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.     

Effects of organic amendments and irrigation waters on the physical and chemical properties of two calcareous soils in Bahrain

The present investigation studies the effects of cow and chicken manure and sewage sludge at different rates of addition and with two irrigation waters of different salinities on two major calcareous soils in Bahrain. The aim was to quantify potential improvements in soil quality, the accumulation of trace metals, and quality of leachates.From the pot experiments it was found that soil waterholding capacity did not change significantly after addition of organic amendments, except in the case of sewage sludge. Total organic carbon and total Kjeldhal nitrogen content increased in the 0–5 cm layer. Low salinity water and sewage applications improved aggregate stability. Extractable phosphorus was enhanced by the chicken manure treatment more than others. Addition of different organic amendments did not affect exchangeable cations. pH values did not show appreciable changes and soils were neutral. Trace metals studied were present at non-toxic levels in the 0–5 cm layer. Zinc and copper were the only metal showing a tendency to leach to the lower soil layer. In all cases metal levels in the surface layer were proportional to the quantities added in the amendments and their levels in the leachate were very low.     

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.     

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.     

Predicting bioavailability of metals from sludge-amended soils

We attempted to develop a protocol for fixing the maximum permissible limit of sludge in agricultural lands based on transfer of metals from sludge-amended soils to human food chain. For this purpose, spinach was grown as a test crop on acid and alkaline soils with graded doses of sludge (0, 1.12, 2.24, 4.48, 8.96, 17.9, 35.8, 71.6, 142 and 285 g kg^?1 of soil) in a pot experiment. Biomass yield of spinach was increased due to sludge application in both acid and alkaline soils. Among the chemical extractants, EDTA extracted the highest amount of metals from sludge-amended soil followed by diethylenetriaminepentaacetic acid (DTPA) and CaCl₂. Elevated levels of Zn, Cu, Fe, Mn, Ni, Cd and Pb in spinach were observed due to sludge application over control. Application of sludge was more effective in increasing metal content in spinach grown on acid soil than alkaline soil. Solubility-free ion activity model as a function of pH, organic carbon and extractable metal was far more effective in predicting metal uptake by spinach grown on sludge-amended soils as compared to that of chemical extractants. Risk in terms of hazard quotient (HQ) for intake of metals through consumption of spinach by humans grown on sludge-treated soils was computed for different metals separately. In a 90-day pot experiment, safe rates of sludge application were worked out as 4.48 and 71.6 g kg^?1 for acid and alkaline soils, respectively.     

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.     

Pollution in the urban soils of Lianyungang,China, evaluated using a pollution index,mobility of heavy metals,and enzymatic activities

Soil samples from 16 urban sites in Lianyungang, China were collected and analyzed. A pollution index was used to assess the potential ecological risk of heavy metals and a sequential extraction procedure was used to evaluate the relative distribution of Cu, Zn, Pb, Cd, Cr, and As in exchangeable, carbonate, Fe/Mn oxide, organic/sulfide, and residual fractions. The mobility of heavy metals and urease (URE) activity, alkaline phosphatase (ALP) activity, and invertase (INV) activity of soils was determined. The results showed that the average concentrations of Cu, Zn, Pb, Cd, Cr, and As in Lianyungang soils were much higher than those in the coastal city soil background values of Jiangsu and China. Among the five studied regions (utilities, commercial, industrial, tourism, and roadside), the industrial region had the highest metal concentrations demonstrating that land use had a significant impact on the accumulation of heavy metals in Lianyungang soils. Compared to the other metals, Cd showed the highest ecological risk. According to chemical partitioning, Cu was associated with the organic/sulfides and Pb and Zn were mainly in the carbonate and the Fe/Mn oxide phase. The greatest amounts of Cd were found in exchangeable and carbonate fractions, while Cr and As were mainly in the residual fraction. Cd had the highest mobility of all metals, and the order of mobility (highest to lowest) of heavy metals in Lianyungang soils was Cd > Zn > Pb > Cu > As > Cr. Soil urease activity, alkaline phosphatase activity, and invertase activity varied considerably in different pollution degree sites. Soil enzyme activities had the lowest levels in roadside and industrial regions. Across all the soil data in the five regions, the total Cu, Zn, Pb, Cd, Cr, and As level was negatively correlated with urease activity, alkaline phosphatase activity, and invertase activity, but the relationship was not significant. In the industrial region, alkaline phosphatase activity had significant negative correlations with total Cu, Pb, Cr, Zn, Cd, and heavy metal fractions. This showed that alkaline phosphatase activity was sensitive to heavy metals in heavily contaminated regions, whereas urease and invertase were less affected. The combination of the various methods may offer a powerful analytical technique in the study of heavy metal pollution in street soil.     

Approaches to soil remediation by complexometric extraction of metal contaminants with regeneration of reagents

Complexometric equilibrations were performed with six chelating reagents to mobilise Cu, Mn, Pb and Zn from a contaminated urban soil. The metal-laden aqueous extract was treated with sodium diethyldithiocarbamate (DEDTC) to precipitate the heavy metals from solution while liberating the chelating reagent. The aqueous supernatant fraction was then re-combined with the soil particulates to extract more pollutants. A sparing quantity of EDTA (ethylenediaminetetraacetic acid; 10 mmol) mobilised 32-54% of the 5 mmol of heavy metals from the soil with three cycles but only 0.1 and 1.0% of the iron and magnesium, respectively, was removed. Whereas DPTA (1,3-diamino-2-hydroxypropane-N,N,N',N'-tetraacetic acid) and citric acid also mobilised each of the heavy metals to some extent and continued to extract these metals during all three cycles, the DTPA (diethylenetriamine pentaacetic acid), although efficient initially, could not be recycled with these conditions. ADA [N-(2-acetamido)iminodiacetate] and SCMC [(S)-carboxymethyl-L-cysteine] were selective for copper and zinc but mobilised only Cu when recycled. An alternate means of regenerating the chelating reagent involved treatment of the aqueous extract with magnesium (Mg0) granules. Excess HEDC [bis(2-hydroxyethyl)dithiocarbamate] mobilised appreciable quantities (19-57%) of heavy metals from the soil and retained its complexing activity when recycled. An appreciable fraction of the mobilised Pb and Cu and a portion of the Zn were cemented to the surfaces of the excess magnesium whereas virtually all of the Fe and Mn was removed from solution as insoluble hydroxides.     

Distribution and fractionation of cadmium, copper, lead, nickel, and zinc in a calcareous sandy soil receiving municipal solid waste

This study was conducted to evaluate the degree of mobility and fractionation of cadmium (Cd), copper (Cu), lead (Pb), nickel (Ni), and zinc (Zn) after the addition of municipal solid sewage sludge (MSS) in a sandy calcareous soil. Treatments were (1) soil application of MSS, (2) soil application of enriched municipal solid waste compost (EMSS), and (3) control soil. The MSS application represented a dose of 200 Mg dry weight per hectare. Soil columns were incubated at room temperature for 15 days and irrigated daily with deionized water to make a total of 505 mm. At the end of leaching experiments, soil samples from each column were divided into 14 layers, each being 1 cm down to 10 and 2.5 cm below that and analyzed for diethylenetriaminepentaacetic acid (DTPA)-extractable Cd, Cu, Pb, Ni, and Zn. The fractionation of the heavy metals in the top five layers of the surface soil samples was investigated by the sequential extraction method. All soil layers of the columns receiving MSS and EMSS had significantly higher concentrations of DTPA-extractable heavy metals than control soil. The maximum concentration of heavy metals in treated soil was in the surface layer and declined significantly with depth. Sequential extraction results showed that in the treated soil, a major proportion of Cd, Pb, and Ni was associated with organic matter (OM) and exchangeable (EXCH) fractions, and a major proportion of Cu and Zn was associated with residual (RES) and OM fractions. Based on relative percent, Pb, Cd, and Ni in the EXCH fraction was higher than Cu and Zn in soil leached with MSS and EMSS, suggesting that application of this MSS to a sandy calcareous soil, at the loading rate used here, may pose a risk in terms of groundwater contamination with Pb, Cd, and Ni.     

Natural attenuation of coal combustion waste in river sediments

The weathering of coal combustion products (CCPs) in a lotic environment was assessed following the Tennessee Valley Authority (Kingston, TN) fly ash release of 2008 into surrounding rivers. Sampled materials included stockpiled ash and sediment collected from 180 to 880 days following the release. Total recoverable concentrations of heavy metals and metalloids in sediment were measured, and percent ash was estimated visually or quantified by particle counts. Arsenic and selenium in sediment were positively correlated with percent ash. For samples collected 180 days after the release, total concentrations of trace elements downstream of the release were greater than reference levels but less than concentrations measured in stockpiled ash. Total concentrations of trace elements remained elevated in ash-laden sediment after almost 2.5 years. A sequential extraction procedure (SEP) was used to speciate selected fractions of arsenic, copper, lead, nickel, and selenium in decreasing order of bioavailability. Concentrations of trace elements in sequentially extracted fractions were one to two orders of magnitude lower than total recoverable trace elements. The bulk of sequentially extractable trace elements was associated with iron-manganese oxides, the least bioavailable fraction of those measured. By 780 days, trace element concentrations in the SEP fractions approached reference concentrations in the more bioavailable water soluble, ion exchangeable, and carbonate-bound fractions. For each trace element, the percentage composition of the bioavailable fractions relative to the total concentration was calculated. These SEP indices were summed and shown to significantly decrease over time. These results document the natural attenuation of leachable trace elements in CCPs in river sediment as a result of the loss of bioavailable trace elements over time.     

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.     

Spatial distribution and potential ecologic risk assessment of heavy metals in the sediments of the Nansi Lake in China

The contamination levels and ecological risks of heavy metals in the sediments of the Nansi Lake were investigated. The contents of Cd, Cr, Cu, Pb, Zn, Ni, and Co in the surface sediments collected at 20 sites ranged from 0.08 to 1.12, 58.92 to 135.62, 38.09 to 78.65, 24.51 to 53.95, 110.51 to 235.36, 11.30 to 65.40, and 4.12 to 20.14 mg/kg, respectively. The results of partitioning analysis revealed that the proportions of soluble and exchangeable fraction were less than 1 %, the proportions of carbonate, amorphous oxides, organic matter, and crystalline oxides fraction were less than 10 %, and 10.52 % of Cd was associated with carbonate. The average proportions in the residual fraction ranged from 48.62 % for Cu to 73.76 % for Ni, indicating low mobility and bioavailability. The geoaccumulation index (I _geo), relative enrichment factor (REF), sediment pollution index (SPI), and potential effect concentration quotient (PECQ) values of the heavy metals in the sediments were not in agreement with each another. The average REF values of Cd and Zn were higher than those of other metals. However, the average PECQ values were higher for Cr and Ni than those of other metals, indicating that these two metals would cause higher adverse biological effects. Therefore, it is suggested that future management and pollution control might focus on Cd, Zn, Cr, and Ni in the sediments of the Nansi Lake.     

Effect of abattoir effluent on the physical and chemical properties of soils

The effect of abattoir effluent on the physical and chemical properties of soils was investigated under natural environment in pot experiment at Ambrose Alli University Teaching and Research farm, Ekpoma, Nigeria. A composite soil sample was used in the experiment. The soil was treated to seven rates of abattoir effluent (viz. 0, 25, 50, 100, 125 and 150 ml/kg soil). The treatments were laid out in randomised complete block design replicated three times. The physical and chemical properties of the soil were determined before pollution and at the end of the experiment, 5 weeks after pollution. Results obtained revealed that abattoir effluent increased pH, available P and micronutrients (Zn, Mn and Fe) significantly in the soil whilst exchangeable cations were reduced significantly when compared to the control.     

Redistribution of zinc, cadmium, and lead among soil fractions in a sandy calcareous soil due to application of poultry litter

This study was conducted to evaluate, using soil columns, the mobilization and redistribution of heavy metals (Zn, Cd, and Pb) among different soil fractions by soluble organic ligands within poultry litter. Uncontaminated soil was amended with Zn, Cd, and Pb to achieve concentration levels of 400, 8, and 200 mg kg⁻¹ soil, respectively. Columns repacked with this amended soil were leached with distilled water, 0.01 M EDTA, 0.01 M CaCl₂, or poultry litter extract (PLE) solutions. After leaching, the soil samples in the columns were sequentially extracted for exchangeable (EXC), carbonate (CARB) organic matter (OM), Mn oxide (MNO), Fe oxide (FEO), and residual (RES) fractions. Considerable mobilization of Zn, Cd, and Pb occurred in soil during EDTA leaching. Leaching with PLE and CaCl₂ solutions significantly decreased Zn and Cd concentrations in the EXC, CARB, and OM fractions. These solutions significantly decreased Pb concentration in the EXC fraction, while PLE solubilized more Pb from EXC fraction than CaCl₂. Thus, the applied poultry litter may change Zn, Cd, and Pb fractions in metal-amended soil and possibly enhance metal mobility.     

Identification of soil contamination hotspots with veterinary antibiotics using heavy metal concentrations and leaching data—a field study in China

In regions with high livestock densities, the usage of antibiotics and metals for veterinary purposes or as growth promoters poses a risk in manured soils. We investigated to which degree the concentrations and depth distributions of Cu, Zn, Cr and As could be used as a tracer to discover contaminations with sulfonamides, tetracyclines and fluoroquinolones. Besides, we estimated the potential vertical translocation of antibiotics and compared the results to measured data. In the peri-urban region of Beijing, China, soil was sampled from agricultural fields and a dry riverbed contaminated by organic waste disposal. The antibiotic concentrations reached 110 μg kg^?1 sulfamethazine, 111 μg kg^?1 chlortetracycline and 62 μg kg^?1 enrofloxacin in the topsoil of agricultural fields. Intriguingly, total concentrations of Cu, Zn, Cr and As were smaller than 65, 130, 36 and 10 mg kg^?1 in surface soil, respectively, therewith fulfilling Chinese quality standards. Correlations between sulfamethazine concentrations and Cu or Zn suggest that in regions with high manure applications, one might use the frequently existing monitoring data for metals to identify potential pollution hotspots for antibiotics in topsoils. In the subsoils, we found sulfamethazine down to ≥2 m depth on agricultural sites and down to ≥4 m depth in the riverbed. As no translocation of metals was observed, subsoil antibiotic contamination could not be predicted from metal data. Nevertheless, sulfonamide stocks in the subsoil could be estimated with an accuracy of 35–200 % from fertilisation data and potential leaching rates. While this may not be sufficient for precise prediction of antibiotic exposure, it may very well be useful for the pre-identification of risk hotspots for subsequent in-depth assessment studies.     

Leaching Characteristics of Heavy Metals and As from Two Urban Roadside Soils

The leaching tests, including the Toxicity Characteristic Leaching Procedure (TCLP), EDTA extraction and BCR sequential extractions before and after EDTA treatments, were performed on two specific soils to elucidate heavy metal-associated mineral fractions and general leachability. The TCLP illustrated the low leachability of heavy metals in soils from two sites. EDTA is a strong chelator and therefore had higher extraction efficiency compared to that of TCLP. The lower extraction percentages by EDTA for As and Sb were found compared to the other heavy metals derived from anthropogenic sources. Sequential extractions showed that the importance of acid-extractable, organically-bound and Fe–Mn oxide fractions was identified for anthropogenic heavy metals with the exception of As and Ni while the importance of residual fraction was identified for endogenous metals. Changes in sequential fractions of heavy metals after leaching with EDTA are very complex and it is difficult to generalize on which fraction was more mobile than the others. These combined results are helpful in elucidating the association of heavy metals to soil fractions and the mobility characteristics of heavy metals under certain environmental conditions.     

Pollution, fractionation, and mobility of Pb, Cd, Cu, and Zn in garden and paddy soils from a Pb/Zn mining area

This study was conducted to investigate the pollution load index, fraction distributions, and mobility of Pb, Cd, Cu, and Zn in garden and paddy soils collected from a Pb/Zn mine in Chenzhou City, China. The samples were analyzed using Leleyter and Probst’s sequential extraction procedures. Total metal concentrations including Pb, Cd, Cu, and Zn exceeded the maximum permissible limits for soils set by the Ministry of Environmental Protection of China, and the order of the pollution index was Cd > Zn > Pb > Cu, indicating that the soils from both sites seriously suffered from heavy metal pollution, especially Cd. The sums of metal fractions were in agreement with the total contents of heavy metals. However, there were significant differences in fraction distributions of heavy metals in garden and paddy soils. The residual fractions of heavy metals were the predominant form with 43.0% for Pb, 32.3% for Cd, 33.5% for Cu, and 44.2% for Zn in garden soil, while 51.6% for Pb, 40.4% for Cd, 40.3% for Cu, and 40.9% for Zn in paddy soil. Furthermore, the proportions of water-soluble and exchangeable fractions extracted by the selected analytical methods were the lowest among all fractions. On the basis of the speciation of heavy metals, the mobility factor values of heavy metals have the following order: Cd (25.2–19.8%) > Cu (22.6–6.3%) > Zn (9.6–6.0%) > Pb (6.7–2.5%) in both contaminated soils.     

Determination of total and EDTA extractable metal distributions in the colloidal fraction of contaminated soils using SdFFF-ICP-HRMS

Newly developed methods involving an on-line combination of sedimentation field-flow fractionation-inductively coupled plasma-high resolution mass spectrometry (SdFFF-ICP-HRMS) have been used to study the distributions of extractable heavy metals in a soil which had been treated with sewage sludge contaminated with Cu or Pb. The relationship of these metals with other elements in the colloidal fraction was also investigated. The colloidal fraction from the soil was obtained by repeated gravitational sedimentation and extracted with 0.11 M acetic acid, 0.1 M hydroxylamine hydrochloride, 0.05 M ethylenediaminetetraacetic acid disodium salt (EDTA) or aqua regia to assess the potential availability of the metals Cu and Pb. Large proportions of the Cu and Pb were extracted by EDTA, approaching that removed by aqua regia, whereas < 10% of the aqua regia extractable metals were removed by acetic acid and hydroxylamine chloride. The distributions of the heavy metals, the major mineral forming element (Al) and the elements forming sesquioxides (Fe and Mn) within different size classes (0.05-1 microm) of the colloidal fraction were measured using SdFFF-ICP-HRMS before and after extraction with EDTA. This information provides an insight into the composition of the colloids and the distributions of metal contaminants. In the contaminated soil colloids, the concentration of Fe, Mn and Pb is greatest in the smaller particles (<0.2 microm). In contrast, the Cu concentration is constant over the size range studied. Iron oxide surface coatings probably play a significant role in Pb adsorption on soil particles, but may be less important for Cu. The combination of selective chemical extraction, SdFFF and ICP-HRMS provides a means of determining the distribution of potentially available heavy metals within the colloidal fraction of contaminated soils.     

Estimation of methane and nitrous oxide emissions from rice field with rice straw management in Cambodia

To estimate the greenhouse gas emissions from paddy fields of Cambodia, the methodology of the Intergovernmental Panel on Climate Change (IPCC) guidelines, IPCC coefficients, and emission factors from the experiment in Thailand and another country were used. Total area under rice cultivation during the years 2005–2006 was 2,048,360 ha in the first crop season and 298,529 ha in the second crop season. The emission of methane from stubble incorporation with manure plus fertilizer application areas in the first crop season was estimated to be 192,783.74 ton higher than stubble with manure, stubble with fertilizer, and stubble without fertilizer areas. The fields with stubble burning emitted the highest emission of methane (75,771.29 ton) followed by stubble burning with manure (22,251.08 ton), stubble burning with fertilizer (13,213.27 ton), and stubble burning with fertilizer application areas (3,222.22 ton). The total emission of methane from rice field in Cambodia for the years 2005–2006 was approximately 342,649.26 ton (342.65 Gg) in the first crop season and 36,838.88 ton (36.84 Gg) in the second crop season. During the first crop season in the years 2005–2006, Battambang province emitted the highest amount of CH₄ (38,764.48 ton) and, in the second crop season during the years 2005–2006, the highest emission (8,262.34 ton) was found in Takeo province (8,262.34 ton). Nitrous oxide emission was between 2.70 and 1,047.92 ton in the first crop season and it ranged from 0 to 244.90 ton in the second crop season. Total nitrous oxide emission from paddy rice field was estimated to be 9,026.28 ton in the first crop season and 1,091.93 ton in the second crop season. Larger area under cultivation is responsible for higher emission of methane and nitrous oxide. Total emission of nitrous oxide by using IPCC default emission coefficient was approximately 2,328.85 ton. The total global warming potential of Cambodian paddy rice soil is 11,723,217.03 ton (11,723 Gg) equivalents of CO₂.     

Mobility of spiromesifen in packed soil columns under laboratory conditions

On percolating water equivalent to 1,156 mm of rainfall, spiromesifen formulation did not leach out of 25-cm long columns, and 62.7 % of this was recovered in 5–10-cm soil depth. In columns treated with the analytical grade, 52.40 % of the recovered spiromesifen was confined to 0–5-cm soil depth, with 0.04 % in leachate fraction, suggesting high adsorption in soil. Results revealed that percolating 400 mL of water, residues of enol metabolite of spiromesifen was detected up to 20–25-cm soil layer, with 23.50 % residues of spiromesifen in this layer and 1.73 % in the leachate fraction indicating that metabolite is more mobile as compared to the parent compound. Results suggested a significant reduction in leaching losses of enol metabolite in amended soil columns with 5 % nano clay, farmyard manure (FYM), and vermicompost. No enol spiromesifen was recovered in the leachate in columns amended with nano clay, vermicompost, and FYM; however, 85.30, 70.5, and 65.40 %, respectively, was recovered from 0–5 cm-soil depth of column after percolating water equivalent to 1,156 mm of rainfall. Spiromesifen formulation is less mobile in sandy loam soil than analytical grade spiromesifen. The metabolite, enol spiromesifen, is relatively more mobile than the parent compound and may leach into groundwater. The study suggested that amendments were very effective in reducing the downward mobility of enol metabolite in soil column. Further, it resulted in greater retention of enol metabolite in the amendment application zone.