Water Treatment Residuals and Scrap Tire Rubber as Green Sorbents for Removal of Stormwater Metals.

Bench scale tests were performed to evaluate two recycled wastes, water treatment residuals (WTR) and scrap tire rubber (STR), for adsorption of selected metals from urban stormwater, and assess their release from used sorbents. Aluminum-WTR alone could rapidly and effectively remove Cu, Pb, and Zn, while STR alone continuously released Zn accompanied with Cu and Pb adsorption. Zn leaching from STR was significantly reduced in the presence of WTR. Very little metals released from used combined adsorbents in NaNO3 solution, and only part of them were extracted with EDTA (a strong chelating agent), suggesting that metal release is not a concern in a typical stormwater condition. A combination of WTR and STR is a new, effective method for mitigation of urban stormwater metals-WTR can inhibit the STR leaching, and STR improves the hydraulic permeability of WTR powders, a limiting factor for stormwater flow when WTR is used alone.

The Role of Tire Leachate in Condition-Specific Competition and the Persistence of a Resident Mosquito from a Competitively Superior Invader.

(1) Background: Condition-specific competition, when the outcome of competition varies with abiotic conditions, can facilitate species coexistence in spatially or temporally variable environments. Discarded vehicle tires degrade to leach contaminants into collected rainwater that provide habitats for competing mosquito species. We tested the hypothesis that more highly degraded tires that contain greater tire leachate alters interspecific mosquito competition to produce a condition-specific advantage for the resident, Culex pipiens, by altering the outcome of competition with the competitively superior invasive Aedes albopictus. (2) Methods: In a competition trial, varying densities of newly hatched Ae. albopictus and Cx. pipiens larvae were added to tires that had been exposed to three different ultraviolet (UV)-B conditions that mimicked full-sun, shade, or no UV-B conditions in the field. We also measured Cx. pipiens and Ae. albopictus oviposition preference among four treatments with varying tire leachate (high and low) and resources (high and low) amounts to determine if adult gravid females avoided habitats with higher tire leachate. (3) Results: We found stronger competitive effects of Cx. pipiens on the population performance and survival of Ae. albopictus in tires exposed to shade and full-sun conditions that had higher concentrations of contaminants. Further, zinc concentration was higher in emergent adults of Ae. albopictus than Cx. pipiens. Oviposition by these species was similar between tire leachate treatments but not by resource amount. (4) Conclusions: These results suggest that degraded tires with higher tire leachate may promote condition-specific competition by reducing the competitive advantage of invasive Ae. albopictus over resident Cx. pipiens and, combined with Cx. pipiens' preferential oviposition in higher resource sites, contribute to the persistence of the resident species.

Biomarkers of mercury exposure in two eastern Ukraine cities.

This study evaluates biomarkers of mercury exposure among residents of Horlivka, a city in eastern Ukraine located in an area with geologic and industrial sources of environmental mercury, and residents of Artemivsk, a nearby comparison city outside the mercury-enriched area. Samples of urine, blood, hair, and nails were collected from study participants, and a questionnaire was administered to obtain data on age, gender, occupational history, smoking, alcohol consumption, fish consumption, tattoos, dental amalgams, home heating system, education, source of drinking water, and family employment in mines. Median biomarker mercury concentrations in Artemivsk were 0.26 µg/g-Cr (urine), 0.92 µg/L (blood), 0.42 µg/g (hair), 0.11 µg/g (toenails), and 0.09 µg/g (fingernails); median concentrations in Horlivka were 0.15 µg/g-Cr (urine), 1.01 µg/L (blood), 0.14 µg/g (hair), 0.31 µg/g (toenails), and 0.31 µg/g (fingernails). Biomarkers of mercury exposure for study participants from Horlivka and Artemivsk are low in comparison with occupationally exposed workers at a mercury recycling facility in Horlivka and in comparison with exposures known to be associated with clinical effects. Blood and urinary mercury did not suggest a higher mercury exposure among Horlivka residents as compared with Artemivsk; however, three individuals living in the immediate vicinity of the mercury mines had elevated blood and urinary mercury, relative to overall results for either city. For a limited number of residents from Horlivka (N = 7) and Artemivsk (N = 4), environmental samples (vacuum cleaner dust, dust wipes, soil) were collected from their residences. Mercury concentrations in vacuum cleaner dust and soil were good predictors of blood and urinary mercury.

Zinc isotopic composition of particulate matter generated during the combustion of coal and coal + tire-derived fuels.

Atmospheric Zn emissions from the burning of coal and tire-derived fuel (TDF) for power generation can be considerable. In an effort to lay the foundation for tracking these contributions, we evaluated the Zn isotopes of coal, a mixture of 95 wt % coal + 5 wt % TDF, and the particulate matter (PM) derived from their combustion in a power-generating plant. The average Zn concentrations and δ(66)Zn were 36 mg/kg and 183 mg/kg and +0.24‰ and +0.13‰ for the coal and coal + TDF, respectively. The δ(66)Zn of the PM sequestered in the cyclone-type mechanical separator was the lightest measured, -0.48‰ for coal and -0.81‰ for coal+TDF. The δ(66)Zn of the PM from the electrostatic precipitator showed a slight enrichment in the heavier Zn isotopes relative to the starting material. PM collected from the stack had the heaviest δ(66)Zn in the system, +0.63‰ and +0.50‰ for the coal and coal + TDF, respectively. Initial fractionation during the generation of a Zn-rich vapor is followed by temperature-dependent fractionation as Zn condenses onto the PM. The isotopic changes of the two fuel types are similar, suggesting that their inherent chemical differences have only a secondary impact on the isotopic fractionation process.

Cardiopulmonary responses of intratracheally instilled tire particles and constituent metal components.

Tire and brake wear particles contain transition metals, and contribute to near-road PM. We hypothesized that acute cardiopulmonary injury from respirable tire particles (TP) will depend on the amount of soluble metals. Respirable fractions of two types of TP (TP1 and TP2) were analyzed for water and acid-leachable metals using ICP-AES. Both TP types contained a variety of transition metals, including zinc (Zn), copper (Cu), aluminum, and iron. Zn and Cu were detected at high levels in water-soluble fractions (TP2 > TP1). Male Wistar Kyoto rats (12-14 wk) were intratracheally instilled, in the first study, with saline, TP1 or TP2 (5 mg/kg), and in the second study, with soluble Zn, Cu (0.5 micromol/kg), or both. Pulmonary toxicity and cardiac mitochondrial enzymes were analyzed 1 d, 1 wk, or 4 wk later for TP and 4 or 24 h later for metals. Increases in lavage fluid markers of inflammation and injury were observed at d 1 (TP2 > TP1), but these changes reversed by wk 1. No effects on cardiac enzymes were noted with either TP. Exposure of rats to soluble Zn and Cu caused marked pulmonary inflammation and injury but temporal differences were apparent (Cu effects peaked at 4 h and Zn at 24 h). Instillation of Zn, Cu, and Zn + Cu decreased the activity of cardiac aconitase, isocitrate dehydrogenase, succinate dehydrogenase, cytochrome-c-oxidase and superoxide dismutase suggesting mitochondrial oxidative stress. The observed acute pulmonary toxicity of TP could be due to the presence of water soluble Zn and Cu. At high concentrations these metals may induce cardiac oxidative stress.

Biomarkers of mercury exposure at a mercury recycling facility in Ukraine.

This study evaluates biomarkers of occupational mercury exposure among workers at a mercury recycling operation in Gorlovka, Ukraine. The 29 study participants were divided into three occupational categories for analysis: (1) those who worked in the mercury recycling operation (Group A, n = 8), (2) those who worked at the facility but not in the yard where the recycling was done (Group B, n = 14), and (3) those who did not work at the facility (Group C, n = 7). Urine, blood, hair, and nail samples were collected from the participants, and a questionnaire was administered to obtain data on age, gender, occupational history, smoking, alcohol consumption, fish consumption, tattoos, dental amalgams, home heating system, education, source of drinking water, and family employment in the former mercury mine/smelter located on the site of the recycling facility. Each factor was tested in a univariate regression with total mercury in urine, blood, hair, and nails. Median biomarker concentrations were 4.04 microg/g-Cr (urine), 2.58 microg/L (blood), 3.95 microg/g (hair), and 1.16 microg/g (nails). Occupational category was significantly correlated (p < 0.001) with both blood and urinary mercury concentrations but not with hair or nail mercury. Four individuals had urinary mercury concentrations in a range previously found to be associated with subtle neurological and subjective symptoms (e.g., fatigue, loss of appetite, irritability), and one worker had a urinary mercury concentration in a range associated with a high probability of neurological effects and proteinuria. Comparison of results by occupational category found that workers directly involved with the recycling operation had the highest blood and urinary mercury levels. Those who worked at the facility but were not directly involved with the recycling operation had higher levels than those who did not work at the facility.

Effects of tire leachate on the invasive mosquito Aedes albopictus and the native congener Aedes triseriatus.

Discarded vehicle tire casings are an important artificial habitat for the developmental stages of numerous vector mosquitoes. Discarded vehicle tires degrade under ultraviolet light and leach numerous soluble metals (e.g., barium, cadmium, zinc) and organic substances (e.g., benzothiazole and its derivatives [BZTs], polyaromatic hydrocarbons [PAHs]) that could affect mosquito larvae that inhabit the tire casing. This study examined the relationship between soluble zinc, a common marker of tire leachate, on mosquito densities in tire habitats in the field, and tested the effects of tire leachate on the survival and development of newly hatched Aedes albopictus and Aedes triseriatus larvae in a controlled laboratory dose-response experiment. In the field, zinc concentrations were as high as 7.26 mg/L in a single tire and averaged as high as 2.39 (SE ± 1.17) mg/L among tires at a single site. Aedes albopictus (37/42 tires, 81.1%) and A. triseriatus (23/42, 54.8%) were the most widespread mosquito species, co-occurred in over half (22/42, 52.4%) of all tires, and A. triseriatus was only collected without A. albopictus in one tire. Aedes triseriatus was more strongly negatively associated with zinc concentration than A. albopictus, and another common mosquito, C. pipiens, which was found in 17 tires. In the laboratory experiment, A. albopictus per capita rate of population change (λ') was over 1.0, indicating positive population growth, from 0-8.9 mg/L zinc concentration (0-10,000 mg/L tire leachate), but steeply declined to zero from 44.50-89.00 mg/L zinc (50,000-100,000 mg/L tire leachate). In contrast, A. triseriatus λ' declined at the lower concentration of 0.05 mg/L zinc (100 mg/L tire leachate), and was zero at 0.45, 8.90, 44.50, and 89.00 mg/L zinc (500, 10,000, 50,000 and 100,000 mg/L tire leachate). These results indicate that tire leachate can have severe negative effects on populations of container-utilizing mosquitoes at concentrations commonly found in the field. Superior tolerance to tire leachate of A. albopictus compared to A. triseriatus, and possibly other native mosquito species, may have facilitated the replacement of these native species as A. albopictus has invaded North America and other regions around the world.

Detection of Helicobacter pylori and fecal indicator bacteria in five North American rivers.

This study examines the use of fecal indicator bacteria (FIB) as a predictor of the presence of Helicobacter spp. A combination of standard culture and molecular techniques were used to detect and quantify FIB, Helicobacter spp. and H. pylori from five North American rivers of different size and with different land use characteristics. Primers designed to amplify genes specific to Helicobacter spp. and H. pylori were evaluated for their efficacy in detection and quantification in environmental samples. Helicobacter spp. were detected in 18/33 (55%) of river samples. H. pylori was detected in 11/33 (33%) of river samples. FIB were found in 32/33 (96%) of river samples. When FIB abundance exceeded USEPA water quality standards for single samples, Helicobacter or H. pylori were detected in 7/15 (47%) cases. No numerical correlation was found between the presence of FIB and either Helicobacter spp. or H. pylori. This suggests that the presence of FIB will be of limited use for detection of Helicobacter spp. or H. pylori by public health agencies.

Sorption of 99mTc radiopharmaceutical compounds by soils.

Study of the sorption of 99mTc radiopharmaceutical compounds by soils has assessed the fate of these compounds in the event of a surface spill and examined the potential of these compounds as hydrologic tracers. Sorption from deionized water, filtered Missouri River water, and artificial seawater by five surface soils was investigated. For all water types, the Tc radiopharmaceutical compounds showed greater sorption than the uncomplexed pertechnetate. The most lipophilic complexes showed the highest sorption on soils.

Uranium mill tailings: nuclear waste and natural laboratory for geochemical and radioecological investigations.

Uranium mill tailings (UMT) are a high volume, low specific activity radioactive waste typically disposed in surface impoundments. This review focuses on research on UMT and related earth materials during the past decade relevant to the assessment of: (1) mineral hosts of radionuclides; (2) the use of soil analogs in predicting long-term fate of radionuclides; (3) microbial and diagenetic processes that may alter radionuclide mobility in the surficial environment; (4) waste-management technologies to limit radionuclide migration; and (5) the impact of UMT on biota.

Zn and Cu isotopes as tracers of anthropogenic contamination in a sediment core from an urban lake.

In this work, we use stable Zn and Cu isotopes to identify the sources and timing of the deposition of these metals in a sediment core from Lake Ballinger near Seattle, Washington, USA. The base of the Lake Ballinger core predates settlement in the region, while the upper sections record the effects of atmospheric emissions from a nearby smelter and rapid urbanization of the watershed. delta(66)Zn and delta(65)Cu varied by 0.50 per thousand and 0.29 per thousand, respectively, over the 500 year core record. Isotopic changes were correlated with the presmelter period ( approximately 1450 to 1900 with delta(66)Zn = +0.39 per thousand +/- 0.09 per thousand and delta(65)Cu = +0.77 per thousand +/- 0.06 per thousand), period of smelter operation (1900 to 1985 with delta(66)Zn = +0.14 +/- 0.06 per thousand and delta(65)Cu = +0.94 +/- 0.10 per thousand), and postsmelting/stable urban land use period (post 1985 with delta(66)Zn = 0.00 +/- 0.10 per thousand and delta(65)Cu = +0.82 per thousand +/- 0.12 per thousand). Rapid early urbanization during the post World War II era increased metal loading to the lake but did not significantly alter the delta(66)Zn and delta(65)Cu, suggesting that increased metal loads during this time were derived mainly from mobilization of historically contaminated soils. Urban sources of Cu and Zn were dominant since the smelter closed in the 1980s, and the delta(66)Zn measured in tire samples suggests tire wear is a likely source of Zn.

Chemical fractionation of Cu and Zn in stormwater, roadway dust and stormwater pond sediments.

This study evaluated the chemical fractionation of Cu and Zn from source to deposition in a stormwater system. Cu and Zn concentrations and chemical fractionation were determined for roadway dust, roadway runoff and pond sediments. Stormwater Cu and Zn concentrations were used to generate cumulative frequency distributions to characterize potential exposure to pond-dwelling organisms. Dissolved stormwater Zn exceeded USEPA acute and chronic water quality criteria in approximately 20% of storm samples and 20% of the storm duration sampled. Dissolved Cu exceeded the previously published chronic criterion in 75% of storm samples and duration and exceeded the acute criterion in 45% of samples and duration. The majority of sediment Cu (92-98%) occurred in the most recalcitrant phase, suggesting low bioavailability; Zn was substantially more available (39-62% recalcitrant). Most sediment concentrations for Cu and Zn exceeded published threshold effect concentrations and Zn often exceeded probable effect concentrations in surface sediments.

Impacts of weathered tire debris on the development of Rana sylvatica larvae.

Highway runoff has the potential to negatively impact receiving systems including stormwater retention ponds where highway particulate matter can accumulate following runoff events. Tire wear particles, which contain about 1% Zn by mass, make up approximately one-third of the vehicle derived particulates in highway runoff and therefore may serve as a stressor to organisms utilizing retention ponds as habitat. In this study, we focused on the potential contribution of tire debris to Zn accumulation by Rana sylvatica larvae and possible lethal or sublethal impacts resulting from exposure to weathered tire debris during development. Eggs and larvae were exposed to aged sediments (containing either ZnCl2 or tire particulate matter, both providing nominal concentrations of 1000 mg Zn kg(-1)) through metamorphosis. Water column Zn was elevated in both the ZnCl2 and tire treatments relative to the control treatment, indicating that aging allowed Zn leaching from tire debris to occur. Tissue Zn was also elevated for the ZnCl2 and tire treatments indicating that Zn in the treatments was available for uptake by the amphibians. Exposure to both ZnCl2 and tire treatments increased the time for larvae to complete metamorphosis in comparison with controls. We also observed that the longer the organisms took to complete metamorphosis, the smaller their mass at metamorphosis. Our results indicate that Zn leached from aged tire debris is bioavailable to developing R. sylvatica larvae and that exposure to tire debris amended sediments can result in measurable physiological outcomes to wood frogs that may influence population dynamics.

Tire-wear particles as a source of zinc to the environment.

Tire-tread material has a zinc (Zn) content of about 1 wt %. The quantity of tread material lost to road surfaces by abrasion has not been well characterized. Two approaches were used to assess the magnitude of this nonpoint source of Zn in the U.S. for the period 1936-1999. In the first approach, tread-wear rates from the automotive engineering literature were used in conjunction with vehicle distance-driven data from the U.S. Department of Transportation to determine Zn releases. A second approach calculated this source term from the volume of tread lost during lifetime tire wear. These analyses showed that the quantity of Zn released by tire wear in the mid-1990s was of the same magnitude as that released from waste incineration. For 1999, the quantity of Zn released by tire wear in the U.S. is estimated to be 10 000-11 000 metric tons. A specific case study focused on Zn sources and sinks in an urban-suburban watershed (Lake Anne) in the Washington, DC, metropolitan area for a time period of the late 1990s. The atmospheric flux of total Zn (wet deposition) to the watershed was 2 microg/cm2/yr. The flux of Zn to the watershed estimated from tire wear was 42 microg/cm2/yr. The measured accumulation rate of total Zn in age-dated sediment cores from Lake Anne was 27 microg/cm2/yr. These data suggest that tire-wear Zn inputs to urban-suburban watersheds can be significantly greater than atmospheric inputs, although the watershed appears to retain appreciable quantities of vehicular Zn inputs.