The sea as a source of atmospheric phosphorus

The geochemical fractionation of phosphorus on the drop produced by bubbles bursting in seawater has been studied using a field sampling system called the Bubble Interfacial Microlayer Sampler (BIMS). The droplets from bursting bubbles were collected on filter samples in Narragansett Bay, Rhode Island during the summer of 1975. Phosphorus was found to be fractionated by the bubble-bursting process. The enrichment factor ranged from 4 to 170. Enrichment was found to increase with decreasing phosphorus concentration at 20 cm depth while it decreases with increasing wind velocity. Enrichment was independent of bubbling depth. Together these facts suggest that the sea-surface microlayer is the source of the phosphorus on the ejected drops. Organic phosphorus on the filter samples was found to be enriched relative to surface-water phosphorus by factors of 100–200, while reactive phosphorus was enriched by factors of only 6–8. This suggests that surface-active organic phosphorus compounds are the source phosphorus in the microlayer.The organic phosphorus content of samples of atmospheric particulates collected over the phosphate-rich upwelling waters near the Peru coast was found to correlate significantly with sea-salt sodium. Enrichments calculated using the average phosphorus concentration of the surface water in this area agree well with the results of the BIMS study. Thus it appears that phosphorus fractionation does occur in nature and may be important in supplying this nutrient to some coastal regions of the world.     

Inputs of organic matter to the ocean

The first objective of this introductory paper is to summarize our present understanding of the quantities of total organic carbon produced in the ocean by photosynthesis and non-biotic photochemical reactions, and the amount entering the ocean from rivers, the atmosphere, and the sediments. In this overview it will become apparent that our knowledge of the primary mechanisms and processes involved with the input of organic matter to the ocean via rivers, the atmosphere, sediments, and in situ photochemical reactions is fragmentary and often completely lacking. This becomes critical when we attempt to estimate the input of certain naturally occurring organic compounds and some synthetic organic compounds, since their primary input to the sea is generally via the atmosphere, rivers, and dumping. Thus the second objective of this paper is to emphasize our need to understand the mechanisms involved in these other input processes and the necessity of developing field programs and mathematical models to evaluate the input of specific organic compounds via these pathways. Polychlorinated biphenyls are used as examples of how necessary it is to understand these other input routes in order to evaluate the cycling of pollutant substances in the ocean.     

Bursting bubbles and their effect on the sea-to-air transport of Fe, Cu and Zn

The effects of the bubble breaking process on the atmospheric geochemical cycles of the elements Fe, Cu and Zn were investigated, in situ, in the estuarine waters of Narragansett Bay, Rhode Island. Enrichment, as defined by the metal-to-sodium ratios in the aerosols produced compared to their ratio in bulk water, occurred for the three metals investigated. The extent and potential geochemical importance of the process were different for each element. Iron enrichment was quite low (enrichment factor (EF) <100) and constant, and scavenging of iron from the water column and subsequent enrichment on the aerosols produced did not appear to occur. Copper enrichment on the aerosols was 200 and appeared to be influenced by both microlayer and scavenging effects. In addition, copper enrichment appears to be correlated to biological processes. Zinc enrichment was approximately the same as Cu; however, a strong scavening effect appeared to occur, suggesting scavenging of Zn by rising bubbles. Scavenging effects suggest that open-ocean enrichments for Cu may be slightly higher than observed here and a great deal higher for Zn.Geochemical implications of the data, together with other existing data, indicate that the sea is an insignificant source of Fe to the atmosphere. The sea may be a significant source (contributing on the order of 10% or more) of the total annual quantity of Cu and Zn to the atmosphere.     

The influence of organic matter and atmospheric deposition on the particulate trace metal concentration of northwest Atlantic surface seawater

Particulate trace metals (PTM), organic carbon (POC), and organic nitrogen (PON) were measured in a series of surface bucket samples collected between the New England coast of the United States and Bermuda. PTM concentrations were lower or equivalent to the lowest PTM concentrations reported in the literature. Examination of the relative variations in PTM with respect to particulate aluminum and carbon led to the conclusion that organic matter was the probable regulator of PTM abundance in open-ocean surface waters and was important in this respect for continental shelf and slope waters as well.Enrichment factors of trace metals relative to their crustal abundances were found to be similar in the atmosphere sampled in Bermuda and in Sargasso Sea surface water particulate matter. A simplistic vertical flux model was constructed which showed atmospheric input of trace metals to the Sargasso Sea to be of the same approximate magnitude as the rate of removal of PTM from the mixed layer by sinking in association with POC. Essentially all of the particulate Al, Fe, and Mn in the Sargasso Sea mixed layer was attributed to aeolian sources. The fate of other atmospherically derived trace metals in the Sargasso Sea mixed layer was suggested to be a function of their solubility in seawater.     

Concentration of particulate trace metals and particulate organic carbon in marine surface waters by a bubble flotation mechanism

The transport of particulate organic carbon (POC) and particulate trace metals (PTM) to the sea surface by rising bubbles in samples of surface water collected in Narragansett Bay was examined using an adsorptive bubble separation technique. Recoveries of POC ranged from 30 to 59% while those of the particulate form of the trace metals, Al, Mn, Fe, V, Cu, Zn, Ni, Pb, Cr and Cd were generally greater than 50%. The recovery data were used to arrive at a rough order of magnitude estimate of the bubble transport of POC and PTM under open-ocean conditions. While transport rates of the trace metals to the sea surface by both bubble transport and atmospheric deposition varied over approximately 3 orders of magnitude, the ratio of bubble transport to atmospheric deposition for most metals varied over approximately one order of magnitude, perhaps suggesting some degree of coupling between atmospheric PTM and bubble-transported PTM.     

The impact of atmospheric aerosols on trace metal chemistry in open ocean surface seawater, 1. Aluminum

Significant quantities of aerosol aluminum are transported from continental regions through the atmosphere to the oceans. Enrichments in the concentration of dissolved aluminum in open ocean surface seawater suggest that dissolution of aerosol aluminum is an important source of dissolved aluminum to these waters. Atmospheric aerosols collected at Enewetak Atoll were exposed to seawater and artificial rain water to determine directly the importance of atmospheric deposition as a source of marine dissolved aluminum.The results of these experiments indicate that 8–10% of the aluminum in atmospheric aerosols of crustal origin over the North Pacific is soluble in seawater. Approximately 5–6% dissolves very rapidly ( < 0.6 hr). An additional 3–4% dissolves within 60 hr. This bimodal dissolution of aerosol aluminum of crustal origin suggests that this aluminum is present in two forms. The rapidly dissolving fraction is likely aluminum already weathered from primary minerals, while the more slowly dissolving fraction is probably aluminum from the aluminosilicate matrix.Nearly the same amount of aerosol aluminum dissolved in artificial rain water (pH= 5.5) in 6 hr as dissolved in seawater (pH= 8) in 60 hr. The lower pH appears to not only increase the dissolution rate but may also increase the quantity of aerosol aluminum that dissolves. Dissolved organic matter in seawater appears to have relatively little effect on aerosol aluminum dissolution.Considering measured total aerosol aluminum fluxes, aluminum dissolution of 5–10% would constitute the major source for dissolved aluminum in surface waters of the open North Pacific. The calculated residence time of dissolved aluminum in the upper 100 m of the tropical North Pacific ranges from 2 to 6 years.     

Deposition of atmospheric mineral particles in the North Pacific Ocean

Total deposition of atmospheric mineral particles (wet plus dry) has been measured during consecutive two-week sampling intervals from January, 1981 to March, 1982 at four island stations (Midway, Oahu, Enewetak, and Fanning) of the SEAREX Asian Dust Study Network in the North Pacific. The total deposition of mineral aerosol during the period from February to June is higher than that during the period from July to January at most of the stations. A systematic geographical trend is apparent in the dust flux, with greater fluxes at higher latitudes. The deposition values are correlated with the atmospheric mineral particle concentrations at these stations. The mineral particles are transported from arid regions in Asia to the North Pacific, and the annual dust deposition to the ocean appears to be dominated by sporadic dust events of short duration. Wet deposition dominates the removal of dust particles from the atmosphere over the North Pacific. The total deposition of atmospheric mineral material to the central North Pacific is estimated to be 20×10¹² g yr^-1.     

Linking pattern to process in reef sediment dynamics at Lady Musgrave Island,southern Great Barrier Reef

Linking surficial sediment patterns in reef environments to the processes that underlie their depositional dynamics enables predictions to be made of how environmental changes will influence reef‐associated sedimentary landforms, such as islands and beaches. Geomorphic linkages between sediment deposition patterns and the biophysical processes that drive them are often poorly resolved, particularly at broad landscape scales where tangible statements can be made about structural changes to landforms. The present study applies geospatial techniques to link patterns in reef sediment dynamics at Lady Musgrave Island to the underlying processes driving them. In situ calcification is characterized by developing a high resolution map of the surficial calcium carbonate producing communities inhabiting the reef platform, and associated sediments across the reef flat are analysed for grain size, kurtosis, sorting and threshold bed shear stress to explore transport pathways across the reef flat and lagoon. Wave energy is modelled across the entire reef platform as a potential driver of sediment dynamics, and morphometric linkages are empirically defined between wave energy and grain size. Findings indicate that carbonate sediments are primarily sourced from calcifying communities colonizing the outer periphery of the reef platform and that sediment grain size can be reliably linked to wave energy by virtue of a linear model.