Further studies using X-ray fluorescence to sample lead contaminated carpeted surfaces

The sampling of carpeted surfaces to test for lead contamination primarily focuses upon vacuum techniques. Vacuum sampling techniques, however, require time-consuming, expensive laboratory analysis of the dusts obtained and are unable to determine total lead load on the carpet. X-ray fluorescence (XRF) analysis is an on-site, inexpensive, non-destructive, quick technique for predicting metals levels in a variety of media, such as water, soil, filter paper and painted surfaces. A 1992 study of the feasibility of XRF to analyze for lead and soil loadings on carpeted surfaces indicated that XRF can detect lead at a low enough level to warrant further study. This paper expands this earlier study and developes lead and soil loading calibration curves for three different carpet types based upon XRF lead L-beta peak areas and XRF iron and barium K-alpha peak and background areas. Results indicate that variation in the data can be reduced through modifications of the XRF analysis technique, thus reducing the statistically determined detection level, and that carpet type does affect the calibration. Detection levels of approximately 70 mg/m² for lead and 5 g/m² for soil were obtained. Overall, good agreement was found between results of this study and the earlier one. XRF shows excellent potential for quantitative analysis of lead on carpeted surfaces.     

Three-dimensional data interpolation for environmental purpose: lead in contaminated soils in southern Brazil

Monitoring of heavy metal contamination plume in soils can be helpful in establishing strategies to minimize its hazardous impacts to the environment. The objective of this study was to apply a new approach of visualization, based on tridimensional (3D) images, of pseudo-total (extracted with concentrated acids) and exchangeable (extracted with 0.5 mol L^?1 Ca(NO₃)₂) lead (Pb) concentrations in soils of a mining and metallurgy area to determine the spatial distribution of this pollutant and to estimate the most contaminated soil volumes. Tridimensional images were obtained after interpolation of Pb concentrations of 171 soil samples (57 points × 3 depths) with regularized spline with tension in a 3D function version. The tridimensional visualization showed great potential of use in environmental studies and allowed to determine the spatial 3D distribution of Pb contamination plume in the area and to establish relationships with soil characteristics, landscape, and pollution sources. The most contaminated soil volumes (10,001 to 52,000 mg Pb kg^?1) occurred near the metallurgy factory. The main contamination sources were attributed to atmospheric emissions of particulate Pb through chimneys. The large soil volume estimated to be removed to industrial landfills or co-processing evidenced the difficulties related to this practice as a remediation strategy.     

Occurrence of phthalic acid esters in Gomti River Sediment, India

Cadmium and lead are important environmental pollutants with high toxicity to animals and human. Soils, though have considerable metal immobilizing capability, can contaminate food chain via plants grown upon them when their built-up occurs to a large extent. Present experiment was carried out with the objective of quantifying the limits of Pb and Cd loading in soil for the purpose of preventing food chain contamination beyond background concentration levels. Two separate sets of pot experiment were carried out for these two heavy metals with graded levels of application doses of Pb at 0.4–150 mg/kg and Cd at 0.02–20 mg/kg to an acidic light textured alluvial soil. Spinach crop was grown for 50 days on these treated soils after a stabilization period of 2 months. Upper limit of background concentration levels (C _ul) of these metals were calculated through statistical approach from the heavy metals concentration values in leaves of spinach crop grown in farmers’ fields. Lead and Cd concentration limits in soil were calculated by dividing C _ul with uptake response slope obtained from the pot experiment. Cumulative loading limits (concentration limits in soil minus contents in uncontaminated soil) for the experimental soil were estimated to be 170 kg Pb/ha and 0.8 kg Cd/ha. Based on certain assumptions on application rate and computed cumulative loading limit values, maximum permissible Pb and Cd concentration values in municipal solid waste (MSW) compost were proposed as 170 mg Pb/kg and 0.8 mg Cd/kg, respectively. In view of these limiting values, about 56% and 47% of the MSW compost samples from different cities are found to contain Pb and Cd in the safe range.     

Determination of lead, cadmium and copper in roadside soil and plants in Elazig, Turkey

The concentrations of lead, cadmium and copper in roadside soil and plants in Elazig, Turkey were investigated. Soil samples were collected at distances of 0, 25 and 50 m from the roadside. The concentrations of lead, cadmium and copper were measured by Flame Atomic Absorption Spectrophotometry (FAAS). A slotted tube atom trap (STAT) was used to increase the sensitivity of lead and cadmium in FAAS. Lead concentrations in soil samples varied from 1.3 to 45 mg kg⁻¹ while mean lead levels in plants ranged from120 ng g⁻¹ for grape in point-4 to 866 ng g⁻¹ for apple leaves in point-2. Lead analyses showed that there was a considerable contamination in both soil and plants affected from traffic intensity. Overall level of Cd in soil samples lies between 78 and 527 ng/g while cadmium concentration in different vegetations varied in the range of 0.8–98.0 ng g⁻¹. Concentrations of copper in soil and plant samples were found in the range of 11.1–27.9 mg kg⁻¹ for soil and 0.8–5.6 mg kg⁻¹ for plants. Standard reference material (SRM) was used to find the accuracy of the results of soil analyses.     

Effects of lead and zinc mining contamination on bacterial community diversity and enzyme activities of vicinal cropland

In the process of mining activity, many kinds of heavy metals enter into soils with dust, causing serious contamination to the environment. In this study, six soils were sampled from cropland at different distances from a lead/zinc mine in Heilongjiang Province, China. The total contents of lead and zinc in the vicinal cropland exceeded the third level of environmental quality standard for soil in China, which indicated that soils in this area were moderately contaminated. Bacterial community diversity and population were greatly decreased when the concentrations of lead and zinc were beyond 1,500 and 995 mg kg(-1), respectively, as analyzed by plate counting and polymerase chain reaction-denaturing gradient gel electrophoresis (PCR-DGGE). The bands of DGGE patterns varied with the degree of contamination. The activities of soil urease, phosphatase, and dehydrogenase were negatively correlated with the concentrations of lead and zinc. The highest inhibitory effect of heavy metals on soil enzyme activities was observed in urease. It was noted that PCR-DGGE patterns combined with soil enzyme activity analysis can be indices for the soil quality assessment by heavy metal contamination.     

Using of high-resolution topsoil magnetic screening for assessment of dust deposition: comparison of forest and arable soil datasets

Magnetic susceptibility (κ) is an easily detectable geophysical parameter that can be used as a proxy or semi-quantitative tracer of atmospheric industrial and urban dusts deposited in topsoil. An enhanced κ value of topsoil is in many cases also associated with high concentrations of soil pollutants (mostly heavy metals). High-resolution magnetic screening of topsoil in areas of high pollution influx is a useful tool for detection of pollution “hot spots”. General and regional screening maps with a grid density of 10 or 5 km have been performed on the basis of forest topsoil measurement only. The purpose of this study was to perform high-resolution magnetic screening with different grid densities in both forested and agricultural areas (arable land). Our large study area (ca. 200 km²) was located in a relatively more polluted region of the central part of Upper Silesia, and a second (small) one (ca. 100 m²) was located in the western part of Upper Silesia, with considerably lower influx of pollution. In the framework of this study, we applied a statistical comparison of data obtained in forested areas and on arable land. The arable soil showed statistically significantly lower κ values, the result of “physical dilution” of the arable layer caused by annual ploughing. Thus arable soils must be avoided during high-resolution field measurement. From semivariograms, it was clear that the spatial correlations in forest topsoil are much stronger than in arable soil, which suggests that a denser measurement grid is required in forested areas.     

Characterization of soil contamination by lead around a former battery factory by applying an analytical hybrid method

Former battery factories have created environmental and health problems for years and the exposure to lead in surface soils has been underestimated. Nonetheless, the identification of lead contamination and its spatial distribution is crucial. The determination of heavy metals in soils can be performed using inductively coupled plasma mass spectrometry (ICP-MS). However, alternative techniques such as X-ray fluorescence (XRF) have been used lately in environmental studies since measurements can be taken in the field in a prompt manner, despite its lower accuracy. In this study, a former battery factory site in Monterrey, Mexico, has been studied in order to detect lead contamination. Soil samples were assessed for contamination by using an analytical hybrid method that comprises both analytical techniques, namely, ICP-MS and XRF. Samples were taken in 215 locations and, after a simple homogenization process, they were analyzed by using a portable XRF device. Within those 215 sampling points, 25 samples were analyzed concurrently by using ICP-MS according to international sampling guidelines. Results obtained were adjusted in order to define an analytical hybrid method, which encompasses the advantages of each technique. An improved characterization was achieved by using the proposed analytical hybrid method since maps of lead distribution and calculated areas of concern showed better predictability. The combination of spectroscopic techniques is of great applicability for environmental agencies and decision makers.     

Evaluating the Applicability of Regulatory Leaching Tests for Assessing Lead Leachability in Contaminated Shooting Range Soils

The toxicity characteristic leaching procedure (TCLP) is the current US-EPA standard protocol to evaluate metal leachability in wastes and contaminated soils. However, application of TCLP to assess lead (Pb) leachability from contaminated shooting range soils may be questionable. This study determined Pb leachability in the range soils using TCLP and another US-EPA regulatory leaching method, synthetic precipitation leaching procedure (SPLP). Possible mechanisms that are responsible for Pb leaching in each leaching protocol were elucidated via X-ray diffraction (XRD). Soil samples were collected from the backstop berms at four shooting ranges, with Pb concentrations ranging from 5,000 to 60,600 mg kg⁻¹ soil. Lead concentrations in the TCLP leachates were from 3 to 350 mg l⁻¹, with all but one soil exceeding the USEPA non-hazardous waste disposal limit of 5 mg l⁻¹. However, continued dissolution of metallic Pb particles from spent Pb bullets and its re-precipitation as cerussite (PbCO₃) prevented the TCLP extraction from reaching equilibrium at the end of the standard leaching period (18 h). Thus, the standard one-point TCLP test would either over- or under-estimate Pb leachability in shooting range soils. Lead concentration in the SPLP leachates ranged from 0.021 to 2.6 mg l⁻¹, with all soils above the USEPA regulatory limit of 0.015 mg l⁻¹. In contrast to TCLP, SPLP leaching had reached equilibrium, with regard to both pH and Pb concentrations, within the standard 18 h leaching period, and the analytical SPLP results were in good agreement with those derived from modeling. Thus, we concluded that SPLP is a more appropriate alternative than TCLP for assessing lead leachability in range soils.     

Lead contamination of an agricultural soil in the vicinity of a shooting range

In this study, coupled Pb concentration/Pb isotope data were used to evaluate the effect of a shooting range (operational for over 30 years) on Pb contamination of adjacent agricultural soils and the associated environmental risks. Lead was mainly concentrated in the arable layer of the contaminated agricultural soils at total concentrations ranging from 573 to 694 mg kg^???1. Isotopic analyses (²⁰⁶Pb/²⁰⁷Pb) proved that Pb originated predominantly from the currently used pellets. Chemical fractionation analyses showed that Pb was mainly associated with the reducible fraction of the contaminated soil, which is in accordance with its predominant soil phases (PbO, PbCO₃). The 0.05 M EDTA extraction showed that up to 62% of total Pb from the contaminated site is potentially mobilizable. Furthermore, Pb concentrations obtained from the synthetic precipitation leaching procedure extraction exceeded the regulatory limit set by the United States Environmental Protection Agency for drinking water. Ion exchange resin bags showed to be inefficient for determining the vertical distribution of free Pb^2?+? throughout the soil profile. Increased Pb concentrations were found in the biomass of spring barley (Hordeum vulgare L.) sampled at the studied site and two possible pathways of Pb uptake have been identified: (1) through passive diffusion-driven uptake by roots and (2) especially through atmospheric deposition, which was also proved by analyses of a bioindicator species (bryophyte Hypnum cupressiforme Hedw.). This study showed that shooting ranges can present an important source of Pb contamination of agricultural soils located in their close vicinity.     

Emissions of NO and N2O from soils

Nitric oxide (NO) and nitrous oxide (N₂O) fluxes were measured from agricultural, forest and moorland environments, using chamber techniques. Maximum emissions of NO and N₂O were measured from the agricultural soils shortly after fertiliser application (7 ng NO-N m^–2 s^–1 and 91 ng N₂O-N m^–2 s^–1). For the non-agricultural soils the NO flux ranged from –0.3 to 0.5 ng NO-N m^–2 s^–1 and the N₂O flux ranged from 1 to 2.7 ng N₂O-N m^–2 s^–1. Emissions, however, were increased 2 to 7 fold when N deposition (uplands) and N fixation (alder plantations) contributed to the pool of soil available N. The best predictors of the NO emission were soil NO ₃ ^– and soil temperature, accounting for 60% of the variability observed. The prediction of N₂O was less successful. Only 30% of the variability could be explained by the soil NO ₃ ^– and the soil moisture content, soil temperature did not have a significant effect on the N₂O emission.     

SOIL PROPERTIES OF TERMITE MOUNDS UNDER DIFFERENT LAND USE TYPES IN A TYPIC PALEUDULT OF MIDWESTERN NIGERIA

The effect of land use, i.e. 2–3 years of cropping, 15–20 years old residential area and fallow land on soilproperties of termite (microtermes sp) mounds in TypicPaleudults was studied in the humid rainforest zone ofMidwestern Nigeria, from January 1995 to May 1995. Termitemound populations increased in the following order: Fallow>Residential> Cropping. Soil sampled from mound surfaces, moundperimeters and surrounding soil was analyzed for routinephysical and chemical properties. The bulk densities werehighest in the mound surface (1.20–1.25 mg m^–3), moundperimeters (1.22–1.23 mg m^–3) and surface soil (1.27–1.28 mg m^–3) of the residential area. There was no significantdifference in the soil textural characteristics among thevarious sampling locations of the three land use types.Particle size distribution in mound perimeters was howeverdependent on land use. With respect to organic carbon, totalN, pH, exchangeable cations and ECEC, no significantdifferences existed, instead they spatially differ from oneanother in terms of land use types and sampling locations.     

Microscopic and chemical studies of metal particulates in tree bark and attic dust: evidence for historical atmospheric smelter emissions, Humberside, UK

Tree barks and attic dusts were examined as historical archives of smelter emissions, with the aim of elucidating the pathways of pollution associated with a plume of Sn and Pb contamination in top soils, found close to the former Capper Pass smelter, Humberside, UK. Samples were collected from three villages within the area of the contamination plume. Scanning electron microscopy (SEM) and bulk chemical analyses were used to assess particle type, number and deposition patterns. SEM analysis of dusts and bark revealed that Sn and Pb particles were present in samples from all three villages along with copper, zinc and iron particles. These were almost entirely <10 microm in diameter and occurred mostly as oxides, frequently forming clusters of sub-micron crystals. Samples further from the smelter contained considerably fewer particles. We present images of smelter derived Sn particles. Chemical assays of the barks and attic dusts demonstrated that concentrations of Sn, Pb, Cu, As, Sb and Cd diminished with increasing distance from the source. Strong positive correlations were found between Sn and Pb, As, Sb and Cd in the attic dusts. Enrichment factors (EF) were calculated for these trace elements based on topsoil element concentrations obtained from the soil survey of the study area. Decreases in these trace element concentrations and EF values with distance away from the smelter are consistent with trends found in the soil survey for Sn and Pb and are typical of deposition patterns around smelter stacks. The study demonstrates that tree bark and attic dusts can be effective archives of metal particulates deposited from large static emission sources.     

Adsorption study of 14C-paraquat in two Malaysian agricultural soils

The adsorption equilibrium time and effects of pH and concentration of ¹⁴C-labeled paraquat (1,1^??-dimethyl-4,4^??-bipyridylium dichloride) in two types of Malaysian soil were investigated. The soils used in the study were clay loam and clay soils from rice fields. Equilibrium studies of paraquat in a soil and pesticide solution were conducted. Adsorption equilibrium time was achieved within 2 h for both soil types. The amount of ¹⁴C-labeled paraquat adsorbed onto glass surfaces increased with increasing shaking time and remained constant after 10 h. It was found that paraquat adsorbed by the two soils was very similar: 51.73 (clay loam) and 51.59 ?? g g^???1 (clay) at 1 ?? g/ml. The adsorption of paraquat onto both types of soil was higher at high pH, and adsorption decreased with decreasing pH. At pH 11, the amounts of ¹⁴C-labeled paraquat adsorbed onto the clay loam and clay soil samples were 4.08 and 4.05 ?? g g^???1, respectively, whereas at pH 2, the amounts adsorbed were 3.72 and 3.57 ?? g g^???1, respectively. Results also suggested that paraquat sorption by soil is concentration dependent.     

Influence of paint chips on lead concentration in the soil of public playgrounds in Tokyo

Lead concentration in the surface soils from 31 playgrounds in a ward in Tokyo was measured to examine if paint chips, peeled off from playing equipment installed in the playgrounds, contribute to elevated Pb concentration in the soil of public playgrounds. Lead concentration in the paint chips sampled from playgrounds ranged from 0.003 to 8.9%. Lead concentration in the surface soil ranged from 15.2 to 237 mg kg(-1) (average, 55.5 mg kg(-1)) and higher Pb concentration was found in the soil near painted playing equipment indicating that paint chips from playing equipment contributed to increase soil Pb level of playgrounds in Tokyo. The degree of peeling-off of paint on the surface of playing equipment in the public playground (peeling-off index: POI) positively correlated with Pb concentration in the soil (Spearman rank-correlation coefficient, r = 0.366, p = 0.043). The stronger correlation between Pb concentration and isotope ratios (207Pb/206Pb and Pb conc., r = 0.536, p = 0.002, 208Pb/206Pb and Pb conc. r = 0.600, p < 0.001) than that between Pb and POI indicated that gasoline Pb contributed more to the playground-to-playground variation in soil Pb concentration. It was concluded that both gasoline Pb of the past and paint chips contributed to increased Pb concentration in the surface soil of playgrounds in Tokyo, though the contribution of paint chips is smaller than gasoline Pb.     

Vehicular stress a cause for heavy metal accumulation and change in physico-chemical characteristics of road side soils in Pahalgam

In an effort to determine vehicular impact on soil quality, soil samples were collected from three different zones (Pahalgam, Batakote, and Chandanwari) in Pahalgam forest ecosystem. Results showed that a significant decrease in moisture content, organic carbon, available nitrogen, and potassium was observed in nearby road side soils. However, pH was observed to be on neutral side and available phosphorus recorded high concentration. The concentration of heavy metals Pb²⁺, Cu²⁺, Zn²⁺, Ni²⁺, and Cd²⁺ estimated was also significantly high. Furthermore, concentration of Pb²⁺ at high vehicular load subzones was observed to be highest (1.168 mg/Kg) followed by Zn²⁺ (0.896 mg/Kg), Ni²⁺ (0.649 mg/Kg), Cu²⁺ (0.415 mg/Kg), and Cd²⁺ (0.079 mg/Kg). An inter-zone analysis revealed that the concentration of the heavy metals (Pb²⁺?>?Ni²⁺?>?Cd²⁺) was observed to follow the trend, Z-I?>?Z-II?>?Z-III. Variation along the temporal gradient and the impact on soil qualities were notably higher in summer. Vehicular pollution to a great extent impacts physico-chemical characteristics and more interestingly adds substantial concentration of heavy metals in soils.     

Assessment of aluminum bioavailability in alum sludge for agricultural utilization

Inorganic aluminum ions, [Al(H₂O)₆]³⁺, [Al(OH)(H₂O)₅]²⁺, and [Al(OH)₂(H₂O)₄]⁺, are toxic to a number of crops. The aim of this study was to estimate the danger of soil contamination of bioavailable aluminum and heavy metals forms because of alum sludge which was a by-product of water, and wastewater treatment technology using aluminum coagulant is introduced into the soil. Aluminum and selected heavy metal fractionation was carried out in the post-coagulation sludge collected at a water treatment plant (where aluminum was used as a coagulant), fermented sewage sludge at a municipal wastewater treatment plant (which did not apply aluminum coagulant), and soil from water treatment plant as well as the mixtures of sludge and soil. It has been found that post-coagulation sludge used as natural fertilizer is a secondary source of bioavailable aluminum, especially when aluminum coagulants are used during water and wastewater treatment. The evaluation of applicability of the sludge to very weak acidic and acidic agricultural soils was carried out. The authors shall debate the question whether, in this case, the Regulation of EU and Polish Government on sewage sludge should also take the bioavailable aluminum into account and add to the list of the elements whose allowable contents are limited.     

Environmental quality assessment studies of coal handling on peripheral land near Kanika siding, Basundhra-Garjanbahal area of MCL, Sundergarh, Orissa, India

Coal has been recognized as the most important source of energy generation in India. The present work was undertaken in order to assess the environmental impact of coal handling on peripheral land under near Kanika siding, Orissa, India. The data on suspended particulates in ambient air indicates an additional load of 50.5–108.7 μg/m³) to the ambient air due to coal loading which is equivalent to 50 × 365 to 108 × 365 kg/year. However, in the southern side (opposite to siding) covering the crop fields, the dust accumulation was maximum, i.e., 0.021 to 0.035 mg/cm² area in comparison to 0.001 to 0.021 in the eastern side and 0.001 to 0.029 in western side of the crop fields. The physical and chemical properties of soil was also assessed. The results reveal that the coal loading has definite negative impact on the peripheral land near the site.     

Metal release from serpentine soils in Sri Lanka

Ultramafic rocks and their related soils (i.e., serpentine soils) are non-anthropogenic sources of metal contamination. Elevated concentrations of metals released from these soils into the surrounding areas and groundwater have ecological-, agricultural-, and human health-related consequences. Here we report the geochemistry of four different serpentine soil localities in Sri Lanka by coupling interpretations garnered from physicochemical properties and chemical extractions. Both Ni and Mn demonstrate appreciable release in water from the Ussangoda soils compared to the other three localities, with Ni and Mn metal release increasing with increasing ionic strengths at all sites. Sequential extraction experiments, utilized to identify “elemental pools,” indicate that Mn is mainly associated with oxides/(oxy)hydroxides, whereas Ni and Cr are bound in silicates and spinels. Nickel was the most bioavailable metal compared to Mn and Cr in all four soils, with the highest value observed in the Ussangoda soil at 168?±?6.40 mg kg^?1 via the 0.01-M CaCl₂ extraction. Although Mn is dominantly bound in oxides/(oxy)hydroxides, Mn is widely dispersed with concentrations reaching as high as 391 mg kg^?1 (Yudhaganawa) in the organic fraction and 49 mg kg^?1 (Ussangoda) in the exchangeable fraction. Despite Cr being primarily retained in the residual fraction, the second largest pool of Cr was in the organic matter fraction (693 mg kg^?1 in the Yudhaganawa soil). Overall, our results support that serpentine soils in Sri Lanka offer a highly labile source of metals to the critical zone.     

Retrospective monitoring and inventory of soil contamination in relation to systematic monitoring

Retrospective monitoring of soil contamination has been performed in the Czech Republic. This kind of monitoring is based on the comparison of the heavy metals content in soil samples taken during a systematic soil survey (1960–1970) and in samples taken at the present time. The anticipated high degree of soil pollution in the Czech Republic has not been proved. Most of the contaminated soils were found to be loaded just 20–35 years ago. Retrospective monitoring is considered to be an accelerating tool for determining the strategy of the systematic monitoring of soil contamination. This procedure stimulated the development of the multi-step system of soil loading limits.     

Spatial Variability and Monitoring of Pb Contamination of Farming Soils Affected by Industry

In this study, the relationship between some physico-chemical properties of soils and lead contamination in soil due to emission from industrial operations in Samsun province of Turkey was investigated. The extent of timely contamination was studied by comparing the obtained results with the results of the study conducted in the same region in 1998. An area of 225 km² (15 km × 15 km), which was divided into 1000 × 1000 m grid squares (16 lines in the east and south directions), was selected within the industrial area. The total of 256 grid points was obtained and soil samples were collected from three depths (0–5, 5–15, and 15–30 cm) of each grid center in 2004. The total Pb concentrations of soil samples were determined as 65.84–527.04 μg g⁻¹ at 0–5 cm in depth, 58.50 – 399.54 μg g⁻¹ at 5–15 cm in depth, and 44.65–330.07 μg g⁻¹ at 15–30 cm in depth. DTPA-extractable Pb concentrations of soils were found to be in the range of 1.52–9.03 μg g⁻¹, 0.54–7.09 μg g⁻¹, 0.19–6.13 μg g⁻¹ at 0–5, 5–15, and 15–30 cm depths, respectively. There were significant relationships between both total or DTPA-extractable Pb concentrations and selected physico-chemical properties of soil. According to enrichment factor (EF) values calculated from the total Pb concentrations, 11.3% of the study area (225 km²) was enriched with Pb in high level, but 77% of the area was in significant enrichment level with Pb. The average total and DTPA-extractable Pb concentrations increased as 11 and 13%, respectively in comparison with the results of 1998.