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The natural lead concentration of dandelion ( Taraxacum officinale) leaves is estimated to be 0.2 μg/g (dry weight), or 1-3 orders of magnitude below most contemporary measurements of that value for dandelions and other plants. This estimate is based on analyses of lead concentrations of dandelions grown in a trace metal clean laboratory, with environmental lead concentrations approximating natural levels. The protocols used in this study paralleled those in our previous study that estimated the natural blood lead level in humans (0.016 μg/dL), which is also 1-3 orders of magnitude below most contemporary measurements. Analyses of the isotopic ratios ( 206 Pb/ 207 Pb: 208 Pb/ 207 Pb) of the lead in the plants grown in the laboratory and greenhouse and those collected in the field, as well as the isotopic ratios of the soils the plants were grown in in the laboratory, indicate that anthropogenic lead makes up a substantial amount of labile lead in today's environments. Consequently, this estimate of the natural lead level in dandelion leaves provides both a benchmark for comparison of lead concentrations in contemporary plants and yet another measure of persistent lead contamination in the biosphere.

We report the continued lead (Pb) contamination of the Northwest Pacific Ocean in 2002 and present the first comprehensive Pb isotope data set for that region. In the upper ocean, a Pb concentration maxima (64-113 pmol kg -1 ) extended throughout the entire North Pacific Subtropical Gyre (NPSG). We determined most of the Pb in this feature was from industrial emissions by many nations in the 1980s and 1990s, with the largest contributions from leaded gasoline emissions. In contrast, the deep water (>1000 m) Pb concentrations were lower (6-37 pmol kg -1 ), and constituted a mix of background (natural) Pb and anthropogenic Pb inputs from preceding decades. Deep water below the Western Subarctic Gyre (WSAG) contained more industrial Pb than below the NPSG, which was attributed to a calculated 60-fold greater flux of particulate Pb to abyssal waters near the Asian continent. Assuming Pb isotope compositions in the North Pacific Ocean were homogeneous prior to large-scale 20th century anthropogenic inputs, this evidence suggests a relatively faster change in Pb isotope ratios of North Pacific deep water below the WSAG versus the NPSG.

The global prevalence of industrial lead (Pb) contamination was exemplified decades ago by the predominance of anthropogenic Pb in samples of Antarctic surface ice and in Southern Ocean surface waters. Decreases in environmental Pb contamination corresponding with the near-global phase-out of leaded automobile gasoline beginning in the 1970s have since been observed. Measurements of Pb concentration in snow and ice core samples from Antarctica show that recent fluxes of industrial Pb to Antarctica have similarly declined. Here, we present measurements of Pb concentrations and isotopic compositions in seawater and surface sediments from the Amundsen Sea continental shelf including the Amundsen Sea Polynya. Both sets of measurements show that most (∼60-95%) of the Pb at our sites, at the time of sampling, is natural in source: that is, derived from the weathering of Antarctic continental rocks. These fluxes of natural Pb then become entrained into polynya waters either from sediment resuspension or from the transport of sediment-laden glacial melt waters to the polynya.

We evaluated both the spatial distribution of gadolinium (Gd) and other rare earth elements (REE) in surface waters collected in a transect of San Francisco Bay (SFB) and their temporal variations within the Bay over two decades. The REE were preconcentrated using the NOBIAS PA-1 resin prior to analysis by high-resolution inductively coupled plasma mass spectrometry. Measurements revealed a temporal increase in the Gd anomaly in SFB from the early 1990s to the present. The highest Gd anomalies were observed in the southern reach of SFB, which is surrounded by several hospitals and research centers that use Gd-based contrast agents for magnetic resonance imaging. Recent increases in that usage presumably contributed to the order of magnitude increase in anthropogenic Gd concentrations in SFB, from 8.27 to 112 pmol kg(-1) over the past two decades, and reach the northeast Pacific coastal waters. These measurements (i) show that "exotic" trace elements used in new high-tech applications, such as Gd, are emerging contaminants in San Francisco Bay and that anthropogenic Gd concentrations increased substantially over a 20 year period; (ii) substantiate proposals that REE may be used as tracers of wastewater discharges and hydrological processes; and (iii) suggest that new public policies and the development of more effective treatment technologies may be necessary to control sources and minimize future contamination by REE that are critical for the development of new technologies, which now overwhelm natural REE anomalies.

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/m(3)) 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 ((206)Pb/(207)Pb = 1.157-1.169; (208)Pb/(206)Pb = 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.

Relatively high levels (4.3 to 51 μg/g) of labile lead (Pb) in ash from the 2009 Jesusita Fire in Santa Barbara County, California attest to the pyrogenic remobilization of historic industrial lead depositions in this relatively pristine area in Southern California, USA. The primarily industrial origin of that lead was evidenced by its poor correlations (simple linear regressions) with lithogenic aluminum (r = 0.18, p = 0.354, n = 30) and iron (r = 0.21, p = 0.270, n = 30) concentrations and by its associated enrichment factors (EFs): EF using aluminum as conservative element (f-Al) vs lead concentration [Pb] (r = 0.79, p < 0.001, n = 30), and EF using iron as conservative element (f-Fe) vs [Pb] (r = 0.83, p < 0.001, n = 30). The industrial origins of much of that lead were corroborated by its isotopic compositions ((206)Pb/(207)Pb and (208)Pb/(207)Pb), which fell between those of natural lead in the Santa Barbara Basin and previous leaded gasoline emissions in Southern California. This apparent pyrogenic remobilization of legacy lead pollution indicates that it-and other persistent pollutants-will increase with the projected increase in the frequency and intensity of forest fires in the Southwest U.S. and elsewhere as a consequence of climate change.

Although trace element (Ag, As, Cd, Co, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Se, and Zn) and methylmercury (MeHg) concentrations have been systematically sampled 1-3 times per year throughout the San Francisco Bay estuary for more than two decades, those collections do not capture episodic events that may govern the biogeochemical cycles of these elements in the Bay and adjacent Pacific coastal waters. Analyses of the partitioning of in situ elemental concentrations between particulate and total dissolved (<0.45 microm) phases coupled with optically based measurements of suspended solids concentration (SSC) showed highly significant (p<0.001) associations between all elemental concentrations and SSC in the Bay. Predictive models were developed to estimate the distribution ratio (D), or partition coefficient (Kd), and total concentration of each element in the water column based solely on SSC measurements. Modeled predictions of total element concentrations and distribution ratios were then coupled with measured SSC to predict the concentrations of dissolved trace elements in the water column. These predicted total and dissolved concentrations of trace elements can provide both better diagnostics of biogeochemical cycling within the estuary and better estimates of fluxes to adjacent coastal waters, overcoming the limitations of the long-running but limited direct measurements of trace elements from existing sampling programs.

Analyses of lead concentration and isotopic composition of recent and archived samples of the lace lichen (Ramalina menziesii) chronicle more than a century of atmospheric lead contamination in central California. The contamination extends back to our oldest sample from 1892, when lead levels in lichen from the northern reach of the San Francisco Bay estuary were 9-12 microg/g and their isotopic composition corresponded to those of high lead emissions from the Selby smelter (e.g., (206)Pb/(207)Pb = 1.165) that were killing horses in adjacent fields at that time. By the mid-1950s lead isotopic compositions of lichens shifted to the more radiogenic leaded gasoline emissions (e.g., (206)Pb/(207)Pb = 1.18-1.22). Lead concentrations in the lichen peaked at 880 microg/g in 1976, corresponding with the maximum of leaded gasoline emissions in California in the 1970s. After that, lead concentrations in lichen declined to current levels, ranging from 0.2 to 4.7 microg/g. However, isotopic compositions of contemporary samples still correspond to those of previous leaded gasoline emissions in California. This correspondence is consistent with other observations that attest to the persistence of environmental lead contamination from historic industrial emissions in central California.

We describe ground and space-based measurements of spatial and temporal variation of NO(2) in four California metropolitan regions. The measurements of weekly cycles and trends over the years 2005-2008 observed both from the surface and from space are nearly identical to each other. Observed decreases in Los Angeles and the surrounding cities are 46% on weekends and 9%/year from 2005-2008. Similar decreases are observed in the San Francisco Bay area and in Sacramento. In the San Joaquin Valley cities of Fresno and Bakersfield weekend decreases are much smaller, only 27%, and the decreasing trend is only 4%/year. We describe evidence that the satellite observations provide a uniquely complete view of changes in spatial patterns over time. For example, we observe variations in the spatial pattern of weekday-weekend concentrations in the Los Angeles basin with much steeper weekend decreases at the eastern edge of the basin. We also observe that the spatial extent of high NO(2) in the San Joaquin Valley has not receded as much as it has for other regions in the state. Analysis of these measurements is used to describe observational constraints on temporal trends in emission sources in the different regions.

Energy production from fossil fuels, and in particular the burning of coal in China, creates atmospheric contamination that is transported across the remote North Pacific with prevailing westerly winds. In recent years this pollution from within Asia has increased dramatically, as a consequence of vigorous economic growth and corresponding energy consumption. During the fourth Intergovernmental Oceanographic Commission baseline contaminant survey in the western Pacific Ocean from May to June, 2002, surface waters and aerosol samples were measured to investigate whether atmospheric deposition of trace elements to the surface North Pacific was altering trace element biogeochemical cycling. Results show a presumably anthropogenic enrichment of Ag and of Se, which is a known tracer of coal combustion, in the North Pacific atmosphere and surface waters. Additionally, a strong correlation was seen between dissolved Ag and Se concentrations in surface waters. This suggests that Ag should now also be considered a geochemical tracer for coal combustion, and provides further evidence that Ag exhibits a disturbed biogeochemical cycle as the result of atmospheric deposition to the North Pacific.

Fluxes of total mercury (Hg(T)) and monomethylmercury (MMHg) associated with submarine groundwater discharge (SGD) at two sites onthe central California coast were estimated by combining measurements of Hg(T) and MMHg in groundwater with the use of short-lived, naturally occurring radium isotopes as tracers of groundwater inputs. Concentrations of Hg(T) were relatively low, ranging from 1.2 to 28.3 pM in filtered groundwater, 0.8 to 11.6 pM in filtered surface waters, and 2.5 to 12.9 pM in unfiltered surface waters. Concentrations of MMHg ranged from < 0.04 to 3.1 pM in filtered groundwater, < 0.04 to 0.53 pM in filtered surface waters, and 0.07 to 1.2 pM in unfiltered surface waters. Multiple linear regression analysis identified significant (p < 0.05) positive correlations between dissolved groundwater concentrations of Hg(T) and those of NH4+ and SiO2, and between dissolved groundwater concentrations of MMHg and those of Hg(T) and NH4+. However, such relationships did not account for the majority of the variability in concentration data for either mercury species in groundwater. Fluxes of Hg(T) via SGD were estimated to be 250 +/- 160 nmol day m(-1) of shoreline at Stinson Beach and 3.0 +/- 2.0 nmol m(-2) day(-1) at Elkhorn Slough. These Hg(T) fluxes are substantially greater than net atmospheric inputs of Hg(T) reported for waters in nearby San Francisco Bay. Calculated fluxes of MMHg to coastal waters via SGD were 10 +/- 12 nmol day(-1) m(-1) of shoreline at Stinson Beach and 0.24 +/- 0.21 nmol m(-2) day at Elkhorn Slough. These MMHg fluxes are similar to benthic fluxes of MMHg out of surface sediments commonly reported for estuarine and coastal environments. Consequently, this work demonstrates that SGD is an important source of both Hg(T) and MMHg to coastal waters along the central California coast.

Dimethyl mercury (DMHg) is commonly detected in the world's oceans, but little is known about the mechanisms responsible for DMHg degradation in natural waters or the products of this degradation. Similarly, the potential for the conversion of DMHg to monomethyl mercury (MMHg) under the acidic conditions commonly used to preserve samples for MMHg analysis has not been fully addressed. We provide evidence suggesting that DMHg in natural seawater is not readily photodegraded by sunlight as previously thought. Other experiments demonstrated that DMHg in seawater is, however, readily decomposed under acidic conditions, with MMHg as the predominant product. This facile conversion of DMHg to MMHg at low pH both necessitates an alternative preservation method to acidification for samples to be analyzed for MMHg when DMHg is present, and requires that data from previous studies of MMHg in seawater employing sample acidification be revisited in instances where appreciable DMHg concentrations were possible.

Depth profiles of dimethylmercury (DMHg) concentration were determined at nearshore to offshore sites in Monterey Bay, California. The onset of spring upwelling in the bay was accompanied by increases in DMHg concentrations. Profiles show DMHg increasing gradually with depth in fall and winter from <0.03 pM at the surface to 0.5 pM at 200 m. During the spring, DMHg concentrations increased between 30 and 100 m, first within Monterey Bay, then offshore. This change was accompanied by an increase in DMHg concentrations in the surface water DMHg between fall/winter (<0.03 pM) and spring (0.06-0.29 pM). Microbial activity associated with the remineralization of sinking organic matter produced by the high primary production in the bay may result in the relatively high DMHg in subsurface water in the bay, which when upwelled may facilitate the incorporation of organomercury into biota. As a result, productive coastal upwelling areas may represent an important source of methylated mercury to surface waters, and thus be an important source of mercury to marine ecosystems.

Ionization air purifiers are increasingly used to remove aerosol particles from indoor air. However, certain ionization air purifiers also emit ozone. Reactions between the emitted ozone and unsaturated volatile organic compounds (VOC) commonly found in indoor air produce additional respirable aerosol particles in the ultrafine (<0.1 microm) and fine (<2.5 microm) size domains. A simple kinetic model is used to analyze the competition between the removal and generation of particulate matter by ionization air purifiers under conditions of a typical residential building. This model predicts that certain widely used ionization air purifiers may actually increase the mass concentration of fine and ultrafine particulates in the presence of common unsaturated VOC, such as limonene contained in many household cleaning products. This prediction is supported by an explicit observation of ultrafine particle nucleation events caused by the addition of D-limonene to a ventilated office room equipped with a common ionization air purifier.

Analyses of lead isotopic compositions (204Pb, 206Pb, 207Pb, and 208Pb) of dated sediment cores from two coastal estuaries and two inland lakes chronicle the predominance of industrial lead emissions in Mexico over the past century. These isotopic ratios exhibit a shift in composition from the turn of the previous century (1900) that corresponds with measurable increases (from 2- to 10-fold) in lead concentrations in the cores above their baseline values (3-22 microg/g)--both changes are consistent with the development of Mexican lead production for export and the manufacture of tetraethyl lead additives for Mexican gasolines. While subsequent changes in lead concentrations in the cores correspond with calculated emissions from the combustion of leaded gasoline in Mexico, isotopic compositions of the cores remain relatively constant throughout most of the 1900s (e.g., 206Pb/207Pb = 1.200 +/- 0.003; 208Pb/207Pb = 2.463 +/- 0.004). That isotopic constancy is attributed to the widespread pollution from lead production in Mexico and the dispersion of some of that lead used as an additive in Mexican gasolines.

Over the past decade, San Francisco Bay surface waters have remained enriched with dissolved (<0.45 microm) silver and lead concentrations (decadal means of 5.7 ng kg(-1) Ag[filtered] and 31 ng kg(-1) Pb[filtered]) compared with those (0.26 ng kg(-1) Ag[filtered] and 2.7 ng kg(-1) Pb[filtered]) of adjacent oceanic surface waters of the northeast Pacific, despite efforts to reduce pollutant loadings to the Bay during that period. While time series models show that there has been a 40% decline in total lead concentrations in the southern reach of the estuarine system between 1989 and 1999, the filtered lead fraction has not changed significantly during that time. That persistence is attributed to (i) the ongoing input from previous atmospheric depositions and industrial lead to its drainage basin, which are slowly being advected into the estuary and (ii) the internal recycling of lead between the surface sediments and the water column within the Bay. In contrast, both filtered and total silver concentrations in the southern reach have declined by 70% and 40%, respectively, within the past decade. These temporal declines are attributed to a 2-fold decrease in silver loadings from publicly owned treatment works and a comparable decline in the silver concentration of surficial sediments within that region during the past decade. In the northern reach, silver and lead concentrations have remained essentially constant between 1989 and 1999, reflecting invariable anthropogenic input of these elements to this embayment over that decade.