Mercury speciation and transport via submarine groundwater discharge at a southern California coastal lagoon system.

We measured total mercury (Hg(T)) and monomethylmercury (MMHg) concentrations in coastal groundwater and seawater over a range of tidal conditions near Malibu Lagoon, California, and used (222)Rn-derived estimates of submarine groundwater discharge (SGD) to assess the flux of mercury species to nearshore seawater. We infer a groundwater-seawater mixing scenario based on salinity and temperature trends and suggest that increased groundwater discharge to the ocean during low tide transported mercury offshore. Unfiltered Hg(T) (U-Hg(T)) concentrations in groundwater (2.2-5.9 pM) and seawater (3.3-5.2 pM) decreased during a falling tide, with groundwater U-Hg(T) concentrations typically lower than seawater concentrations. Despite the low Hg(T) in groundwater, bioaccumulative MMHg was produced in onshore sediment as evidenced by elevated MMHg concentrations in groundwater (0.2-1 pM) relative to seawater (∼0.1 pM) throughout most of the tidal cycle. During low tide, groundwater appeared to transport MMHg to the coast, resulting in a 5-fold increase in seawater MMHg (from 0.1 to 0.5 pM). Similarly, filtered Hg(T) (F-Hg(T)) concentrations in seawater increased approximately 7-fold during low tide (from 0.5 to 3.6 pM). These elevated seawater F-Hg(T) concentrations exceeded those in filtered and unfiltered groundwater during low tide, but were similar to seawater U-Hg(T) concentrations, suggesting that enhanced SGD altered mercury partitioning and/or solubilization dynamics in coastal waters. Finally, we estimate that the SGD Hg(T) and MMHg fluxes to seawater were 0.41 and 0.15 nmol m(-2) d(-1), respectively - comparable in magnitude to atmospheric and benthic fluxes in similar environments.

Spatial and temporal variations in silver contamination and toxicity in San Francisco Bay.

Although San Francisco Bay has a "Golden Gate", it may be argued that it is the "Silver Estuary". For at one time the Bay was reported to have the highest levels of silver in its sediments and biota, along with the only accurately measured values of silver in solution, of any estuarine system. Since then others have argued that silver contamination is higher elsewhere (e.g., New York Bight, Florida Bay, Galveston Bay) in a peculiar form of pollution machismo, while silver contamination has measurably declined in sediments, biota, and surface waters of the Bay over the past two to three decades. Documentation of those systemic temporal declines has been possible because of long-term, ongoing monitoring programs, using rigorous trace metal clean sampling and analytical techniques, of the United States Geological Survey and San Francisco Bay Regional Monitoring Program that are summarized in this report. However, recent toxicity studies with macro-invertebrates in the Bay have indicated that silver may still be adversely affecting the health of the estuarine system, and other studies have indicated that silver concentrations in the Bay may be increasing due to new industrial inputs and/or the diagenetic remobilization of silver from historically contaminated sediments being re-exposed to overlying surface waters and benthos. Consequently, the Bay may not be ready to relinquish its title as the "Silver Estuary".

Natural occurrence of hexavalent chromium in the Aromas Red Sands Aquifer, California.

To address increasing concerns of chromium contamination in the drinking water of Santa Cruz County, we designed a study to investigate the source(s) and spatial gradients of the chromium concentration and speciation in local aquifers. This study was catalyzed by a report (January 2001) bythe Soquel Creek Water District of elevated hexavalent chromium concentrations ranging from 6 to 36 microg L(-1), approaching the state's maximum concentration limit of 50 microg L(-1), in the Aromas Red Sands aquifer. To test the accuracy of those preliminary measurements, we collected groundwater using trace metal clean techniques from 11 sites in Santa Cruz County, including 10 from the aquifer with reportedly elevated chromium concentrations and 1 from an adjacent aquifer, the Purisima, and analyzed them fortotal chromium using inductively couple plasma mass spectrometry. Nine of the reportedly 10 contaminated sites had total chromium concentrations ranging from 5 to 39 microg L(-1), while one from the control site was below the limit of detection (0.01 microg L(-1)). We also measured the speciation of chromium at all sites using a solid supported membrane extraction coupled with graphite furnace atomic absorption spectrometry and determined that on average 84% of total chromium was Cr(VI). In addition to the groundwater analyses, a series of extractions were performed on sediment samples from both the Aromas Red Sands and Purisima aquifers. These tests were used to empirically characterize sediment trace metal (Cr, Fe, Mn) distributions in five phases providing information about the origin, availability, reactivity, and mobilization of these trace metals. Results from groundwater and sediment samples indicate that the chromium is naturally occurring in the Aromas Red Sands aquifer, possibly by Cr(III) mineral deposits being oxidized to Cr(VI) by manganese oxides in the aquifer.

New isotopic evidence for chronic lead contamination in the San Francisco Bay estuary system: implications for the persistence of past industrial lead emissions in the biosphere.

Measurements of lead isotope compositions in unfiltered San Francisco Bay waters from 1989 to 1998 have brought new insights into the cycling of anthropogenic lead in estuaries. Isotopic compositions of lead in the shallow (<2 m) southern reach were essentially invariant ( approximately 90% derived from 1960s-1970s leaded gasoline) during the study period because of limited hydraulic flushing and the remobilization of lead from bottom sediments. In contrast, in the northern reach freshwater flushing from the San Joaquin and Sacramento rivers produced seasonal and decadal variations in lead isotope compositions. The seasonal shifts are attributed to advection of soils containing late 1980s gasoline lead into the bay during winter rains. Mass balance calculations indicate that only a small fraction (1-10%) of this leaded gasoline fallout from the late 1980s has been washed out of the San Joaquin and Sacramento rivers' drainage basin by 1995. Superimposed on this seasonal cycling was a long-term systematic shift in the component of gasoline lead expressed in the river systems, with a small ( approximately 5-10%) decrease in the amount of 1960s-1970s gasoline lead in river and North Bay waters. The retention of gasoline lead in the river systems draining into the bay as well as San Francisco Bay sediments indicates that historic gasoline deposits may remain in the combined riparian/estuarine system for decades. Such a persistence is in contraindication to recent reports of rapid (annual) decreases in lead contamination in other environments, and the link between climate and contaminant transport suggests local or global climate change will have an impact on contaminant distribution and fate.

Lead in calcium supplements.

Intercalibrated measurements of lead in calcium supplements indicate the importance of rigorous analytical techniques to accurately quantify contaminant exposures in complex matrices. Without such techniques, measurements of lead concentrations in calcium supplements may be either erroneously low, by as much as 50%, or below the detection limit needed for new public health criteria. In this study, we determined the lead content of 136 brands of supplements that were purchased in 1996. The calcium in the products was derived from natural sources (bonemeal, dolomite, or oyster shell) or was synthesized and/or refined (chelated and nonchelated calcium). The dried products were acid digested and analyzed for lead by high resolution-inductively coupled plasma-mass spectrometry. The method's limit of quantitation averaged 0.06 microg/g, with a coefficient of variation of 1.7% and a 90-100% lead recovery of a bonemeal standard reference material. Two-thirds of those calcium supplements failed to meet the 1999 California criteria for acceptable lead levels (1.5 microg/daily dose of calcium) in consumer products. The nonchelated synthesized and/or refined calcium products, specifically antacids and infant formulas, had the lowest lead concentrations, ranging from nondetectable to 2.9 microg Pb/g calcium, and had the largest proportion of brands meeting the new criteria (85% of the antacids and 100% of the infant formulas).

Lead isotopes in the western North Atlantic: transient tracers of pollutant lead inputs.

In the early 1980s, Patterson and colleagues demonstrated that most lead in oceanic surface waters had an anthropogenic origin. Their discovery occurred during the phasing out of leaded gasoline in North America initiated in the previous decade. The corresponding decrease in the anthropogenic lead emissions, verified by Pb/210Pb ratios, accounted for the systematic decline in lead concentrations in surface waters of the western Sargasso Sea. Subsequent changes in anthropogenic lead inputs to the western Sargasso Sea surface waters have been documented by measurements of lead concentrations, isotopic compositions (206Pb/207Pb, 208Pb/206Pb), and Pb/210Pb ratios in precipitation and seawater for the period of 1981 to 1994. These data indicate the easterly trade winds are now the primary source of atmospheric lead in Bermuda, and they confirm that the decline of lead concentrations in the North Atlantic is associated with the phasing out of leaded gasoline in North America and western Europe over the past decade. Moreover, temporal variations in the relative contribution of industrial lead inputs from the two sides of the North Atlantic over that period can be quantified based on differences in their isotopic composition. The transient character of those isotopic signatures also allows calculations of pollutant lead penetration rates into the mixed layer and upper thermocline of the western Sargasso Sea.

Blood lead concentrations in marine mammals validate estimates of 10(2)- to 10(3)-fold increase in human blood lead concentrations.

Measurements of ultra-low ambient blood lead (PbB) concentrations (mean +/- SD = 0.13 +/- 0.06 micrograms/dL) in Northern elephant seal (Mirounga angustirostris) validate previous estimates of ultra-low PbB levels in preindustrial humans. These estimates had been unsubstantiated, since PbB levels in this range had never been measured in any organisms prior to this study. Similarities in PbB levels among these contemporary and preindustrial mammals are consistent with similarities in their measured and estimated lead exposures, respectively. The marginally higher PbB levels and rates of lead exposure in contemporary marine mammals are, also, consistent with lead isotopic composition analyses that indicate their PbB levels have been elevated from exposure to industrial lead. Consequently, these analyses substantiate concerns that current baseline PbB levels in humans, which are estimated to be two to three orders of magnitude above natural levels, may still constitute public health risks.

Use of endogenous, stable lead isotopes to determine release of lead from the skeleton.

The stable lead isotope methodology can be used to study the release of lead from bone into the circulation because of its potential to distinguish circulatory lead from "older" and isotopically different skeletal lead that may have been accumulated years or decades earlier. Here we report the initial results from a larger ongoing study that evaluates the skeleton as a source of lead to the circulation in environmentally exposed human subjects. Lead concentrations and stable lead isotopic compositions were measured in blood and trabecular bone samples obtained from five patients who underwent total hip or knee joint replacement. All subjects contained low blood (1-6 micrograms/dl) and bone (0.6-7 micrograms/g dry weight) lead concentrations typical of environmentally exposed individuals. There were relatively large differences in the lead isotopic compositions between the paired blood and bone samples from each subject. These isotopic differences are attributed to differences in the lead isotopic compositions of past versus current lead exposures and to the long elimination half-life of lead in the skeleton compared to lead in the circulation. Based on these data, we determined that the skeleton contributed 40-70% of the lead in the blood of these subjects. This initial study demonstrates the utility of the stable lead isotope methodology for investigating the release of lead from the skeleton. It also shows that the skeleton can be an important endogenous source of lead exposure in environmentally exposed humans.

Measurements of environmental lead contamination and human exposure.

The importance of accurate measurements of environmental lead exposure and toxicity is substantiated by analyses documenting the global contamination of the biosphere with industrial lead and the pervasiveness of measurable lead toxicity in human populations. Those data demonstrating environmental lead contamination and toxicity have, in part, led to regulations that limit the amount of lead in some products (e.g., paint, solder, and gasolines) in many industrialized countries. These regulations have resulted in a substantial reduction in some lead discharges to the environment. In spite of these reductions, current environmental lead levels are still often more than 10-fold, and sometimes more than 10,000-fold, higher than natural levels. Further, environmental lead concentrations are expected to remain elevated for a protracted period due to continued emissions of relatively large amounts of industrial lead to the environment and the persistence of contaminant lead in the environment. Discharges of contaminant lead have resulted in increases in organism and human lead levels comparable to increases documented in environmental matrices, as indicated by a recent estimate of the natural level of lead in blood of preindustrial humans (0.016 microgram/dL or 0.8 nM). This estimate is 175-fold lower than average blood lead levels in the United States (2.8 micrograms/dL or 140 nM) and 600-fold lower than the recently (1991) revised Centers for Disease Control (CDC) action level of concern for early toxic effects in children (10 micrograms/dL or 480 nM). The significance of these comparisons to public health is corroborated by numerous studies suggesting that there may be no lower threshold for sublethal toxicity in contemporary (i.e., lead-contaminated) humans. Those data also indicate that environmental lead concentrations that were previously considered innocuous may be deleterious to human health. It is apparent that the extent of sublethal lead toxicity in humans may be best addressed by studies that consider control populations possessing natural (i.e., preindustrial) lead burdens, as well as state-of-the-art, trace-metal-clean techniques and advanced instrumentation. Trace-metal-clean techniques are required to prevent the inadvertent lead contamination of samples, which has plagued many previous analyses of environmental and human lead levels. Advanced instrumentation is required to provide the sensitivity, accuracy, and precision that are needed to quantify the sublethal effects of lead concentrations at environmental levels of exposure. Fortunately, methodologies utilizing these advancements are now capable of addressing many of the important issues (e.g., lead biomolecular speciation, low exposure effects) in environmental and human lead toxicology.

The effects of succimer on the absorption of lead in adults determined by using the stable isotope 204Pb.

The chelating agent succimer (meso-2,3-dimercaptosuccinic acid) is orally effective at inducing a urinary lead diuresis and a decrease in blood lead levels in lead poisoned children and adults. However, there are concerns that succimer may increase the absorption of lead from the gastrointestinal (GI) tract during treatment, particularly in cases of continuing lead exposure, which would compromise its effectiveness in reducing whole body lead stores. This preliminary study investigated the effects of succimer on the absorption of lead in adults using a stable lead isotopic tracer (204Pb). Twelve male subjects were divided into control (no succimer), 10, and 30 mg succimer/kg body wt treatment groups of 4 individuals each. All subjects ingested a single tracer dose (200 micrograms) of 204Pb, followed by a single oral dose of placebo (control) or succimer. Whole blood was collected at intervals of 0, 2, 4, and approximately 26 hr following ingestion of the 204Pb tracer, and composite urine and feces samples were collected over the duration of the study (approximately 26 hr). Mean intestinal excretion of 204Pb was reduced in the succimer-treated groups compared to the control (placebo), whereas urinary diuresis of 204Pb was higher in the succimer groups. The amount of lead 204Pb tracer accounted for at the end of the study was lower in the succimer-treated groups. These results suggest that GI lead absorption was enhanced by succimer and that succimer mediated the redistribution of lead from the circulation to other tissues. However, none of the differences between treatment groups were statistically significant (P < 0.05, t test) because of the relatively large within-group variability. This study demonstrates the utility of microgram doses of a stable lead isotopic tracer to assess the efficacy of clinical chelating agents in humans. Future studies are necessary to further clarify the effects of succimer on the absorption and retention of lead in adults and children. Although, based upon these preliminary data, it appears advisable that patients be maintained in a lead-safe environment while being treated with succimer.

Stable isotopic tracers of lead mobilized by DMSA chelation in low lead-exposed rats.

The ability of DMSA to mobilize skeletal lead or effect a redistribution of endogenous lead to other target organs in low lead-exposed organisms is unclear. Discrepant results of past studies of DMSA and other lead chelators (e.g., CaNa2EDTA) may be due, in part, to experimental differences and difficulties in distinguishing mobilized skeletal lead from other endogenous or exogenous lead sources. Therefore, the influence of DMSA on the mobilization and redistribution of lead in skeletal and soft tissue compartments of low lead-exposed female Wistar (115-125 g) rats was investigated using ultraclean stable lead isotope tracer techniques. Rats that had been reared on a low lead-level diet (lead intake approximately 80 ng Pb/g body/day) were fed 206Pb-enriched drinking water (210 ng Pb/ml) for 1.5 days and then were chelated with a single ip injection of a 0.11 mmol/kg dose of DMSA. Blood, kidney, brain, tibia, urine and feces were collected 24 hr after chelation and analyzed for lead concentrations by graphite furnace atomic absorption spectrometry and for lead isotopic compositions by thermal ionization mass spectrometry. These analyses demonstrated that DMSA chelation significantly increased (15-fold) the diuresis of labile soft tissue lead, but not skeletal lead. DMSA also appeared to effect a redistribution and input of a comparable amount of lead to the skeleton and smaller relative amounts of lead to the soft tissues (blood, kidney) of the chelated animals. The clinical significance of these latter observations beyond the context of this preliminary study is not clear.

Current needs for increased accuracy and precision in measurements of low levels of lead in blood.

Needs for accurate and precise measurements of low levels of lead in blood are discussed. Current methodologies are sufficient for measuring blood lead (PbB) levels greater than 0.5 microM, but the accuracy and precision of those methodologies are inadequate for measuring lower (less than 0.5 microM) PbB concentrations. These analytical limitations are primarily due to contamination bias incurred during sample collection, processing, and analyses. Consequently, trace metal-clean procedures should be adopted to elucidate the contribution of environmental lead to the PbB levels of the U.S. population and to estimate the threshold(s) of subclinical lead toxicity.

Stable isotope labeling of lead compartments in rats with ultralow lead concentrations.

The role of the mammalian skeleton as an endogenous lead source is unclear. This is due in part to difficulties in distinguishing mobilized skeletal lead from other endogenous and exogenous lead sources. Therefore, we have applied ultraclean stable lead isotope techniques to label skeletal and soft tissue lead compartments within the rat with distinguishable lead isotopic signatures. Female Wistar (defined flora) rats were fed 206Pb-enriched drinking water ([Pb] = 110 ng/ml) and sacrificed after durations of 2, 4, 7, and 14 days. Blood, kidney, vertebra, and tibia tissues were analyzed for lead concentrations and stable isotopic compositions. The resulting isotopic ratios in soft (blood and kidney) and skeletal (vertebrae and tibia) tissues differed by approximately 40% after 2 days exposure to the 206Pb tracer. More than 90% of the tracer isotopic signature was contained in the soft tissues after 10 days exposure, while skeletal tissues acquired only approximately 50% of the tracer by the end of the study. Because these animals were maintained under trace metal-clean conditions, they contained lead concentrations in whole blood (0.3-3 ng/g), kidney (11-27 ng/g dry wt), and bone (35-70 ng/g dry wt) tissues that are the lowest known reported for contemporary terrestrial mammals, and they (in bone) are comparable to levels in preindustrial mammals. The elevated concentrations of lead in kidney (fresh weight) relative to levels in blood are consistent with the presence of specific lead-binding sites in the kidney at very low levels of exposure.

Lead sources to California sea otters: industrial inputs circumvent natural lead biodepletion mechanisms.

Lead levels (as Pb/Ca atom ratios) and stable isotopic compositions were measured in teeth of preindustrial and contemporary California sea otters (Enhydra lutris) to determine if postindustrial changes had occurred in the magnitude and source of accumulated lead. Lead/calcium atom ratios (means +/- SD) in teeth of some contemporary animals (110 +/- 37 x 10(-8), n = 3) were significantly elevated compared to levels in other contemporary (13 +/- 6.0 x 10(-8), n = 4) and preindustrial (7.3 +/- 3.9 x 10(-8), n = 6) otters. The isotopic ratios (means +/- 2 sigma means) revealed a change in the sources of accumulated leads, from natural continental-derived leads in the preindustrial animals (207Pb/206Pb = 0.820 +/- 0.002) to industrial sources dominated by aerosol leads in the contemporary otters (207Pb/206Pb = 0.836 +/- 0.003). The one exception was a contemporary Monterey Bay animal (207Pb/206Pb = 0.853), who contained lead derived from an industrial waste lead deposit in Monterery Harbor. These data establish distinguishable sources of lead assimilated by sea otters, and indicate that elevated exposures to some animals circumvented the natural biodepletion of lead through marine trophic pathways.

Skeletal concentrations of lead, cadmium, zinc, and silver in ancient North American Pecos Indians.

Bone samples of 14 prehistoric North American Pecos Indians from circa 1400 A.D. were analyzed for lead, cadmium, zinc, and silver by graphite furnace atomic absorption spectrometry to establish the baseline levels of these elements in an ancient North American population. Measurements of outer and inner bone fractions indicate the former were contaminated postmortem for lead, zinc, and cadmium. The contamination-adjusted average (mean +/- SD) level of lead (expressed as the ratio of atomic lead to atomic calcium) in bones of the Indians was 8.4 +/- 4.4 x 10(-7)), which was similar to ratios in bones of ancient Peruvians (0.9 to 7.7 x 10(-7)) and significantly lower than ratios in bones of modern adults in England and the United States (210 to 350 x 10(-7]. The adjusted average concentrations (microgram per gram dry weight) of biologic cadmium, silver, and zinc in the Pecos Indian bones were 0.032 +/- 0.013, 0.094 +/- 0.044, and 130 +/- 66, as compared to concentrations of 1.8, 0.01 to 0.44, and 75 to 170 in the bones of modern people, respectively. Therefore, cadmium concentrations in Pecos Indian bones are also approximately 50-fold lower than those of contemporary humans. These data support earlier findings that most previously reported natural concentrations of lead in human tissues are erroneously high and indicate that natural concentrations of cadmium are also between one and two orders of magnitude lower than contemporary concentrations.