Using Community Science to Better Understand Lead Exposure Risks.

Lead (Pb) is a neurotoxicant that particularly harms young children. Urban environments are often plagued with elevated Pb in soils and dusts, posing a health exposure risk from inhalation and ingestion of these contaminated media. Thus, a better understanding of where to prioritize risk screening and intervention is paramount from a public health perspective. We have synthesized a large national data set of Pb concentrations in household dusts from across the United States (U.S.), part of a community science initiative called "DustSafe." Using these results, we have developed a straightforward logistic regression model that correctly predicts whether Pb is elevated (>80 ppm) or low (<80 ppm) in household dusts 75% of the time. Additionally, our model estimated 18% false negatives for elevated Pb, displaying that there was a low probability of elevated Pb in homes being misclassified. Our model uses only variables of approximate housing age and whether there is peeling paint in the interior of the home, illustrating how a simple and successful Pb predictive model can be generated if researchers ask the right screening questions. Scanning electron microscopy supports a common presence of Pb paint in several dust samples with elevated bulk Pb concentrations, which explains the predictive power of housing age and peeling paint in the model. This model was also implemented into an interactive mobile app that aims to increase community-wide participation with Pb household screening. The app will hopefully provide greater awareness of Pb risks and a highly efficient way to begin mitigation.

Road sediment, an underutilized material in environmental science research: A review of perspectives on United States studies with international context.

Road sediment is a pervasive environmental medium that acts as both source and sink for a variety of natural and anthropogenic particles and often is enriched in heavy metals. Road sediment is generally understudied in the United States (U.S.) relative to other environmental media and compared to countries such as China and the United Kingdom (U.K.). However, the U.S. is an ideal target for these studies due to the diverse climates and wealth of geochemical, socioeconomic, demographic, and health data. This review outlines the existing U.S. road sediment literature while also providing key international perspectives and context. Furthermore, the most comprehensive table of U.S. road sediment studies to date is presented, which includes elemental concentrations, sample size, size fraction, collection and analytical methods, as well as digestion procedure. Overall, there were observed differences in studies by sampling time period for elemental concentrations, but not necessarily by climate in the U.S. Other key concepts addressed in this road sediment review include the processes controlling its distribution, the variety of nomenclature used, anthropogenic enrichment of heavy metals, electron microscopy, health risk assessments, remediation, and future directions of road sediment investigations. Going forward, it is recommended that studies with a higher geographic diversity are performed that consider smaller cities and rural areas. Furthermore, environmental justice must be a focus as community science studies of road sediment can elucidate pollution issues impacting areas of high need. Finally, this review calls for consistency in sampling, data reporting, and nomenclature to effectively expand work on understudied elements, particles, and background sediments.

Quantification of Pb pollution sources in complex urban environments through a multi-source isotope mixing model based on Pb isotopes in lichens and road sediment.

Despite a growing focus on anthropogenic toxic metal pollution in urban environments, few studies have addressed the problem of quantification when more than two pollution sources are likely present, particularly within complex urban settings in the United States (U.S.). In this study, we utilize the MixSIAR package in R for source apportionment based on Pb isotopic signatures in lichen and road sediment in two urban-industrial centers in SW Ohio (OH). We show that ranges of pollutant contributions are more useful than only visualizing mean or raw values of source apportionment, because this avoids overinterpretation of data when certain sources have a large range of uncertainty. We point out both the dominance of industrial pollution as well as the legacy of leaded gasoline pollution in typical mid-sized U.S. cities, which is evident in both road sediment and lichens. Leaded gasoline contribution to Pb in Middletown, OH lichens mostly vary between ~10 and 25%, while in Hamilton, OH the contribution to lichens and road sediment tends to be relatively negligible except for two road sediment samples and one lichen sample, where median contributions are ~20-30%. Industrial combustion pollution source contributions vary between ~25 and 75% in Hamilton, and ~50-100% in Middletown, OH. Furthermore, comparing pollution sources in lichens to modern particulate matter can provide a record of how pollutant sources change over time, such as our traffic lichen (Sample Li-9) plotting closer to leaded gasoline on a bivariate mixing diagram than modern traffic particulate matter, or our coke plant lichen containing slightly less Pb contribution from industrial combustion sources relative to modern coke plant particulate matter. Lastly, when applicable, multi-source mixing models should be complimented in future studies with additional isotopic source tracers such as Cu, Zn, Nd, and Os to further elucidate unique sources of metal pollutants in addition to Pb.

Investigation of Pb-contaminated soil and road dust in a polluted area of Philadelphia.

A multi-analytical geochemical investigation of Pb-contaminated collocated road dust and soils, at two size fractions, was performed in Fishtown, Philadelphia, PA, USA. The combinations of methods employed in this case study were chosen to better characterize the contamination, enhance identification of pollution sources, improve understanding of the impact of former Pb smelters, and to study the relationships between two media and between two size fractions. High concentrations of Cu and Sn were observed in both bulk and finer road dust, whereas large concentrations of Zn and Pb were found in both bulk and finer soil samples, implying pollution. There were no obvious associations between Pb soil concentrations and former smelter locations. Therefore, the primary source of the high mean Pb content in bulk (595 ppm) and fine soils (687 ppm) was likely legacy lead paint and/or leaded-gasoline products. Using electron microscopy, we found that Pb particles were mainly 0.1-10 µm in diameter and were ubiquitous in both soil and dust samples. Two-way analysis of variance tests revealed that, for most chemical elements explored here, there were statistically significant differences in concentrations based on media and size fractions, with finer sizes being more polluted than the bulk. The mineralogical composition and the sources of several pollutant elements (Cr, Cu, Zn, Pb), however, were similar for both soil and dust, pointing to material exchange between the two media. We suggest that future investigations of collocated road dust and soils in urban environments use the methodologies applied in this study to obtain detailed insights into sources of roadside pollution and the relationships between neighboring media.

Monitoring uranium mine pollution on Native American lands: Insights from tree bark particulate matter on the Spokane Reservation, Washington, USA.

The uranium boom in the United States from the 1940's to the 1980's was a period of extensive uranium mining on Native American lands. However, detailed environmental investigations of the resulting uranium pollution are sparse and typically ignore contributions from airborne particulate matter. The Midnite Mine is a 350-acre inactive open pit uranium mine located on the Spokane Indian Reservation in eastern Washington that operated from 1954 to 1981. Approximately 2.4 million tons of ore and 33 million tons of waste rock were left behind in stockpiles and have also been utilized as gravel on access and haul roads. Although the Midnite Mine is now a Superfund Site, and governmental investigations of water and soil contamination have been done, no investigations of airborne particulate matter pollution have been conducted. This study applies tree bark from 31 Pinus ponderosa trees as a biomonitor of this airborne particulate matter. Bulk trace elemental analyses via inductively coupled plasma - mass spectrometry (ICP-MS) of tree bark show that U is the most abundant trace element of interest present up to 232 ppb. Other metals that are of potential human health concern include Th, Pb, and As which are present at 20 ppb, 104 ppb, and 20 ppb respectively. Calculated geoaccumulation indices determine these metals to be at high (U), moderate (Th), and low (Pb and As) levels of contamination. Detailed scanning electron microscopy (SEM) investigations of particulate matter from the surface of tree bark confirm that U and Th-bearing particulate matter exist in the

Alteration of yellow traffic paint in simulated environmental and biological fluids.

Pollution from heavy metals in urban environments is a topic of growing concern because many metals, including Pb and Cr, are a human health hazard. Exposure to Pb and Cr has been linked to the inhibition of neurological development as well as toxic effects on many organs. Yellow traffic paint (YTP) is a mixture that contains organic polymers, binders, and pigments, which in some cases consist of crocoite (PbCrO4) that may be coated by silica. The primary aim of this study was to investigate the behavior of the crocoite pigment grains within YTP and their silica coatings in simulated environmental and human body conditions. To do this, both YTP and asphalt were collected in Philadelphia, PA, USA. These samples as well as a standard PbCrO4 were investigated with powder X-ray diffraction, X-ray fluorescence, environmental scanning electron microscopy (ESEM), transmission electron microscopy, and energy-dispersive X-ray spectroscopy. Using this multi-analytical approach, mineral phases were determined in the YTP, their shape, dimensional distributions, crystallinity, and chemical composition, as well as elemental distributions before and after experimental interactions. Three batch dissolution experiments with YTP, asphalt, and standard PbCrO4 were performed to simulate ingestion, inhalation, and environmental interaction with rainwater. Elemental releases were determined with inductively coupled plasma-optical emission spectrometry, and results indicated that little (ingestion) to no (environmental and inhalation) Pb and Cr were leached from the YTP during the three experimental procedures. This is likely due to the silica coating that encapsulates the crocoite particles, which persisted during all interactions. The ESEM results for YTP showed dimensional reductions after interactions with all three fluids. The silica coating must be further explored to determine how it breaks down in real environmental conditions.

Reflective spectroscopy investigations of clothing items to support law enforcement, search and rescue, and war crime investigations.

Clothing articles are important pieces of evidence in criminal, search and rescue, and search and recovery investigations. Hyperspectral remote sensing of clothing will be an important tool for supporting such investigations in the near future. This study investigated over 300 items of clothing that varied in fabric type, texture, color, and pattern. Clothing items were analyzed using an ASD FieldSpec 4 High Resolution spectroradiometer with a contact probe attachment. Of the clothing items analyzed, there were 141 having endmember fabrics (100% single fabric type composition): 89 were cotton, 39 were polyester, 5 were wool, 1 was cashmere, 3 were acrylic, 1 was leather, and 3 were rayon. The remaining 164 clothing items were various fabric blends. Spectral features relating to different fabric types exhibit sufficient differences that allow them to be discriminated from the surrounding environment, as well as from one another in many, but not all, cases. Cotton and polyester, in particular, two of the most widely-used fabrics, exhibit numerous features in the near infrared (NIR) and shortwave infrared (SWIR) that would allow them to easily be distinguished from geologic materials in the environment such as rocks and soil. Plant based fibers, especially cotton, possess similar reflectance features to vegetation owing to their cellulose content. Outdoor aging experiments were conducted for 19 weeks on selected fabrics. Although significant changes were observed in aged garments, the variability observed in the reflectance of the aged garments does not support the derivation of a metric for aging, at least over the relatively short time scale of this effort. Results from this study should support numerous forensic efforts globally for non-destructive investigation of clothing items in the field and in lab settings with a spectroradiometer, enhance the potential for remote sensing searches, and in the future, potentially documenting crime scenes with hyperspectral imaging.

The first pollution investigation of road sediment in Gary, Indiana: Anthropogenic metals and possible health implications for a socioeconomically disadvantaged area.

An investigation of road sediment in Gary, Indiana revealed high levels of various trace metals such as Zn, Mn, and Cr, often exceeding those of background reference concentrations as shown through geoaccumulation indices and contamination factors. The hazard index (HI) value for Mn in children was >1 (1.7), suggesting possible long-term non-carcinogenic health risk. Mn HI for children is even higher for the five samples closest to a US Steel facility, with an HI of 2.8. Through SEM-EDS analysis, the prevalence of small particulates (PM2.5 and PM2.5-10) containing potentially harmful elements such as Mn and Pb illustrate a health risk through direct inhalation or ingestion. The small nature of particulates in general may also pose an increased health risk for respiratory diseases such as asthma. Mn concentrations in the road sediment were particularly high, with 30 out of 32 samples exceeding 1800 ppm. Mn and V concentrations show a strong spatial trend of decreasing concentration away from a US Steel facility. These spatial trends along with correlation plots of the bulk chemistry suggest that industrial steel manufacturing, particularly US Steel in Gary, is a major contributing source of Mn and V. Fe and Cr show a moderate decrease in concentrations away from the US Steel facility, which suggests some sourcing from the steel facility when coupled with bulk chemistry plots. Zn and Cu do not show much evidence of sourcing from the US Steel facility, likely due to increased mixing from other sources. Further work constraining anthropogenic sources, the bioaccessible fraction of metals, and analysis of direct atmospheric particulates can help with remedial activity and risk assessment.

Metal pollution investigation of Goldman Park, Middletown Ohio: Evidence for steel and coal pollution in a high child use setting.

A geochemical investigation of both ballfield sediment and street sediment in a park adjacent to a major steel manufacturing site in Middletown, Ohio revealed Pb, Cu, Cr and Zn exceeded background levels, but in heterogeneous ways and in varying levels of health concern. Pb, Sn, and Zn had geoaccumulation values>2 (moderate to heavy pollutants) in street sediment samples. Cr had a geoaccumulation value>1, while Ni, W, Fe and Mn had geoaccumulation values between 1 and 0 in street sediment. Street sediment contamination factors for respective elements are Zn (10.41), Sn (5.45), Pb (4.70), Sb (3.45), Cr (3.19), W (2.59), and Mn (2.43). The notable elements with the highest factors for ball fields are Zn (1.72), Pb (1.36), Cr (0.99), V (0.95), and Mn (1.00). High correlation coefficients of known constituents of steel, such as Fe and Mo, Ni and Cr, W and Co, W and V, as well as particulate steel and coal spherule fragments found by SEM suggest probable sourcing of some of the metals from the AK Steel facility directly adjacent to the park. However, overall extensive heterogeneity of metal pollutants in the area points to the difficulties in sourcing pollutant metals, with many outside sources likely contributing as well. This study demonstrates that different sediment media can be impacted by significantly different metal pollutants even when in very close proximity to a single source and points to unrecognized complexity in urban pollution processes in the region. This study pertains to large-scale regional importance, as Middletown, Ohio is indicative of a typical post-industrial Midwestern U.S. city where limited investigation has been conducted regarding urban pollution and sourcing of materials.

Kinetic sorption of contaminants of emerging concern by a palygorskite-montmorillonite filter medium.

Kinetic sorption of bisphenol A (BPA), carbamazepine (CMZ) and ciprofloxacin (CIP) by three palygorskite-montmorillonite (Pal-Mt) granule sizes was studied. For BPA, CMZ and CIP, apparent sorption equilibrium was reached within about 3, 5 and 16 h, respectively. The highest and the lowest sorption capacities were by the small and the large granule sizes, respectively. Experimental results were compared to various sorption kinetics models to gain insights regarding the sorption processes and achieve a predictive capacity. The pseudo-second order (PSO) and the Elovich models performed the best while the pseudo-first order (PFO) model was only adequate for CMZ. The intraparticle-diffusion (IPD) model showed a two-step linear plot of BPA, CMZ and CIP sorption versus square root of time that was indicative of surface-sorption followed by IPD as a rate-limiting process before equilibrium was reached. Using the pseudo-first order (PFO) and the pseudo-second order (PSO) rate constants combined with previously-established Langmuir equilibrium sorption models, the kinetic sorption (ka) and desorption (kd) Langmuir kinetic rate constants were theoretically calculated for BPA and CIP. Kinetic sorption was then simulated using these theoretically calculated ka and kd values, and the simulations were compared to the observed behavior. The simulations fit the observed sorbed concentrations better during the early part of the experiments; the observed sorption during later times occurred more slowly than expected, supporting the hypothesis that IPD becomes a rate-limiting process during the course of the experiment.

Sorption-desorption of carbamazepine by palygorskite-montmorillonite (PM) filter medium.

Palygorskite-montmorillonite (PM) was studied as a potential sewage treatment effluent filter material for carbamazepine. Batch sorption experiments were conducted as a function of granule size (0.3-0.6, 1.7-2.0 and 2.8mm) and different sewage effluent conditions (pH, ionic strength and temperature). Results showed PM had a mix of fibrous and plate-like morphologies. Sorption and desorption isotherms were fitted to the Freundlich model. Sorption is granule size-dependent and the medium granule size would be an appropriate size for optimizing both flow and carbamazepine retention. Highest and lowest sorption capacities corresponded to the smallest and the largest granule sizes, respectively. The lowest and the highest equilibrium aqueous (Ce) and sorbed (qe) carbamazepine concentrations were 0.4 mg L(-1) and 4.5 mg L(-1), and 0.6 mg kg(-1) and 411.8 mg kg(-1), respectively. Observed higher relative sorption at elevated concentrations with a Freundlich exponent greater than one, indicated cooperative sorption. The sorption-desorption hysteresis (isotherm non-singularity) indicated irreversible sorption. Higher sorption observed at higher rather than at lower ionic strength conditions is likely due to a salting-out effect. Negative free energy and the inverse sorption capacity-temperature relationship indicated the carbamazepine sorption process was favorable or spontaneous. Solution pH had little effect on sorption.

A mineralogical and geochemical investigation of street sediment near a coal-fired power plant in Hamilton, Ohio: an example of complex pollution and cause for community health concerns.

The Hamilton Municipal Electric Plant is a 125 MW coal-fired power plant, owned and operated by the City of Hamilton in Butler County, Ohio. The plant is located within 110 m of 50 homes. Bulk chemical investigation of street sediment near these homes indicates average concentrations of 25 ppm Cr, 40 ppm Cu, 15 ppm Ni, 215 ppm Pb, and 500 ppm Zn. Lead and Zn have maximum concentrations of 1207 ppm and 1512 ppm, respectively. Scanning electron microscopy indicates coal ash spherules are present in the street sediment as well as a variety of Pb, Ni, Cr, W, and BaSO4 particulates. Transmission electron microscopy indicates heavy metals are sorbed onto clay particles with some preference for illite over chlorite. This investigation shows bulk chemistry and electron microscopy approaches are very effective tools to investigate particulate pollutants and identify contexts in complex urban settings involving coal pollution.

Transmission electron microscopy (TEM) investigations of Mn-oxide rich cathodic material from spent disposable alkaline batteries.

Transmission electron microscopy (TEM) techniques were used to investigate the spent cathodic material of a single common brand of disposable alkaline batteries. Mn-oxide particles are anhedral and irregular in shape and compose an estimated 99-95% of the < 10 microm size fraction of sample material. Diameters of particles vary widely and typically are between 50 nm and 3 microm; however, most particles are approximately 200-400 nm in diameter. Chemical composition varies for Mn-oxide particles with concentrations being SiO2 (0.00-1.52 wt%), TiO2 (0.49-4.58 wt%), MnO (65.85-92.06 wt%), ZnO (1.00-7.53 wt%), K2O (4.97-20.48 wt%) and SO3 (0.43-2.21 wt%). Discrete prismatic zinc crystals occur and vary from a maximum of approximately 0.8 microm long x 0.15 microm wide, to 100 nm long x 20 nm wide. Titanium metal was also observed in samples and composes approximately 0.25-1.0% of the < 10 microm size fraction of sample material. Results of this study suggest that battery components may be recycled in some special applications. Examples are low energy-low material requirement products such as paint pigments and Zn nanoparticles. This investigation provides detailed constraints on the nature of spent cathodic materials to improve existing recycling methods and develop new technologies.