Mert Guney

Exposure assessment and risk characterization from trace elements following soil ingestion by children exposed to playgrounds, parks and picnic areas.

Soil ingestion is an important pathway for exposure to metals for children. The objectives of this study were to: (1) Assess urban soil contamination by selected metals (As, Cr, Cu, Ni, Pb, and Zn) in 24 sites (127 soil samples) in Istanbul, Turkey, (2) Investigate relationships between soil contamination and site properties (type of site, equipment type, soil properties), (3) Characterize the risk for critically contaminated sites by taking oral metal bioaccessibility and two soil ingestion scenarios into account. Average metal concentrations were similar in the 17 playgrounds, 4 parks and 3 picnic areas sampled. Five out of 24 sites (all equipped with treated wood structures) had systematically higher contamination than background for As, Cu, Cr or Zn, and measured concentrations generally exceeded Turkish regulatory values. High Cu concentrations in these sites were attributed to the leaching from wood treated with Cu-containing preservatives other than chromated copper arsenate (CCA). Risk characterization for these sites showed that hazard index was below one in both involuntary soil ingestion and soil pica behaviour scenarios for all metals. However, probabilistic carcinogenic risk for As uptake exceeded 1x10(-6) in both scenarios. A sensitivity analysis showed that soil ingestion rate was the most important parameter affecting risk estimation. Risk from As uptake for children from soils of parks, playgrounds and picnic areas may be serious, especially if soil pica behaviour is present.

Heavy metals in toys and low-cost jewelry: Critical review of U.S. and Canadian legislations and recommendations for testing

High metal contamination in toys and low-cost jewelry is a widespread problem, and metals can become bioavailable, especially via oral pathway due to common child-specific behaviors of mouthing and pica. In this review, the U.S., Canadian, and European Union (EU) legislations on metals in toys and jewelry are evaluated. A literature review on content, bioavailability, childrens exposure, and testing of metals in toys and low-cost jewelry is provided. A list of priority metals is presented, and research needs and legislative recommendations are addressed. While the U.S. and Canadian legislations put emphasis on lead exposure prevention, other toxic elements like arsenic and cadmium in toy materials are not regulated except in paint and coatings. The EU legislation is more comprehensive in terms of contaminants and scientific approach. Current toy testing procedures do not fully consider metal bioavailability. In vitro bioaccessibility tests developed and validated for toys and corresponding metal bioaccessibility data in different toy matrices are lacking. The U.S. and Canadian legislations should put more emphasis on metal bioavailability and on other metals in addition to lead. A two-step management approach with mandatory testing of toys for total metal concentrations followed by voluntary bioaccessibility testing could be implemented.

Contamination by ten harmful elements in toys and children's jewelry bought on the North American market.

Toys and childrens jewelry may contain metals to which children can be orally exposed. The objectives of this research were (1) to determine total concentrations (TCs) of As, Ba, Cd, Cr, Cu, Mn, Ni, Pb, Sb, and Se in toys and jewelry (n = 72) bought on the North American market and compare TCs to regulatory limits, and (2) to estimate oral metal bioavailability in selected items (n = 4) via bioaccessibility testing. For metallic toys and childrens jewelry (n = 24) 20 items had TCs exceeding migratable concentration limits (European Union). Seven of seventeen jewelry items did not comply with TC limits in U.S. and Canadian regulations. Samples included articles with very high Cd (37% [w/w]), Pb (65%), and Cu (71%) concentrations. For plastic toys (n = 18), toys with paint or coating (n = 12), and brittle or pliable toys (n = 18), TCs were below the EU migration limits (except in one toy for each category). Bioaccessibility tests showed that a tested jewelry item strongly leached Pb (gastric: 698 μg, intestinal: 705 μg) and some Cd (1.38 and 1.42 μg). Especially in metallic toys and jewelry, contamination by Pb and Cd, and to a lesser extent by Cu, Ni, As, and Sb, still poses an acute problem in North America.

Bioaccessibility of As, Cd, Cu, Ni, Pb, and Sb in Toys and Low-Cost Jewelry

Children can be exposed to toxic elements in toys and jewelry following ingestion. As, Cd, Cu, Ni, Pb, and Sb bioavailability was assessed (n = 24) via the in vitro gastrointestinal protocol (IVG), the physiologically based extraction test (PBET), and the European Toy Safety Standard protocol (EN 71-3), and health risks were characterized. Cd, Cu, Ni, and Pb were mobilized from 19 metallic toys and jewelry (MJ) and one crayon set. Bioaccessible Cd, Ni, or Pb exceeded EU migratable concentration limits in four to six MJ, depending on the protocol. Using two-phase (gastric + intestinal) IVG or PBET might be preferable over EN 71-3 since they better represent gastrointestinal physiology. Bioaccessible and total metal concentrations were different and not always correlated, indicating that bioaccessibility measurement may provide more accurate risk characterization. More information on impacts of multiple factors affecting metals mobilization from toys and jewelry is needed before recommending specific tests. Hazard index (HI) for Cd, Ni, or Pb were >1 for all six MJ exceeding the EU limits. For infants (6-12 mo old), 10 MJ had HI > 1 for Cd, Cu, Ni, or Pb (up to 75 for Cd and 43 for Pb). Research on prolonged exposure to MJ and comprehensive risk characterization for toys and jewelry exposure is recommended.

Lung bioaccessibility of contaminants in particulate matter of geological origin

Human exposure to particulate matter (PM) has been associated with adverse health effects. While inhalation exposure to airborne PM is a prominent research subject, exposure to PM of geological origin (i.e., generated from soil/soil-like material) has received less attention. This review discusses the contaminants in PM of geological origin and their relevance for human exposure and then evaluates lung bioaccessibility assessment methods and their use. PM of geological origin can contain toxic elements as well as organic contaminants. Observed/predicted PM lung clearance times are long, which may lead to prolonged contact with lung environment. Thus, certain exposure scenarios warrant the use of in vitro bioaccessibility testing to predict lung bioavailability. Limited research is available on lung bioaccessibility test development and test application to PM of geological origin. For in vitro tests, test parameter variation between different studies and concerns about physiological relevance indicate a crucial need for test method standardization and comparison with relevant animal data. Research is recommended on (1) developing robust in vitro lung bioaccessibility methods, (2) assessing bioaccessibility of various contaminants (especially polycyclic aromatic hydrocarbons (PAHs)) in PM of diverse origin (surface soils, mine tailings, etc.), and (3) risk characterization to determine relative importance of exposure to PM of geological origin.

Impact of deforestation on soil carbon stock and its spatial distribution in the Western Black Sea Region of Turkey

Land use management is one of the most critical factors influencing soil carbon storage and the global carbon cycle. This study evaluates the impact of land use change on the soil carbon stock in the Karasu region of Turkey which in the last two decades has undergone substantial deforestation to expand hazelnut plantations. Analysis of seasonal soil data indicated that the carbon content decreased rapidly with depth for both land uses. Statistical analyses indicated that the difference between the surface carbon stock (defined over 0-5 cm depth) in agricultural and forested areas is statistically significant (Agricultural = 1.74 kg/m(2), Forested = 2.09 kg/m(2), p = 0.014). On the other hand, the average carbon stocks estimated over the 0-1 m depth were 12.36 and 12.12 kg/m(2) in forested and agricultural soils, respectively. The carbon stock (defined over 1 m depth) in the two land uses were not significantly different which is attributed in part to the negative correlation between carbon stock and bulk density (-0.353, p < 0.01). The soil carbon stock over the entire study area was mapped using a conditional kriging approach which jointly uses the collected soil carbon data and satellite-based land use images. Based on the kriging map, the spatially soil carbon stock (0-1 m dept) ranged about 2 kg/m(2) in highly developed areas to more than 23 kg/m(2) in intensively cultivated areas as well as the averaged soil carbon stock (0-1 m depth) was estimated as 10.4 kg/m(2).

Children's exposure to harmful elements in toys and low-cost jewelry: Characterizing risks and developing a comprehensive approach

Contamination problem in jewelry and toys and childrens exposure possibility have been previously demonstrated. For this study, risk from oral exposure has been characterized for highly contaminated metallic toys and jewelry ((MJ), n=16) considering three scenarios. Total and bioaccessible concentrations of Cd, Cu, Ni, and Pb were high in selected MJ. First scenario (ingestion of parts or pieces) caused unacceptable risk for eight items for Cd, Ni, and/or Pb (hazard index (HI)>1, up to 75, 5.8, and 43, respectively). HI for ingestion of scraped-off material scenario was always <1. Finally, saliva mobilization scenario caused HI>1 in three samples (two for Cd, one for Ni). Risk characterization identified different potentially hazardous items compared to United States, Canadian, and European Union approaches. A comprehensive approach was also developed to deal with complexity and drawbacks caused by various toy/jewelry definitions, test methods, exposure scenarios, and elements considered in different regulatory approaches. It includes bioaccessible limits for eight priority elements (As, Cd, Cr, Cu, Hg, Ni, Pb, and Sb). Research is recommended on metals bioaccessibility determination in toys/jewelry, in vitro bioaccessibility test development, estimation of material ingestion rates and frequency, presence of hexavalent Cr and organic Sn, and assessment of prolonged exposure to MJ.

Estimating children's exposure to toxic elements in contaminated toys and children's jewelry via saliva mobilization

Childrens potential for exposure to potentially toxic elements in contaminated jewelry and toys via mouth contact has not yet been fully evaluated. Various toys and jewelry (metallic toys and jewelry [MJ], plastic toys, toys with paint or coating, and brittle/pliable toys; n = 32) were tested using the saliva extraction (mouthing) compartment of the DIN and RIVM bioaccessibility protocols to assess As, Ba, Cd, Cr, Cu, Mn, Ni, Pb, Sb, and Se mobilization via saliva. Total concentrations of As, Cd, Cu, Ni, Pb, and Sb were found elevated in analyzed samples. Four metals were mobilized to saliva from 16 MJ in significant quantities (>1 μg for highly toxic Cd and Pb, >10 μg for Cu and Ni). Bioaccessible concentrations and hazard index values for Cd exceeded limit values, for young children between 6 mo- and 3 yr-old and according to both protocols. Total and bioaccessible metal concentrations were different and not always correlated, encouraging the use of bioaccessibility for more accurate hazard assessments. Bioaccessibility increased with increasing extraction time. Overall, the risk from exposure to toxic elements via mouthing was high only for Cd and for MJ. Further research on childrens exposure to toxic elements following ingestion of toy or jewelry material is recommended.

Bioaccessibility and other key parameters in assessing oral exposure to PAH-contaminated soils and dust: A critical review

ABSTRACT Soil ingestion is an important pathway for human exposure to polycyclic aromatic hydrocarbon (PAH)-contaminated soils and dust for children (via ingesting hand residue) as well as for adults (via occupational exposure). An appropriate selection of exposure parameter values is essential for having an accurate risk assessment. This review addresses key parameters for estimating oral exposure to PAH-contaminated soils/dust, discusses their variability and uncertainty, and provides recommendations for value selection. Bioaccessibility (contaminant fraction solubilized in gastro-intestinal tract, available for entering bloodstream and reaching target organs) and soil ingestion rate are two key parameters for exposure assessment (usually characterized by large variability and/or uncertainty), followed by exposure frequency/duration and body weight.

Lung bioaccessibility of As, Cu, Fe, Mn, Ni, Pb, and Zn in fine fraction (< 20 μm) from contaminated soils and mine tailings

The present study aims (1) to characterize contaminated soils (n=6) and mine tailings samples (n=3) for As, Cu, Fe, Mn, Ni, Pb, and Zn content; and (2) to assess elemental lung bioaccessibility in fine fraction (d<20μm which might contribute to airborne particulate matter (PM) and thus be inhaled) by means of in vitro tests using Gambles solution (GS) and an artificial lysosomal fluid (ALF). Elemental concentrations were high in the majority of samples, particularly for As (up to 2040mg·kg-1), Fe (up to 30.7%), Mn (up to 4360mg·kg-1), and Zn (up to 4060mg·kg-1); and elemental concentrations (As, Cu, and Ni) in the sieved fraction (d<20μm) obtained from contaminated soils were significantly higher than in the bulk fraction (<160μm). In vitro tests with ALF yielded much higher bioaccessibility than tests with GS, and the use of ALF in addition to GS is recommended to assess lung bioaccessibility. Bioaccessibility in ALF was high for all elements after 2weeks of testing both in terms of concentration (e.g. up to 1730mg·kg-1 for As) and percentages (e.g. up to 81% for Pb). The elemental solubilization rate generally declined rapidly and continuously with time. Similarly, bioaccessibility increased rapidly and tended to reach a plateau with time for most samples and metals. However, it is not possible to recommend a general testing duration as the solubilization behavior was highly element and sample-specific.