Natural Lead Levels in Dandelions ( Taraxacum officinale): A Weed, Folk Medicine, and Biomonitor.

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 (206Pb/207Pb:208Pb/207Pb) 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.

Mercury offloaded in Northern elephant seal hair affects coastal seawater surrounding rookery.

Methylmercury (MeHg) is a potent neurotoxin that is biomagnified approximately 1-10 million-fold in aquatic carnivores such as the Northern elephant seal (Mirounga angustirostris), whose excreta and molted pelage, in turn, constitute a source of environmental MeHg contamination at the base of marine food chains. The potential for this top-down contamination is greatest in coastal areas with productive marine ecosystems that provide ideal habitats for large marine mammal colonies that can number in the thousands. This recycling of MeHg was evidenced by comparing total mercury (HgT) and MeHg concentrations in seawater, and HgT in molted pelage of M. angustirostris, at the Año Nuevo State Reserve pinniped rookery with concentrations at neighboring coastal sites in Central California. Seawater MeHg concentrations around the rookery (average = 2.5 pM) were markedly higher than those at the comparison coastal sites (average = 0.30 pM), and were as high as 9.5 pM during the M. angustirostris molting season. As a consequence, excreta and molts from this marine mammal colony, and presumably other marine predator populations, constitute a major source of MeHg at the base of the local marine food chain.

Historic and Industrial Lead within the Northwest Pacific Ocean Evidenced by Lead Isotopes in Seawater.

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.

Increases in Anthropogenic Gadolinium Anomalies and Rare Earth Element Concentrations in San Francisco Bay over a 20 Year Record.

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.

Lead Sources to the Amundsen Sea, West Antarctica.

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.

Total and monomethyl mercury in terrestrial arthropods from the central California coast.

The aim of this project was to obtain a baseline understanding and investigate the concentration of mercury (Hg) in the tissue of terrestrial arthropods. The 4-month sampling campaign took place around Monterey Bay, California. Total mercury (HgT) concentrations (x ± SD, dry weight) for the captured specimens ranged from 22 to 188 ng g(-1) in the Jerusalem crickets (Orthoptera: Stenopelmatidae); 65-233 ng g(-1) in the camel crickets (Orthoptera: Rhaphidophoridae); 25-227 ng g(-1) in the pill bugs (Isopoda: Armadillidiidae); 19-563 ng g(-1) in the ground beetles (Coleoptera: Carabidae); 140-441 ng g(-1) in the variegated meadowhawk dragonflies (Odonata: Libellulidae); 607-657 ng g(-1) in the pacific spiketail dragonflies (Odonata: Cordulegastridae); and 81-1,249 ng g(-1) in the wolf spiders (Araneae: Lycosidae). A subset of samples analyzed for monomethyl mercury (MMHg) suggest detrital pill bugs have a higher MMHg/HgT ratio than predatory ground beetles.

Pyrogenic remobilization of historic industrial lead depositions.

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.

Asian industrial lead inputs to the North Pacific evidenced by lead concentrations and isotopic compositions in surface waters and aerosols.

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.

Modeled trace element concentrations and partitioning in the San Francisco estuary, based on suspended solids concentration.

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.

Distinguishing between Natural and Industrial Lead in Consumer Products and Other Environmental Matrices.

California's Safe Drinking Water and Toxic Enforcement Act of 1986 (Proposition 65) was designed to protect the state's populace from exposures to toxic levels of chemicals in consumer products, including foods, by requiring businesses to warn the public about any of those hazards. There is, however, one qualification in the legislation, which is that warnings are not required if the source of that contamination is natural, as opposed to industrial. That qualification is especially problematic for lead because "natural" and "industrial" lead have a common origin and behave the same in the environment and industrial lead contamination has been pandemic for millennia. As a result of that historic and ongoing contamination, ambient lead levels in the biosphere may be orders of magnitude above natural levels, limiting comparisons of "natural" versus "industrial" lead concentrations in products. Further complicating those comparisons are reports of erroneously high measurements of lead concentrations in the biosphere as a result of sample contamination during collection, storage, and analysis. Some of those problems may be addressed with measurements of lead concentrations using rigorous trace metal clean techniques. These techniques often yield lead concentrations that are below the Act's maximum exposure in foods and non-foods of 0.5 µg/day, eliminating the need for a public alert. Those techniques have also been used to derive natural lead concentrations in a few organisms (marine fish, humans, rats, and dandelions), which range from 2- to 100-fold below ambient levels. However, extrapolating from those few determinations to establish natural lead levels in other organisms is complicated and often inappropriate. Complementary stable lead isotopic composition measurements have also been used to estimate the percent of natural and industrial lead in some consumer products, including foods, wine, and dietary supplements. These measurements, however, require the isotopic compositions of both the "natural" and "industrial" lead end members, which may be poorly defined. In addition, the global market has further complicated identification of the "industrial" lead end member, because lead contamination of foods can occur during production, harvesting, storage, shipping, processing, and packaging, which can happen in different locales within a country, different countries, and even different continents.

Anthropogenic contamination of residential environments from smelter As, Cu and Pb emissions: Implications for human health.

Communities in low-income and middle-income countries (LMIC) are disproportionally affected by industrial pollution compared to more developed nations. This study evaluates the dispersal and associated health risk of contaminant-laden soil and dust at a copper (Cu) smelter in Tsumeb, Namibia. It is Africa's only smelter capable of treating complex Cu ores that contain high arsenic (As) contents (<1%). The analyses focused on the primary trace elements associated with ore processing at the smelter: As, Cu, and lead (Pb). Portable X-Ray fluorescence spectrometry (pXRF) of trace elements in soils (n = 83) and surface dust wipes (n = 80) showed that elemental contamination was spatially associated with proximity to smelter operations. Soil concentrations were below US EPA soil guidelines. Dust wipe values were elevated relative to sites distal from the facility and similar to those at other international smelter locations (As = 1012 µg/m2 (95% CI 687-1337); Cu = 1838 µg/m2 (95% CI 1191-2485); Pb = 1624 µg/m2 (95% CI 862-2385)). Source apportionment for Pb contamination was assessed using Pb isotopic compositions (PbIC) of dust wipes (n = 22). These data revealed that the PbIC of 73% (n = 16/22) of these wipes corresponded to the PbIC of smelter slag and tailings, indicating contribution from industrial emissions to ongoing exposure risk. Modeling of carcinogenic risk showed that dust ingestion was the most important pathway, followed by inhalation, for both adults and children. Dermal contact to trace elements in dust was also determined to pose a carcinogenic risk for children, but not adults. Consequently, contemporary smelter operations remain an ongoing health risk to the surrounding community, in spite of recent efforts to improve emissions from the operations.

Mercury concentrations and loads in a large river system tributary to San Francisco Bay, California, U.S.A.

In order to estimate total mercury (HgT) loads entering San Francisco Bay, U.S.A., via the Sacramento-San Joaquin River system, unfiltered water samples were collected between January 2002 and January 2006 during high flow events and analyzed for HgT. Unfiltered HgT concentrations ranged from 3.2 to 75 ng/L and showed a strong correlation (r2 = 0.8, p < 0.001, n=78) to suspended sediment concentrations (SSC). During infrequent large floods, HgT concentrations relative to SSC were approximately twice as high as observed during smaller floods. This difference indicates the transport of more Hg-contaminated particles during high discharge events. Daily HgT loads in the Sacramento-San Joaquin River at Mallard Island ranged from below the limit of detection to 35 kg. Annual HgT loads varied from 61 +/- 22 kg (n=5) in water year (WY) 2002 to 470 +/- 170 kg (n=25) in WY 2006. The data collected will assist in understanding the long-term recovery of San Francisco Bay from Hg contamination and in implementing the Hg total maximum daily load, the long-term cleanup plan for Hg in the Bay.

Comparison of mass discrimination correction methods and sample introduction systems for the determination of lead isotopic composition using a multicollector inductively coupled plasma mass spectrometer.

The influence of sample introduction system on Neptune MC-ICPMS lead isotopic ratio measurements was tested on dilute solutions of the lead certified material NIST SRM 981 ([Pb] = 0.2-170 ng g(-1)) using (1) a SIS spray chamber, (2) a MCN 6000 desolvating system, or (3) an Apex inlet system. The impact of using a high-efficiency X-cone in place of a standard H-cone with the MCN and Apex was also investigated. Performance of the sample introduction systems varied with lead concentration. Over 10 ng g(-1), no system was significantly more precise or accurate. As lead concentrations decreased, both accuracy and precision diminished, and below 1 ng g(-1), use of an X-cone in combination with the Apex and particularly with the MCN system notably improved the quality of the measurements. Various mathematical methods of mass bias correction using thallium additions were tested. Selection of (205)Tl/(203)Tl for NIST SRM 997 to optimize data (1) daily, (2) for each introduction system, and (3) over all sessions significantly improved the data, with no major difference in the output between the three methods. Consistency of the (205)Tl/(203)Tl ratio (2.3888) optimized over all data with previous observations by others supports the use of this value for future measurements.

Mercury in the San Francisco Estuary.

This review presents some of the published and other important literature on mercury contamination in San Francisco Estuary. Studies on human consumption of contaminated sportfish and on detecting ecological impacts of this contamination in wetland areas validate concerns regarding mercury's toxicity in this system. Mining, industrial, and environmental uses of mercury have occurred for more than a century, resulting in its large historic and continuing transport to the estuary. Consequently, there is a widespread distribution in the estuary, but more work is needed to show its relative chemical and biological availability from these sources. The uptake of mercury in the estuary has been shown in phytoplankton, but studies on biomagnification in local food webs have yet to draw a clear path to impairment in sportfish and waterbirds. In light of these concerns of impairment and the need for further information, large restoration activities planned for the estuary will require new technical approaches to solve important management questions, such as the location of key areas of methylmercury production.

Lead pollution in subtropical ecosystems on the SE Gulf of California Coast: a study of concentrations and isotopic composition.

Lead pollution was investigated in environmental matrices and biological indicators collected from two typical subtropical coastal ecosystems in the southeast Gulf of California, Mexico. Lead concentrations and isotopic compositions ((206)Pb/(207)Pb and (208)Pb/(207)Pb) were measured using high resolution inductively-coupled plasma-mass spectrometry (HR-ICP-MS) and thermal ionization mass spectrometry (TIMS), respectively. Lead in surface estuary sediments (10.0-34.2microgg(-1)) and particulate Pb (25.0-128.7microgg(-1), >98% of total Pb) in the water column were significantly higher than levels in natural bedrock soils (15.1+/-8.3microgg(-1)) and river runoff (1.9+/-1.4microgg(-1)). Aquatic plants had Pb concentrations between 2.5 and 7.2microgg(-1), while those in macroalgae ranged from 3 to 5microgg(-1). The ranges of mean Pb concentrations in the aquatic animals studied (ranges in microgg(-1)) were as follows: zooplankton 32+/-3, mussels 2.3-3.9, oysters 1.9-7.9, snail 2.0-7.7, barnacles 0.1-18.5, fish 1.4-8.9, crab 6.3-40.2 and polychaetae 8.5-16.7. Pb values in 20-40% of oyster and fish samples and in all samples of crab exceeded acceptable levels for a food source for human consumption. Pb isotope ratios (206)Pb/(207)Pb, (208)Pb/(207)Pb in biota ranged from 1.188 to 1.206 and 2.448 to 2.470, respectively. A plot of (206)Pb/(207)Pb versus (208)Pb/(207)Pb for the environmental and biological samples collected from two study areas indicates that they contain lead from ores mined in Mexico and used in the past to produce leaded gasoline in use until 1997, natural Pb weathered from the Sierra Madre Occidental mother rock, and the later influence of inputs from a more radiogenic source related to industrial activity in the United States. Statistical software IsoSource results revealed that the Pb contained in environmental matrices and biomonitors is mostly derived from gasoline (20-90%) and US emissions (10-40%).

Lead contamination in cocoa and cocoa products: isotopic evidence of global contamination.

In this article we present lead concentrations and isotopic compositions from analyses of cocoa beans, their shells, and soils from six Nigerian cocoa farms, and analyses of manufactured cocoa and chocolate products. The average lead concentration of cocoa beans was

Evaluation of mussel immune responses as indicators of contamination in San Francisco Bay.

Several immune parameters were evaluated in two species of mussels (Mytilus californianus and M. galloprovincialis/M. trossulus) as bioindicators of contaminant effects. The mussels were deployed in San Francisco Bay Estuary and a control site at Bodega Marine Laboratory. Assays for phagocytosis and phagocytic index (average number of particles engulfed per hemocyte) were conducted with hemocytes in their own hemolymph-the "Serum" method. The responses were compared with contaminant concentrations in those mussels. For both species, the contaminated South Bay Dumbarton Bridge and Redwood Creek sites had elevated phagocytosis relative to the Bodega control site, indicating contaminant stress. The results also showed that M. californianus had higher percentages of phagocytosis (74%) and a higher phagocytic index (4.6 particles per cell) than those of M. galloprovincialis/M. trossulus (60% phagocytosis and 3.5 particles per cell). As there is a difference in immune response to contaminants, it is suggested that future San Francisco Estuary monitoring should be conducted with endemic M. galloprovincialis/M. trossulus rather than with the currently utilized M. californianus, which is not found in the estuary.

Trace metal inventories and lead isotopic composition chronicle a forest fire's remobilization of industrial contaminants deposited in the angeles national forest.

The amounts of labile trace metals: [Co] (3 to 11 µg g-1), [Cu] (15 to 69 µg g-1), [Ni] (6 to 15 µg g-1), [Pb] (7 to 42 µg g-1), and [Zn] (65 to 500 µg g-1) in ash collected from the 2012 Williams Fire in Los Angeles, California attest to the role of fires in remobilizing industrial metals deposited in forests. These remobilized trace metals may be dispersed by winds, increasing human exposures, and they may be deposited in water bodies, increasing exposures in aquatic ecosystems. Correlations between the concentrations of these trace metals, normalized to Fe, in ash from the fire suggest that Co, Cu, and Ni in most of those samples were predominantly from natural sources, whereas Pb and Zn were enriched in some ash samples. The predominantly anthropogenic source of excess Pb in the ash was further demonstrated by its isotopic ratios (208Pb/207Pb: 206Pb/207Pb) that fell between those of natural Pb and leaded gasoline sold in California during the previous century. These analyses substantiate current human and environmental health concerns with the pyrogenic remobilization of toxic metals, which are compounded by projections of increases in the intensity and frequency of wildfires associated with climate change.

Lead isotopic compositions of ash sourced from Australian bushfires.

This study identifies natural and industrial lead remobilized in ash deposits from three bushfires in relatively pristine areas of Australia in 2011 using lead isotopic compositions ((208)Pb/(207)Pb; (206)Pb/(207)Pb). Lead concentrations in the ash ranged from 1 to 36 mg/kg, bracketing the range of lead (4-23 mg/kg) in surface soils (0-2 cm), subsurface (40-50 cm) soils and rocks. The lead isotopic compositions of ash and surface soil samples were compared to subsurface soils and local bedrock samples. The data show that many of the ash and surface soil lead isotopic compositions were a mixture of natural lead and legacy industrial lead depositions (such as leaded petrol combustion). However, some of the ash samples at each of the sites had lead isotopic compositions that did not fit a simple two end-member mixing model, indicating other, unidentified sources.