High-precision Pb isotopes of drinking water lead pipes: Implications for human exposure to industrial Pb in the United States.

Millions of lead (Pb) pipes are still used in the drinking water distribution systems in many regions in the world. Human exposure to Pb from contaminated drinking water continues to be of concern in the United States (U.S.), as illustrated by the widely publicized "Flint Water Crisis" in 2015. The Pb isotopic composition of Pb-pipes potentially can be useful to identify human exposure to Pb from lead service lines (LSLs). In addition, as the LSLs were likely manufactured from similar industrial Pb sources as other Pb objects and materials in the USA, the Pb-pipes isotope data can provide information about the overall isotopic composition of the U.S. industrial Pb. In this work we present high-precision Pb isotope data from Pb-pipes excavated from different U.S. municipalities. The Pb-pipes show an extremely wide range of Pb isotopic compositions, with 206Pb/204Pb ranging from 17.004 to 22.010, 207Pb/204Pb from 15.460 to 15.921, and 208Pb/204Pb from 36.687 to 41.120. The wide isotope range is observed even in a single town, suggesting that no regional Pb isotope patterns can be expected within the continental USA. However, the high-precision MC-ICP-MS Pb data form a clear linear trend that, depending on the context, can be used to identify human Pb exposure. Furthermore, as the linear trend is a result of utilization of Pb ores from different domestic and international sources and secondary recycling of metallic Pb, it is likely representative of the overall isotopic composition of the U.S. industrial Pb pool. Therefore, the identified trend is the most accurate isotope representation of the U.S. anthropogenic Pb at present and can be used as first-order evaluation to determine if a person with elevated blood Pb levels was exposed to U.S. industrial Pb sources.

Children's exposure to environmental lead: A review of potential sources, blood levels, and methods used to reduce exposure.

Lead has been used for thousands of years in different anthropogenic activities thanks to its unique properties that allow for many applications such as the manufacturing of drinking water pipes and its use as additives to gasoline and paint. However, knowledge of the adverse impacts of lead on human health has led to its banning from several of its applications, with the main goal of reducing environmental pollution and protecting human health. Human exposure to lead has been linked to different sources of contamination, resulting in high blood lead levels (BLLs) and adverse health implications, primarily in exposed children. Here, we present a summary of a literature review on potential lead sources affecting blood levels and on the different approaches used to reduce human exposure. The findings show a combination of different research approaches, which include the use of inspectors to identify problematic areas in homes, collection and analysis of environmental samples, different lead detection methods (e.g. smart phone applications to identify the presence of lead and mass spectrometry techniques). Although not always the most effective way to predict BLLs in children, linear and non-linear regression models have been used to link BLLs and environmental lead. However, multiple regressions and complex modelling systems would be ideal, especially when seeking results in support of decision-making processes. Overall, lead remains a pollutant of concern and many children are still exposed to it through environmental and drinking water sources. To reduce exposure to lead through source apportionment methods, recent technological advances using high-precision lead stable isotope ratios measured on multi-collector induced coupled plasma mass spectrometry (MC-ICP-MS) instruments have created a new direction for identifying and then eliminating prevalent lead sources associated with high BLLs.

The zooarchaeology and isotopic ecology of the Bahamian hutia (Geocapromys ingrahami): Evidence for pre-Columbian anthropogenic management.

Bahamian hutias (Geocapromys ingrahami) are the only endemic terrestrial mammal in The Bahamas and are currently classified as a vulnerable species. Drawing on zooarchaeological and new geochemical datasets, this study investigates human management of Bahamian hutias as cultural practice at indigenous Lucayan settlements in The Bahamas and the Turks & Caicos Islands. In order to determine how hutia diet and distribution together were influenced by Lucayan groups we conducted isotopic analysis on native hutia bone and tooth enamel recovered at the Major's Landing site on Crooked Island in The Bahamas and introduced hutias from the Palmetto Junction site on Providenciales in the Turks & Caicos Islands. Results indicate that some hutias consumed 13C-enriched foods that were either provisioned or available for opportunistic consumption. Strontium isotope ratios for hutia tooth enamel show a narrow range consistent with local origin for all of the archaeological specimens. In contrast, analysis of strontium isotopes in modern Bahamian hutia teeth from animals relocated to Florida from The Bahamas demonstrates that these animals rapidly lost their Bahamian signature and adopted a Florida signature. Therefore, strontium should be used cautiously for determining hutia provenance, particularly for individuals that were translocated between islands. Overall, our findings suggest that ancient human presence did not always result in hutia vulnerability and that the impact to hutia populations was variable across pre-Columbian indigenous settlements.

"The dead shall be raised": Multidisciplinary analysis of human skeletons reveals complexity in 19th century immigrant socioeconomic history and identity in New Haven, Connecticut.

In July 2011, renovations to Yale-New Haven Hospital inadvertently exposed the cemetery of Christ Church, New Haven, Connecticut's first Catholic cemetery. While this cemetery was active between 1833 and 1851, both the church and its cemetery disappeared from public records, making the discovery serendipitous. Four relatively well-preserved adult skeletons were recovered with few artifacts. All four individuals show indicators of manual labor, health and disease stressors, and dental health issues. Two show indicators of trauma, with the possibility of judicial hanging in one individual. Musculoskeletal markings are consistent with physical stress, and two individuals have arthritic indicators of repetitive movement/specialized activities. Radiographic analyses show osteopenia, healed trauma, and other pathologies in several individuals. Dental calculus analysis did not identify any tuberculosis indicators, despite osteological markers. Isotopic analyses of teeth indicate that all four were likely recent immigrants to the Northeastern United States. Nuclear and mitochondrial DNA were recovered from three individuals, and these analyses identified ancestry, hair/eye color, and relatedness. Genetic and isotopic results upended our initial ancestry assessment based on burial context alone. These individuals provide biocultural evidence of New Haven's Industrial Revolution and the plasticity of ethnic and religious identity in the immigrant experience. Their recovery and the multifaceted analyses described here illuminate a previously undescribed part of the city's rich history. The collective expertise of biological, geochemical, archaeological, and historical researchers interprets socioeconomic and cultural identity better than any one could alone. Our combined efforts changed our initial assumptions of a poor urban Catholic cemetery's membership, and provide a template for future discoveries and analyses.

87Sr/86Sr and 14C evidence for peccary (Tayassuidae) introduction challenges accepted historical interpretation of the 1657 Ligon map of Barbados.

Contemporary West Indian biodiversity has been shaped by two millennia of non-native species introductions. Understanding the dynamics of this process and its legacy across extended temporal and spatial scales requires accurate knowledge of introduction timing and the species involved. Richard Ligon's 17th century account and celebrated map of early colonial Barbados records the translocation of several Old World species to the island in the post-contact era, including pigs (Sus scrofa) believed to have been released by passing sailors the century prior. Here we challenge this long-accepted historical narrative, presenting evidence that Ligon's "pigs" were in fact peccaries, a New World continental mammal often confused with wild boars. We document the first recorded instance of non-native peccary (Tayassuidae) on Barbados based on a securely identified mandibular specimen from a historic archaeological context. Results of specimen 87Sr/86Sr and AMS radiocarbon assays, along with newly reported data from Sr isotope environmental analyses, indicate a local origin dating to AD 1645-1670/1780-1800. These data support the presence of living peccary on Barbados some time during the first 175 years of English settlement, which, based on review of historical and archaeological data, most likely arises from 16th century peccary introduction from the Guianas/Trinidad by the Spanish or Portuguese. We argue dimorphic representations of "pigs" on Ligon's map reflect the co-occurrence of peccary and European domestic swine on historic Barbados. Our findings overturn conventional history and provide greater taxonomic and chronological resolution for Caribbean bioinvasion studies, helping to refine our understanding of potential ecological impacts. In addition, the new bioavailable 87Sr/86Sr data for Barbados reported here advance current efforts toward mapping the Caribbean Sr isoscape.

Concerns about Quadrupole ICP-MS Lead Isotopic Data and Interpretations in the Environment and Health Fields.

There has been a massive increase in recent years of the use of lead (Pb) isotopes in attempts to better understand sources and pathways of Pb in the environment and in man or experimental animals. Unfortunately, there have been many cases where the quality of the isotopic data, especially that obtained by quadrupole inductively coupled plasma mass spectrometry (Q-ICP-MS), are questionable, resulting in questionable identification of potential sources, which, in turn, impacts study interpretation and conclusions. We present several cases where the isotopic data have compromised interpretation because of the use of only the major isotopes 208Pb/206Pb and 207Pb/206Pb, or their graphing in other combinations. We also present some examples comparing high precision data from thermal ionization (TIMS) or multi-collector plasma mass spectrometry (MC-ICP-MS) to illustrate the deficiency in the Q-ICP-MS data. In addition, we present cases where Pb isotopic ratios measured on Q-ICP-MS are virtually impossible for terrestrial samples. We also evaluate the Pb isotopic data for rat studies, which had concluded that Pb isotopic fractionation occurs between different organs and suggest that this notion of biological fractionation of Pb as an explanation for isotopic differences is not valid. Overall, the brief review of these case studies shows that Q-ICP-MS as commonly practiced is not a suitable technique for precise and accurate Pb isotopic analysis in the environment and health fields.

Earliest isotopic evidence in the Maya region for animal management and long-distance trade at the site of Ceibal, Guatemala.

This study uses a multiisotope (carbon, nitrogen, oxygen, and strontium) approach to examine early animal management in the Maya region. An analysis of faunal specimens across almost 2,000 years (1000 BC to AD 950) at the site of Ceibal, Guatemala, reveals the earliest evidence for live-traded dogs and possible captive-reared taxa in the Americas. These animals may have been procured for ceremonial functions based on their location in the monumental site core, suggesting that animal management and trade began in the Maya area to promote special events, activities that were critical in the development of state society. Isotopic evidence for animal captivity at Ceibal reveals that animal management played a greater role in Maya communities than previously believed.

Using Carbon, Oxygen, Strontium, and Lead Isotopes in Modern Human Teeth for Forensic Investigations: A Critical Overview Based on Data from Bulgaria.

Isotopic data obtained from human remains can provide information about an individual's origin, migration, and diet. We evaluate the usefulness of carbon, oxygen, strontium, and lead isotopes for forensic investigations by comparing data from Bulgarian teeth with data from other regions. Geo-referencing based on oxygen or strontium isotopes can be misleading due to overlap with other countries in Europe and other continents. Carbon and lead isotopes, in combination with oxygen and strontium isotopes, provide the most useful information for identification of local vs foreigner status. In particular, high-precision Pb isotopes show a distinct "Bulgarian" range; however, it is possible that individuals from other countries in Eastern Europe and/or central to western Asia could have overlapping isotopic values. Additional high-precision multi-isotope data from modern humans from different regions in the world are required to transition from speculative to more quantitative estimation of a geographical place of origin for unidentified human remains.

Lead (Pb) Isotope Baselines for Studies of Ancient Human Migration and Trade in the Maya Region.

We examined the potential use of lead (Pb) isotopes to source archaeological materials from the Maya region of Mesoamerica. The main objectives were to determine if: 1) geologic terrains throughout the Maya area exhibit distinct lead isotope ratios (206Pb/204Pb, 207Pb/204Pb, and 208Pb/204Pb), and 2) a combination of lead and strontium ratios can enhance sourcing procedures in the Mesoamerica region. We analyzed 60 rock samples for lead isotope ratios and a representative subset of samples for lead, uranium, and thorium concentrations across the Maya region, including the Northern Lowlands of the Mexican Yucatan Peninsula, the Southern Lowlands of Guatemala and Belize, the Volcanic Highlands, the Belizean Maya Mountains, and the Metamorphic Province/Motagua Valley. Although there is some overlap within certain sub-regions, particularly the geologically diverse Metamorphic Province, lead isotopes can be used to distinguish between the Northern Lowlands, the Southern Lowlands, and the Volcanic Highlands. The distinct lead isotope ratios in the sub-regions are related to the geology of the Maya area, exhibiting a general trend in the lowlands of geologically younger rocks in the north to older rocks in the south, and Cenozoic volcanic rocks in the southern highlands. Combined with other sourcing techniques such as strontium (87Sr/86Sr) and oxygen (δ18O), a regional baseline for lead isotope ratios can contribute to the development of lead isoscapes in the Maya area, and may help to distinguish among geographic sub-regions at a finer scale than has been previously possible. These isotope baselines will provide archaeologists with an additional tool to track the origin and movement of ancient humans and artifacts across this important region.

Evidence for Patterns of Selective Urban Migration in the Greater Indus Valley (2600-1900 BC): A Lead and Strontium Isotope Mortuary Analysis.

Just as modern nation-states struggle to manage the cultural and economic impacts of migration, ancient civilizations dealt with similar external pressures and set policies to regulate people's movements. In one of the earliest urban societies, the Indus Civilization, mechanisms linking city populations to hinterland groups remain enigmatic in the absence of written documents. However, isotopic data from human tooth enamel associated with Harappa Phase (2600-1900 BC) cemetery burials at Harappa (Pakistan) and Farmana (India) provide individual biogeochemical life histories of migration. Strontium and lead isotope ratios allow us to reinterpret the Indus tradition of cemetery inhumation as part of a specific and highly regulated institution of migration. Intra-individual isotopic shifts are consistent with immigration from resource-rich hinterlands during childhood. Furthermore, mortuary populations formed over hundreds of years and composed almost entirely of first-generation immigrants suggest that inhumation was the final step in a process linking certain urban Indus communities to diverse hinterland groups. Additional multi disciplinary analyses are warranted to confirm inferred patterns of Indus mobility, but the available isotopic data suggest that efforts to classify and regulate human movement in the ancient Indus region likely helped structure socioeconomic integration across an ethnically diverse landscape.

The Pb isotopic record of historical to modern human lead exposure.

Human teeth and bones incorporate trace amounts of lead (Pb) from the local environment during growth and remodeling. Anthropogenic activities have caused changes in the natural Pb isotopic background since historical times and this is reflected in the Pb isotopes of historical European teeth. Lead mining and use increased exponentially during the last century and the isotopic compositions of modern human teeth reflect the modern anthropogenic Pb. USA teeth show the most radiogenic Pb and Australian teeth show the least radiogenic Pb, a result of different Pb ores used in the two regions. During the last century the Australian Pb was exported to Europe, Asia, South America, and Africa, resulting in swamping of the local environmental Pb signal by the imported Pb. As a result, the modern human teeth in Europe show a significant drop to lower isotopic values compared with historical times. Similarly, modern human teeth in other regions of the world show similar Pb isotopic ratios to modern European teeth reflecting the Pb imports. The specific pattern of human Pb exposure allows us to use the Pb isotopic signal recorded in the skeleton as a geo-referencing tool. As historical European teeth show a distinct Pb signal, we can identify early European skeletal remains in the New World and likely elsewhere. In modern forensic investigations we can discriminate to some extent Eastern Europeans from Western and Northern Europeans. Australians can be identified to some extent in any region in the world, although there is some overlap with Western European individuals. Lead isotopes can be used to easily identify foreigners in the USA, as modern USA teeth are distinct from any other region of the world. By analogy, USA individuals can be identified virtually in any other region of the world.

Direct (Hetero)arylation Polymerization: An Effective Route to 3,4-Propylenedioxythiophene-Based Polymers with Low Residual Metal Content.

We report the use of direct (hetero)arylation polymerizations (DHAP) as a means of obtaining 3,4-propylenedioxythiophene-based conjugated polymers for use in electrochromics. This method offers a rapid route to achieving polymers in high yields with simplified purification procedures and low residual metal content, as determined by inductive coupled plasma-mass spectrometry (ICP-MS). The studied polymers possess comparable electrochromic properties to those previously reported by our group, implying that their switching ability from a colored to a transmissive state is independent of the residual metallic impurities.