Structural modifications toward improved lead-203/lead-212 peptide-based image-guided alpha-particle radiopharmaceutical therapies for neuroendocrine tumors.

PURPOSE: The lead-203 (203Pb)/lead-212 (212Pb) elementally identical radionuclide pair has gained significant interest in the field of image-guided targeted alpha-particle therapy for cancer. Emerging evidence suggests that 212Pb-labeled peptide-based radiopharmaceuticals targeting somatostatin receptor subtype 2 (SSTR2) may provide improved effectiveness compared to beta-particle-based therapies for neuroendocrine tumors (NETs). This study aims to improve the performance of SSTR2-targeted radionuclide imaging and therapy through structural modifications to Tyr3-octreotide (TOC)-based radiopharmaceuticals. METHODS: New SSTR2-targeted peptides were designed and synthesized with the goal of optimizing the incorporation of Pb isotopes through the use of a modified cyclization technique; the introduction of a Pb-specific chelator (PSC); and the insertion of polyethylene glycol (PEG) linkers. The binding affinity of the peptides and the cellular uptake of 203Pb-labeled peptides were evaluated using pancreatic AR42J (SSTR2+) tumor cells and the biodistribution and imaging of the 203Pb-labeled peptides were assessed in an AR42J tumor xenograft mouse model. A lead peptide was identified (i.e., PSC-PEG2-TOC), which was then further evaluated for efficacy in 212Pb therapy studies. RESULTS: The lead radiopeptide drug conjugate (RPDC) - [203Pb]Pb-PSC-PEG2-TOC - significantly improved the tumor-targeting properties, including receptor binding and tumor accumulation and retention as compared to [203Pb]Pb-DOTA0-Tyr3-octreotide (DOTATOC). Additionally, the modified RPDC exhibited faster renal clearance than the DOTATOC counterpart. These advantageous characteristics of [212Pb]Pb-PSC-PEG2-TOC resulted in a dose-dependent therapeutic effect with minimal signs of toxicity in the AR42J xenograft model. Fractionated administrations of 3.7 MBq [212Pb]Pb-PSC-PEG2-TOC over three doses further improved anti-tumor effectiveness, resulting in 80% survival (70% complete response) over 120 days in the mouse model. CONCLUSION: Structural modifications to chelator and linker compositions improved tumor targeting and pharmacokinetics (PK) of 203/212Pb peptide-based radiopharmaceuticals for NET theranostics. These findings suggest that PSC-PEG2-TOC is a promising candidate for Pb-based targeted radionuclide therapy for NETs and other types of cancers that express SSTR2.

Strong evidence for the continued contribution of lead deposited during the 20th century to the atmospheric environment in London of today.

Although leaded gasoline was banned at the end of the last century, lead (Pb) remains significantly enriched in airborne particles in large cities. The remobilization of historical Pb deposited in soils from atmospheric removal has been suggested as an important source providing evidence for the hypothetical long-term persistency of lead, and possibly other pollutants, in the urban environment. Here, we present data on Pb isotopic composition in airborne particles collected in London (2014 to 2018), which provide strong support that lead deposited via gasoline combustion still contributes significantly to the lead burden in present-day London. Lead concentration and isotopic signature of airborne particles collected at a heavily trafficked site did not vary significantly over the last decade, suggesting that sources remained unchanged. Lead isotopic composition of airborne particles matches that of road dust and topsoils and can only be explained with a significant contribution (estimate of 32 ± 10 to 43 ± 9% based on a binary mixing model) of Pb from leaded gasoline. The lead isotopes furthermore suggest significant contributions from nonexhaust traffic emissions, even though isotopic signatures of anthropogenic sources are increasingly overlapping. Lead isotopic composition of airborne particles collected at building height shows a similar signature to that collected at street level, suggesting effective mixing of lead within the urban street canyon. Our results have important implications on the persistence of Pb in urban environments and suggest that atmospheric Pb reached a baseline in London that is difficult to decrease further with present policy measures.

Anthropogenic lead pervasive in Canadian Arctic seawater.

Anthropogenic Pb is widespread in the environment including remote places. However, its presence in Canadian Arctic seawater is thought to be negligible based on low dissolved Pb (dPb) concentrations and proxy data. Here, we measured dPb isotopes in Arctic seawater with very low dPb concentrations (average ∼5 pmol ⋅ kg-1) and show that anthropogenic Pb is pervasive and often dominant in the western Arctic Ocean. Pb isotopes further reveal that historic aerosol Pb from Europe and Russia (Eurasia) deposited to the Arctic during the 20th century, and subsequently remobilized, is a significant source of dPb, particularly in water layers with relatively higher dPb concentrations (up to 16 pmol ⋅ kg-1). The 20th century Eurasian Pb is present predominantly in the upper 1,000 m near the shelf but is also detected in older deep water (2,000 to 2,500 m). These findings highlight the importance of the remobilization of anthropogenic Pb associated with previously deposited aerosols, especially those that were emitted during the peak of Pb emissions in the 20th century. This remobilization might be further enhanced because of accelerated melting of permafrost and ice along with increased coastal erosion in the Arctic. Additionally, the detection of 20th century Eurasian Pb in deep water helps constrain ventilation ages. Overall, this study shows that Pb isotopes in Arctic seawater are useful as a gauge of changing particulate and contaminant sources, such as those resulting from increased remobilization (e.g., coastal erosion) and potentially also those associated with increased human activities (e.g., mining and shipping).

Ex novo development of lead glassmaking in early Umayyad Spain.

This study investigates glass finds from the Iberian Peninsula as a proxy for identifying the mechanisms underlying technological transformations and innovation in the wake of the Arab conquest in the seventh and eighth centuries CE. High-resolution laser ablation inductively coupled plasma mass spectrometry data combined with lead isotope analyses of a precisely dated (mid-eighth century to 818 CE) glass assemblage from the Rabad of Saqunda in Cordoba, capital of Umayyad Spain, enabled us to trace the origins of an Iberian glassmaking industry and to unambiguously link it to the exploitation of local raw materials. The analytical data reveal increased recycling, some isolated imports of Islamic plant ash glasses from Mesopotamia, and, most notably, the development of a new type of glassmaking technology that resorted to the use of lead slag from silver and lead mining and processing in the region around Cordoba. The production of this type of lead glass from Saqunda was short-lived and was subsequently refined by introducing additional fluxing agents. The technological innovation of Islamic glassmaking in Spain evidently drew inspiration from adjacent high-temperature technologies. The revival of glass and the development of a local glassmaking tradition was indirectly related to the wider processes of Islamization, such as the introduction of glazed ceramics that are compositionally related to the lead glasses from Saqunda.

Anthropogenic Asian aerosols provide Fe to the North Pacific Ocean.

Fossil-fuel emissions may impact phytoplankton primary productivity and carbon cycling by supplying bioavailable Fe to remote areas of the ocean via atmospheric aerosols. However, this pathway has not been confirmed by field observations of anthropogenic Fe in seawater. Here we present high-resolution trace-metal concentrations across the North Pacific Ocean (158°W from 25°to 42°N). A dissolved Fe maximum was observed around 35°N, coincident with high dissolved Pb and Pb isotope ratios matching Asian industrial sources and confirming recent aerosol deposition. Iron-stable isotopes reveal in situ evidence of anthropogenic Fe in seawater, with low δ56Fe (-0.23‰ > δ56Fe > -0.65‰) observed in the region that is most influenced by aerosol deposition. An isotope mass balance suggests that anthropogenic Fe contributes 21-59% of dissolved Fe measured between 35° and 40°N. Thus, anthropogenic aerosol Fe is likely to be an important Fe source to the North Pacific Ocean.

Pollution revealed by stable lead isotopes in recent snow from the northern and central Tibetan Plateau.

Lead (Pb) isotopes are less fractionated than those from different sources, and thus were used to trace the sources of Pb in the environment. To investigate the sources of Pb in the atmosphere of the Tibetan Plateau, stable Pb isotopes (206Pb, 207Pb and 208Pb) in acidified snow pit samples collected from five glaciers (i.e., Qiyi-QY, Meikuang-MK, Yuzhufeng-YZF, Hariqin-HRQ and Xiaodongkemadi-XDKMD) in May 2016 of the northern and central Tibetan Plateau were measured. The results showed narrow ranges of 1.158-1.187 for 206Pb/207Pb and 2.450-2.489 for 208Pb/207Pb respectively. The 206Pb/207Pb ratios in all samples were obviously lower than the environmental background value of 1.196, indicating the primary contributions of anthropogenic sources. At least 60% of Pb was contributed by various human activities, which was supported by the Pb isotopes in the snow pit samples from the QY, MK, YZF, HRQ and XDKMD glaciers. By comparing Pb isotope data, we found that the primary anthropogenic sources are coal combustion, mining and smelting activities in northwestern China and mixed emissions from cities located in western China and close to the glaciers. These sources contributed to the Pb in the northern glaciers (QY and MK) in particular. Coal combustion in India probably contributes to the central glaciers (HRQ and XDKMD). Another potential source could be parts of central Asia (e.g., Kyrgyzstan and Uzbekistan) through long range transport. The above potential source areas of contaminants were traced further by the air mass back-trajectory tracing method.

Redox-Driven Recrystallization of PbO2.

Lead(IV) oxide (PbO2) is one of the lead corrosion products that forms on the inner surface of lead pipes used for drinking water supply. It can maintain low dissolved Pb(II) concentrations when free chlorine is present. When free chlorine is depleted, PbO2 and soluble Pb(II) will co-occur in these systems. This study used a stable lead isotope (207Pb) as a tracer to examine the interaction between aqueous Pb(II) and solid PbO2 at conditions with no net change in dissolved Pb concentration. While the dissolved Pb(II) concentration remained unchanged, significant isotope exchange occurred that indicated that substantial amounts (24.3-35.0% based on the homogeneous recrystallization model) of the Pb atoms in the PbO2 solids had been exchanged with those in solution over 264 h. Neither α-PbO2 nor ß-PbO2 displayed a change in mineralogy, particle size, or oxidation state after reaction with aqueous Pb(II). The combined isotope exchange and solid characterization results indicate that redox-driven recrystallization of PbO2 had occurred. Such redox-driven recrystallization is likely to occur in water that stagnates in lead pipes that contain PbO2, and this recrystallization may alter the reactivity of PbO2 with respect to its stability and susceptibility to reductive dissolution.

Lead Isotopic Constraints on the Provenance of Antarctic Dust and Atmospheric Circulation Patterns Prior to the Mid-Brunhes Event (~430 kyr ago).

A lead (Pb) isotopic record, covering the two oldest glacial-interglacial cycles (~572 to 801 kyr ago) characterized by lukewarm interglacials in the European Project for Ice Coring in Antarctica Dome C ice core, provides evidence for dust provenance in central East Antarctic ice prior to the Mid-Brunhes Event (MBE), ~430 kyr ago. Combined with published post-MBE data, distinct isotopic compositions, coupled with isotope mixing model results, suggest Patagonia/Tierra del Fuego (TdF) as the most important sources of dust during both pre-MBE and post-MBE cold and intermediate glacial periods. During interglacials, central-western Argentina emerges as a major contributor, resulting from reduced dust supply from Patagonia/TdF after the MBE, contrasting to the persistent dominance of dust from Patagonia/TdF before the MBE. The data also show a small fraction of volcanic Pb transferred from extra-Antarctic volcanoes during post-MBE interglacials, as opposed to abundant transfer prior to the MBE. These differences are most likely attributed to the enhanced wet removal efficiency with the hydrological cycle intensified over the Southern Ocean, associated with a poleward shift of the southern westerly winds (SWW) during warmer post-MBE interglacials, and vice versa during cooler pre-MBE ones. Our results highlight sensitive responses of the SWW and the associated atmospheric conditions to stepwise Antarctic warming.

Regional and global perspectives of honey as a record of lead in the environment.

Honey from Apis mellifera is a useful and inexpensive biomonitor for mapping metal distributions in urban centers. The sampling resolution of a biomonitoring survey (e.g., city versus global scale) determines which geochemical processes are reflected in the results. This study presents Pb isotopic compositions and metal concentrations in honey from around the world, sampled at varying resolutions: honey from Canada (n = 21), the United States (n = 111), Belgium (n = 25), and New Zealand (n = 10), with additional samples from Afghanistan, Brazil, Cuba, Germany, Liberia, Taiwan, and Turkey. Honey was sampled at high resolution in two uniquely different land-use settings (New York Metro Area and the Hawaiian island of Kaua'i), at regional-scale resolution in eastern North America (including the Great Lakes region), and Pb isotopic compositions of all samples were compared on a global scale. At high sampling resolution, metal concentrations in honey reveal spatially significant concentration gradients: in New York City, metals associated with human activity and city infrastructure (e.g., Pb, Sb, Ti, V) are more concentrated in honey collected within the city compared to honey from upstate New York, and metal concentrations in honey from Kaua'i suggest polluting effects of nearby agricultural operations. At lower resolution (regional and global scales), lead isotopic compositions of honey are more useful than metal concentrations in revealing large-scale Pb processes (e.g., the enduring legacy of global leaded gasoline use throughout the twentieth century) and the continental origin of the honey. Lead isotopic compositions of honey collected from N. America (especially from the eastern USA) are more radiogenic (206Pb/207Pb: 1.132-1.253, 208Pb/206Pb: 2.001-2.129) compared to European honey, and honey from New Zealand, which has the least radiogenic isotopic compositions measured in this study (206Pb/207Pb: 1.077-1.160, 208Pb/206Pb: 2.090-2.187). Thus, biomonitoring using honey at different resolutions reflects differing processes and, to some extent, a honey terroir defined by the Pb isotopic composition. The data presented here provide important (and current) global context for future studies that utilize Pb isotopes in honey. Moreover, this study exhibits community science in action, as most of the honey was collected by collaborators around the world, working directly with local apiarists and hobby beekeepers.

Translating Analytical Techniques in Geochemistry to Environmental Health.

From human health exposure related to environmental contamination to ancient deep-Earth processes related to differentiation of the Earth's geochemical reservoirs, the adaptability of inductively coupled plasma mass spectrometry (ICP-MS) has proven to be an indispensable standard technique that transcends disciplines. Continued advancements in ICP-MS, including improved auxiliary applications such as laser ablation (LA), ion/liquid chromatography (IC), automated pre-concentration systems (e.g., seaFAST), and improved desolvating nebulizer systems (e.g., Aridus and Apex) have revolutionized our ability to analyze almost any sample matrix with remarkable precision at exceedingly low elemental abundances. The versatility in ICP-MS applications allows for effective interdisciplinary crossover, opening a world of analytical possibilities. In this communication, we discuss the adaptability of geochemical techniques, including sample preparation and analysis, to environmental and biological systems, using Pb isotopes for source apportionment as a primary example.

Childhood lead exposure of Amerindian communities in French Guiana: an isotopic approach to tracing sources.

In French Guiana were detected high lead (Pb) levels in blood of Amerindian people. Lead exposure is a serious hazard that can affect the cognitive and behavior development. People can be exposed to Pb through occupational and environmental sources. Fingerprinting based on stable Pb isotopes in environmental media is often used to trace natural and anthropogenic sources but is rarely paired with blood data. The objective of this study was to determine the main factors associated with high Blood Lead Levels (BLL). Soil, manioc tubers, food bowls, beverages, wild games, lead pellets and children blood were sampled in small villages along the Oyapock River. children BLL ranged between 5.7 and 35 µg dL-1, all exceeding 5 µg dL-1, the reference value proposed in epidemiologic studies for lead poisoning. Among the different dietary sources, manioc tubers and large game contained elevated Pb concentrations while manioc-based dishes were diluted. The isotopes ratios (207Pb/206Pb and 208Pb/206Pb) of children blood overlapped these of lead shots and meals. These first results confirm for the first time, the diary consumption of manioc-based food as the main contributor to Amerindian children's BLL in French Guiana, but don't exclude the occasional exposure to lead bullets by hunting activities. This is a specific health concern, since previous studies have shown that these same villagers present high levels of mercury (Hg). These communities are indeed subject to a double exposure to neurotoxic metals, Hg and Pb, both through their diet. The farming activity is based on manioc growing, and explaining that this ancestral practice can induce serious health risks for the child's development may seriously affect their food balance and cultural cohesion.

Application of Stable Isotopic Ratio Analysis to Identify the Cause of Acute Versus Chronic Lead Poisoning of a Tundra Swan (Cygnus columbianus): A Case Study.

We utilized lead (Pb) stable isotopes to identify the source of acute Pb poisoning in a Tundra Swan (Cygnus columbianus) and evaluated overall Pb exposure. Upon necropsy, we obtained samples of blood, liver, kidney, heart, thigh, breast, femur, and metallic objects (i.e., fishing sinker, spring and swivels) from the gizzard for Pb isotopic analysis. Pb isotope ratios of blood and soft tissues were essentially identical to the Pb ratios of the sinker, the likely source of acute poisoning. The spring and swivels had lower Pb content and ratios distinct from tissue, suggesting no significant contribution to poisoning. Femur Pb isotopic composition was the most distinct biological sample and indicative of a combination of sources. These results demonstrate isotopic analysis as a viable method for determining the source of acute Pb poisoning, and that Pb isotope ratios in bone most likely record a lifetime-averaged metric of Pb exposure.

Lead contamination of the mining and smelting district in Mitrovica, Kosovo.

Lead contamination in topsoil of the mining and smelting area of Mitrovica, Kosovo, was investigated for total concentrations and chemical fractions by sequential extraction analysis, mineralogical fractions by X-ray diffraction (XRD) and scanning electron microscopy with energy-dispersive X-ray spectrometer (SEM-EDX). The study revealed that all samples contained Pb exceeding USEPA standard of 400 mg kg-1. The highest total concentration of Pb (125,000 mg kg-1) was the soil from the former smelter. Sequential extraction results showed that the predominant form of Pb was associated with Fe-Mn oxide-bound fraction which ranged from 45.37 to 71.61% of total concentrations, while carbonate and silicate Pb-binding fractions were dominant when physical measurements (XRD and SEM-EDX) were applied. Application of Pb isotope ratios (206Pb/207Pb and 208Pb/206Pb), measured by inductively coupled plasma mass spectrometry, identified that Pb contamination is originated from similar anthropogenic source. The results reflected that the Pb contamination in the soil of this area is serious. In order to provide proper approaches on remediation and prevention of health impacts to the people in this area, a continuous monitoring and health risk assessment are recommended.

The vertical migration and speciation of the Pb in the paddy soil: A case study of the Yangtze River Delta, China.

Migration of Pb in the soil can be enhanced by acidification and frequent change of environmental condition. The paddy soil, where the environmental condition such as redox fluctuates frequently due to soil submergence and drainage, may offer a favorable condition for Pb migrating to deeper soil and further contaminate groundwater by leaching or irrigation. To date, not much is known about how quickly Pb migrates in the soil and the relevant transformation of Pb. We use long-term soil profile monitoring, sequential extraction and isotopic measurement to examine the temporal change of concentrations and isotopic ratios of Pb associated with different soil components in the paddy soil profile in the Yangtze River Delta area during 2011-2017. We find that Pb vertical migration in the paddy soil is faster. Pb in the shallow soil may migrate downward up to 60 cm during six years. The migration of Pb is dominated by the carbonate, and secondarily influenced by Fe/Mn oxides. Our results also imply that the mechanism of Pb migration in soils is changing. The mechanism which is now characterized as the carbonate-dominating will be replaced as the Fe/Mn oxides-dominating in the near future as the carbonate in shallow soil is becoming depleted.

Effects of Atmospheric Fallout on Lead Contamination of Wheat Tissues Based on Stable Isotope Ratios.

In order to trace the source of Pb pollution in wheat, the contribution ratio of soil and atmospheric fallout source was quantified based on stable isotope ratios. Results showed that the average Pb content of soil was significantly lower than that of fallout, and Pb in the fallout had a higher weak acid fraction than soil. Pb in wheat had a distinct distribution in its tissues and the content of Pb in wheat roots was significantly higher than it in shoots. The 206Pb/207Pb ratio of soil was significantly higher than that in atmospheric fallout (p < 0.05). According to a binary mixing model, the 206Pb/207Pb ratio in wheat roots, leaves, and grains reflect 67%, 65%, and 90% of Pb content contributions from fallout, respectively. This results suggest that fallout Pb was absorbed by wheat leaves and transferred to other organs, and it is important to develop effective strategies to control fallout Pb risks.

Suitability of selected bioindicators of atmospheric pollution in the industrialised region of Ostrava, Upper Silesia, Czech Republic.

This study is a continuation of our preceding research identifying suitable environmental samples for the tracing of atmospheric pollution in industrial areas. Three additional types of environmental samples were used to characterise contamination sources in the industrial area of Ostrava city, Czech Republic. The region is known for its extensive metallurgical and mining activities. Fingerprinting of stable Pb isotopes was applied to distinguish individual sources of anthropogenic Pb. A wide range of 206Pb/207Pb ratios was observed in the investigated samples: 206Pb/207Pb = 1.168-1.198 in mosses; 206Pb/207Pb = 1.167-1.215 in soils and 206Pb/207Pb = 1.158-1.184 in tree cores. Black and brown coal combustion, as well as metallurgical activities, is the two main sources of pollution in the area. Fossil fuel burning in industry and households seems to be a stronger source of Pb emissions than from the metallurgical industry. Concentration analyses of tree rings showed that a significant increase in As concentrations occurred between 1999 and 2016 (from 0.38 mg kg-1 to 13.8 mg kg-1). This shift corresponds to the use of brown coal from Bílina, Czech Republic, with an increased As concentration. The burning of low-quality fuels in households remains a problem in the area, as small ground sources have a greater influence on the air quality than do industrial sources.

Tracing fetal and childhood exposure to lead using isotope analysis of deciduous teeth.

We report progress in using the isotopic composition and concentration of Pb in the dentine and enamel of deciduous teeth to provide a high resolution time frame of exposure to Pb during fetal development and early childhood. Isotope measurements (total Pb and (208)Pb/(206)Pb, (207)Pb/(206)Pb ratios) were acquired by laser ablation inductively coupled mass spectrometry at contiguous 100 micron intervals across thin sections of the teeth; from the outer enamel surface to the pulp cavity. Teeth samples (n=10) were selected from two cohorts of children, aged 5-8 years, living in NE England. By integrating the isotope data with histological analysis of the teeth, using the daily incremental lines in dentine, we were able to assign true estimated ages to each ablation point (first 2-3 years for molars, first 1-2 years for incisors+pre-natal growth). Significant differences were observed in the isotope composition and concentration of Pb between children, reflecting differences in the timing and sources of exposure during early childhood. Those born in 2000, after the withdrawal of leaded petrol in 1999, have the lowest dentine Pb levels (<0.2µgPb/g) with (208)Pb/(206)Pb (mean ±2σ: 2.126-2.079) (208)Pb/(206)Pb (mean ±2σ: 0.879-0.856) ratios that correlate very closely with modern day Western European industrial aerosols (PM10, PM2.5) suggesting that diffuse airborne pollution was probably the primary source and exposure pathway. Legacy lead, if present, is insignificant. For those born in 1997, dentine lead levels are typically higher (>0.4µgPb/g) with (208)Pb/(206)Pb (mean ±2σ: 2.145-2.117) (208)Pb/(206)Pb (mean ±2σ: 0.898-0.882) ratios that can be modelled as a binary mix between industrial aerosols and leaded petrol emissions. Short duration, high intensity exposure events (1-2 months) were readily identified, together with evidence that dentine provides a good proxy for childhood changes in the isotope composition of blood Pb. Our pilot study confirms that laser ablation Pb isotope analysis of deciduous teeth, when carried out in conjunction with histological analysis, permits a reconstruction of the timing, duration and source of exposure to Pb during early childhood. With further development, this approach has the potential to study larger cohorts and appraise environments where the levels of exposure to Pb are much higher.

Linking cases of illegal shootings of the endangered California condor using stable lead isotope analysis.

Lead poisoning is preventing the recovery of the critically endangered California condor (Gymnogyps californianus) and lead isotope analyses have demonstrated that ingestion of spent lead ammunition is the principal source of lead poisoning in condors. Over an 8 month period in 2009, three lead-poisoned condors were independently presented with birdshot embedded in their tissues, evidencing they had been shot. No information connecting these illegal shooting events existed and the timing of the shooting(s) was unknown. Using lead concentration and stable lead isotope analyses of feathers, blood, and recovered birdshot, we observed that: i) lead isotope ratios of embedded shot from all three birds were measurably indistinguishable from each other, suggesting a common source; ii) lead exposure histories re-constructed from feather analysis suggested that the shooting(s) occurred within the same timeframe; and iii) two of the three condors were lead poisoned from a lead source isotopically indistinguishable from the embedded birdshot, implicating ingestion of this type of birdshot as the source of poisoning. One of the condors was subsequently lead poisoned the following year from ingestion of a lead buckshot (blood lead 556 µg/dL), illustrating that ingested shot possess a substantially greater lead poisoning risk compared to embedded shot retained in tissue (blood lead ~20 µg/dL). To our knowledge, this is the first study to use lead isotopes as a tool to retrospectively link wildlife shooting events.

Elevated lead mobility in sediments of a eutrophic drinking water reservoir during spring and summer seasons: Insights from isotopic signatures.

Lead (Pb) pollution in sediments remains a major concern for ecosystem quality due to the robust interaction at the sediment/water interface, particularly in shallow lakes. However, understanding the mechanism behind seasonal fluctuations in Pb mobility in these sediments is lacking. Here, the seasonal variability of Pb concentration and isotopic ratio were investigated in the uppermost sediments of a shallow eutrophic drinking lake located in southeast China. Results reveal a sharp increase in labile Pb concentration during autumn-winter period, reaching ∼ 3-fold higher levels than during the spring-summer seasons. Despite these fluctuations, there was a notable overlap in the Pb isotopic signatures within the labile fraction across four seasons, suggesting that anthropogenic sources are not responsible for the elevated labile Pb concentration in autumn-winter seasons. Instead, the abnormally elevated labile Pb concentration during autumn-winter was probably related to reduction dissolution of Fe/Mn oxides, while declined labile Pb concentration during spring-summer may be attributed to adsorption/precipitation of Fe/Mn oxides. These large seasonal changes imply the importance of considering seasonal effects when conducting sediment sampling. We further propose a solution that using Pb isotopic signatures within the labile fraction instead of the bulk sediment can better reflect the information of anthropogenic Pb sources.

Measuring Pb isotope ratios in fresh snow filtrate refines the apportioning of contaminant sources in the Arctic.

The remoteness and low population in the Arctic allow us to study global environmental processes, where the analysis of indicators can provide useful information about local and distant pollution sources. Fresh snow represents a convenient indicator of regional and transboundary atmospheric contamination sources, entrapping aerosols, and particulates like a natural autosampler of the environment. Lead stable isotopes are widely used to trace and monitor local and distant pollution sources. However, the behavior of Pb within different snow components is still not thoroughly studied, and its significance could be underestimated if only larger particulates are accounted for. We collected snow and samples from potential sources (fuel, rocks, coal) in three Arctic localities: Nuuk (Greenland), Reykjavik (Iceland), and Longyearbyen (Svalbard). We separated the filtrate from the filter residue through 0.45 µm nitrocellulose membranes to isolate the low-diameter particles associated with long-range transport from larger particles of mostly local natural origin. Filtrates yielded higher EFs (enrichment factor as the Pb/Al ratio relative to the upper crust) than filtration residues (80 ± 104 and 2.1 ± 1.1, respectively), and Pb isotope signals similar to fuel and coal (206Pb/207Pb are 1.199 ± 0.028 in coal, 1.168 ± 0.029 in filtrates, 1.163 ± 0.013 in fuel, 1.137 ± 0.045 in residues, and 0.985 ± 0.020 in rocks). In contrast to filtrates, the filter residues present wider ranges of Pb isotope compositions and crustal contributions and lower EFs, so we suggest that filtrate contains Pb from fuel combustion more selectively, while the residue carries a more considerable contribution of local mineral dust that can mask the contribution of other anthropogenic or distant natural sources. These findings add weight to the notion that filtrates are a more selective measure of metal deposition from long-range anthropogenic emissions compared to analyzing bulk melted snow or only filter residues.