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.

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.

Pollution by metals and toxicity assessment using Caenorhabditis elegans in sediments from the Magdalena River, Colombia.

The Magdalena River is the most important river in Colombia, supplying over 70% of the population of fish and drinking water, and it also is the main river transportation way of the country. It receives effluents from multiple sources along its course such as contaminant agricultural and industrial discharges. To evaluate the toxicity profile of Magdalena River sediments through endpoints such as survival, locomotion, and growth, wild type strains of Caenorhabditis elegans were exposed to aqueous extracts of the sediments. To identify changes in gene expression, GFP transgenic strains were used as reporter genes. Physiological and biochemical data were correlated with metal concentration in the sediments, identifying patterns of toxicity along the course of the river. Levels of some metals such as Cd, Cu, and Ni were above TEC and PEC limits. Effects in survival, growth, and locomotion were observed in most of the samples, and changes in gene expression were evident in the genes mtl-2, sod-4, and gst-1 using fluorescence expression. Cadmium and lead were the metals which were primarily associated with sediment toxicity, and the sampling sites with the highest increased expression of stress response genes were Barrancabermeja and Girardot. However, the diverse nature of toxic profiles observed in C. elegans in the study area showed the pervasiveness of different types of discharges throughout the river system.

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.

Assessing a novel room temperature DNA storage medium for forensic biological samples.

The ability to properly collect, analyze and preserve biological stains is important to preserving the integrity of forensic evidence. Stabilization of intact biological evidence in cells and the DNA extracts from them is particularly important since testing is generally not performed immediately following collection. Furthermore, retesting of stored DNA samples may be needed in casework for replicate testing, confirmation of results, and to accommodate future testing with new technologies. A novel room temperature DNA storage medium, SampleMatrix™ (SM; Biomatrica, Inc., San Diego, CA), was evaluated for stabilizing and protecting samples. Human genomic DNA samples at varying amounts (0.0625-200 ng) were stored dry in SM for 1 day to 1 year under varying conditions that included a typical ambient laboratory environment and also through successive freeze-thaw cycles (3 cycles). In addition, spiking of 1-4 × SM into samples prior to analysis was performed to determine any inhibitory effects of SM. Quantification of recovered DNA following storage was determined by quantitative PCR or by agarose gel electrophoresis, and evaluation of quantitative peak height results from multiplex short tandem repeat (STR) analyses were performed to assess the efficacy of SM for preserving DNA. Results indicate no substantial differences between the quality of samples stored frozen in liquid and those samples maintained dry at ambient temperatures protected in SM. For long-term storage and the storage of low concentration samples, SM provided a significant advantage over freezer storage through higher DNA recovery. No detectable inhibition of amplification was observed at the recommended SM concentration and complete profiles were obtained from genomic DNA samples even in the presence of higher than recommended concentrations of the SM storage medium. The ability to stabilize and protect DNA from degradation at ambient temperatures for extended time periods could have tremendous impact in simplifying and improving sample storage conditions and requirements. The current work focuses on forensics analysis; however this technology is applicable to all endeavors requiring storage of DNA.

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.