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.     

Distribution of heavy metal contents of urban soils in parks of Seville

Several metals in urban soils of Seville were extracted by two methods, which respectively give estimates of the available and ‘quasi total’ contents. Although the soils did not show strong heterogeneity in their general properties, high dispersion of the contents in those metals with greater relative availability, Cu, Pb and Zn, as compared to others suggested that pollution with these three metals could occur in some sampling sites. It was shown that the contents in these metals tend to increase as the historic quarters of the city are approached. Using reference values given by the Québec Ministry of Environment it was shown that those green areas closer to the historic centre present contents in Pb, Zn and particularly Cu that often exceed the acceptable limits for residential, recreational and institutional sites. From background contents for Seville soils estimated from a park located on the outskirts, a pollution load index (PLI) for each sampling site was calculated for the set of these three metals. It was shown that the PLI tends to increase as traffic density increases and as distance from main traffic decreases, but poor regressions were obtained, suggesting that other variables different from traffic should be considered.     

Effects of iron(III)chelates on the solubility of heavy metals in calcareous soils

In this study I evaluated the effects of complexing agents on the solubility of heavy metals in an incubation experiment up to 56 days when complexing agents were applied as Fe-chelates (Fe-EDDS(S,S), Fe-EDDS(mix), Fe-EDTA and Fe-EDDHA) on calcareous soils at a level sufficient to correct Fe chlorosis (0.1 mmol kg⁻¹). Of these ligands, EDDHA was the most efficient in keeping Fe in water-soluble form, and EDDS increased the solubility of Cu and Zn most, and only EDTA increased the solubility of Cd and Pb. EDTA increased the solubility of Ni steadily during the incubation period, equalling about 5-8% of the added EDTA concentration. [S,S]-EDDS was biodegraded within 56 days, whereas EDDS(mix) was less biodegradable. Ni-chelates were the most recalcitrant against biodegradation. The study shows that even a moderate input of chelates to soil increases the solubility of toxic heavy metals and their risk of leaching.     

Soil pollution assessment and identification of hyperaccumulating plants in chromated copper arsenate (CCA) contaminated sites, Korea

In recent decades, heavy metal contamination in soil adjacent to chromated copper arsenate (CCA) treated wood has received increasing attention. This study was conducted to determine the pollution level (PL) based on the concentrations of Cr, Cu and As in soils and to evaluate the remediative capacity of native plant species grown in the CCA contaminated site, Gangwon Province, Korea. The pollution index (PI), integrated pollution index (IPI), bioaccumulation factors (BAF_shoots and BAF_roots) and translocation factor (TF) were determined to ensure soil contamination and phytoremediation availability. The 19 soil samples from 10 locations possibly contaminated with Cr, Cu and As were collected. The concentrations of Cr, Cu and As in the soil samples ranged from 50.56-94.13 mg kg⁻¹, 27.78-120.83 mg kg⁻¹, and 0.13-9.43 mg kg⁻¹, respectively. Generally, the metal concentrations decreased as the distance between the CCA-treated wood structure and sampling point increased. For investigating phytoremediative capacity, the 19 native plant species were also collected in the same area with soil samples. Our results showed that only one plant species of Iris ensata, which presented the highest accumulations of Cr (1120 mg kg⁻¹) in its shoot, was identified as a hyperaccumulator. Moreover, the relatively higher values of BAF_shoot (3.23-22.10) were observed for Typha orientalis, Iris ensata and Scirpus radicans Schk, suggesting that these plant species might be applicable for selective metal extraction from the soils. For phytostabilization, the 15 plant species with BAF_root values > 1 and TF values < 1 were suitable; however, Typha orientalis was the best for Cr.     

Spatial distribution of metals in soils in Baltimore, Maryland: role of native parent material, proximity to major roads, housing age and screening guidelines

We investigated the spatial distribution of heavy metal above-background (anthropic) contents of Cd, Co, Cu, Cr, Fe, Mn, Ni, Pb, Ti, V, and Zn in Baltimore City surface soils and related these levels to potential contaminating sources. Composite soil samples (0-10 cm depth) were digested using a nitric and hydrochloric extraction technique. Slightly more than 10% of plots exceeded United States Environmental Protection Agency screening guidelines for Pb. In a principal component analysis, the first component corresponded to Co, Cr, and Fe, which are constituents of local mafic rocks. The second component corresponded to Cu, Pb, and Zn which were significantly higher within than beyond a 100 m buffer of the major roads within the city; furthermore, Pb and Zn were higher in older residential lots.     

Sequential sorption of lead and cadmium in three tropical soils

It is important to examine mechanisms of Pb and Cd sorption in soils to understand their bioavailability. The ability of three tropical soils to retain Pb, Cd, and Ca was evaluated. The objectives of this study were to (1) determine the extent to which soil sorption sites are metal specific, (2) investigate the nature of reactions between metals and soil surfaces, and (3) identify how metals compete for sorption sites when they are introduced to soils sequentially or concurrently. Lead was shown to be much less exchangeable than Cd and inhibited Cd sorption. Cadmium had little effect on Pb sorption, though both Ca and Cd inhibited the adsorption of Pb at exchange sites. Lead appears to more readily undergo inner-sphere surface complexation with soil surface functional groups than either Cd or Ca. Thus, regardless of when Pb is introduced to a soil, it should be less labile than Cd.     

Long-term (1992-2004) record of lead, cadmium, and zinc air contamination in Warsaw, Poland: Determination by chemical analysis of moss bags and leaves of Crimean linden

Between 1992 and 2004, air contamination with lead (Pb), cadmium (Cd), and zinc (Zn) in Warsaw, Poland, was monitored annually with moss (Sphagnum fallax) bags on a network of 230 sites covering the entire city. During the study the highest contamination was near the Warszawa Steel Mill, northwestern Warsaw. Lead concentrations in moss bags decreased in time, while those of Cd and Zn did not show clear trends. Between 1994 and 2004, Pb, Cd, and Zn were also monitored in the Crimean linden (Tilia Euchlora) foliage along the main city avenue and in a northwestern warsaw park. Lead concentrations decreased more near the avenue than in the park, indicating that the phasing-out of leaded gasoline had a major effect on reduced Pb contamination in Warsaw. At the same time, foliar concentrations of Cd and Zn in both areas decreased much less.     

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.     

Bioaccessibility and health risk of arsenic, mercury and other metals in urban street dusts from a mega-city, Nanjing, China

The oral bioaccessibility and the human health risks of As, Hg and other metals (Cu, Pb, Zn, Ni, Co, Cd, Cr, Mn, V and Fe) in urban street dusts from different land use districts in Nanjing (a mega-city), China were investigated. Both the total contents and the oral bioaccessibility estimated by the Simple Bioaccessibility Extraction Test (SBET) of the studied elements varied with street dusts from different land use districts. Cd, Zn, Mn, Pb, Hg and As showed high bioaccessibility. SBET-extractable contents of elements were significantly correlated with their total contents and the dust properties (pH, organic matter contents). The carcinogenic risk probability for As and Cr to children and adults were under the acceptable level (<1 × 10⁻⁴). Hazard Quotient values for single elements and Hazard Index values for all studied elements suggested potential non-carcinogenic health risk to children, but not to adults.     

Survey of heavy metal pollution and assessment of agricultural soil in Yangzhong district, Jiangsu Province, China

We investigated concentrations of Hg, Cd, Pb, Zn, Cu, As, Ni, and Cr in samples of soil, cereal, and vegetables from Yangzhong district, China. Compared to subsoils, the sampled topsoils are enriched in Hg, Cd, Cu, Pb, Zn, and As. High levels of Cd and Hg are observed in most agricultural soils. Concentrations of Cr and Ni show little spatial variation, and high Cu, Pb, and Zn contents correspond well to areas of urban development. High As contents are primarily recorded at the two ends of the sampled alluvion. The contents of Cd, Hg, and total organic carbon (TOC) increase gradually to maximum values in the upper parts of soil profiles, while Cr and Ni occur in low concentrations within sampled profiles. As, Pb, Cu, and Zn show patterns of slight enrichment within the surface layer. Compared to data obtained in 1990, Cd and Hg show increased concentrations in 2005; this is attributed to the long-term use of agrochemicals. Cr and Ni contents remained steady over this interval because they are derived from the weathering of parent material and subsequent pedogenesis. The measured As, Cu, Pb, and Zn contents show slight increases over time due to atmospheric deposition of material sourced from urban anthropogenic activity. Low concentrations of heavy metals are recorded in vegetables and cereals because the subalkaline environment of the soil limits their mobility. Although the heavy metal concentrations measured in this study do not pose a serious health risk, they do affect the quality of agricultural products.     

Accumulation and Chemical Fractionation of Heavy Metals in Andisols after a Different, 6-year Fertilization Management (8 pp)

Goal, Scope and Background Andisols are widespread in Japan and have some special properties such as high anion exchange capacity, low bulk density, and high organic matter content, which might influence the accumulation or chemical fractionation of heavy metals. However, few such data exist in Japanese andisols. The primary objective of this study was to investigate the distribution and chemical fractions of Cu, Zn, Ni, and Cr in the soil profiles and subsequently to assess their potential environmental hazard. Materials and Methods Soil samples were taken from a field experiment conducted on Japanese andisols, which had received either swine compost or chemical fertilizers for 6 years. Concentrations of Cu, Zn, Ni, and Cr were determined for all of the obtained extract solutions by ICP-AES. Results and Discussion Considerably higher total concentrations of Cu and Zn were observed in the top 20 cm layer of the compost-amended soil, relative to the unfertilized soil, while chemical fertilizers had little effect. Application of the swine compost increased the concentrations of Cu and Zn, but not Ni and Cr, in all fractions in the top 20 cm layer. The greatest increase in the organically bound fraction (OM) Cu and dilute acid-exchangeable fraction (DAEXCH) Zn was observed. This suggests that Cu and Zn are potentially bioavailable and mobile in the andisol profiles after 6-year consecutive applications of the swine compost. On the other hand, distribution of Cu, Zn, Ni and Cr among various soil fractions was generally unaffected by chemical fertilizers. Conclusions We observed that 6-year consecutive applications of the swine compost led to an increase in total metals of Cu and Zn, as well as their all-chemical fractions, in the top 20 cm soil layers. Potential hazard of heavy metals, especially of Cu and Zn, as a result of the use of swine compost on andisols, must be taken into account. Recommendations and Outlook The long-term effect of the accumulation of heavy metals, particularly Cu and Zn, in various plant tissues and soils, as well as their potential risk to surface water via runoff and groundwater via leaching, needs to be carefully considered. Further investigations in the long-term experiments are therefore necessary. - Abbreviations. EXCH, exchangeable fraction of metals; DAEXCH, dilute acid-exchangeable fraction of metals; FeMnOX, iron and manganese-oxide-bound fraction; OM, organically-bound fraction; RESD, residual fraction. COMPOST, SRNF, RANF, and CONTROL stand for compost (from swine wastes), slow-release nitrogen fertilizer (coated urea), readily available nitrogen fertilizer (including NH4-N, P, and K fertilizers), and no fertilizer application, respectively.     

Date palm (Phoenix dactylifera L.) leaves as biomonitors of atmospheric metal pollution in arid and semi-arid environments

The leaves of date palms were evaluated as a possible biomonitor of heavy metal contamination in Ma’an city, Jordan. Concentrations of (Fe), (Pb), (Zn), (Cu), (Ni), and (Cr) were determined in washed and unwashed leaves and soil samples collected from different sites with different degrees of metal contamination (urban, suburban, industrial, highway and rural sites); separate leaves were taken from outside the city to be used as a control sample. Samples collected from industrial sites were found to have high concentrations of all metals except those of Cu, Ni and Pb, which were found at high levels in the highway site samples which is associated with the road traffic. The difference between unwashed and washed samples showed that metal pollutants exist as contaminants, particularly Pb, Zn and Ni, which varied in concentration, depending on the source of the metal.     

Trees as bioindicator of heavy metal pollution in three European cities

Concentrations of four heavy metals were determined in tree leaves and bark collected from polluted and non-polluted areas of three European cities (Salzburg, Belgrade and Thessaloniki) for a comparative study. Platanus orientalis L. and Pinus nigra Arn., widespread in urban northern and southern Europe, were tested for their suitability for air quality biomonitoring. Leaves and barks were collected uniformly of an initial quantity of about 30 g of each sample. Analysis was accomplished by electrothermal atomic absorption spectrometry after total digestion. Site-dependent variations were found with the highest concentration level measured in Belgrade, followed by Thessaloniki and Salzburg. A higher accumulation of heavy metals was found in bark compared to leaves. Pine tree bark, accumulating higher concentrations of trace metals compared to plane tree bark, shows a higher efficiency as bioindicator for urban pollution. Both indicator species are suitable for comparative studies on bioindication of urban air pollution.     

Laboratory study highlights the key influences of stormwater sediment thickness and bioturbation by tubificid worms on dynamics of nutrients and pollutants in stormwater retention systems

In urban area, the accumulation of polluted stormwater sediments (SWS) in retention ponds may be a source of dissolved pollutants and nutrients for the aquatic ecosystems. Our objective was to quantify the influence of the thickness of SWS layer and the occurrence of tubificid worms on organic matter processing (O(2) uptake and fluxes of NH(4)(+), NO(3)(-), PO(4)(3-), and dissolved organic carbon between sediment and water), releases of 17 PAHs and 4 heavy metals, and microbial characteristics. Results showed that oxidation of SWS organic matter (O(2) and NO(3)(-) uptakes) and releases of nutrients were significantly increased by the quantity of accumulated SWS and the worm bioturbation. Releases of acenaphtene and naphthalene from sediments were significantly increased by the thickness of the SWS layer. In contrast, tubificid worms did not promote the mobilization of pollutants. In conclusion, biological activities and stormwater sediment characteristics need to be assessed to quantify the fate of pollutants and nutrients in stormwater retention ponds.     

Analysis of heavy metal distribution in superficial estuarine sediments (estuary of Bilbao, Basque Country) by open-focused microwave-assisted extraction and ICP-OES

Open-focused microwave-assisted extraction and ICP-OES determination of As, Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn from surface sediments of the estuary of Bilbao (Basque Country, North of Spain) was carried out. All the samples were collected at three different tributaries of the estuary (Asua, Galindo and Nerbioi-Ibaizabal) every two months during 1999. The digestion procedure was proposed from the conclusions of a fractionated factorial design, and the precision and accuracy of the method was verified using a certified reference sediment (RTC008-050). The results of the analysis were statistically treated by means of principal component analysis and correlation analysis. The principal component analysis of sediment data (32 samples × 9 metals) indicated different patterns of contamination regarding the tributary and sampling station. The two main patterns observed were a steady increment of the metal concentration along all the campaigns in the samples collected in the Galindo River and a seasonal variation in the Nerbioi-Ibaizabal River, with higher metallic content during summertime and lower content during wintertime.     

Exposure of an anoxic and contaminated canal sediment: Mobility of metal(loid)s

A derelict canal contains an estimated 9800 tonnes of anoxic sediment with highly elevated concentrations of trace elements. Lack of maintenance, reduced water levels and vegetation colonization threaten the stability of pollutants by removing existing waterlogged reduced conditions. A column leaching study of the sediment under increasingly oxidized conditions showed reductions in As mobility but increased heavy metal concentrations. In a reduced state, As mobility was higher (as a consequence of enhanced Fe and organic carbon solubility) whilst heavy metal concentrations in leachates were lower (due to markedly higher pH). Over 10 contiguous wetting and drying cycles, the consequences were profound; all trace elements were continuously leached with enhanced flushing of Fe, As, Zn and Cu. This raises concern over possible mobilization of pollutants to the wider environment, including groundwater. Options for management to stabilize contaminants are discussed that point to the importance of limiting water flow through the sediment.     

Accumulation of potentially toxic elements in plants and their transfer to human food chain

Abstract

Contaminated soils can be a source for crop plants of such elements like As, Cd, Cr, Cu, Ni, Pb, and Zn. The excessive transfer of As, Cu, Ni, and Zn to the food chain is controlled by a “soil‐plant barrier”; however, for some elements, including Cd, the soil‐plant barrier fails. The level of Cd ingested by average person in USA is about 12 μg/day, which is relatively low comparing to Risk Reference Dose (70 μg Cd/day) established by USEPA. Food of plant origin is a main source of Cd intake by modern society. Fish and shellfish may be a dominant dietary sources of Hg for some human populations. About half of human Pb intake is through food, of which more than half originates from plants. Dietary intake of Cd and Pb may be increased by application of sludges on cropland with already high levels of these metals. Soils amended with sludges in the USA will be permitted (by USEPA‐503 regulations) to accumulate Cr, Cd, Cu, Pb, Hg, Ni, and Se, and Zn to levels from 10 to 100 times the present baseline concentrations. These levels are very permissive by international standards. Because of the limited supply of toxicity data obtained from metals applied in sewage sludge, predictions as to the new regulations will protect crop plants from metal toxicities, and food chain from contamination, are difficult to make.     

Threat of heavy metal pollution in halophytic and mangrove plants of Tamil Nadu, India

Mangrove and halophytic plants occur along the coastal areas of Tamil Nadu, south India and these plants have been used in traditional medicine for centuries. Heavy metals are known to pose a potential threat to terrestrial and aquatic biota. However, little is known on the toxic levels of heavy metals found in mangrove and halophytic plants that are used in traditional medicine in India. To understand heavy metal toxicity, we investigated the bioconcentration factors (BCF) of heavy metals in leaves collected from eight mangroves and five halophytes in the protected Pichavaram mangrove forest reserve in Tamil Nadu State, south India. Data presented in this paper describe the impact of essential (Cu, Fe, Mg, Mn and Zn) and non-essential/environmentally toxic trace metals (Hg, Pb and Sn) in mangrove and halophytic medicinal plants. The concentrations of Pb among 13 plant species were higher than the normal range of contamination reported for plants. The average concentration of Hg in the halophytic plants (0.43+/-0.37mug/g) was seven times higher than mangrove plants (0.06+/-0.03mug/g) and it indicated pollutants from industrial sources affecting halophytes more than mangroves.     

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.     

Heavy metal distribution and bioaccumulation in Chihuahuan Desert Rough Harvester ant (Pogonomyrmex rugosus) populations

Heavy metal contamination can negatively impact arid ecosystems; however a thorough examination of bioaccumulation patterns has not been completed. We analyzed the distribution of As, Cd, Cu, Pb and Zn in soils, seeds and ant (Pogonomyrmex rugosus) populations of the Chihuahuan Desert near El Paso, TX, USA. Concentrations of As, Cd, Cu, and Pb in soils, seeds and ants declined as a function of distance from a now inactive Cu and Pb smelter and all five metals bioaccumulated in the granivorous ants. The average bioaccumulation factors for the metals from seeds to ants ranged from 1.04× (As) to 8.12× (Cd). The findings show bioaccumulation trends in linked trophic levels in an arid ecosystem and further investigation should focus on the impacts of heavy metal contamination at the community level.