phototrophic benthic biofilms can control the transport of some metals across the sand–water interface, and processes in this very thin surficial layer should be considered when evaluating chemical fluxes in permeable sediments.

Description: Trace metals in the ocean act as both essential micro-nutrients and as toxins. There are relatively few multi-element studies of dissolved trace metals in the ocean, and none from the Gulf of Aqaba, Red Sea. This semi-enclosed basin surrounded by desert is a natural laboratory for studying the impact of atmospheric dry deposition of trace metals on the ocean surface. We have combined measurement of dissolved metals in seawater with measurements of the flux of metals associated with dry deposition. The total dissolved trace metal concentrations in Gulf of Aqaba water are generally higher (Fe, Cu, Zn, Co, Mn, Pb) or similar (Ni, Al, Cd, Mo) to those measured in the open North Atlantic Ocean. The concentrations of elements that are highly enriched in aerosols relative to Al (e.g. Cd, Pb, Zn and Cu) are not necessarily proportionally enriched in surface seawater when compared to Al, indicative of the high reactivity of these elements in seawater. Iron concentrations in the Gulf of Aqaba are high relative to Al, despite the fact that the aerosols are not more enriched in Fe relative to Al. There may be additional sources of dissolved iron to the Gulf of Aqaba, not associated with Al. Alternatively, intense photochemically-driven redox cycling may act to enhance Fe dissolution from aerosols, or may otherwise increase the lifetime of Fe in the water column, relative to Al. Copper concentrations in the Gulf of Aqaba are close to the value found to be a threshold for Cu toxicity in this region. A surface maximum in Cd:P is found in the Gulf of Aqaba, in contrast to the more typical surface minimum in this ratio observed in other locations. The surface maximum appears to be driven by atypically low uptake of Cd relative to P. A low Cd:P uptake ratio for this region is consistent with known environmental determinants of low Cd:P uptake, such as high concentrations of dissolved Zn and Fe, and a predominance of small phytoplankton including cyanobacteria. Highlights ► We measured dissolved trace metal concentrations in the Gulf of Aqaba four times. ► Iron concentrations are high relative to Al concentrations. ► Cu concentrations are close to the threshold for Cu toxicity in this region. ► A surface maximum in Cd:P is driven by unusually low uptake of Cd relative to PO4. ► This is consistent with the dominance of small phytoplankton and high Fe levels.

Description: The effect of phototrophic biofilm activity on advective transport of cadmium (Cd), copper (Cu), nickel (Ni), and lead (Pb) in sandy sediments was examined using percolated columns. Cd and Ni in the effluent exhibited clear diel cycles in biofilm-containing columns, with concentrations at the end of dark periods exceeding those during illumination by up to 4.5- and 10-fold for Ni and Cd, respectively. Similar cycles were not observed for Pb or Cu. Breakthrough of the latter metals was greatly retarded and incomplete relative to Cd and Ni, and trends in biofilm treatments did not differ greatly from those in control columns. Inhibition of photosystem II by DCMU (3-(3,4-dichlorophenyl)-1,1-dimethylurea) proved that diel cycles of Cd and Ni were controlled by oxygenic photosynthesis, and microsensor measurements showed that metal cycles closely matched metabolic activity-driven pH variations. The sorption edge pH for the sand/biofilm substrate followed the order Ni 〉 Cd 〉 Cu 〉 Pb, and for Ni and Cd, was within the pH 7–10 range observed in the biofilm-containing column. Adsorption dynamics over the light periods matched pH increases, but desorption during dark periods was incomplete and slower than the rate of change of pH. Over a diel cycle, desorption was less than adsorption, resulting in net binding of dissolved metals due to the biofilm metabolic activity. Extraction with selective reagents indicated that the adsorbed metals were readily exchangeable, and potentially bioavailable. Thus, phototrophic benthic biofilms can control the transport of some metals across the sand–water interface, and processes in this very thin surficial layer should be considered when evaluating chemical fluxes in permeable sediments.