Associations of cadmium, zinc, and lead in soils from a lead and zinc mining area as studied by single and sequential extractions

An exploratory study of the area surrounding a historical Pb?CZn mining and smelting area in Zawar, India, detected significant contamination of the terrestrial environment by heavy metals. Soils (n?=?87) were analyzed for pH, EC, total organic matter (TOM), Pb, Zn, Mn, and Cd levels. The statistical analysis indicated that the frequency distribution of the analyzed parameters for these soils was not normal. The median concentrations of metals in surface soils were: Pb 420.21 ?? g/g, Zn 870.25 ?? g/g, Mn 696.70 ?? g/g, and Cd 2.09 ?? g/g. Zn concentrations were significantly correlated with Cd (r?=?0.867), indicating that levels of Cd are dependent on Zn. However, pH, electrical conductivity and total organic matter were not correlated significantly with Cd, Pb, Zn, and Mn. To assess the potential mobility of Cd, Pb, and Zn in soils, single (EDTA) as well as sequential extraction scheme (modified BCR) were applied to representative (n?=?23) soil samples. The amount of Cd, Pb, and Zn extracted by EDTA and their total concentrations showed linear positive correlation, which are statistically significant (r values for Cd, Pb, and Zn being 0.901, 0.971, and 0.795, respectively, and P values being <0.001). The correlation coefficients indicate a strong relation between EDTA-extractable metal and total metal. These results appear to justify the use of ??total?? metal contents as a useful preliminary indicator of areas where the risks of metal excess or deficiency are high. The EDTA extractability was maximum for Cd followed by Pb and Zn in soils from all the locations. As indicated by single extraction, the apparent mobility and potential bioavailability of metals in soils followed the order: Cd ?? Pb >?> Zn. Soil samples were sequentially extracted (modified BCR) so that solid pools of Cd, Zn, and Pb could be partitioned into four operationally defined fractions viz. acid-soluble, reducible, oxidizable, and residual. Cadmium was present appreciably (39.41%) in the acid-soluble fraction and zinc was predominantly associated (32.42%) with residual fraction. Pb (66.86%) and Zn (30.44%) were present mainly in the reducible fraction. Assuming that the mobility and bioavailability are related to solubility of geochemical forms of metals and decrease in the order of extraction, the apparent mobility and potential metal bioavailability for these contaminated soil samples is Cd > Zn > Pb.     

Spatial variability of soil total and DTPA-extractable cadmium caused by long-term application of phosphate fertilizers, crop rotation, and soil characteristics

Increasing cadmium (Cd) accumulation in agricultural soils is undesirable due to its hazardous influences on human health. Thus, having more information on spatial variability of Cd and factors effective to increase its content on the cultivated soils is very important. Phosphate fertilizers are main contamination source of cadmium (Cd) in cultivated soils. Also, crop rotation is a critical management practice which can alter soil Cd content. This study was conducted to evaluate the effects of long-term consumption of the phosphate fertilizers, crop rotations, and soil characteristics on spatial variability of two soil Cd species (i.e., total and diethylene triamine pentaacetic acid (DTPA) extractable) in agricultural soils. The study was conducted in wheat farms of Khuzestan Province, Iran. Long-term (27-year period (1980 to 2006)) data including the rate and the type of phosphate fertilizers application, the respective area, and the rotation type of different regions were used. Afterwards, soil Cd content (total or DTPA extractable) and its spatial variability in study area (400,000 ha) were determined by sampling from soils of 255 fields. The results showed that the consumption rate of di-ammonium phosphate fertilizer have been varied enormously in the period study. The application rate of phosphorus fertilizers was very high in some subregions with have extensive agricultural activities (more than 95 kg/ha). The average and maximum contents of total Cd in the study region were obtained as 1.47 and 2.19 mg/kg and DTPA-extractable Cd as 0.084 and 0.35 mg/kg, respectively. The spatial variability of Cd indicated that total and DTPA-extractable Cd contents were over 0.8 and 0.1 mg/kg in 95 and 25 % of samples, respectively. The spherical model enjoys the best fitting and lowest error rate to appraise the Cd content. Comparing the phosphate fertilizer consumption rate with spatial variability of the soil cadmium (both total and DTPA extractable) revealed the high correlation between the consumption rate of P fertilizers and soil Cd content. Rotation type was likely the main effective factor on variations of the soil DTPA-extractable Cd contents in some parts (eastern part of study region) and could explain some Cd variation. Total Cd concentrations had significant correlation with the total neutralizing value (p?<?0.01), available P (p?<?0.01), cation exchange capacity (p?<?0.05), and organic carbon (p?<?0.05) variables. The DTPA-extractable Cd had significant correlation with OC (p?<?0.01), pH, and clay content (p?<?0.05). Therefore, consumption rate of the phosphate fertilizers and crop rotation are important factors on solubility and hence spatial variability of Cd content in agricultural soils.     

Cadmium background concentrations to establish reference quality values for soils of São Paulo State,Brazil

Proper assessment of soil cadmium (Cd) concentrations is essential to establish legislative limits. The present study aimed to assess background Cd concentrations in soils from the state of São Paulo, Brazil, and to correlate such concentrations with several soil attributes. The topsoil samples (n?=?191) were assessed for total Cd contents and for other metals using the USEPA 3051A method. The background concentration was determined according to the third quartile (75th). Principal component analysis, Spearman correlation, and multiple regressions between Cd contents and other soil attributes (pH, cation exchange capacity (CEC), clay content, sum of bases, organic matter, and total Fe, Al, Zn, and Pb levels) were performed. The mean Cd concentration of all 191 samples was 0.4 mg kg^?1, and the background concentration was 0.5 mg kg^?1. After the samples were grouped by parent material (rock origin) and soil type, the background Cd content varied, i.e., soils from igneous, metamorphic, and sedimentary rocks harbored 1.5, 0.4, and 0.2 mg kg^?1 of Cd, respectively. The background Cd content in Oxisols (0.8 mg kg^?1) was higher than in Ultisols (0.3 mg kg^?1). Multiple regression demonstrated that Fe was primarily attributed to the natural Cd contents in the soils (R ²?=?0.79). Instead of a single Cd background concentration value representing all São Paulo soils, we propose that the concentrations should be specific for at least Oxisols and Ultisols, which are the primary soil types.     

Characteristics and distribution of analyzed metals in soil profiles in the vicinity of a postflotation waste site in the Bukowno region, Poland

The lead–zinc industry in the Bukowno region of southern Poland has polluted the surface layer of the surrounding soils mainly with lead (Pb), cadmium (Cd), zinc (Zn), arsenic (As), and thallium (Tl). Analysis of six soil profiles, taken on the east side of the postflotation waste site of the Mining and Metallurgical Plants ZGH "Boles?aw" in Bukowno, showed that they were podzol soils, taking form of loose sands with neutral pH and reducing conditions. Concentration of organic matter in the horizons ranged from 2 to 80 %. The main components of the mineral soil were quartz, carbonates, K-feldspars, plagioclases, and micas (sericite). The highest total concentrations of metals were found in the O, A, and B horizons. Over 90 % of the Cd content, 80 % of the Pb content, 60 % of the Zn content, ～60 % of the Tl content, and 20 % of the As content occurred as mobile forms. The corresponding total concentrations were 10 mg/kg Cd, 922 mg/kg Pb, 694 mg/kg Zn, <1 mg/kg Tl, and <5 mg/kg As. This can potentially be taken up from the soil and transported in the trophic chain. Comparing the total metal content with the legal limits in Poland, it is observed, that the investigated soils exceeded the permissible levels of Cd, Pb, and Zn for agricultural soils. Arsenic and Tl are not reflected in the chemical quality of soil classifications.     

EDTA-enhanced phytoremediation of contaminated calcareous soils: heavy metal bioavailability,extractability, and uptake by maize and sesbania

Natural and chemically enhanced phytoextraction potentials of maize (Zea mays L.) and sesbania (Sesbania aculeata Willd.) were explored by growing them on two soils contaminated with heavy metals. The soils, Gujranwala (fine, loamy, mixed, hyperthermic Udic Haplustalf) and Pacca (fine, mixed, hyperthermic Ustollic Camborthid), were amended with varying amounts of ethylenediaminetetraacetic acid (EDTA) chelating agent, at 0, 1.25, 2.5, and 5.0 mM kg^?1 soil to enhance metal solubility. The EDTA was applied in two split applications at 46 and 60 days after sowing (DAS). The plants were harvested at 75 DAS. Addition of EDTA significantly increased the lead (Pb) and cadmium (Cd) concentrations in roots and shoots, uptake, bioconcentration factor, and phytoextraction rate over the control. Furthermore, addition of EDTA also significantly increased the soluble fractions of Pb and Cd in soil over the controls; the maximum increase of Pb and Cd was 13.1-fold and 3.1-fold, respectively, with addition of 5.0 mM EDTA kg^?1soil. Similarly, the maximum Pb and Cd root and shoot concentrations, translocation, bioconcentration, and phytoextraction efficiency were observed at 5.0 mM EDTA kg^?1 soil. The results suggest that both crops can successfully be used for phytoremediation of metal-contaminated calcareous soils.     

Assessment of heavy metal pollution in vegetables and relationships with soil heavy metal distribution in Zhejiang province,China

There are increasing concerns on heavy metal contaminant in soils and vegetables. In this study, we investigated heavy metal pollution in vegetables and the corresponding soils in the main vegetable production regions of Zhejiang province, China. A total of 97 vegetable samples and 202 agricultural soil samples were analyzed for the concentrations of Cd, Pb, As, Hg, and Cr. The average levels of Cd, Pb, and Cr in vegetable samples [Chinese cabbage (Brassica campestris spp. Pekinensis), pakchoi (Brassica chinensis L.), celery (Apium graveolens), tomato (Lycopersicon esculentum), cucumber (Colletotrichum lagenarium), cowpea (Vigna unguiculata), pumpkin (Cucurbita pepo L.), and eggplant (Solanum melongena)] were 0.020, 0.048, and 0.043 mg kg^?1, respectively. The Pb and Cr concentrations in all vegetable samples were below the threshold levels of the Food Quality Standard (0.3 and 0.5 mg kg^?1, respectively), except that two eggplant samples exceeded the threshold levels for Cd concentrations (0.05 mg kg^?1). As and Hg contents in vegetables were below the detection level (0.005 and 0.002 mg kg^?1, respectively). Soil pollution conditions were assessed in accordance with the Chinese Soil Quality Criterion (GB15618-1995, Grade II); 50 and 68 soil samples from the investigated area exceeded the maximum allowable contents for Cd and Hg, respectively. Simple correlation analysis revealed that there were significantly positive correlations between the metal concentrations in vegetables and the corresponding soils, especially for the leafy and stem vegetables such as pakchoi, cabbage, and celery. Bio-concentration factor values for Cd are higher than those for Pb and Cr, which indicates that Cd is more readily absorbed by vegetables than Pb and Cr. Therefore, more attention should be paid to the possible pollution of heavy metals in vegetables, especially Cd.     

Heavy metal enrichment in the soil along the Delhi–Ulan section of the Qinghai–Tibet railway in China

The pollutants that are discharged from roads and traffic have attracted much attention recently. Nonetheless, most studies have mainly focused on highways and seldom on railways. In this study, soil samples were selected at the embankment and perpendicularly at different distances (2, 5, 10, 20, 30, 50, 60, 70, 80, 100, and 150 m) from the embankment bottom of the Qinghai–Tibet railway. Furthermore, soils were selected at four soil depths (5, 10, 20, and 30 cm) of each sample at the flat. The enrichment of nine heavy metals (V, Cr, Co, Ni, Cu, Zn, Rb, Cd, and Pb) in soils along the Delhi–Ulan section of the Qinghai–Tibet railway was studied. The results indicated that the mean concentrations of Cr, Ni, Cu, Zn, Pb, and Cd were highest at the embankment. The Cu concentrations in soils decreased by an S-curve-shaped function with increasing distance from the embankment, while Cd, Pb, and Zn decreased by inverse functions (p?<?0.0001). The concentrations of other studied metal did not show significant changes with increasing distance. After performing a statistical analysis, Pb, Cd, and Zn in soils were considered to be influenced by railway operations. However, the influence was weak and only spanned less than 5 m from the bottom of the embankment horizontally and 10 cm from the surface vertically. The mean concentrations of heavy metals in soils along the Delhi–Ulan section of the Qinghai–Tibet railway were considered lower compared with those along other railways.     

Enhanced uptake of heavy metals in municipal solid waste compost by turfgrass following the application of EDTA

Enhancement of multiple heavy metal uptake from municipal solid waste (MSW) compost by Lolium perenne L. in a field experiment was investigated with application of EDTA. EDTA was added in solution at six rates (0–30 mmol kg^???1) after 50 days of plant growth. Two weeks later, plants were harvested for the first crop and then all the turfgrasses were mowed. After another 30 days of growth, EDTA was added again at above six rates to the corresponding sites and the second crop was harvested 2 weeks later. The results showed that EDTA significantly increased heavy metal accumulation in both crops of L. perenne. For the first crop, the concentrations of Mn, Ni, Cd, and Pb in the shoots increased remarkably with increasing EDTA supply, peaked at 25 mmol kg^???1 EDTA, and shoots of 0–5 cm height (shoots from medium surface to 5 cm height) had higher metal concentrations than 5–10 cm and >10 cm shoots. The highest concentration of Mn, Ni, Cd, and Pb was 2.3-, 2.3-, 2.6-, and 3.2-fold, respectively, in 0–5 cm shoots higher than control. For the second crop, the concentrations of Mn, Cu, and Pb in shoots were, in general, less than those in the first crop. However, the second crop was significantly higher (P?< 0.05) than the first crop in dry biomass, so the total amount of metals removed by the second crop was more than the first crop. In addition, EDTA significantly increased the translocation ratios of most heavy metals from roots to shoots. For the first crop, 38% of the total Zn, 51% of Cd, 49% of Pb, 60% Mn, 55% Ni, and 45% Cu taken up by the plant was translocated in the shoots of 0–5 cm height. Turfgrass would have potential for use in remediation of heavy metals in MSW compost or contaminated soils.     

Prediction of the solubility of zinc, copper, nickel, cadmium, and lead in metal-contaminated soils

Risk assessment of metal-contaminated soil depends on how precisely one can predict the solubility of metals in soils. Responses of plants and soil organisms to metal toxicity are explained by the variation in free metal ion activity in soil pore water. This study was undertaken to predict the free ion activity of Zn, Cu, Ni, Cd, and Pb in metal-contaminated soil as a function of pH, soil organic carbon, and extractable metal content. For this purpose, 21 surface soil samples (0–15 cm) were collected from agricultural lands of various locations receiving sewage sludge and industrial effluents for a long period. One soil sample was also collected from agricultural land which has been under intensive cropping and receiving irrigation through tube well water. Soil samples were varied widely in respect of physicochemical properties including metal content. Total Zn, Cu, Ni, Cd, and Pb in experimental soils were 2,015?±?3,373, 236?±?286, 103?±?192, 29.8?±?6.04, and 141?±?270 mg kg^?1, respectively. Free metal ion activity, viz., pZn²⁺, pCu²⁺, pNi²⁺, pCd²⁺, and pPb²⁺, as estimated by the Baker soil test was 9.37?±?1.89, 13.1?±?1.96, 12.8?±?1.89, 11.9?±?2.00, and 11.6?±?1.52, respectively. Free metal ion activity was predicted by pH-dependent Freundlich equation (solubility model) as a function of pH, organic carbon, and extractable metal. Results indicate that solubility model as a function of pH, Walkley–Black carbon (WBC), and ethylenediaminetetraacetic acid (EDTA)-extractable metals could explain the variation in pZn²⁺, pCu²⁺, pNi²⁺, pCd²⁺, and pPb²⁺ to the extent of 59, 56, 46, 52, and 51 %, respectively. Predictability of the solubility model based on pH, KMnO₄-oxidizable carbon, and diethylenetriaminepentaacetic acid-extractable or CaCl₂-extractable metal was inferior compared to that based on EDTA-extractable metals and WBC.     

Comparison of diffusive gradients in thin film technique with traditional methods for evaluation of zinc bioavailability in soils

The technique of diffusive gradients in thin film (DGT) has been shown to be a promising tool to assess zinc (Zn) bioavailability in soils, but there exists considerable debate on its suitability. In this study, Zn bioavailability was systematically investigated in wheat- and maize-grown soils using this technique and seven traditional methods, including soil solution concentration and six widely used single-step extraction methods (HAc, EDTA, NaAc, NH₄Ac, CaCl₂, and MgCl₂). The concentrations of Zn in the shoots and roots of these two plant species increased continuously with increasing additions of Zn to the soils, accompanied by significant decreases in shoot biomass and root biomass at Zn concentrations greater than 400 mg kg^?1 for maize and 800 mg kg^?1 for wheat. Zinc uptake and accumulation was higher in maize roots than in wheat roots. Both the concentrations of bioavailable Zn measured by DGT (C _DGT) and soil solutions (C _sol) increased linearly with increasing additions of Zn to the soils, while no strong linear relationships were observed for the extraction methods. Higher concentrations of extractable Zn, lower values of C _sol, and larger values of R (i.e., the ratio of C _DGT to C _sol) were observed in maize-grown soils compared with those of wheat-grown soils, while the values of C _DGT between the two plants were similar. These findings demonstrate that there likely exists a stronger resupply of Zn from the soil solid phases in maize-grown soils to satisfy a higher Zn uptake and accumulation in this plant. Linear correlation analyses showed that C _DGT had the highest correlation coefficients with plant Zn concentrations compared with other traditional methods, implying that the DGT technique is more sensitive and robust in reflecting Zn bioavailability in soils to plants.     

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.     

Soil characteristics and heavy metal accumulation by native plants in a Mn mining area of Guangxi,South China

Revegetation and ecological restoration of a Mn mineland are important concerns in southern China. To determine the major constraints for revegetation and select suitable plants for phytorestoration, pedological and botanical characteristics of a Mn mine in Guangxi, southern China were investigated. All the soils were characterized by low pH and low nitrogen and phosphorus levels except for the control soil, suggesting that soil acidity and poor nutrition were disadvantageous to plant growth. In general, the studied mine soils had normal organic matter (OM) and cation exchange capacity (CEC). However, OM (8.9 g/kg) and CEC (7.15 cmol/kg) were very low in the soils from tailing dumps. The sandy texture and nutrient deficiency made it difficult to establish vegetation on tailing dumps. Mn and Cd concentrations in all soils and Cr and Zn concentrations in three soils exceeded the pollution threshold. Soil Mn and Cd were above phytotoxic levels, indicating that they were considered to be the major constraints for phytorestoration. A botanical survey of the mineland showed that 13 plant species grew on the mineland without obvious toxicity symptoms. High Mn and Cd concentrations have been found in the aerial parts of Polygonum pubescens, Celosia argentea, Camellia oleifera, and Solanum nigrum, which would be interesting for soil phytoremediation. Miscanthus floridulus, Erigeron acer, Eleusina indica, and Kummerowia striata showed high resistance to the heavy metal and harsh condition of the soils. These species could be well suited to restore local degraded land in a phytostabilization strategy.     

Effect of wastewater irrigation on vegetables in relation to bioaccumulation of heavy metals and biochemical changes

The present study was conducted to determine the heavy metal contamination in soil with accumulation in edible parts of plants and their subsequent changes in biochemical constituents due to wastewater irrigation. Though the wastewater contains low levels of the heavy metals (Fe, Mn, Pb, Cd, and Cr), the soil and plant samples show higher values due to accumulation. The trend of metal accumulation in wastewater-irrigated soil is in the order: Fe > Pb > Mn > Cr > Cd. Of the three species Colocasia esculentum, Brassica nigra, and Raphanus sativus that are grown, the order of total heavy metal accumulation in roots is Raphanus sativus > Colocasia esculentum, while in shoots the order is Brassica nigra > Colocasia esculentum > Raphanus sativus. The enrichment factor (EF) of the heavy metals in contaminated soil is in the sequence of Cd (3) > Mn (2.7) > Cr (1.62) > Pb (1.46) > Fe (1.44), while in plants EF varies depending upon the species and plant part. C. esculentum and R. sativus show a higher EF for Cr and Cd. All plants show a high transfer factor (TF > 1) for Cd signifying a high mobility of Cd from soil to plant whereas the TF values for Pb are very low as it is not bioavailable. Results of the biochemical parameters show decrease in total chlorophyll and total amino acid levels in plants and an increase in amounts of soluble sugars, total protein, ascorbic acid, and phenol except B. nigra for protein in plants grown in soil irrigated with wastewater as compared to control site.     

Heavy metal phytoextraction—natural and EDTA-assisted remediation of contaminated calcareous soils by sorghum and oat

The abilities of sorghum (Sorghum bicolor L.) and oat (Avena sativa L.) to take up heavy metals from soils amended with ethylenediaminetetraacetic acid (EDTA) were assessed under greenhouse conditions. Both plants were grown in two soils contaminated with heavy metals (Gujranwala—silty loam and Pacca—clay loam). The soils were treated with 0, 0.625, 1.25, and 2.5 mM EDTA kg^?1 soil applied at both 45 and 60 days after sowing (DAS); the experiment was terminated at 75 DAS. Addition of EDTA significantly increased concentrations of Cd, Cr, and Pb in roots and shoots, and bio-concentration factors and phytoextraction rates were also increased. Post-harvest soil analysis showed that soluble fractions of metals were also increased significantly. The increase in Cd was ≈ 3-fold and Pb was ≈ 15-fold at the highest addition of EDTA in Gujranwala soil; in the Pacca soil, the increase was less. Similarly, other phytoremediation factors, such as metal translocation, bio-concentration factor, and phytoextraction, efficiency were also maximum when soils were treated with 2.5 mM EDTA kg^?1 soil. The study demonstrated that sorghum was better than oat for phytoremediation.     

Trace element concentration and speciation in selected urban soils in New York City

A long history of urbanization and industrialization has affected trace elements in New York City (NYC) soils. Selected NYC pedons were analyzed by aqua regia microwave digestion and sequential chemical extraction as follows: water soluble (WS); exchangeable (EX); specifically sorbed/carbonate bound (SS/CAR); oxide-bound (OX); organic/sulfide bound (OM/S). Soils showed a range in properties (e.g., pH 3.9 to 7.4). Sum of total extractable (SUM_TE) trace elements was higher in NYC parks compared to Bronx River watershed sites. NYC surface horizons showed higher total extractable (TE) levels compared to US non-anthropogenic soils. TE levels increased over 10 year in some of the relatively undisturbed and mostly wooded park sites. Surface horizons of park sites with long-term anthropogenic inputs showed elevated TE levels vs. subsurface horizons. Conversely, some Bronx River watershed soils showed increased concentrations with depth, reflective of their formation in a thick mantle of construction debris increasing with depth and intermingled with anthrotransported soil materials. Short-range variability was evident in primary pedons and satellite samples (e.g., Pb 253?±?143 mg/kg). Long-range variability was indicated by Pb_TE (348 versus 156 mg/kg) and Hg_TE (1 versus 0.3 mg/kg) concentrations varying several-fold in the same soil but in different geographic locations. Relative predominance of fractions: RES (37 %)?>?SS/CAR (22 %)?>?OX (20 %)?>?OM/S (10 %)?>?EX (7 %)?>?WS (4 %). WS and EX fractions were greatest for Hg (7 %) and Cd (14 %), respectively. RES was predominant fraction for Co, Cr, Ni, and Zn (41 to 51 %); SS/CAR for Cd and Pb (40 and 63 %); OM/S for Cu and Hg (36 and 37 %); and OX for As (59 %).     

Accumulation dynamics and cellular locations of Pb, Zn and Cd in resident and transplanted Flavocetraria nivalis lichens near a former Pb–Zn mine

Accumulation dynamics and cellular locations of lead (Pb), zinc (Zn) and cadmium (Cd) were studied in Flavocetraria nivalis lichens near the former Black Angel Pb–Zn Mine in West Greenland. Natural resident thalli were collected from four dust-contaminated sites near the mine. In addition, thalli were taken from an uncontaminated reference site and transplanted to the contaminated sites followed by a collection 1 year after. Total thalli metal contents were determined, and thalli were subjected to a sequential extraction procedure. After 1 year of transplantation, total Pb thalli contents were significantly elevated compared with initial concentrations at all sites (for Zn and Cd contents only at the two sites closest to the mine). However, transplanted thalli contained significantly less Pb (26?±?12 %), Zn (64?±?13 %) and Cd (34?±?7 %) compared with resident thalli from these sites. Results from the sequential extraction procedure showed marked differences among Pb, Zn and Cd in the extracellular, intracellular and residual fraction. The lower total metal concentrations in transplanted compared with resident thalli at the contaminated sites were mostly due to a larger metal content bound in the residual fraction in resident thalli. In contrast, the metal content bound in the extracellular fraction were not significantly different in transplanted and resident thalli. The results indicate that extracellular-bound Pb, Zn and Cd in F. nivalis can be used as a proxy for recent (annual) atmospheric metal deposition whereas the large residual metal fraction in resident lichens indicate an accumulation of metal-containing particles in the thalli over time that includes several years of uptake.     

Ferti-irrigational impact of sugar mill effluent on agronomical characteristics of Phaseolus vulgaris (L.) in two seasons

Ferti-irrigation response of 5, 10, 25, 50, 75, and 100 % concentrations of the sugar mill effluent (SME) on French bean (Phaseolus vulgaris L., cv. Annapurna) in the rainy and summer seasons was investigated. The fertigant concentrations produced significant (P?+), potassium (K⁺), calcium (Ca²⁺), magnesium (Mg²⁺), total Kjeldahl nitrogen (TKN), phosphate (PO₄ ^3?), sulfate (SO₄ ^2?), ferrous (Fe²⁺), cadmium (Cd), chromium (Cr), copper (Cu), manganese (Mn), and zinc (Zn), in both seasons. The contents of Cr, Cu, Mn, and Zn except Cd were found to be below the maximum levels permitted for soils in India. The agronomic performance of P. vulgaris was gradually increased at lower concentrations, i.e., from 5 to 25 %, and decreased at higher concentrations, i.e., from 50 to 100 %, of the SME in both seasons when compared to controls. The accumulations of heavy metals were increased in the soil and P. vulgaris from 5 to 100 % concentrations of the SME in both seasons. The contents of Cu, Mn, and Zn except Cd and Cr were noted under the permissible limit of Food and Agriculture Organization (FAO)/World Health Organization (WHO) standards. Most contents of biochemical components like crude proteins, crude fiber, and total carbohydrates were found with 25 % concentration of the SME in both seasons. The contamination factor (Cf) of various metals was in the order of Cd > Cr > Zn > Mn > Cu for soil and Mn > Zn > Cu > Cr > Cd for P. vulgaris in both seasons after fertigation with SME. Therefore, the SME can be used to improve the soil fertility and yield of P. vulgaris after appropriate dilution.     

Contamination assessment of arsenic and heavy metals in a typical abandoned estuary wetland—a case study of the Yellow River Delta Natural Reserve

Coastal and estuarine areas are often polluted by heavy metals that result from industrial production and agricultural activities. In this study, we investigated the concentration trait and vertical pattern of trace elements, such as As, Cd, Ni, Zn, Pb, Cu, and Cr, and the relationship between those trace elements and the soil properties in coastal wetlands using 28 profiles that were surveyed across the Diaokouhe Nature Reserve (DKHNR). The goal of this study is to investigate profile distribution characteristics of heavy metals in different wetland types and their variations with the soil depth to assess heavy metal pollution using pollution indices and to identify the pollution sources using multivariate analysis and sediment quality guidelines. Principal component analysis, cluster analysis, and pollution level indices were applied to evaluate the contamination conditions due to wetland degradation. The findings indicated that the concentration of trace elements decreased with the soil depth, while Cd increases with soil depth. The As concentrations in reed swamps and Suaeda heteroptera surface layers were slightly higher than those in other land use types. All six heavy metals, i.e., Ni, Cu, As, Zn, Cr, and Pb, were strongly associated with PC1 (positive loading) and could reflect the contribution of natural geological sources of metals into the coastal sediments. PC2 is highly associated with Cd and could represent anthropogenic sources of metal pollution. Most of the heavy metals exhibited significant positive correlations with total concentrations; however, no significant correlations were observed between them and the soil salt and soil organic carbon. Soil organic carbon exhibited a positive linear relationship with Cu, Pb, and Zn in the first soil layer (0–20 cm); As, Cr, Cu, Ni, Pb, and Zn in the second layer (20–40 cm); and As, Cr, Cu, Ni, Pb, and Zn in the third layer (40–60 cm). Soil organic carbon exhibited only a negative correlation with Cd (P?I _geo values), which averaged less than 0 in the three soil layers, this finding indicates that the soils have remained unpolluted by these heavy metals. The mean concentrations of these trace elements were lower than Class I criteria. The degradation wetland restoration suggestions have also been provided in such a way as to restore the reserved flow path of the Yellow River. The results that are associated with trace element contamination would be helpful in providing scientific directions to restore wetlands across the world.     

Trace metals in soil and vegetables and associated health risk assessment

The objective of this study was to assess the contamination level of trace metals in soil and vegetables and health risk to the urban population in Bangladesh. The range of Cr, Ni, Cu, As, Cd, and Pb in agricultural soils was 158–1160, 104–443, 157–519, 41–93, 3.9–13, and 84–574 mg/kg, respectively. Sequential extraction tests revealed that the studied metals were predominantly associated with the residual fraction, followed by the organically bound phase. Concerning Cu, Ni, Cd, and Pb in vegetables, more than 50 % samples exceeded the FAO/WHO recommended permissible limits. Considering the transfer of metals from soil to vegetables, Cu and Cd exhibited higher transfer factor (TF) values than the other metals. Target hazard quotient (THQ) for individual metal was below 1, suggesting that people would not experience significant health hazards if they ingest a single metal from vegetables. However, total metal THQ signifies the potential non-carcinogenic health hazard to the highly exposed consumers. The carcinogenic risk (TR) of As (1.9?×?10^?4) and Pb (2.3?×?10^?5) through consumption of vegetables were higher than the USEPA threshold level (10^?6), indicating potential cancer risks.     

Metal speciation in sediment and bioaccumulation in <Emphasis Type="Italic">Meretrix lyrata</Emphasis> in the Tien Estuary in Vietnam

The concentrations of seven toxic metals (cadmium (Cd), nickel (Ni), chromium (Cr), arsenic (As), lead (Pb), copper (Cu), and zinc (Zn)) were determined in sediments and the soft tissues of a bivalve species (Meretrix lyrata) collected from the Tien Estuary in Tien Giang Province, South Vietnam. The total metal concentrations in sediments (mg/kg dry weight) increased as Cd (0.06) < Cu (5.0) < Pb (13.9) < As (16.3) < Ni (24) < Cr (50) < Zn (62). Speciation analysis revealed that these metals existed mainly in the residual fraction (43–94%), followed by the Fe-Mn oxide-bound (5–35%) and organic/sulfide-bound (0.6–9.2%) fractions. The metal concentrations in M. lyrata (mg/kg dry weight) were in the ranges of 1.3–1.9 (Cd), 1.5–2.8 (Ni), 1.8–3.4 (Cr), 11–16 (As), 0.3–0.6 (Pb), 6.9–8.7 (Cu), and 95–128 (Zn), which are safe for human consumption. The order of the mean biota-sediment accumulation factor (BSAF) of the metals in the non-residual fractions of the sediment for M. lyrata was Cd > Cu > As > Zn > Cr > Ni > Pb. The Risk Assessment Codes (RACs) suggest that the highest mobility of Cd (with RAC = 37%) poses greater environmental risk to aquatic biota. Correlation analysis results show that M. lyrata can be used as a biomonitor of Cd and Cu pollution in the exchangeable, acid-soluble, and non-residual sediment fractions.