Distribution, availability, and sources of trace metals in different particle size fractions of urban soils in Hong Kong: Implications for assessing the risk to human health

The concentration and loading distribution of trace metals (Cu, Zn, Pb, Co, Ni, Cr, and Mn) and major elements (Al, Ca, Fe, and Mg) in different particle size fractions (2000-280, 280-100, 100-50, 50-10, 10-2, and <2 μm) of surface soils from highly urbanized areas in Hong Kong were studied. The enrichment of Pb, Cu, and Zn in the urban soils was strongly influenced by anthropogenic activities, and Pb accumulated in fine particles was mainly derived from past vehicular emissions as shown by Pb isotopic signatures. Trace metals primarily accumulated in clay, fine silt, and very fine sand fractions, and might pose potential health risks via the inhalation of resuspended soil particles in the air (PM₁₀ or PM_2.5), and ingestion of adhered soils through the hand-to-mouth pathway. The mobility, bioavailability, and human bioaccessibility of Pb and Zn in bulk soils correlated significantly with metal concentrations in fine silt and/or very fine sand fractions.     

In vitro and in vivo approaches for the measurement of oral bioavailability of lead (Pb) in contaminated soils: a review

We reviewed the published evidence of lead (Pb) contamination of urban soils, soil Pb risk to children through hand-to-mouth activity, reduction of soil Pb bioavailability due to soil amendments, and methods to assess bioaccessibility which correlate with bioavailability of soil Pb. Feeding tests have shown that urban soils may have much lower Pb bioavailability than previously assumed. Hence bioavailability of soil Pb is the important measure for protection of public health, not total soil Pb. Chemical extraction tests (Pb bioaccessibility) have been developed which are well correlated with the results of bioavailability tests; application of these tests can save money and time compared with feeding tests. Recent findings have revealed that fractional bioaccessibility (bioaccessible compared to total) of Pb in urban soils is only 5-10% of total soil Pb, far lower than the 60% as bioavailable as food-Pb presumed by U.S.-EPA (30% absolute bioavailability used in IEUBK model).     

Surfactant-induced mobilisation of trace metals from estuarine sediment: implications for contaminant bioaccessibility and remediation

The mobilisation of metals (Al, Fe, Cd, Cu, Mn, Ni, Pb, Sn, Zn) from contaminated estuarine sediment has been examined using commercially available surfactants. Metal release by the anionic surfactant, sodium dodecyl sulphate (SDS), increased with increasing amphiphile concentration up to and above its critical micelle concentration (CMC). Metal mobilisation by the bile acid salt, sodium taurocholate, and the nonionic surfactant, Triton X-100, however, did not vary with amphiphile concentration. SDS was the most efficient surfactant in mobilising metals from the sample, and Cd, Cu and Ni were released to the greatest extents (12-18% of total metal at [SDS] > CMC). Metal mobilisation appeared to proceed via complexation with anionic amphiphiles and denudation of hydrophobic host phases. Surfactants may play an important role in the solubilisation of metals in the digestive environment of deposit-feeding animals and, potentially, in the remediation of metal-contaminated soil and sediment.     

Seasonal and spatial distribution of metals in surface sediment of an urban estuary

Aquatic pollution by metals is of concern because of various toxic effects to marine life. The Tolka Estuary, Co. Dublin, Ireland, is a typical Irish urban estuary. It has a significant metal loading originating from the urban environment. Results of a 25month analysis of cadmium, copper, lead and zinc spatial and temporal distribution over 10 sample locations in this estuary are presented in this paper. Metal concentrations were analysed using differential pulse polarography. Significant seasonal and spatial trends in metal distribution were observed over the 25months. Sediment metal concentrations gradually increased (30-120%) in spring to a maximum at the end of summer which was followed by a decrease in winter months (30-60%). Sediment organic matter (OM) concentrations exhibited similar seasonal trends and a positive correlation between OM and metal distributions was observed, implying OM had an influence on metal distributions over time.     

Metal accumulation and performance of nestlings of passerine bird species at an urban brownfield site

The use of passerine species as bioindicators of metal bioaccumulation is often underutilized when examining the wildlife habitat value of polluted sites. In this study we tested feathers of nestlings of two common bird species (house wren and American robin) for accumulation of Pb, Zn, As, Cr, Cu, Fe in comparison of a polluted, urban brownfield with a rural, unpolluted site. House wren nestlings at the study site accumulated significantly greater concentrations of all target metals except Zn. At the polluted site we found significant species differences of metal concentrations in feathers, with house wrens accumulating greater concentrations of Pb, Fe, and Zn but slightly lesser accumulations of Cr and Cu than American robins. Although house wren nestlings demonstrated significant accumulation of metals, these concentrations showed little effect on size metrics or fledge rates during the breeding season compared to nestlings from the control site.     

Metal contamination of short-term snow cover near urban crossroads: correlation analysis of metal content and fine particles distribution

Snow samples were collected near crossroads in Novi Sad, Serbia, during December 2009 to assess metal concentrations (Ca, K, Zn, Fe, Cu, Mn, Al, Pb and Na), fine particle distribution and pH value. The filtered samples of melted snow were analysed, with a focus on particles smaller than a few μm. The most common values of the frequency number distribution curve were either in the range of 0.05-0.07 μm or one order of magnitude higher (0.2-0.5 μm). At examined locations metal concentrations varied from 0.0004 mg L⁻¹ for Pb to 18.9 mg L⁻¹ for Na. Besides Na, which mostly originated from de-icing salt, Ca is found to be the most abundant element in snow indicating the dominant influence of natural factors on snow chemistry. No significant difference was found in concentration of the elements at locations near crossroads with either low or high traffic volume, except for Na and Zn.To investigate how metals were related a correlation analysis was done for the concentrations of metals and with respect to the particle size distribution parameters and pH values. The major influence on the fine particle volume (mass) was concluded to be due to the elements from anthropogenic sources. This conclusion was based on the significant positive correlation between Fe, Zn and Al and the fine particle volume based distribution parameters.     

Determination of polycyclic aromatic hydrocarbons in urban street dust: implications for human health

The determination of sixteen polycyclic aromatic hydrocarbons in urban street dust has been done. Samples were collected from 12 sampling locations in a city centre location (Newcastle upon Tyne, north east England) and extracted using in situ pressurised fluid extraction followed by gas chromatography mass spectrometry. From the results it was possible to identify three groups, with respect to PAH concentration, with PAH contents ranging between 0.6-2.3 mg kg⁻¹, 15.6-22.5 mg kg⁻¹ and 36.1-46.0 mg kg⁻¹. The total PAH content of samples from these sampling sites has been compared to 22 urban locations around the world; comparable levels were found in these samples compared to the other cities around the world.The potential source of PAHs has been investigated by investigating the proportion of pyrogenic and petrogenic material in urban street dust using specific individual PAH ratios. The results indicate that the PAH content of urban street dust from the chosen sites are more likely to be due to pyrogenic sources i.e. vehicle exhaust emissions. The particle size fractions (<63 μm; 63-125 μm; 125-250 μm; 250-500 μm; 500-1000 μm; and 1000-2000 μm) of individual PAHs in three selected sampling sites was investigated. In two of the selected sites the PAH content was independent of particle size whereas in sampling site 10 elevated PAH levels are noted in the <63 μm size fraction. Sampling site 10 is located at the junction of three road tributaries which are used as major access points to the east of the city centre. Finally, the potential health risk for unintentional consumption of PAHs was assessed in terms of a mean daily intake (based on an ingestion rate of 100 mg d⁻¹). It was found that all 4-6 membered ring PAHs had concentrations in excess of the mean daily intake thereby reflecting a potential health risk, particularly in the smallest size particle fractions.     

Source characterization and identification by real-time single particle mass spectrometry

A Real-Time Single Particle Mass Spectrometer, RSMS-3, was deployed to Wilmington, Delaware to study regional and local contributions to fine and ultra-fine urban particulate matter (PM). Approximately two-thirds of PM₁ consisted of internally mixed secondary aerosol. The remaining one-third was externally mixed including biomass burning (13%), fossil fuel combustion (7%) and various industrial sources (13%). In this last group, particle classes containing specific combinations of transition and/or heavy metals gave wind-rose plots consistent with specific point sources. For example, particles containing V and Ni were detected from different wind directions than those containing V and Fe. Samples from two industrial emission stacks, a steel manufacturing facility 10 km away and a coal-fired electrical power generation facility 5 km away, were analyzed and compared to the ambient data set. In each case, a direct correlation was found: a Pb–Zn–K–Na class for the steel manufacturing facility and an Fe–La/Ce class for the power generation facility. The ambient particle classes showed additional small signals from secondary components indicating atmospheric processing. Ambient particle classes containing only a subset of these elements, such as Zn only, Fe only and Pb–K only, were nonspecific, that is, the wind-rose plots were more diffuse and the particles could not be mapped to individual sources. The merits of stack sampling as an aid to interpreting single particle data sets are discussed.     

Environmental monitoring of PCDD/Fs and metals in the vicinity of a cement plant after using sewage sludge as a secondary fuel

In 2005, the partial substitution (20%) of fossil fuel by sewage sludge was tested in a Spanish cement plant. In order to establish the environmental impact for the surroundings, in 2006, the levels of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and heavy metals (As, Cd, Co, Cr, Cu, Hg, Mn, Ni, Pb, Sn, Tl, V, and Zn) were monitored in soil and vegetation samples collected near the cement plant. The temporal trends in the pollutant levels were studied by comparing the concentrations with those obtained in a previous survey (2003) in the same sampling sites. Very slight changes of the PCDD/F concentrations in both monitors were registered in the period 2003–2006 (0.17–0.15 and 0.94–1.10 ng I-TEQ kg⁻¹ dw in herbage and soil, respectively). In turn, there was a notable heterogeneity in the evolution of metal levels, which varied according to each particular element. Anyhow, the current levels of organic and inorganic pollutants are in the low part of the range in comparison with other zones impacted by cement plants, as well as industrial and urban areas worldwide. The human health risks derived from the exposure to PCDD/Fs and metals were also assessed. Although the cancer risks due to PCDD/Fs slightly increased, a reduction of the total carcinogenic risks, including metals, was noted. In conclusion, there were not observed impact changes for the environmental and the local population as a consequence of using sewage sludge as secondary fuel.     

Availability and bio-accessibility of metals in the clay fraction of urban soils of Sevilla

The availability of Cd, Cr, Cu, Ni, Mn, Pb and Zn present in the finest size particles of urban soils is studied by comparing the concentrations in the clay fraction with those extracted from the whole soil by either single-extraction or sequential extraction method. Many metals are preferentially present in the finest particles as compared to coarser fractions. This is true for most metals studied, except Mn and, perhaps, Cd. Those metals present in the clay fraction are often in easily bio-accessible forms, especially Cu, Pb and Zn. The results suggest that bio-accessible forms of these three metals are distributed among the three sequential fractions, and even the fraction considered as ‘residual’ is also bio-accessible to a significant extent. The statistical analysis shows some distinctions among metals that are compared to the ‘urban’, ‘natural’, or intermediate behaviour of the various metals as proposed earlier in the literature.     

Assessment of oral bioaccessibility of arsenic in playground soil in Madrid (Spain): a three-method comparison and implications for risk assessment

Three methodologies to assess As bioaccessibility were evaluated using playground soil collected from 16 playgrounds in Madrid, Spain: two (Simplified Bioaccessibility Extraction Test: SBET, and hydrochloric acid-extraction: HCl) assess gastric-only bioaccessibility and the third (Physiologically Based Extraction Test: PBET) evaluates mouth-gastric-intestinal bioaccessibility. Aqua regia-extractable (pseudo total) As contents, which are routinely employed in risk assessments, were used as the reference to establish the following percentages of bioaccessibility: SBET - 63.1; HCl - 51.8; PBET - 41.6, the highest values associated with the gastric-only extractions. For Madrid playground soils - characterised by a very uniform, weakly alkaline pH, and low Fe oxide and organic matter contents - the statistical analysis of the results indicates that, in contrast with other studies, the highest percentage of As in the samples was bound to carbonates and/or present as calcium arsenate. As opposed to the As bound to Fe oxides, this As is readily released in the gastric environment as the carbonate matrix is decomposed and calcium arsenate is dissolved, but some of it is subsequently sequestered in unavailable forms as the pH is raised to 5.5 to mimic intestinal conditions. The HCl extraction can be used as a simple and reliable (i.e. low residual standard error) proxy for the more expensive, time consuming, and error-prone PBET methodology. The HCl method would essentially halve the estimate of carcinogenic risk for children playing in Madrid playground soils, providing a more representative value of associated risk than the pseudo-total concentrations used at present.     

Effect of an organic amendment on availability and bio-accessibility of some metals in soils of urban recreational areas

A composted biosolid from wastewater treatment was added to soils of two public parks of Sevilla, and successive samples were taken during one year. In one of the parks, a second addition of biosolid was carried out after the first year. The soil contents in metals (pseudo-total) and their plant-available and oral bio-accessible fractions were significantly altered when the soils were amended with biosolid. Increase of the bio-accessible metal contents represents a deterioration of the environmental quality of recreational areas, where hand-to-mouth transfer of pollutants to children is likely to occur, although part of the metals added might be leached by rainfall or irrigation. The limits established in several countries for metal contents of soils in recreational areas are often exceeded after application of the biosolid. A careful study of the metal contents of recycled wastes is thus recommended before being used for green area maintenance.     

Bioaccessibility of metals in soils and dusts contaminated by marine antifouling paint particles

Fragments of antifouling paint and environmental geosolids have been sampled from the island of Malta and analysed for total and bioaccessible metals. Total concentrations of Ba, Cd, Cu, Pb, Sn and Zn were two to three orders of magnitude higher in spent antifouling composites relative to respective values in background soils and road dusts. Paint fragments were visible in geosolids taken from the immediate vicinity of boat maintenance facilities and mass balance calculations, based on Ba as a paint tracer, suggested that the most contaminated soils, road dusts and boatyard dusts contained about 1%, 7% and 9%, respectively, of antifouling particles. Human bioaccessibilities of metals were evaluated in selected samples using a physiologically based extraction technique. Accessibilities of Cd, Cu, Pb and Zn in the most contaminated solids were sufficient to be cause for concern for individuals working in the boat repair industry and to the wider, local community.     

Transformation of tetrabromobisphenol A in the presence of different solvents and metals

Solvent-based separation method is presumably an efficient and environmentally beneficial approach for elimination of brominated flame retardants (BFRs) from waste electrical and electronic equipment (WEEE). The overall goal of this study was to evaluate possible effects of organic solvent on the behavior of BFRs during solvent-based processing of WEEE. We initiated a set of batch experiments for examining the rates and possible pathways of transformation of a representative BFR (tetrabromobisphenol A, TBBPA) using acetone, toluene, and methanol as the solvents. Our results showed that toluene and methanol had no effect on the transformation of TBBPA, but approximately 20% of TBBPA (100 mg L⁻¹) was transformed by acetone within 2 h at 50 °C. Analysis of the products with GC-MS showed that two high-molecular-weight products (MW = 586) were major products of the transformation reactions. The role of acetone as a reactant in the transformation of TBBPA was further validated with dueterated acetone. In addition, the effects of co-existing metals in WEEE (i.e., Zn, Cu, and Ni) on the transformation of TBBPA in the solvent systems were investigated. These metals tested were found to greatly enhance the rates of TBBPA transformation. The metal facilitated solvent reactions with TBBPA may lower the extractability of TBBPA by formation of larger and less soluble products, hence potentially increasing the cost for separating the chemical from WEEE.     

Pedogenesis, geochemical forms of heavy metals, and artifact weathering in an urban soil chronosequence, Detroit, Michigan

An urban soil chronosequence in downtown Detroit, MI was studied to determine the effects of time on pedogenesis and heavy metal sequestration. The soils developed in fill derived from mixed sandy and clayey diamicton parent materials on a level late Pleistocene lakebed plain under grass vegetation in a humid-temperate (mesic) climate. The chronosequence is comprised of soils in vacant lots (12 and 44 years old) and parks (96 and 120 years old), all located within 100 m of a roadway. An A-horizon 16 cm thick with 2% organic matter has developed after only 12 years of pedogenesis. The 12 year-old soil shows accelerated weathering of iron (e.g. nails) and cement artifacts attributed to corrosion by excess soluble salts of uncertain origin. Carbonate and Fe-oxide are immobilizing agents for heavy metals, hence it is recommended that drywall, plaster, cement and iron artifacts be left in soils at brownfield sites for their ameliorating effects.     

Year-to-year correlations in blood metal levels among individuals of two species of North American sea ducks

Sea duck populations have declined in North America. Contaminants, especially metals, have been listed as possible contributing factors. Sea ducks are long-lived. Thus, individuals chronically exposed to elevated metal levels may be at greatest risk. Information about long-term exposure (> or =1year) of individuals to metals is absent. To address this information gap, we examined year-to-year correlations among individual White-Winged Scoters and King Eiders in levels of blood cadmium, lead, mercury and selenium. Positive correlations (r> or =0.43), were found in six, five, five and two of seven correlations for cadmium, selenium, lead and mercury. Thus, certain individuals of these species may be exposed over two or more years to higher levels of cadmium, selenium and lead (but apparently not mercury) than other individuals. Single blood samples are appropriate metrics of exposure for studies that examine long-term effects of certain metals on these birds.     

Seasonal variation of heavy metals in ambient air and precipitation at a single site in Washington, DC

Atmospheric samples of precipitation and ambient air were collected at a single site in Washington, DC, for 7 months (for ambient air samples) and 1 year (for wet deposition samples) and analyzed for arsenic, cadmium, chromium and lead. The ranges of heavy metal concentrations for 6-day wet deposition samples collected over the 1-year period were 0.20-1.3 microg/l, 0.060-5.1 microg/l, 0.062-4.6 microg/l and 0.11-3.2 microg/l for arsenic, cadmium, chromium and lead, respectively, with a precision better than 5% for more than 95% of the measurements. The ranges of heavy metal concentrations for the 6-day ambient air samples were 0.800-15.7 ng/m(3), 1.50-30.0 ng/m(3), 16.8-112 ng/m(3), and 2.90-137 ng/m(3) for arsenic, cadmium, chromium and lead, respectively, with a precision better than 10%. The spread in the heavy metal concentration over the observation period suggests a high seasonal variability for heavy metal content in both ambient air and wet deposition samples.     

Inconsistency and comprehensiveness of risk assessments for heavy metals in urban surface sediments

Numerous indices have been developed to assess environmental risk of heavy metals in surface sediments, including the total content based geoaccumulation index (I_geo), exchangeable fraction based risk assessment code (RAC), and biological toxicity test based sediment quality guidelines (SQGs). In this study, the three indices were applied to freshwater surface sediments from 10 sections along an urbanization gradient of the Grand Canal, China to assess the environmental risks of heavy metals (Cu, Pb, Zn, Cd, and Cr) and to understand discrepancies of risk assessment indices and urbanization effects regarding heavy metal contamination. Results showed that Cd, Zn, and Pb were the most enriched metals in urban sections assessed by I_geo and over 95% of the samples exceeded the Zn and Pb thresholds of the effect range low (ERL) of SQGs. According to RAC, Cu, Zn, Cd, and Cr had high risks of adversely affecting the water quality of the Grand Canal due to their remarkable portions of exchangeable fraction in surface sediment. However, Pb showed a relative low risk, and was largely bounded to Fe/Mn oxides in the urban surface sediments. Obviously, the three assessment indices were not consistent with each other in terms of predicting environmental risks attributed to heavy metals in the freshwater surface sediments of this study. It is recommended that risk assessment by SQGs should be revised according to availability and site specificity. However, the combination of the three indices gave us a comprehensive understanding of heavy metal risks in the urban surface sediments of the Grand Canal.     

Modeling non-linear changes in an urban setting: From pro-environmental affordances to responses in behavior,emissions and air quality

Interactions in urban environment were investigated using a multidisciplinary model combination, with focus on traffic, emissions and atmospheric particles. An agent-based model was applied to simulate the evolution of unsustainable human behavior (usage of combustion-based personal vehicles) as a function of pro-environmental affordances (opportunities for sustainable choices). Scenarios regarding changes in multi-pollutant emissions were derived, and the non-linear implications to atmospheric particles were simulated with a box model. Based on the results for a Nordic city, increasing pro-environmental affordances by 10%, 50% or 100% leads to emission reductions of 15%, 30% and 40% within 2 years. To reduce ambient particle mass, emissions from traffic should decrease by > 15%, while the lung deposited surface area decreases in all scenarios (-23%, -32% and -36%, correspondingly). The presented case is representative of one season, but the approach is generic and applicable to simulating a full year, given meteorological and pollution data that reflects seasonal variation. This work emphasizes the necessity to consider feedback mechanisms and non-linearities in both human behavior and atmospheric processes, when predicting the outcomes of changes in an urban system.Supplementary InformationThe online version contains supplementary material available at 10.1007/s13280-022-01827-8.