An Overview of the Chemical Cycling of Pb (Lead) in the Global Ocean System Daniel Hossfeld The current understanding of lead cycling in the ocean includes human-dominated sources and relatively short residence time due to the bonding capabilities of lead isotopes (Noble, 2014 & Schaule, 1981). The study of lead in the oceans shows the impact that humans can manage across just decades of changing inputs. Lead inputs into the atmosphere increased dramatically in the industrial revolution, and peaked alongside the maximum leaded gasoline use in the 1970’s (Noble, 2014). Sources of atmospheric lead includes gasoline, smelting, coal burning, and incineration. Oceanographic surveys suggest that atmospheric deposition peaked alongside leaded gas usage, and dipped sharply after a planned switch into unleaded fuels (Nriagu, 1989). Concentrations range from 10-12 to 10-4 mol per kg of seawater (Bruland, 2003). The undisputed major source of dissolved lead in the ocean is accumulated through atmospheric dust deposition (Bruland, 2003). No other inputs are specified in publications. According to Noble et al (2014), input rates decreased drastically from 1979 to 2011, although input rates can only be estimated from measured dissolved lead in the water column. It is clear that deposition has decreased across all lead isotopes since 1979, but location of deposition is tied to high lead injection into the atmosphere. Many sites with higher lead deposition are downwind of areas of high industrial activity. Input rates are highly variable, but Bruland et al (2003) estimated current atmospheric input in the North Atlantic to be 820 picomoles per square centimeter per year, compared with 14 pmol/cm2yr before industry. The Central North Pacific and the Central South Pacific are estimated to have higher input rates compared with ancient times as well, but are not as drastic (240:1.4 pmol/cm2yr & 14:1.4 pmol/cm2yr, respectively). The major significant source of lead removal is the binding of lead isotopes to descending particulates from the euphotic zone (Bruland, 2003). Detritus provides a removal source by sinking through the water column, collecting lead, and landing in the sediment. Corals also provide a pathway to removal by taking up small amounts of lead during growth (Noble, 2014). Sedimentation provides a stable removal rate, and is a major influence on the decreasing levels of lead since the reduction of leaded gasoline use. Removal rates are also only understood as relative amounts through water column surveying. Passive scavenging distribution is the best fit behavior for lead. Lead is not present in phytoplankton proteins- it is not required for the growth of primary producers, it only binds opportunistically (Reuer, 2002). An impressive result of the consistent surveying of the oceans is the visualization of human-made lead pollution throughout the timescale of the industrial revolution. Fascinating ice core studies in Greenland have found proof of Greek and Roman era increases in lead due to small scale industrial increases (Hong, 1994). At certain stations, the water column shows high concentrations of lead in the intermediate level relative to the surface layer and down to 1000m (Noble, 2014). These high concentrations align with areas of high lead emissions during the industrial revolution and subsequent reliance on leaded gasoline when modeled alongside wind and atmospheric dust patterns. A point in accordance with this observation is the drastic decrease in lead concentrations across ocean stations when moving geographically further away from major emission zones (industrial cities) (Bruland, 2003). Surface lead concentrations change are so dependent on geographic area that remote locations can be orders of magnitude lower than regions nearby to high industrial lead output (Bruland, 2003). Due to the varying amount of input across the survey period, residence times are not certain and apparently depend on geographic location as well as available phytoplankton and biological uptake. Oligotrophic surface waters are modeled to have a ~2 year lead residence time due to active binding abilities with high phytoplankton concentrations, while deeper waters are expected to be “decades to a century” (Noble, 2014 & Flegal, 1983). Scavenged-type dissolved particles (lead included) are known to have short residence times (Bruland, 2003). The two stations chosen for water column distribution observations are geographically distant and provide an understanding of the different behaviors at distinct locations due to variable atmospheric dust input. Both Figures 1 & 2 show scavenged-type distributions, but the sites experience different atmospheric input and resultant divergent concentration levels throughout the water column, although both show the characteristic decrease of dissolved lead with depth. Differences in concentrations through the water column can be attributed to currents bringing in lead from sites experiencing variable amounts of time without exposure to atmospheric input. Station ER-10 in the Indian Ocean shows high concentrations at the surface (~50 pmol/kg) with an exponential decrease throughout the water column down to stability at ~10 pmol/kg around 2000m (Figure 1). According to published sources, this distribution is understood to reflect a site with relatively recent high lead inputs and low past inputs. The site could be downwind of a high-output region. The sharp rate of decline is likely due to high productivity, which is expected to allow lead to bind to sinking matter and exit the system quickly. Station 2 in the Atlantic Ocean shows intermediate concentration levels at the surface (~30 pmol/kg) with a very slow rate of decline until 2000m where decline occurs rapidly (Figure 2). Concentrations are almost steady at 30 pmol/kg from the surface to 1000m depth, suggesting a steady input of lead at this site for an extended period of time. This site could have experienced less productivity than its Indian Ocean counterpart, which could explain a high level of intermediate lead. An alternative reason could be very high input in the past, so much so that lead was removed at a similar rate to the Indian Ocean station but after removal, concentration remained high. The North Atlantic experienced high lead concentrations due to the downwind location in relation to high leaded gasoline usage sites in the United States, so the second suggestion is very possible. The sharp decline near 2000m could be a signal of a time before high lead input, or a different current of water that had not seen surface deposition recently. Lead is a known toxic substance in high concentrations and has documented effects on humans, wildlife, plants and livestock (Demayo, 1982). The ocean is a perfect example of humanity quickly passing natural process timescales and incurring environmental harm due to industrial scale activities. While lead use has been curbed due to strict environmental regulations in some locations, input still remains a problem and contamination remains a concern. Scientists have heavily documented the contamination process, but further investigations into how to curb lead emissions is a crucial part of remediation. While survey methods continue to improve, it is possible to begin asking questions and predicting answers about future lead emissions. Modeling can predict the effects of a revitalized coal economy in the United States, as well as other industrial shifts expected from an anti-environment administration. Figures Figure 1. Indian Ocean lead distribution from Station ER-10, Surface to 5000m depth Figure 2. Atlantic Ocean lead distribution from Station 2, surface to 2500m depth Sources Bruland K.W. and Lohan M.C. 2003. Controls of Trace Metals in Seawater. In Treatise on Geochemistry (ed. H. Elderfield) Vol. 6 Treatise on Geochemistry (eds H.D. Holland and K.K. Turekian). Elsevier-Pergamon, Oxford. Pp. 23-47. Demayo, A., Taylor, M.C., Taylor, K.W., Hodson, P.V., Hammond, P.B. 1982. Toxic effects of lead and lead compounds on human health, aquatic life, wildlife plants, and livestock. C R C Critical Reviews In Environmental Control Vol. 12 , Iss. 4,1982 Flegal, A. R., and Patterson, C. C., 1983. Vertical concentration profiles of lead in the central Pacific at 15° N and 20° S. Earth Planet. Sci. Lett. 64: 19-32. Hong, S., Candelone, J., Patterson, C.C., Boutron, C.F. 1994. Greenland ice evidence of hemispheric lead pollution two millennia ago by Greek and Roman civilizations. Science, vol. 265 no. 5180 (1994) p. 1841+. Noble, A.E., Echegoyen-Sanz, Y., Boyle, E.A., Ohnemus, D.C., Lam, P.J., Kayser, R., Reuer, M., Wu, J., Smethie, W. 2014. Dynamic variability of dissolved Pb and Pb isotope composition from the U.S. North Atlantic GEOTRACES transect. Deep-Sea Research II Vol. 116 (2015) 208-225. Nriagu J. 1989. The rise and fall of leaded gasoline. Sci. Total Environ. 92, 13–28. Reuer, M.K., 2002. Data of centennial-scale elemental and isotopic variability in the tropical and Subtropical North Atlantic Ocean, Ph.D. Thesis, MIT/WHOI Joint Program in Oceanography. Schaule, B. K. and Patterson, C. C., 1981. Lead concentrations in the Northeast Pacific: evidence for global anthropogenic perturbations. Earth Planet. Sci. Lett., 54: 97-116.
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