ARTICLE pubs.acs.org/est
Asian Industrial Lead Inputs to the North Pacific Evidenced by Lead Concentrations and Isotopic Compositions in Surface Waters and Aerosols Celine Gallon,*,†,‡ Mara A. Ranville,‡ Christopher H. Conaway,†,‡ William M. Landing,§ Clifton S. Buck,§ Peter L. Morton,§ and A. Russell Flegal†,‡ †
Institute of Marine Sciences, 1156 High Street, University of California-Santa Cruz, Santa Cruz, California 95064, United States WIGS Laboratory, Department of Microbiology and Environmental Toxicology, 1156 High Street, University of California-Santa Cruz, Santa Cruz, California 95064, United States § Department of Earth, Ocean, and Atmospheric Science, Florida State University, Tallahassee, Florida 32306-4320, United States ‡
ABSTRACT: Recent trends of atmospheric lead deposition to the North Pacific were investigated with analyses of lead in aerosols and surface waters collected on the fourth Intergovernmental Oceanographic Commission Contaminant Baseline Survey from May to June, 2002. Lead concentrations of the aerosols varied by 2 orders of magnitude (0.1 26.4 pmol/m3) due in part to variations in dust deposition during the cruise. The ranges in lead aerosol enrichment factors relative to iron (1 119) and aluminum (3 168) were similar, evidencing the transport of Asian industrial lead aerosols across the North Pacific. The oceanic deposition of some of those aerosols was substantiated by the gradient of lead concentrations of North Pacific waters, which varied 3-fold (32.7 103.5 pmol/ kg), were highest along with the Asian margin of the basin, and decreased eastward. The hypothesized predominance of Asian industrial lead inputs to the North Pacific was further corroborated by the lead isotopic composition of ocean surface waters (206Pb/207Pb = 1.157 1.169; 208Pb/206Pb = 2.093 2.118), which fell within the range of isotopic ratios reported in Asian aerosols that are primarily attributed to Chinese industrial lead emissions.
’ INTRODUCTION The distribution of lead in ocean surface waters in the preceding century was dominated by atmospheric inputs of industrial aerosols, including those from smelting, coal combustion, and leaded gasoline emissions. The latter emissions, which accounted for the majority of those inputs, peaked in the late 1970s and early 1980s.1,2 After that, the nearly global phase-out of leaded gasoline resulted in a decrease in lead concentrations in North Atlantic surface waters3 and a corresponding shift in their isotopic composition.4 Unfortunately, there has been no corresponding documentation of the impact of the virtual elimination of leaded gasoline on lead concentrations in the North Pacific because there have been very few measurements of lead concentrations, much less lead isotopic compositions, of those waters. For example, lead isotopic compositions have only been measured in two deep vertical profiles in the eastern North Pacific5,6 and one shallow vertical profile in the California coastal current system.7 Two of those three data sets are over 20 years old.5,7 Moreover, quite a bit has changed since most of the studies on lead in the North Pacific were conducted, including the virtual elimination of leaded gasoline in the US in 19918 and China in 2000.9 As a consequence, coal combustion has become the principal source of eolian lead in China,10 13 which is now the r 2011 American Chemical Society
world’s largest coal consumer.14 In addition to adversely impacting the air quality in China,15 its industrial lead aerosols have been observed in Korea,16 Taiwan,17 and Japan,18,19 and it has been proposed that Asian emissions of industrial lead from fossil fuel combustion are now impacting atmospheric lead concentrations in the United States20 22 and Canada.23 Consequently, we hypothesized that Asian industrial emissions have also measurably impacted lead levels in North Pacific surface waters, which have recently been found to have elevated levels of other metals associated with Asian fossil fuel combustion.24 Here, we present measurements of lead isotopic compositions, along with corresponding lead concentrations, of surface waters in the western and central North Pacific that were collected on the 2002 Intergovernmental Oceanographic Commission Contaminant Baseline Survey (IOC-IV), whose overall purpose was to investigate the effects of the Asian dust deposition on the chemical composition of the North Pacific Ocean.25 In addition to measurements in seawater, we made complementary analysis of lead concentrations in aerosols that were collected concurrently Received: June 15, 2011 Accepted: October 18, 2011 Revised: October 6, 2011 Published: October 18, 2011 9874
dx.doi.org/10.1021/es2020428 | Environ. Sci. Technol. 2011, 45, 9874–9882
Environmental Science & Technology during that survey. These samples, although representing ephemeral atmospheric conditions, provide information on the composition and source of atmospheric depositions to the North Pacific. Together, the two data sets support our hypothesis that lead fluxes to North Pacific surface waters are now predominantly eolian inputs from coal combustion in China.
’ EXPERIMENTAL SECTION Concurrent aerosol and surface water samples were collected across the northwest Pacific during the fourth Intergovernmental Oceanographic Commission Contaminant Baseline Survey (IOC-IV), from May 1 to June 3, 2002. The cruise transect (∼15,000 km in length) extended northeast from Osaka Bay, Japan across the Kuroshio Current, into the subarctic Pacific a high-nutrient low-chlorophyll (HNLC) region, then south and east into the North Pacific Subtropical Gyre.25 Atmospheric Sampling and Analysis. Aerosol (>0.4 μm) samples (average of 15 m3 of filtered air) were collected for approximately 10 h with the aerosol sampling system and protocols detailed by Buck et al.26 The filters were kept intact for the initial measurements of aluminum and iron by energy-dispersive X-ray fluorescence (EDXRF) at the National Oceanic and Atmospheric Administration Pacific Marine Environmental Laboratory, as described elsewhere.26 The filters were then digested at the University of California-Santa Cruz (UCSC) with ultrapure (Optima grade, Fisher Scientific), concentrated (10:1) HNO3 and HClO4, which dissolved all of the particulate lead except for a small fraction of lead sequestered in refractory aluminosilicate minerals. The digests were evaporated to neardryness, the digestion was repeated, and the samples then dissolved up in 1.5 M ultrapure HNO3 for lead concentration measurements. Those were made with a magnetic-sector highresolution inductively coupled plasma mass spectrometer (HR ICP-MS; Finnigan Element) at UCSC using a rhenium spike as an internal standard. All lead data were corrected for field and procedural blanks that were processed and analyzed concurrently. Precision, calculated as the % relative standard deviation of replicate analyses (n = 6) of a mid-range standard, was
